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WO2025090983A1 - Traitement de produits organiques pour la production de petits composés organiques halogénés - Google Patents

Traitement de produits organiques pour la production de petits composés organiques halogénés Download PDF

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Publication number
WO2025090983A1
WO2025090983A1 PCT/US2024/053142 US2024053142W WO2025090983A1 WO 2025090983 A1 WO2025090983 A1 WO 2025090983A1 US 2024053142 W US2024053142 W US 2024053142W WO 2025090983 A1 WO2025090983 A1 WO 2025090983A1
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Prior art keywords
acid
small
organic compound
halogenated organic
mixture
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Inventor
Nichole N. PRICE
Stephen D. ARCHER
Hannah Eva BLOSSOM
Kevin M. POSMAN
Athanasios FOUKIS
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BIGELOW LABORATORY FOR OCEAN SCIENCES
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BIGELOW LABORATORY FOR OCEAN SCIENCES
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
    • C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/135—Purification; Separation; Use of additives by gas-chromatography
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y111/00—Oxidoreductases acting on a peroxide as acceptor (1.11)
    • C12Y111/01—Peroxidases (1.11.1)
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y111/00—Oxidoreductases acting on a peroxide as acceptor (1.11)
    • C12Y111/02—Oxidoreductases acting on a peroxide as acceptor (1.11) with H2O2 as acceptor, one oxygen atom of which is incorporated into the product (1.11.2)

Definitions

  • small organic halogenated compounds can competitively inhibit the activity of methyl -coenzyme M reductase (mMCR) and coenzyme M methyltransferase, the enzyme that catalyzes the final step of CH4 synthesis by methanogens found in the rumen (Wood, J. M. et al. Biochemistry (1968) 7(5): 1707-1713; Ferry, J.G. Anm Rev Microbiol (2010) 64:3117-3126).
  • mMCR methyl -coenzyme M reductase
  • coenzyme M methyltransferase the enzyme that catalyzes the final step of CH4 synthesis by methanogens found in the rumen
  • the present disclosure features methods for producing small, halogenated organic compounds from an organic product via a halogenation reaction, wherein the method comprises: (i) preparing the organic product to provide a slurry (e.g., dry slurry); (ii) contacting the slurry with a halogen source and an acid to form a mixture; (iii) mixing the mixture; and/or (iv) acquiring information about the small, halogenated organic compound.
  • the small, halogenated organic compound may comprise 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms.
  • small, halogenated organic compound comprises 1, 2, or 3 halogen atoms.
  • halogen atom is selected from fluorine, chlorine, bromine, and iodine.
  • the small, halogenated organic compound comprises 0, 1, 2, or 3 bromine atoms.
  • the small, halogenated organic compound comprises 0, 1, 2, or 3 chlorine atoms.
  • the small, halogenated organic compound comprises 0, 1, 2, or 3 iodine atoms.
  • small, halogenated organic compound comprises a haloalkyl, a ketone, or an aldehyde.
  • the acid is a peroxyacid.
  • the acid may comprise an inorganic peroxyacid or an organic peroxyacid.
  • the acid comprises a percarboxylic acid.
  • the acid selected from a combination of performic acid, peracetic acid, perpropionic acid, perbutyric acid, pervaleric acid, percaproic acid, perenanthic acid, percaprylic acid, perpelargonic acid, percapric acid, peêtcylic acid, and perlauric acid.
  • the acid comprises peracetic acid (PAA).
  • the acid may comprise an additional peroxide source.
  • the peracid comprises peracetic acid (PAA) and H2O2 as the additional peroxide source.
  • the method further comprises a stabilizing agent.
  • the stabilizing agent comprises canola oil, egg lecithin, or soybean lecithin.
  • the stabilizing agent comprises canola oil.
  • the producing comprises: (i) increasing the amount of the small, halogenated organic compound; or (ii) enhancing the generation of the amount of the small halogenated organic compound, or a combination thereof.
  • the producing comprises: (i) increasing the amount of the small, halogenated organic compound.
  • the producing comprises: (ii) enhancing the generation of the amount of the small, halogenated organic compound.
  • the method may further comprise (v) extracting the small, halogenated organic compound from the mixture.
  • the method comprises acquiring information about the small, halogenated organic compound of step (iv) comprises characterizing the small, halogenated organic compound, e.g., directly or indirectly.
  • acquiring information about the small, halogenated organic compound comprises characterizing the chemical structure, molecular weight, activity, or other feature of the small, halogenated organic compound.
  • the method further comprises concentrating the small, halogenated organic compound responsive to the acquiring information.
  • the concentrating comprises increasing the concentration of the small, halogenated organic compound in a mixture.
  • the preparing may comprises one or more of: (a) optionally thawing the organic product; (b) rinsing the organic product, e.g., with an aqueous solution, e.g., with water; (c) blanching the organic product; (d) quenching the blanching process; (e) allowing the organic product to drip, e g., to decrease a liquid:mass ratio; (f) measuring the moisture content of the organic product, e.g., to determine the liquid:mass ratio, e.g., to achieve an optimal liquid: mass ratio for carrying out the halogenation reaction; (g) measuring the pH, e.g., with a pH strip; (h) pulverizing or homogenizing the organic product, e.g., with a processor; (i) disposing the organic product in a container , e.g., a container suitable for cold storage; and, (j) freezing the organic product, e.g., at -20°C or
  • the preparing comprises (a). In an embodiment, the preparing comprises (b). In an embodiment, the preparing comprises (c). In an embodiment, the preparing comprises (d). In an embodiment, the preparing comprises (e). In an embodiment, the preparing comprises (f). In an embodiment, the preparing comprises (g). In an embodiment, the preparing comprises (h). In an embodiment, the preparing comprises (i). In an embodiment, the preparing comprises (j). In an embodiment, the preparing comprises (b)-(j). In an embodiment, the preparing comprises (b)-(f). In an embodiment, the preparing comprises (c) and (f). In an embodiment, the preparing comprises (b), (c) and (f). In an embodiment, the preparing comprises (b), (c) and (f).
  • the preparing comprises (a), (b), (c) and (f). In an embodiment, the preparing comprises (b) and (c). In an embodiment, the preparing comprises (a)-(h). In an embodiment, the preparing comprises (b)-(h). In an embodiment, the preparing comprises (c), (f) and (h). In an embodiment, the preparing comprises (a), (b), (c), (d), (e), (f), (h), (i), and (j). In an embodiment, the preparing comprises (b), (c), (d), (e), (f), (h), (i), and (j). In an embodiment, the preparing comprises (a), (b), (c), (d), (e), (f) and (h). In an embodiment, the preparing comprises (b), (c), (d), (e), (f) and (h). In an embodiment, the preparing comprises (b), (c), (d), (e), (f) and (h). In an embodiment, the preparing comprises (b), (c), (d), (e), (
  • the contacting comprises one or more of (k) adding the halogen source; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the solution comprising NaOH.
  • the contacting comprises one or more of (k) adding the halogen source; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the solution comprising NaOH.
  • the contacting comprises
  • the contacting comprises (1). In an embodiment, the contacting comprises (m). In an embodiment, the contacting comprises (n). In an embodiment, the contacting comprises (k and (1). In an embodiment, the contacting comprises (k) and (m). In an embodiment, the contacting comprises (k) and (n). In an embodiment, the contacting comprises
  • the contacting comprises (1) and (n). In an embodiment, the contacting comprises (m) and (n). In an embodiment, the contacting comprises (k), (1), and (m). In an embodiment, the contacting comprises (k), (1), and (n). In an embodiment, the contacting comprises (k), (m), and (n).
  • the step (m) may comprise an alkali metal salt, an alkali metal salt, or a transition metal salt.
  • the salt is NaCl.
  • the additive capable of adjusting the pH of step (n) may be a base.
  • the additive capable of adjusting the pH is NaOH.
  • the contacting comprises: (k) adding the acid comprising PAA, optionally comprising H2O2; then (1) adding the halogen source comprising KBr; (m) optionally adding the salt NaCl; and (n) optionally adding the additive NaOH (iii) mixing the mixture; and (iv) acquiring information about the small, halogenated organic compound, thereby producing a small, halogenated organic compound.
  • the method may further comprises one or more of the following steps: (o) adding lactic acid to the mixture comprising the small, halogenated organic compound; (p) decreasing the pH of the mixture, comprising incorporating an additive that lowers the pH of the mixture; (q) adding a silage inoculant to the mixture comprising a bacterial inoculum capable of undergoing anaerobic fermentation in the presence of lactic acid; and (r) disposing the mixture in a container suitable for anaerobic fermentation and long-term storage.
  • the present disclosure features methods for producing small, halogenated organic compounds from an organic product via a halogenation reaction, the method comprising: (i) preparing the organic product to provide a slurry, wherein the preparing comprises one or more of: (a) optionally thawing the organic product; (b) rinsing the organic product, e.g., with an aqueous solution, e.g., with water; (c) blanching the organic product; (d) quenching the blanching process; (e) allowing the organic product to drip, e.g., to decrease a liquid:mass ratio; (f) measuring the moisture content of the organic product, e.g., to determine the liquid: mass ratio, e.g., to achieve an optimal liquid:mass ratio for carrying out the halogenation reaction; (g) measuring the pH, e g., with a pH strip; (h) pulverizing or homogenizing the organic product, e g., with a
  • the blanching temperature may be in a range between 60°C to 100°C, 65°C to 95°C, 70°C to 90°C, or 75°C to 85°C. In an embodiment, the blanching temperature is in a range between 60°C to 100°C. In an embodiment, the blanching temperature is in a range between 65°C to 95°C. In an embodiment, the blanching temperature is in a range between 70°C to 90°C. In an embodiment, the blanching temperature is in a range between 75°C to 85°C.
  • the blanching temperature is 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71 °C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81 °C, 82°C,
  • the blanching temperature is 60°C, 75°C, 80°C, or 85°C. In an embodiment, the blanching temperature is 60°C. In an embodiment, the blanching temperature is 75°C. In an embodiment, the blanching temperature is 80°C. In an embodiment, the blanching temperature is 85°C.
  • the organic product comprises an organic material derived from cyanobacteria, Kingdom plantae, and Kingdom fungi.
  • the organic product is the organic material derived from cyanobacteria.
  • the organic product is the organic material derived from Kingdom plantae.
  • the organic product is the organic material derived from Kingdom fungi.
  • the organic material is derived from Kingdom plantae is an alga.
  • the alga is a macroalga.
  • the macroalga is selected from the genus Saccharina and the genus Graciliaria.
  • the macroalga comprises Saccharina latissima.
  • the method may further comprise extracting the small, halogenated organic compound, thereby producing an extractant comprising the small, halogenated organic compound.
  • the extraction comprises liquid-phase extraction or solid-phase extraction.
  • the extracting comprises the use of an extraction solvent.
  • the extraction solvent comprises hexane or methanol.
  • the extraction solvent is hexane.
  • the extraction solvent is methanol.
  • the acquiring further comprises characterizing the extractant of any of the previous claims for the small, halogenated organic compound with an analytical method.
  • the analytical method comprises gas chromatography (GC), mass spectrometry (MS), or gas chromatography-mass spectrometry(GC-MS).
  • the analytical method is gas chromatography (GC) or a variant thereof.
  • the analytical method is mass spectrometry (MS) or a variant thereof.
  • the analytical method is gas chromatography-mass spectrometry (GC-MS).
  • the present disclosure feature features methods further comprising: (o) adding lactic acid to the solution comprising the small, halogenated organic compound; (p) decreasing the pH of the solution, comprising incorporating an additive that lowers the pH of the solution; (q) adding a silage inoculant to the solution comprising a bacterial inoculum capable of undergoing anaerobic fermentation in the presence of lactic acid; and (r) disposing the solution in a container suitable for anaerobic fermentation and favorable for long-term storage.
  • the method further comprises measuring the concentration of acid comprising the use of a test strip capable of detecting the presence of acid; and (t) monitoring side reactions.
  • the KBr concentration may be selected from 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, and 100 mM.
  • the reaction time may be selected from 1 min, 5 min, 10 min, 20 min, 30 min, 1 h, 2 h, 3 h, 6 h, 12 h, 24 h, 36 h, 48 h, 72 h or 1 week.
  • the reaction temperature may be between 5°C-50°C, 10 °C-45 °C, 15°C-40°C, 15 °C-35 °C, 15°C-30°C, or 15°C-25°C. In an embodiment, the reaction temperature is between 15°C to 25°C.
  • the method may further comprise an enzyme.
  • the enzyme comprises an oxidoreductase, an amylase, a lipase, a protease, a cellulase, or a glucanase.
  • the enzyme is a catalase.
  • enzyme is an oxidoreductase.
  • the oxidoreductase is a peroxidase.
  • the peroxidase is a haloperoxidase.
  • the enzyme is a vanadium haloperoxidase (VHPO).
  • the vanadium haloperoxidase may comprise a vanadium bromoperoxidase, vanadium chloroperoxidase, or a vanadium iodoperoxidase.
  • the vanadium haloperoxidase is a vanadium bromoperoxidase.
  • the enzyme may be a combination of enzymes.
  • the present disclosure features methods for producing a small, halogenated organic compound from a organic product via a halogenation reaction, the method comprising: (i) preparing the organic product to provide a slurry; (ii) contacting the slurry with a halogen source and an enzyme to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small, halogenated organic compound, thereby producing a small, halogenated organic compound.
  • the methods of the present disclosure feature contacting the slurry with an acid.
  • the present disclosure features methods for producing a small halogenated organic compound from an organic product via a halogenation reaction, the method comprising: (i) preparing the organic product to provide a slurry, wherein the preparing comprises: (a) optionally thawing the organic product; (b) rinsing the organic product, e.g., with an aqueous solution, e.g., with water; (c) blanching the organic product; (d) quenching the blanching process; (e) allowing the organic product to drip, e.g., to decrease a liquid:mass ratio; (f) measuring the moisture content of the organic product, e.g., to determine the liquid:mass ratio, e.g., to achieve an optimal liquid: mass ratio for carrying out the halogenation reaction; (g) measuring the pH, e.g., with a pH strip; (h) pulverizing or homogenizing the organic product, e g., with a processor; (i) dispos
  • Heterocyclyl refers to a radical of a 3- to 10-membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, sulfur, boron, phosphorus, and silicon (“3-10 membered heterocyclyl”).
  • the point of attachment can be a carbon or nitrogen atom, as valency permits.
  • a heterocyclyl group may be described as, e.g., a 3-7-membered heterocyclyl, wherein the term “membered” refers to the nonhydrogen ring atoms, i.e., carbon, nitrogen, oxygen, sulfur, boron, phosphorus, and silicon, within the moiety.
  • Each instance of heterocyclyl may be independently optionally substituted, i.e., unsubstituted (an “unsubstituted heterocyclyl”) or substituted (a “substituted heterocyclyl”) with one or more substituents.
  • the heterocyclyl group is unsubstituted 3-10 membered heterocyclyl.
  • the heterocyclyl group is substituted 3- 10 membered heterocyclyl.
  • the agricultural feedstock may comprise waste and/or waste products.
  • Exemplary waste or waste products may include an animal product (e.g., manure), municipal waste, industrial waste, solid waste, wet waste, unprocessed waste, or processed waste.
  • the agricultural feedstock may comprise a waste management system, such as an aqueous waste management system or an industrial waste management system.
  • An exemplary aqueous waste management system includes a lagoon.
  • the agricultural feedstock comprises a municipal waste management system.
  • the methods described herein for modulating the production of a small halogenated organic compound features a plant-derived material, e.g., a corn or soya- derived organic material.
  • the methods described herein for modulating the production of a small halogenated organic compound features an alga.
  • the alga is a microalga.
  • the alga is a cyanobacterium.
  • the alga is a macroalga.
  • the methods described herein for modulating the production of a small organic compound features a macroalga.
  • the macroalga is a brown macroalga, a green macroalga, or a red macroalga.
  • the macroalga is a brown macroalga.
  • the macroalga is a green macroalga.
  • the macroalga is a red macroalga.
  • the macroalga is derived from a littoral zone. In some embodiments, the macroalga is derived from an intertidal zone. In some embodiments, macroalga is derived from an algaculture, e.g., a seaweed farm, or a seaweed cultivator. In some embodiments, the methods described herein for modulating the production of a small organic compound features a macroalga from the genera: Caulerpa, Fucus, Gracilaria, Laminaria, Macrocystis, Monostroma, Porphyra, Saccharina and Sar gassum. In some embodiments, the macroalga belongs to the genus Caulerpa.
  • the macroalga belongs to the genus Fucus. In some embodiments, the macroalga belongs to the genus Gracilaria. In some embodiments, the macroalga belongs to the genus Laminaria. In some embodiments, the macroalga belongs to the genus Macrocystis. In some embodiments, the macroalga belongs to the genus Monostroma. In some embodiments, the macroalga belongs to the genus Porphyra. In some embodiments, the macroalga belongs to the genus Saccharina. In some embodiments, the macroalga belongs to the genus Sargassum. In some embodiments, the microalga belongs to the genus Alaria.
  • Marine plants such as macroalgae are especially preferred as halogenation substrates.
  • Exemplary macroalgae comprising a small organic compound or a plurality of small organic compounds serving as halogenation substrates include species belonging to the genera Saccharina and Gracilaria.
  • the present disclosure features methods for producing a small halogenated organic compound from an agricultural feedstock, e.g., via treatment with an acid.
  • the acid may comprise an organic acid, e.g., comprising a C1-C25 alkyl, e.g., a Ci alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, Ce alkyl, C7 alkyl, Cs alkyl, C9 alkyl, C10 alkyl, Cn alkyl, C12 alkyl, C13 alkyl, C14 alkyl, C15 alkyl, Ci6 alkyl, C17 alkyl, Cis alkyl, C19 alkyl, C20 alkyl, C21 alkyl, C22 alkyl, C23 alkyl, C24 alkyl, or C25 alkyl acid moiety.
  • a Ci alkyl e.g., a Ci alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, Ce alkyl, C7 alkyl, Cs alkyl, C9 alkyl
  • the organic acid comprises a C2-C26 alkenyl, e.g., a C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, Ce alkenyl, C7 alkenyl, Cs alkenyl, C9 alkenyl, C10 alkenyl, C11 alkenyl, C12 alkenyl, C13 alkenyl, C14 alkenyl, C15 alkenyl, Cie alkenyl, C17 alkenyl, Cis alkenyl, C19 alkenyl, C20 alkenyl, C21 alkenyl, C22 alkenyl, C23 alkenyl, C24 alkenyl, or C25 alkenyl acid moiety.
  • a C2-C26 alkenyl e.g., a C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, Ce alkenyl, C7 alkenyl
  • the organic acid comprises a C2-C26 alkynyl, e.g., a C2 alkynyl, C3 alkynyl, C4 alkynyl, C5 alkynyl, Ce alkynyl, C7 alkynyl, Cs alkynyl, C9 alkynyl, C10 alkynyl, Cn alkynyl, C12 alkynyl, C13 alkynyl, C14 alkynyl, C15 alkynyl, Ci6 alkynyl, C17 alkynyl, Cis alkynyl, C19 alkynyl, C20 alkynyl, C21 alkynyl, C22 alkynyl, C23 alkynyl, C24 alkynyl, or C25 alkynyl acid moiety.
  • a C2-C26 alkynyl e.g., a C2 alkynyl, C3 alkyny
  • the organic acid comprises a C1-C25 heteroalkyl, e.g., a Ci heteroalkyl, C2 heteroalkyl, C3 heteroalkyl, C4 heteroalkyl, C5 heteroalkyl, Ce heteroalkyl, C7 heteroalkyl, Cs heteroalkyl, C9 heteroalkyl, C10 heteroalkyl, Cn heteroalkyl, C12 heteroalkyl, C13 heteroalkyl, C14 heteroalkyl, C15 heteroalkyl, Cie heteroalkyl, C17 heteroalkyl, Cis heteroalkyl, C19 heteroalkyl, C20 heteroalkyl, C21 heteroalkyl, C22 heteroalkyl, C23 heteroalkyl, C24 heteroalkyl, or C25 heteroalkyl acid moiety.
  • a Ci heteroalkyl e.g., a Ci heteroalkyl, C2 heteroalkyl, C3 heteroalkyl, C4 heteroalkyl, C5 heteroalkyl, Ce hetero
  • the method for modulating the production of a small, halogenated compound features a C1-C25 heteroalkyl, including at least one carbon atom and at least one heteroatom selected from the group consisting of O, N, P, Si, and S, and wherein the nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen heteroatom may optionally be quatemized.
  • the heteroatom(s) O, N, P, S, and Si may be placed at any position of the heteroalkyl group.
  • the organic acid comprises a C3-C10 cycloalkyl, e.g., a C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, Ce cycloalkyl, C7 cycloalkyl, Cs cycloalkyl, C9 cycloalkyl, or C10 cycloalkyl acid moiety.
  • the organic acid comprises a C3-C10 heterocyclyl, e.g., a C3 heterocyclyl, C4 heterocyclyl, C5 heterocyclyl, Ce heterocyclyl, C7 heterocyclyl, Cs heterocyclyl, C9 heterocyclyl, or C10 heterocyclyl acid.
  • the organic acid comprises a C3-C10 aryl, e.g., a C3 aryl, C4 aryl, C5 aryl, Ce aryl, C7 aryl, Cs aryl, C9 aryl, or C10 aryl acid.
  • the organic acid comprises a C3-C10 heteroaryl, e.g., a C3 heteroaryl, C4 heteroaryl, C5 heteroaryl, Ce heteroaryl, C7 heteroaryl, Cs heteroaryl, C9 heteroaryl, or C10 heteroaryl acid.
  • a C3-C10 heteroaryl e.g., a C3 heteroaryl, C4 heteroaryl, C5 heteroaryl, Ce heteroaryl, C7 heteroaryl, Cs heteroaryl, C9 heteroaryl, or C10 heteroaryl acid.
  • the organic acid comprises a carboxylic acid.
  • the organic acid comprises an alkyl (e.g., heteroalkyl), cycloalkyl (e.g., heterocyclyl), alkenyl, alkynyl, or aryl (e.g., heteroaryl) moiety.
  • alkyl e.g., heteroalkyl
  • cycloalkyl e.g., heterocyclyl
  • alkenyl alkynyl
  • aryl e.g., heteroaryl
  • the organic acid is capable of undergoing a keto-enol tautomerization.
  • the organic acid is capable of oxidizing an electrophilic halide compound to its hypohalous acid, e.g., HOF, H0C1, HOI, or HOBr.
  • hypohalous acid e.g., HOF, H0C1, HOI, or HOBr.
  • the organic acid is a Lewis acid. In some embodiments, the organic acid is a Bronsted-Lowry acid.
  • the organic acid is a strong acid. In some embodiments, the organic acid is a weak acid. In some embodiments, the organic acid is a superacid.
  • the method for modulating the production of a small halogenated organic compound features an organic acid, wherein the pKa of the organic acid is between about -10 and +20, about -9 and +20, about -8 and +20, about -7 and +20, about -6 and +20, about -5 and +20, about -4 and +20, about -3 and +20, about -2 and +20, about -1 and +20, about 0 and +20, about +1 and +20, about +2 and +20, about +3 and +20, about +4 and +20, about +5 and +20, about +6 and +20, about +7 and +20, about +8 and +20, about +9 and +20, about +10 and +20, about +11 and +20, about +12 and +20, about +13 and +20, about +14 and +20, about +15 and +20, about +16 and +20, about +17 and +20, about +18 and +20, or about +19 and +20.
  • the organic acid is a Ci organic acid, e.g., carbonic acid or formic acid.
  • the organic acid is a C2 organic acid, e.g., acetic acid, glycolic acid, glyoxylic acid, or oxalic acid.
  • the organic acid is a C3 organic acid, e.g., acrylic acid, 2,2-dihydroxypropanedioic acid, 2,3 -diox opropanoic acid , glyceric acid, glycidic acid, 3 -hydroxypropionic acid, lactic acid, malonic acid, mesoxalic acid, 3-oxopropanoic acid, propiolic acid, propionic acid, pyruvic acid, or tartronic acid.
  • a C3 organic acid e.g., acrylic acid, 2,2-dihydroxypropanedioic acid, 2,3 -diox opropanoic acid , glyceric acid, glycidic acid, 3 -hydroxypropionic acid, lactic acid, malonic acid, mesoxalic acid, 3-oxopropanoic acid, propiolic acid, propionic acid, pyruvic acid, or tartronic acid.
  • the organic acid is a C4 organic acid, e.g., butanoic acid, 2-methylpropanoic acid, (E)-but-2-enoic acid, (Z)- but-2-enoic acid, 2-methylpropenoic acid, but-3-enoic acid, but-2-ynoic acid, 2-hydroxybutanoic acid, 3 -hydroxybutanoic acid, 4-hydroxybutanoic acid, 2-oxobutanoic acid, 3-oxobutanoic acid, 4-oxobutanoic acid, butanedioic acid, 2-methylpropanedioic acid, (E)-butenedioic acid, (Z)- butenedioic acid, butynedioic acid, hydroxy butanedioic acid, 2,3 -dihydroxybutanedioic acid, oxobutanedioic acid, dioxobutanedioic acid.
  • C4 organic acid e.g., buta
  • the organic acid is a C5 organic acid, e.g., pentanoic acid, 3-methylbutanoic acid, 2-methylbutanoic acid, 2- methylbutanoic acid, 2,2-dimethylpropanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, 3 -hydroxy-3 -methylbutanoic acid, pentanedioic acid, 2-oxopentanedioic acid, 3- oxopentanedioic acid, furan-2-carboxylic acid, or tetrohydrofuran-2-carboxylic acid.
  • C5 organic acid e.g., pentanoic acid, 3-methylbutanoic acid, 2-methylbutanoic acid, 2- methylbutanoic acid, 2,2-dimethylpropanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, 3 -hydroxy-3 -methylbutanoic acid, pentanedioic acid, 2-o
  • the organic acid is a Ce organic acid, e.g., hexanoic acid, hexanedioic acid, 2,3- dimethylbutanoic acid, 3,3-dimethylbutanoic acid, citric acid, prop-l-ene-l,2,3-tricarboxylic acid, l-hydroxypropane-l,2,3-tricarboxylic acid, (2E,4E)-hexa-2,4-dienoic acid.
  • Ce organic acid e.g., hexanoic acid, hexanedioic acid, 2,3- dimethylbutanoic acid, 3,3-dimethylbutanoic acid, citric acid, prop-l-ene-l,2,3-tricarboxylic acid, l-hydroxypropane-l,2,3-tricarboxylic acid, (2E,4E)-hexa-2,4-dienoic acid.
  • the organic acid is a C7 organic acid, e g., heptanoic acid, heptandioic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, 2,2-dimethylpentanoic acid, 2,3- dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3, 3 -dimethylpentanoic acid, 2- ethylpentanoic acid, 3 -ethylpentanoic acid, 2-methylhexanoic acid, 3 -methylhexanoic acid, 2,2,3 -trimethylbutanoic acid, 2-ethyl-2-methylbutanoic acid or 2-ethyl-3methylbutanoic acid.
  • the organic acid is a Cs organic acid, e.g., caprylic acid, phthalic acid, isphthalic acid, terephthalic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4- methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2,2-dimethylhexanoic acid, 2,3 -dimethylhexanoic acid, 2,4-dimethylhexanoic acid, 2,5-dimethylhexanoic acid, 3,3- dimethylhexanoic acid, 3,4-dimethylhexanoic acid, 3,5-dimethylhexanoic acid, 4,4- dimethylhexanoic acid, 4,5-dimethylhexanoic acid, 5,5-dimethylhexanoic acid, 2-ethanehexanoic acid, 3 -ethanehexanoic acid, 4 -ethanehexanoic acid, 5-
  • the organic acid is a C9 organic acid, e.g., pelargonic acid, trimesic acid, or cinnamic acid.
  • the organic acid is a C10 organic acid, e.g., capric acid or sebacic acid.
  • the organic acid is a Cn organic acid, e g., undecanoic acid.
  • the organic acid is a C12 organic acid, e.g., lauric acid or mellitic acid.
  • the organic acid is a C13 organic acid, e.g., tridecylic acid.
  • the organic acid is a C14 organic acid, e.g., myristic acid.
  • the organic acid is a C15 organic acid, e.g., pentadecylic acid. In some embodiments, the organic acid is a Ci6 organic acid, e.g., palmitic acid. In some embodiments, the organic acid is a C17 organic acid, e.g., margaric acid. In some embodiments, the organic acid is a Ci8 organic acid, e.g., stearic acid, oleic acid, linoleic acid, a-linolenic acid, y-linolenic acid, or stearidonic acid. In some embodiments, the organic acid is a C19 organic acid, e.g., nonadecylic acid.
  • the organic acid is a C20 organic acid, e.g., arachidic acid, Mead’s acid, arachidonic acid, or eicosapentanoic acid.
  • the organic acid is a C21 organic acid, e.g., heneicosanoic acid.
  • the organic acid is a C22 organic acid, e.g., behenic acid or docosahexaenoic acid.
  • the organic acid is a C23 organic acid, e.g., trocosylic acid.
  • the organic acid is a C24 organic acid, e.g., lignoceric acid.
  • the organic acid is a C25 organic acid, e.g., pentacosylic acid.
  • the organic acid is a Cs organic acid, e.g., hexacosanoic acid.
  • the concentration of the organic acid is less than 10 mM, less than 9 mM, less than 8 mM, less than 7 mM, less than 6 mM, less than 5 mM, less than 4 mM, less than 3 mM, less than 2 mM, or less than 1 mM. In some embodiments, the concentration of the the organic acid is less than 10 mM. In some embodiments, the concentration of the organic acid is less than 9 mM. In some embodiments, the concentration of the organic acid is less than 8 mM. In some embodiments, the concentration of the organic acid is less than 7 mM. In some embodiments, the concentration of the organic acid is less than 6 mM.
  • the organic acid is a peroxyacid, e.g., an organic peroxyacid (also commonly referred to as a peracid) with an -OOH moiety.
  • the organic peroxyacid is a percarboxylic acid.
  • Exemplary peroxyacids suitable for the invention include performic acid, peracetic acid, perpropionic acid, perbutyric acid, pervaleric acid, percaproic acid, perenanthic acid, percaprylic acid, perpelargonic acid, percapric acid, peêtcylic acid, and perlauric acid, or a combination thereof.
  • the acid is peracetic acid (PAA).
  • the organic acid e.g., peracetic acid (PAA) is a mixture of substances, e.g., a mixture of acids.
  • PAA peracetic acid
  • the PAA comprises about 10% w/v to about 80% w/v acetic acid; about 10% w/v to about 50% w/v peracetic acid, about 1% w/v to about 20% w/v hydrogen peroxide, and about 0.1% w./v to about 10% w/v sulfuric acid.
  • the method for producing the small halogenated organic compound comprise use of a peroxy acid, such as peracetic acid (PAA).
  • a peroxy acid such as peracetic acid (PAA).
  • PAA peracetic acid
  • the peroxy acid e.g., PAA
  • the method for producing the small, halogenated organic compound, as well as related compositions thereof features PAA as the acid, wherein PAA is less than 10 mM.
  • the method for producing the small, halogenated organic compound, as well as related compositions thereof features PAA as the acid, wherein PAA is less than 9 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 8 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 7 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 6 mM.
  • the method for producing the small, halogenated organic compound, as well as related compositions thereof features PAA as the acid, wherein PAA is less than 5 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 4 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 3 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 2 mM. In embodiments, the method for producing the small, halogenated organic compound, as well as related compositions thereof, features PAA as the acid, wherein PAA is less than 1 mM.
  • the methods described herein for modulating the production of a small, halogenated organic compound further comprise use of an oxidizing agent.
  • the oxidizing agent is an electron acceptor.
  • the oxidizing agent is an atom-transfer reagent.
  • Exemplary oxidizing agents include dioxygen (O2), ozone (O3), hydrogen peroxide, sodium chlorate, magnesium chlorate, potassium chlorate, lithium hypochlorite, sodium hypochlorite, calcium hypochlorite, barium hypochlorite, sodium perchlorate, ammonium perchlorate, potassium perchlorate, or perchloric acid.
  • the oxidizing agent comprises a chlorine bleach, e.g., sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, chloramine, tosylchloramide sodium salt, sodium dichloroisocyanurate, 4-((dichloroamino)sulfonyl)benzoic acid, and chlorine dioxide.
  • a chlorine bleach e.g., sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, chloramine, tosylchloramide sodium salt, sodium dichloroisocyanurate, 4-((dichloroamino)sulfonyl)benzoic acid, and chlorine dioxide.
  • the oxidizing agent comprises a non-chlorine bleach, e.g., sodium perborate, sodium percarbonate or sodium perborate.
  • the oxidizing agent comprises a non-chlorine bleach optionally comprising an activator, e.g., tetraacetylethylenediamine or sodium nonanoyloxybenzenesulfonate.
  • the organic acid is a mixture of an organic acid and an oxidizing agent.
  • the oxidizing agent is a peroxide.
  • the oxidizing agent is hydrogen peroxide (H2O2).
  • the organic acid comprises a mixture of PAA and H2O2.
  • the present disclosure features methods for modulating the production of small, halogenated organic compounds comprising a halogen source.
  • the halogen source is an organic halide salt or an inorganic halide salt.
  • the halogen source is an inorganic halide salt, wherein the metal cation is an alkali metal cation (e.g., Li + , Na + , K + ), alkali earth (e.g., Mg 2+ , Ca 2+ ), Mn 2+ , or Zn 2+ , inter alia.
  • the halogen source is an inorganic halide salt, wherein the halide is F’, Cl', Br', or I'.
  • the halogen source is selected from LiF, LiCl, LiBr, Lil, NaF, NaCl, NaBr, Nal, KF, KC1, KBr, KI, MgF 2 , MgCl 2 , MgBr 2 , Mgl 2 , CaF 2 , CaCl 2 , CaBr 2 , Cal 2 , MnF 2 , MnCl 2 , MnBr2, Mnl 2 , ZnF 2 , ZnCl 2 , ZnBr 2 , and Znl 2 .
  • the halogen source is KBr, NaCl, or KI.
  • the halogen source is potassium bromide (KBr).
  • the KBr concentration is less than 5 mM, less than 4.5 mM, less than 4 mM, less than 3.5 mM, less than 3 mM, less than 2.5 mM, less than 2mM, less than 1 .5 mM, less than 1.0 mM, less than 0.5 mM, or less than 0.1 mM. In some embodiments, the KBr concentration is less than 5 mM. In some embodiments, the KBr concentration is less than 4.5 mM. In some embodiments, the KBr concentration is less than 4 mM. In some embodiments, the KBr concentration is less than 3.5 mM. In some embodiments, KBr concentration is less than 3 mM.
  • the KBr concentration is less than 2.5 mM. In some embodiments, KBr concentration is less than 2 mM. In some embodiments, the KBr concentration is less than 1.5 mM. In some embodiments, the KBr concentration is less than 1 mM. In some embodiments, the KBr concentration is less than 0.5 mM. In some embodiments, the KBr concentration is less than 0.1 mM.
  • the methods described herein may further comprise use of an enzyme to facilitate production of a small halogenated organic compound.
  • the enzyme may be a peroxidase enzyme, such as a haloperoxidase.
  • a haloperoxidase is an enzyme which catalyzes the conversion of an organic compound to a halogenated organic compound in the presence of a peroxide source, e.g., hydrogen peroxide.
  • the peroxidase may be any peroxidase known in nature, including a haloperoxidase.
  • the haloperoxidase is a vanadium haloperoxidase (VHPO).
  • the VHPO is a vanadium chloroperoxidase (VCPO), vanadium bromoperoxidase (VBPO), or vanadium iodoperoxidase (VIPO).
  • VHPO vanadium chloroperoxidase
  • VBPO vanadium bromoperoxidase
  • VIPO vanadium iodoperoxidase
  • the VHPO is a VBPO.
  • the peroxidase may be an algal haloperoxidase (e.g., derived from an algal species) or a fungal haloperoxidase (e.g., derived from a fungal species).
  • the peroxidase is a fungal haloperoxidase (e.g., derived from a fungal species).
  • the peroxidase may be derived from an organism selected from Curvularia inaequalis, Halomicronema hongdechloris, Moorea bouillonii, Trichodesmium erylhraeum, Aphanocapsa montana, Lyngbya confervoides, Synechococcus sp. PCC7335, and Corallina officinalis.
  • the peroxidase is derived from Corallina officinalis.
  • the peroxidase is derived from Aphanocapsa montana.
  • the peroxidase is derived from Curvularia inaequalis.
  • the peroxidase comprises a sequence of a peroxidase described herein, e.g., a peroxidase sequence provided in Table 1.
  • the peroxidase may be produced in a host cell microorganism, e.g., overexpressed in a host cell microorganism.
  • the host cell microorganism is selected from Pichia pastoris, Aspergillus niger, Saccharomyces cerevisiae, o Escherichia coli.
  • expression of the peroxidase produced in the host cell microorganism is increased by about 1.5- fold, 2-fold, 3-fold, 4-fold, 5-fold, 6-fold, 7-fold, 8-fold, or 10-fold, e.g., over a peroxidase produced in its native host.
  • the amino acid sequence of the peroxidase is selected from an amino acid sequence listed in Table 2.
  • the peroxidase has at least 75% sequence identity (e.g., at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99%, or 99.5% sequence identity) to a peroxidase sequence selected from the list in Table 2.
  • the peroxidase is a sequence selected from any one of SEQ ID NOs. 1-50.
  • the peroxidase has at least 75% sequence identity (e.g., at least 80%, 85%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 99%, or 99.5% sequence identity) to a peroxidase sequence selected from SEQ ID NOs: 1-50.
  • the peroxidase an amino acid sequence selected from any one of SEQ ID NOs. 1-50.
  • the enzyme is provided as an extract, e.g., a crude or purified concentrate of the enzyme. In an embodiment, the enzyme is provided as a crude extract.
  • the peroxidase (e g., haloperoxidase) comprises an amino acid sequence of Formula (I): X1GHAX2, wherein Xi is serine or alanine, and X2 is valine or threonine.
  • the amino acid sequence of Formula (I) is selected from SGHAV, SGHAT, AGHAV, and AGHAT.
  • the peroxidase comprises an amino acid sequence of Formula (I-a): X3YG X1GHAX2, wherein Xi is serine or alanine, X2 is valine or threonine, and X3 is serine or alanine.
  • the amino acid sequence of Formula (I-a) is selected from SYGSGHAV, SYGSGHAT, AYGAGHAV, AYGAGHAT, SYGSGHAV, SYGSGHAT, AYGAGHAV, and AYGAGHAT.
  • the peroxidase (e.g., the haloperoxidase) comprises an amino acid sequence of Formula (I-b): HPX3YG X1GHAX2, wherein Xi is serine or alanine, X2 is valine or threonine, and X3 is serine or alanine.
  • the amino acid sequence of Formula (I-a) is selected from HPSYGSGHAV, HPSYGSGHAT, HP AYGAGHAV, HP AYGAGHAT, HPSYGSGHAV, HPSYGSGHAT, HP AYGAGHAV, and HP AYGAGHAT.
  • the enzyme is a combination of haloperoxidases, e.g., a bromoperoxidase and a chloroperoxidase.
  • the small, halogenated organic compound comprises an alkenyl or alkynyl group. In an embodiment, the small, halogenated organic compound comprises an aldehyde or a ketone group. In an embodiment, the small, halogenated organic compound comprises an a,0- unsaturated ketone. In an embodiment, the small, halogenated organic compound comprises 1, 2, 3, 4 ,5, 6, 7, or 8 carbon atoms. In an embodiment, the small, halogenated organic compound comprises 1, 2, or 3 halogen atoms. In an embodiment, the small, halogenated organic compound comprises 1, 2, or 3 bromine atoms. In an embodiment, the small, halogenated organic compound comprises 1, 2, or 3 chlorine atoms.
  • the small, halogenated organic compound comprises 1,1 -diiodoacetone, 1,3- diiodoacetone, iodoacetone, iodopentanedione, iodoform, 1,1,1 -triiodoacetone.
  • the small, halogenated organic compound is 1 -bromo- 1 -chloroacetone, l-bromo-3- chloroacetone, 1 -bromo- 1 -iodoacetone, 1 -chloro- 1 -iodoacetone, l-chloro-3 -iodoacetone, dibromochloromethane, dibromoiodomethane, bromodichloromethane, bromodiiodomethane, dichloroiodomethane, bromochloroiodomethane, or chlorodiiodomethane.
  • the small, halogenated organic compound is 1 -bromo- 1 -chloro- 1 -iodoacetone, 1 -bromo- 1- di chloroacetone, 1 -dibromo- 1 -chloroacetone, 1 -bromo- 1 -diiodoacetone, 1 -dibromo- 1- iodoacetone, or 1 -chloro- 1 -diiodoacetone.
  • the small, halogenated organic compound comprises 1,1 -dibromoacetone, bromoacetone, 3-bromo-2,4-pentanedione, bromoform, 1,1, 3 -tribromoacetone, or 1,1,1 -tribromoacetone.
  • the small, halogenated organic compound comprises 1,1 -di chloroacetone, 1,1 -diiodoacetone, 1-bromo- chloroacetone, 1 -bromo- 1 -iodoacetone.
  • the small, halogenated organic compound is 3-chloro-2,4-pentanedione or 3-iodo-2,4-pentadione.
  • the small, halogenated organic compound comprises chloroform or iodoform.
  • the small, halogenated organic compound comprises 1,1,1 -tri chloroacetone, 1,1, 3 -tri chloroacet one, 1,1,1 -triiodoacetone, 1,1,3-triiodoacetone, 1,1 -dibrom o-l -chloroacetone, l,l-dibromo-3- chloroacetone, 1,3 -dibromo- 1 -chloroacetone, 1 -bromo- 1,1 -dichloroacetone, l-bromo-3,3- di chloroacetone, 1 -bromo- 1,3-di chloroacetone, 1,1 -dibromo- 1 -iodoacetone, l,l-dibromo-3- iodoacetone, 1,3 -dibromo- 1 -iodoacetone,
  • the small, halogenated compound comprises dichloroiodomethane, dichlorobromomethane, dibromoiodomethane, diiodochloromethane, or diiodobromomethane.
  • the small, halogenated organic compound comprises 1,1 -dibromoacetone, bromoacetone, 3-bromo-2,4-pentanedione, bromoform, 1,1, 3 -tribromoacetone, or 1 , 1 , 1 -tribromoacetone, dichloroiodomethane, dichlorobromomethane, dibromoiodomethane, diiodochloromethane, or diiodobromomethane.
  • the small, halogenated organic compound comprises 1,1 -dichloroacetone, chloroacetone, 3-chloro-2,4-pentanedione, chloroform, 1,1,1 -tri chloroacetone, 1,1,3- tri chloroacetone, dichloroiodomethane, dichlorobromomethane, dibromoiodomethane, diiodochloromethane, or diiodobromomethane.
  • the small, halogenated organic compound comprises 1,1 -diiodoacetone, iodoacetone, 3-iodo-2,4-pentanedione, iodoform, 1,1,1 -triiodoacetone, 1,1,3-triidoacetone, dichloroiodomethane, dichlorobromomethane, dibromoiodomethane, diiodochloromethane, or diiodobromomethane.
  • the small, halogenated organic compound comprises bromoform or iodoform.
  • the small, halogenated organic compound may comprise any halogen atom, such as a chlorine atom, a bromine atom, or an iodine atom.
  • the small, halogenated organic compound comprises 1, 2, 3, 4, 5, 6, or more halogen atoms.
  • the small, halogenated organic compound comprises 1, 2, 3, 4, 5, 6, or more chlorine atoms.
  • the small, halogenated organic compound comprises 1, 2, 3, 4, 5, 6, or more bromine atoms.
  • the small, halogenated organic compound comprises 1, 2, 3, 4, 5, 6, or more iodine atoms.
  • the small, halogenated organic compound comprises bromoacetone, dibromoacetone, bromopetandione, bromoform, tribromoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises 1,1 -dibromoacetone, bromoacetone, 3-bromo-2,4-pentanedione, bromoform, 1,1,3- tribromoacetone, 1,1,1 -tribromoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises dichloroacetone, chloroacetone, chloropentanedione, chloroform, tri chloroacetone or a variant or analog thereof.
  • the small, halogenated organic compound comprises 1,1 -diiodoacetone, 1,3- diiodoacetone, iodoacetone, iodopentandione, iodoform, 1,1,1 -triiodoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises 1- bromo-1 -chloroacetone, l-bromo-3 -chloroacetone, 1 -bromo- 1 -iodoacetone, 1 -chloro- 1- iodoacetone, 1 -chi oro-3 -iodoacetone, dibromochloromethane, dibromoiodomethane, bromodichloromethane, bromodiiodomethane, dichloroiodomethane, bromochloroiodomethane, chlorodiiodomethane, or a variant or analog thereof.
  • the small, halogenated organic compound comprises 1 -bromo- 1 -chloro- 1 -iodoacetone, 1 -bromo- 1 -dichloroacetone, 1- dibromo-1 -chloroacetone, 1 -bromo- 1 -diiodoacetone, 1 -dibromo- 1 -iodoacetone, 1 -chloro- 1- diiodoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises halomethanes, e.g., dihalomethanes and trihalomethanes.
  • the small, halogenated organic compound comprises haloacetones, e g., dihaloacetones and trihaloacetones.
  • the small, halogenated organic compound comprises bromoacetone, 1,1 -dibromoacet one, 1,1, 3 -tribromoacetone, 1,1,1 -tribromoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises chloroacetone, 1,1 -dichloroacetone, 1,1,3-trichloroacetone, 1,1,1 -tri chloroacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises iodoacetone, 1,1 -diiodoacetone, 1,1, 3 -triiodoacetone, 1,1,1 -triiodoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises bromomethane, dibromethane, bromoform, or a variant or analog thereof.
  • the small, halogenated organic compound comprises chloromethane, dichloromethane, chloroform, or a variant or analog thereof.
  • the small, halogenated organic compound is iodomethane, diiodomethane, iodoform, or a variant or analog thereof.
  • the small, halogenated organic compound comprises a compound of Formula (Z): or a salt, tautomer, or isomer thereof, wherein each of R la , R lb , R lc , R 2a , R 2b , R 3a , R 3b , R 4a , R 4b , R 5a , R 5b , and R 5c is independently hydrogen, halogen, Ci-Ce alkyl, Ci-Cg heteroalkyl, C2-C6 alkenyl, C2-C6 alkynyl, cycloalkyl, or heterocyclyl, wherein each alkyl, heteroalkyl, alkenyl, alkynyl, cycloalkyl or heterocyclyl is optionally substituted with one or more R 6 , and at least one of R la , R lb , R lc , R 2a , R 2b , R 3a , R 3b , R 4a , R 4
  • R 2b and R 3b is independently absent.
  • each of R la , R lb , and R lc is independently halogen or hydrogen, wherein at least one of R la , R lb , and R lc is halogen.
  • the halogen is selected from chlorine, bromine, or iodine.
  • each of R la , R lb , R lc is independently halogen or hydrogen, wherein at least two of R la , R lb , and R lc is halogen.
  • the halogen is selected from two of chlorine, bromine, or iodine.
  • each of R la , R lb , R lc is independently halogen.
  • the halogen is selected from chlorine, bromine, or iodine.
  • each of R 5a , R 5b , and R 5c is independently halogen or hydrogen, wherein at least one of R 5a , R 5b , and R 3C is halogen.
  • each of R 3a , R 5b , and R ?c is independently halogen or hydrogen, wherein at least two of R 5a , R 5b , and R 5c is halogen.
  • each of R 5a , R 5b , and R ?c is independently halogen.
  • - is a single bond.
  • each of m and n is independently selected from 0, 1, 2, or 3, and - is a single bond.
  • the present disclosure features methods for producing small halogenated organic compounds, as well as related compositions thereof, e.g., with other additives.
  • the additive is capable of modulating the pH, e.g., an acid or a base.
  • the additive is a base.
  • the base is a Lewis base.
  • the base is a Bronsted base.
  • the base is a strong base.
  • the base is a weak base.
  • the method described herein features a base, wherein the pKb of the base is between about 0-14, between about 1-14, between about 2- 14, between about 3-14, between about 4-14, between about 5-14, between about 6-14, between about 7-14, between about 8-14, between about 9-14, between about 10-14, between about 11- 14, between about 12-14, or between about 13-14.
  • the method described herein for modulating the production of small, halogenated organic compounds features a base, wherein the pKb of the base is about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, or about 14.
  • the base features a hydroxyl moiety.
  • the base is an inorganic base. In an embodiment, the base is an organic base.
  • Exemplary bases useful in the invention include KOH, NaOH, Mg(OH)2, Ca(OH)2, KHCO3, Nal ICO3, and the like. Preferred bases include NaOH.
  • the method described herein for modulating the production of small, halogenated organic compounds features a buffer, e.g., a combination of a weak acid and a weak base in equilibrium to maintain the pH of the mixture at a designated value or within a range of designated values.
  • the buffer maintains the pH of the halogenation reaction between about pH 4 to about pH 9, between about pH 4 to about pH 8, or between about pH 4 to about pH 7.
  • Exemplary buffers useful in the invention include (l-benzyl-4- triazoyl)methyl amine hydrochloride (Tris HCl), sodium hydrogen phosphate (e.g., phosphate buffered saline or PBS, 2-(N-morpholino)ethanesulfonic acid hydrochloride (MES HCI), sodium hydrogen carbonate, and the like.
  • the buffer comprises citric acid or a salt, ester or hydrate thereof
  • the buffer is citric acid monohydrate.
  • the buffer is citrate buffer.
  • the methods described herein for modulating the production of a small, halogenated organic compound includes a salt.
  • the salt is an inorganic salt, an organic salt, or a combination thereof.
  • the salt is an inorganic salt.
  • the salt is an organic salt.
  • the salt is an alkali metal salt, an alkali earth metal salt, or a transition metal salt.
  • the salt is an alkali metal salt.
  • the salt is an alkali earth metal salt.
  • the salt is a transition metal salt.
  • the salt is a halide salt, wherein the anion is a halide selected from fluoride, bromide, chloride, or iodide.
  • the salt is an akali metal halide salt or an alkali earth metal halide salt.
  • the salt is an alkali earth metal salt.
  • the methods described herein for modulating the production of small, halogenated organic compounds features one or more of the following steps, the method including (i) preparing the agricultural feedstock to provide a slurry; (ii) contacting the slurry with a halogen source and an acid to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small, halogenated organic compound.
  • the methods described herein feature (i) preparing the agricultural feedstock to provide a slurry.
  • the methods described herein for modulating the production of small, halogenated organic compounds features (ii) contacting the slurry with a halogen source and an acid to form a mixture.
  • the methods described herein feature (iii) mixing the mixture. In embodiments, the methods described herein feature (iv) acquiring information about the small halogenated organic compound. In embodiments, the methods described herein feature (ii) contacting the slurry with a halogen source and an acid to form a mixture; and (iii) mixing the mixture. In embodiments, the methods described herein feature (ii) contacting the slurry with a halogen source and an acid to form a mixture; and (iv) acquiring information about the small halogenated organic compound. In embodiments, the methods described herein feature (ii) contacting the slurry with a halogen source and an acid to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small halogenated organic compound.
  • the methods described herein for modulating the production of small, halogenated organic compounds features one or more of the following steps: (i) preparing the agricultural feedstock to provide a slurry; (ii) contacting the slurry with a halogen source, an enzyme, and an acid to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small, halogenated organic compound.
  • the methods described herein feature (i) preparing the agricultural feedstock to provide a slurry.
  • the methods described herein feature (ii) contacting the slurry with a halogen source, an enzyme, and an acid to form a mixture.
  • the methods described herein feature (iii) mixing the mixture.
  • the methods described herein feature feature
  • (iii) mixing the mixture feature: (ii) contacting the slurry with a halogen source, an enzyme, and an acid to form a mixture; and (iv) acquiring information about the small halogenated organic compound.
  • the methods described herein feature: (ii) contacting the slurry with a halogen source, an enzyme and an acid to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small halogenated organic compound.
  • the methods described herein for modulating the production of small, halogenated organic compounds features one or more of the following steps: (i) preparing the agricultural feedstock to provide a slurry; (ii) contacting the slurry with a halogen source and an enzyme to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small, halogenated organic compound.
  • the methods described herein feature: (i) preparing the agricultural feedstock to provide a slurry.
  • the methods described herein feature: (ii) contacting the slurry with a halogen source and an enzyme to form a mixture.
  • the methods described herein feature (iii) mixing the mixture.
  • the methods described herein feature: (ii) contacting the slurry with a halogen source and an enzyme to form a mixture; (iii) mixing the mixture; and (iv) acquiring information about the small halogenated organic compound.
  • the methods described herein for modulating the production of small, halogenated organic compounds comprises any of the aforementioned steps (i)-(iv), wherein the halogenation reaction temperature is between 5°C-50°C, between 10°C-45 °C, between 15°C- 40°C, between 15°C-35 °C, between 15°C-30°C, or between 15°C-25°C.
  • the methods described herein for modulating the production of small, halogenated organic compounds comprises any of the aforementioned steps (i)-(iv), wherein the halogenation reaction temperature is between 15°C to 25°C.
  • the temperature of the halogenation reaction is 15°C. In some embodiments, the temperature of the halogenation reaction is 16°C. In some embodiments, the temperature of the halogenation reaction is 17°C. In some embodiments, the temperature of the halogenation reaction is 18°C. In some embodiments, the temperature of the halogenation reaction is 19°C. In some embodiments, the temperature of the halogenation reaction is 20°C. In some embodiments, the temperature of the halogenation reaction is 21°C. In some embodiments, the temperature of the halogenation reaction is 22°C. In some embodiments, the temperature of the halogenation reaction is 23°C. In some embodiments, the temperature of the halogenation reaction is 24°C. In some embodiments, the temperature of the halogenation reaction is 25°C.
  • the methods described herein for modulating the production of small, halogenated organic compounds comprises any of the aforementioned steps (i)-(iv), wherein the reaction time is about 1 min, about 5 min, about 10 min, about 20 min, about 30 min, about 1 h, about 2 h, about 3 h, about 6 h, about 12 h, about 24 h, about 36 h, about 48 h, about 72 h or about 1 week.
  • the reaction time is about 1 min.
  • the reaction time is about 5 min.
  • the reaction time is about 10 min.
  • the reaction time is about 20 min.
  • the reaction time is about 30 min.
  • the reaction time is about 1 h. In some embodiments, the reaction time is about 2 h. In some embodiments, the reaction time is about 3 h. In some embodiments, the reaction time is about 6 h. In some embodiments, the reaction time is about 12 h. In some embodiments, the reaction time is about 24 h. In some embodiments, the reaction time is about 36 h. In some embodiments, the reaction time is about 48 h. In some embodiments, the reaction time is about 72 h. In some embodiments, the reaction time is about 1 week.
  • the methods described herein for modulating the production of small, halogenated organic compounds comprises at least one of the following steps for preparing the agricultural feedstock: (a) optionally thawing the agricultural feedstock; (b) rinsing the agricultural feedstock e.g., with an aqueous solution, e.g., with water; (c) blanching the agricultural feedstock; (d) quenching the blanching process; (e) allowing the agricultural feedstock to drip; e.g., to decrease the liquid:mass ratio; (f) measuring the moisture content of the agricultural feedstock, e.g., to determine the liquid:mass ratio, e.g., to achieve the optimal liquid:mass ratio for carrying out the halogenation reaction; (g) measuring the pH, e.g., with a pH strip; (h) pulverizing or homogenizing the agricultural feedstock, e.g., with a processor; (i) disposing the agricultural feedstock in a container, e.g.,
  • the agricultural feedstock may be obtained such that it is cured, frozen, or otherwise preserved, such that the agricultural feedstock is subject to at least one of steps (a)-(j) for use in the methods described herein for modulating the production of small, halogenated organic compounds.
  • the agricultural feedstock may be obtained such that it is frozen, such that the agricultural feedstock is subject to at least step (a) thawing the agricultural feedstock.
  • the agricultural feedstock may be obtained such that it is suitable for direct use in the methods described herein for modulating the production of small, halogenated organic compounds without any preparation, wherein the preparing comprises (a)-(j ).
  • the agricultural feedstock may be obtained for direct use in the methods described herein for modulating the production of small, halogenated organic compounds and be subject to any of the steps (b)-(j) of the preparing.
  • the preparing comprises (b) rinsing the agricultural feedstock, e.g., with an aqueous solution, e.g., with water.
  • the preparing comprises (c) blanching the agricultural feedstock.
  • the preparing comprises (d) quenching the blanching process.
  • the preparing comprises (e) allowing the agricultural feedstock to drip; e.g., to decrease the liquid:mass ratio. In some embodiments, the preparing comprises (f) measuring the moisture content of the agricultural feedstock, e.g., to determine the liquid:mass ratio, e.g., to achieve the optimal liquid:mass ratio for carrying out the halogenation reaction. In some embodiments, the preparing comprises (g) measuring the pH, e.g., with a pH strip. In some embodiments, the preparing comprises (h) pulverizing or homogenizing the agricultural feedstock, e.g., with a processor.
  • Blanching is a process of subjecting an agricultural feedstock to hot (e.g., 60°C-100°C) water for a short amount of time.
  • the agricultural feedstock may be optionally rinsed with an aqueous solution, e.g., water, to facilitate the blanching process.
  • blanching is followed by a quenching step in which the agricultural feedstock subsequent to the blanching step is rapidly cooled with cold water or ice.
  • the preparing comprises (b) rinsing the agricultural feedstock, e.g., with an aqueous solution, e.g., with water; and (c) blanching the agricultural feedstock.
  • the preparing comprises (c) blanching the agricultural feedstock; and (d) quenching the blanching process.
  • preparing comprises (b) rinsing the agricultural feedstock, e.g., with an aqueous solution, e.g., with water; (c) blanching the agricultural feedstock; the preparing comprises (d) quenching the blanching process.
  • the blanching temperature may be modulated in the methods described herein for modulating the production of small, halogenated organic compounds.
  • the blanching temperature is 60-100°C, e.g., 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C , 97°C, 98°C, 99°C, or 100°C.
  • the blanching temperature is between 60°C to 100°C, between 65°C to 95°C, between 70°C to 90°C, between 65°C to 95°C, between 70°C to 90°C, or between 75°C to 85°C. In some embodiments, the blanching temperature is 60°C, 75°C, 80°C, or 85°C. In some embodiments, the blanching temperature is 60°C. In some embodiments, the blanching temperature is 75°C. In some embodiments, the blanching temperature is 80°C. In some embodiments, the blanching temperature is 85°C. In addition to allowing for the modulation of the blanching temperature, the blanching time may vary to prepare the agricultural feedstock.
  • the blanching time may correspond to the duration of step (c) blanching the agricultural feedstock of the preparing.
  • the agricultural feedstock is subject to the blanching process of step (c) for 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, or 120 s.
  • the blanching time may refer to the duration of steps (b)-(c), (c)-(d), or (b)-(d) of the preparing.
  • the agricultural feedstock is subject to the blanching process of steps (b)-(c), (c)-(d), or (b)-(d) of the preparing for 120 s, 180 s, 240 s, 300 s, 600 s, 1200 s, or longer.
  • the pH of the blanching liquid may be modulated to prepare a variety of substrates for production of the small halogenated organic compound.
  • the pH of the blanching liquid is between about pH 3 to about pH 10, about pH 4 to about pH 9, about pH 5 to about pH 8, or about pH 6 to about pH 7.
  • the methods described herein feature a pH of the blanching liquid between about pH 3 to about pH 10.
  • the methods described herein feature a pH of the blanching liquid between about pH 4 to about pH 9.
  • the methods described herein feature a pH of the blanching liquid between about pH 5 to about pH 8.
  • the methods described herein feature a pH of the blanching liquid between about pH 6 to about pH 7.
  • the liquid:mass ratio is the ratio of the amount of liquid, e.g., an aqueous solution comprising one or more of a halogen source, an acid, an enzyme, a salt, an additive capable of adjusting the pH, a silage inoculant (e g., lactic acid, and the like) to the amount of solid material, e.g., of the agricultural feedstock, e.g., comprising seaweed tissue.
  • the liquid:mass ratio is a critical parameter in optimizing the yield and reaction extent of the production of the small, halogenated organic compound. Without being bound by theory, a decrease in the liquid: mass ratio will increase the reaction velocity.
  • the preparing features (e) allowing the agricultural feedstock to drip; e.g., to decrease the liquid:mass ratio.
  • the moisture content of the agricultural feedstock is measured to acquire information about the liquid:mass ratio. Responsive to this measurement, the moisture content may be adjusted, e.g., by allowing the agricultural feedstock to drip to obtain a predetermined liquid:mass ratio, e.g., to achieve an optimal liquid:mass ratio for carrying out the reaction.
  • the preparing features (f) measuring the moisture content of the agricultural feedstock e.g., to determine the liquid:mass ratio, e.g., to achieve the optimal liquid:mass ratio for carrying out the halogenation reaction.
  • the preparing features (e) allowing the agricultural feedstock to drip; e.g., to decrease the liquid:mass ratio and (f) measuring the moisture content of the agricultural feedstock of the agricultural feedstock, e.g., to determine the liquid:mass ratio, e.g., to achieve the optimal liquid:mass ratio for carrying out the halogenation reaction.
  • the liquid:mass ratio may be chosen to modulate the production of the small, halogenated organic compound.
  • the liquid:mass ratio is 99: 1, 98:2, 97:3, 96:4, 95:5, 94: 6, 93:7: 92:8, 91 :9: 90: 10, 89: 11, 88: 12, 87:13, 86:14, 85: 15, 84: 16 83:17, 82: 18, 81: 19, or 80:20.
  • the liquid:mass ratio is 99: 1.
  • the liquid:mass ratio is 98:2.
  • the liquid:mass ratio is 97:3.
  • the liquid:mass ratio is 96:4.
  • the liquid:mass ratio is 95:5. In some embodiments, the liquid:mass ratio is 94:6. In some embodiments, the liquid:mass ratio is 93:7. In some embodiments, the liquid:mass ratio is 92:8. In some embodiments, the liquid:mass ratio is 91:9. In some embodiments, the liquid:mass ratio is 90:10. In some embodiments, the liquid:mass ratio is 89: 11. In some embodiments, the liquid:mass ratio is 88: 12. In some embodiments, the liquid:mass ratio is 87: 13. In some embodiments, the liquid:mass ratio is 86: 14. In some embodiments, the liquid:mass ratio is 85: 15. In some embodiments, the liquid:mass ratio is 84: 16.
  • the liquid:mass ratio is 83: 17. In some embodiments, the liquid:mass ratio is 82:18. In some embodiments, the liquid:mass ratio is 81: 19. In some embodiments, the liquid:mass ratio is 80:20.
  • the pH of the mixture may be determinative, in part, of the reaction extent and yield of the halogenation reaction. Therefore, it is contemplated that the preparing may comprise acquiring information about the initial pH, e.g., with a test strip. Responsive to the pH, the pH may be adjusted to carry out the reaction to produce the small, halogenated organic compound. For example, an additive capable of adjusting the pH, e.g., an additive comprising an acid or a base, may be added.
  • acquiring the initial pH of the agricultural feedstock may be useful in further processing the small, halogenated organic compound, e.g., in preserving the small, halogenated organic compound, e.g., by varying the amount of acid or silage inoculant employed for ensiling.
  • the agricultural feedstock may be subject to a homogenization step to facilitate the creation of a uniform slurry for contacting with the halogen source, and optionally an acid, an enzyme, a salt, and an additive for adjusting the pH, in order to produce the small, halogenated organic compound.
  • the homogenizing features homogenizing or pulverizing with a processor, e.g., a food processor or a food blender.
  • the homogenizing features homogenizing or pulverizing with a sonicator, e.g., a probe-tip sonicator, a bath sonicator, or an ultrasonic cleaner.
  • the preparing features (g) pulverizing or homogenizing the agricultural feedstock e.g., with a processor.
  • the agricultural feedstock may be prepared such that the halogenation reaction to produce the small, halogenated organic compound is initiated at a later time.
  • preparing the agricultural feedstock entails the disposition of the agricultural feedstock in a container for storage.
  • the prepared agricultural feedstock is stored at a particular temperature, e.g., -20°C or -80°C; or it is protected from air, sunlight, or excessive humidity.
  • the agricultural feedstock may be frozen, e.g., flash frozen with liquid nitrogen, or it may be combined with suitable excipients and lyophilized. Suitable excipients include those known in the art such as trehalose and leucine.
  • the preparing features (i) disposing the agricultural feedstock in a container, e.g., a container suitable for cold storage.
  • the preparing features(j) freezing the agricultural feedstock, e.g., at -20°C or -80°C, e.g., with a suitable excipient.
  • the preparing features (i) disposing the agricultural feedstock in a container, e.g., a container suitable for cold storage; and (j) freezing the agricultural feedstock, e.g., at -20°C or -80°C, e.g., with a suitable excipient.
  • the methods described herein for modulating the production of small, halogenated organic compounds comprises contacting the slurry to form a mixture.
  • the contacting includes one or more of: (k) adding the halogen source; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features include (k) adding the halogen source.
  • the contacting features (1) adding the acid.
  • the contacting features (m) adding a salt.
  • the contacting features n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features : (k) adding the halogen source; and (1) adding the acid.
  • the contacting features (k) adding the halogen source; (1) adding the acid; and (m) adding a salt.
  • the contacting features (k) adding the halogen source; (1) adding the acid; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the solution comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features : (k) adding KBr; and (1) adding the acid.
  • the contacting features : (k) adding KBr; (1) adding the acid; and (m) adding a salt.
  • the contacting features (k) adding KBr; (1) adding the acid; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding the halogen source; (1) adding PAA; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features : (k) adding the halogen source; and (1) adding PAA.
  • the contacting features : (k) adding the halogen source; (1) adding PAA; and (m) adding a salt.
  • the contacting features (k) adding the halogen source; (1) adding PAA; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding the halogen source; (1) adding PAA comprising an additional oxidant; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features: (k) adding the halogen source; and
  • the contacting features (k) adding the halogen source; (1) adding PAA comprising an additional oxidant; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of (k) adding the halogen source; (1) adding PAA comprising H2O2; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding the halogen source; and (1) adding PAA comprising H2O2.
  • the contacting features (k) adding the halogen source; (1) adding PAA comprising H2O2; and (m) adding a salt.
  • the contacting features (k) adding the halogen source; (1) adding PAA comprising H2O2; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr; (1) adding PAA; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features : (k) adding KBr; and (1) adding PAA.
  • the contacting features : (k) adding KBr; (1) adding PAA; and (m) adding a salt.
  • the contacting features (k) adding KBr; (1) adding PAA; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr; (1) adding PAA; (m) adding NaCl and (n) adding NaOH.
  • the contacting features : (k) adding KBr; and (1) adding PAA.
  • the contacting features : (k) adding KBr; (1) adding PAA; and (m) adding NaCl.
  • the contacting features : (k) adding KBr; (1) adding PAA; and (n) adding NaOH.
  • the contacting includes one or more of: (k) adding the halogen source and an enzyme; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features : (k) adding the halogen source and an enzyme.
  • the contacting features : (k) adding the halogen source and an enzyme; and (m) adding a salt.
  • the contacting features (k) adding the halogen source and an enzyme; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and an enzyme; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and an enzyme; and (m) adding a salt.
  • the contacting features (k) adding KBr and an enzyme; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a peroxidase; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a peroxidase; and (m) adding a salt.
  • the contacting features (k) adding KBr and a peroxidase; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a haloperoxidase; (m) adding a salt; and (n) adding an additive, e g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a haloperoxidase; and (m) adding a salt.
  • the contacting features (k) adding KBr and a haloperoxidase; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a vanadium haloperoxidase (VHPO); (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); and (m) adding a salt.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a vanadium haloperoxidase (VHPO); (m) adding NaCl; and (n) adding NaOH.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); and (m) adding NaCl.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); and (n) adding NaOH.
  • the contacting includes one or more of: (k) adding KBr and an enzyme; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and an enzyme; (1) adding the acid; and (m) adding a salt.
  • the contacting includes one or more of: (k) adding KBr and a peroxidase; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a peroxidase; (1) adding the acid; and (m) adding a salt.
  • the contacting features (k) adding KBr and a peroxidase; (1) adding the acid; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a haloperoxidase; (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a haloperoxidase; (1) adding the acid; and (m) adding a salt.
  • the contacting features (k) adding KBr and a haloperoxidase; (1) adding the acid; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding the acid; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding the acid; and (m) adding a salt.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding the acid; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • VHPO vanadium haloperoxidase
  • the contacting includes one or more of: (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding the acid; (m) adding NaCl; and (n) adding NaOH.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding the acid; and (m) adding NaCl.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding the acid; and (n) adding NaOH.
  • the contacting includes one or more of: (k) adding KBr and an enzyme; (1) adding PAA; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and an enzyme; (1) adding PAA; and (m) adding a salt.
  • the contacting includes one or more of: (k) adding KBr and a peroxidase; (1) adding PAA; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a peroxidase; (1) adding PAA; and (m) adding a salt.
  • the contacting features (k) adding KBr and a peroxidase; (1) adding PAA; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of: (k) adding KBr and a haloperoxidase; (1) adding PAA; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting features (k) adding KBr and a haloperoxidase; (1) adding PAA; and (m) adding a salt.
  • the contacting features (k) adding KBr and a haloperoxidase; (1) adding PAA; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding PAA; (m) adding a salt; and (n) adding an additive, e.g., an additive capable of adjusting the pH of the mixture comprising NaOH.
  • the contacting includes one or more of (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding PAA; (m) adding NaCl; and (n) adding NaOH.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding PAA; and (m) adding NaCl.
  • the contacting features (k) adding KBr and a vanadium haloperoxidase (VHPO); (1) adding PAA; and (n) adding NaOH.
  • the reaction to produce a small, halogenated organic compound is initiated at the time the slurry is contacted with the halogen source. In other embodiments, the reaction to produce a small, halogenated organic compound is initiated at the time the slurry is contacted with the halogen source and the acid. In other embodiments, the reaction to produce a small, halogenated organic compound is initiated at the time the slurry is contacted with the halogen source and an enzyme. In other embodiments, the reaction to produce a small, halogenated organic compound is initiated at the time the slurry is contacted with the halogen source, the acid, and an enzyme.
  • the reaction is initiated at some time after the slurry is initially contacted with the halogen source, or the halogen source and the acid, or the halogen source and an enzyme, or the halogen source, the acid, and an enzyme, e.g., the reaction is initiated at the time the mixture is mixed.
  • the reaction is initiated provided that (a) the slurry is in contact with the halogen source; or the halogen source and the acid; or, the halogen source and an enzyme; or, the halogen source, the acid, and an enzyme; and the temperature is sufficient to initiate production of the small, halogenated organic compound.
  • initiation of the halogenation reaction refers to acquiring information about the production of the small, halogenated organic compound from the mixture, either directly or indirectly, thereby confirming that the reaction has been initiated.
  • the mixture including the agricultural feedstock, the halogen source, and optionally the acid, an enzyme, a salt, and an additive the adjusts the pH is mixed.
  • the mixing may be performed continuously during the course of the halogenation reaction or intermittently to modulate the production of the small, halogenated organic compound. Mixing may enhance the reaction kinetics or augment the yield of the small, halogenated organic compound, or lessen the production of undesired byproducts.
  • the mixing may be initiated simultaneously with, or subsequent to, contacting the slurry comprising the agricultural feedstock and the halogen source, and optionally the acid, an enzyme, a salt, and an additive the adjusts the pH, thereby forming the mixture.
  • the reaction to produce a small, halogenated organic compound is initiated at the time the mixing is initiated.
  • Acquiring information about the small, halogenated organic compound entails, within certain modes of the methods described herein, characterizing the small, halogenated organic compound, e.g., directly or indirectly.
  • the acquiring comprises characterizing the chemical structure, molecular weight, activity, or other feature of the small, halogenated organic compound.
  • the method comprises acquiring information about the small, halogenated organic compound, wherein the acquiring is accomplished directly.
  • the method for modulating the production of small, halogenated organic compounds the method comprises acquiring information about the small, halogenated organic compound, wherein the acquiring is accomplished indirectly.
  • the method features acquiring information, wherein the acquiring includes monitoring the reaction (e.g., its reaction extent), the consumption of a reagent, the production of a product (e.g., the small, halogenated organic compound, a byproduct, e.g., the production of a byproduct), pH, reaction temperature, viscosity, color, turbidity, miscibility of components, reaction time, reaction selectivity (e.g., the selectivity of the halogenation reaction to produce the small, halogenated organic compound, e.g., bromoform, relative to the production of other byproducts, e.g., small, halogenated organic compounds other than the product bromoform).
  • the reaction e.g., its reaction extent
  • the production of a product e.g., the small, halogenated organic compound, a byproduct, e.g., the production of a byproduct
  • pH e.g., reaction temperature, viscosity, color, turbid
  • the method features acquiring information, wherein the acquiring includes monitoring the reaction extent. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the consumption of a reagent. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the production of a product, e.g., the small, halogenated organic compound. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the production of a byproduct.
  • the method features acquiring information, wherein the acquiring includes monitoring the pH. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the reaction temperature. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the viscosity. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the color.
  • the method features acquiring information, wherein the acquiring includes monitoring the turbidity. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the miscibility of components. In embodiments of the method for modulating the production of small, halogenated organic compounds, the method features acquiring information, wherein the acquiring includes monitoring the reaction time.
  • the method features acquiring information, wherein the acquiring includes monitoring the reaction selectivity, e.g., the selectivity of the halogenation reaction to produce the small, halogenated organic compound, e.g., bromoform, relative to the production of a product, e.g., a small, halogenated organic compound other than the product bromoform.
  • the reaction selectivity e.g., the selectivity of the halogenation reaction to produce the small, halogenated organic compound, e.g., bromoform
  • the method features acquiring information, wherein the acquiring includes monitoring a byproduct, e.g., the chemical structure, molecular weight, activity, or other feature of the byproduct, the production of the byproduct, the consumption of the byproduct, the degradation of the byproduct, and the effect of the byproduct on the reaction extent, reaction temperature, reaction yield, reaction selectivity, pH, inter alia.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a byproduct, wherein the byproduct is a small, halogenated organic compound.
  • the byproduct includes small, halogenated organic compounds with 1,2, 3, 4, 5, 6, 7, 8, or more carbon atoms. In embodiments, the byproducts include small, halogenated organic compounds with 1, 2, 3, 4, 5, 6, or more halogen atoms. In embodiments, the byproduct includes small, halogenated organic compounds with 1, 2, 3, 4, 5, 6 or more chlorine atoms. In embodiments, the byproduct includes small, halogenated organic compounds with 1, 2, 3, 4, 5, 6 or more bromine atoms. In embodiments, the byproduct includes small, halogenated organic compounds with 1, 2, 3, 4, 5, 6 or more iodine atoms.
  • the byproduct includes a small, halogenated organic compound comprising a functional group, e.g., an aldehyde, ketone, acetyl, acyl, hydroxyl, ester, ether, amine, amide, aryl, heteroaryl, carboxylate, heterocyclyl, or cycloalkyl group.
  • the byproduct features a small, halogenated organic compound comprising an alkenyl or alkynyl group.
  • the byproduct includes a small, halogenated organic compound comprising an aldehyde or a ketone group.
  • the byproduct includes a small, halogenated organic compound comprising an a, -unsaturated ketone. In an embodiment, the byproduct includes a small, halogenated organic compound comprising an acetone moiety. In an embodiment, the byproduct includes small, halogenated organic compounds comprising bromoacetone, dibromoacetone, bromopetandione, tribromoacetone, or a variant or analog thereof. In an embodiment, the byproduct includes small, halogenated organic compounds comprising di chloroacetone, chloroacetone, chloropentanedione, chloroform, tri chloroacetone or a variant or analog thereof.
  • the byproduct includes the small, halogenated organic compound comprises 1,1 -diiodoacetone, 1,3 -di iodoacetone, iodoacetone, iodopentandione, iodoform, 1,1,1 -triiodoacetone, or a variant or analog thereof.
  • the byproduct includes small, halogenated organic compounds comprising 1- bromo-1 -chloroacetone, l-bromo-3 -chloroacetone, 1 -bromo- 1 -iodoacetone, 1 -chloro- 1- iodoacetone, 1 -chi oro-3 -iodoacetone, dibromochloromethane, dibromoiodomethane, bromodichloromethane, bromodiiodomethane, dichloroiodomethane, bromochloroiodomethane, chlorodiiodomethane, or a variant or analog thereof.
  • the small, halogenated organic compound comprises iodoacetone, 1,1 -diiodoacetone, 1,1, 3 -triiodoacetone, 1,1,1 -triiodoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises halomethanes, e.g., dihalomethanes and trihalomethanes.
  • the small, halogenated organic compound comprises haloacetones, e.g., dihaloacetones and trihaloacetones.
  • the small, halogenated organic compound comprises bromoacetone, 1,1 -dibromoacetone, 1,1,3- tribromoacetone, 1,1,1 -tribromoacetone, or a variant or analog thereof.
  • the byproduct includes small, halogenated organic compounds comprising chloroacetone, 1,1- di chloroacetone, 1,1, 3 -tri chloroacet one, 1,1,1 -tri chloroacet one, or a variant or analog thereof.
  • the byproduct includes iodoacetone, 1,1 -diiodoacetone, 1,1, 3 -triiodoacetone, 1,1,1 -triiodoacetone, or a variant or analog thereof.
  • the small, halogenated organic compound comprises bromomethane, dibromomethane, bromoform, or a variant or analog thereof.
  • the byproduct includes small, halogenated organic compounds comprising chloromethane, di chloromethane, chloroform, or a variant or analog thereof.
  • the byproduct includes small, halogenated organic compounds comprising iodomethane, diiodomethane, iodoform, or a variant or analog thereof.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is bromoform and the byproduct is selected from one or more of bromochloromethane, chloroacetic acid, bromochloroacetic acid, dibromoacetic acid, and 1,3- dichloro-2-propanone.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is bromoform and the byproduct is bromochloromethane.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is bromoform and the byproduct is chloroacetic acid.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is bromoform and the byproduct is bromochloroacetic acid.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is bromoform and the byproduct is dibromoacetic acid.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is bromoform and the byproduct is l,3-dichloro-2-propanone.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is iodoform and the byproduct is selected from one or more of bromochloromethane, bromoiodomethane, chloroiodomethane, bromoacetic acid, chloroacetic acid, bromochloroacetic acid, dibromoacetic acid, di chloroacetic acid, l,3-dibromo-2-propanone, and l,3-dichloro-2-propanone.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is iodoform and the byproduct is bromochloromethane or chloroiodomethane.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is iodoform and the byproduct is chloroacetic acid or bromoacetic acid.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is iodoform and the byproduct is bromochloroacetic acid or chloroiodoacetic acid.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is iodoform and the byproduct is dibromoacetic acid or diiodoacetic acid.
  • the method for modulating the production of small, halogenated organic compounds features acquiring information about a product and/or a byproduct, wherein the product is iodoform and the byproduct is l,3-dichloro-2-propanone or l,3-dibromo-2-propanone.
  • the measurement and characterization of the small halogenated organic compound may optionally feature extracting the small, halogenated organic compound from the mixture to form an extractant, e.g., via solid-phase or liquid-phase extraction, e.g., with a suitable solvent.
  • Solvents include canola oil, methanol and hexane.
  • the methods described herein for modulating the production of small, halogenated organic compounds comprises extracting the small, halogenated organic compound from a mixture, e.g., a mixture prepared in the method comprising the reactants and/or products of a halogenation reaction.
  • the extracting comprises: (a) performing the extracting with a liquid extraction solvent, thereby providing an extractant; and (b) subjecting the extractant from step (a) to an analytical method to detect a small, halogenated organic compound.
  • Suitable extraction solvents include canola oil, methanol and hexane.
  • a preferred extraction solvent for use in the invention is canola oil.
  • Exemplary analytical methods for detecting small, halogenated organic compounds in the methods described herein include gas chromatography (GC), mass spectrometry (MS), e.g., , and tandem techniques, e.g., gas chromatography-mass spectrometry (GC-MS).
  • the method for extracting a small, halogenated organic compound comprises the following steps: adding oil at a a predetermined ratio of the amount oil to the reaction volume (can vary based on the desired small, halogenated organic compound concentration); agitating the oil/reaction mixture for a predetermined amount of time to extract the small, halogenated organic compound; allowing the mixture to sit for phase separation; and removing the oil containing the extracted small, halogenated organic compound, thereby regenerating the reaction for further small, halogenated organic compound production.
  • the oil comprising the small, halogenated organic compound may also also be used for extraction again depending on the desired concentration of the small, halogenated organic compound.
  • the ratio of the oil to the volume of reaction is about 1 : 1, 1 :5, 1 : 10, 1 :20, 1 :30, l;40, 1 :50, 1 :60, 1 :70, 1 :80, 1 :90, or 1 : 100 w/v.
  • the ratio of the oil to the volume of reaction is about 1 :50.
  • the agitating is for about 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 20 min, 30 min, or 1 h. In some embodiments, the agitating is for about 5 min.
  • the oil is canola oil or coconut oil.
  • the small, halogenated organic compound is bromoform.
  • the method optionally features concentrating the small, halogenated organic compound.
  • the concentrating entails increasing the concentration of the small, halogenated organic compound.
  • the concentrating may be intended to increase the concentration such that it facilitates the acquisition of information or characterization of the small, halogenated organic compound.
  • the concentrating may be intended to increase the concentration such that it facilitates fermentation or ensilation.
  • the methods described herein for modulating the production of small organic compounds features ensiling.
  • Ensilation is a fermentation process conventionally employed to make livestock feed.
  • the method for modulating the production of small, halogenated organic compounds comprises ensiling the products of a halogenation reaction, e.g., the small, halogenated organic compound.
  • the ensiling comprises: (o) adding lactic acid to the solution comprising the small, halogenated organic compound; (p) decreasing the pH of the solution comprising the small, halogenated organic compound, the step comprising incorporating an additive that lowers the pH of the solution; (q) adding a silage inoculant to the solution, the silage inoculum comprising a bacterial inoculum capable of undergoing anaerobic fermentation in the presence of lactic acid; and (r) disposing the solution in a container suitable for anaerobic fermentation and favorable for long-term storage.
  • the ensiling comprises acquiring information about the small, halogenated organic compound, either directly or indirectly.
  • the acquisition of information about the small, halogenated organic compound comprises extraction, e.g., liquid-phase extraction or solid-phase extraction, optionally accompanied by an analytical method to characterize the small, halogenated organic compound, its decomposition, or the presence of byproducts employing an analytical technique, e.g., gas chromatography (GC), mass spectrometry (MS), or gas chromatography-mass spectrometry (GC-MS).
  • extraction e.g., liquid-phase extraction or solid-phase extraction
  • an analytical method to characterize the small, halogenated organic compound, its decomposition, or the presence of byproducts employing an analytical technique, e.g., gas chromatography (GC), mass spectrometry (MS), or gas chromatography-mass spectrometry (GC-MS).
  • GC gas chromatography
  • MS mass spectrometry
  • GC-MS gas chromatography-mass spectrometry
  • Exemplary silage inoculants include lactic acid bacteria of the lactobacillus family, e.g., lactobacillus fermentum , lactobacillus plantarum, lactobacillus buchneri, and the like.
  • the methods described herein further comprise encapsulating the small, halogenated organic compounds and related compositions thereof.
  • the encapsulating agent comprises a wax, a surfactant, a lipid, a saccharide, a polymer, or a mixture thereof.
  • the small halogenated organic compound may be encapsulated in a wax.
  • the wax typically comprises esters prepared by the condensation of fatty alcohols and fatty acids.
  • the wax may be saturated or unsaturated, e.g., monounsaturated.
  • the wax is a natural wax.
  • the wax is a synthetic wax.
  • the synthetic wax may be a hydrogenated from of a natural wax.
  • the wax is an animal wax. Exemplary animal waxes include beeswax, lanolin, spermaceti, shellac wax and the like.
  • the wax is derived from a plant. Exemplary plant waxes include carnauba wax, candelilla wax, soy wax, and jojoba oil.
  • the wax is derived from petroleum, e.g., paraffin wax.
  • the small, halogenated organic compound may be encapsulated in a surfactant.
  • the surfactant may be an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, an amphoteric surfactant, or a nonionic surfactant.
  • Exemplary surfactants include docusate sodium, sodium dodecyl sulfate, sodium lauryl sulfate, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, 3-[3-cholamidopropyl)dimethylammonio]-l -propanesulfonate (CHAPS), polysorbate 20 (Tween 20), polysorbate 40 (Tween 40), polysorbate 60 (Tween 60), polysorbate 80 (Tween 80), sorbitan monolaurate (Span 20), sorbitan monostearate (Span 60), sorbitan tristearate (Span 65), Triton X-100, nonoxynol-9, octyl polyglucoside, glycerol monostearate, cocamide diethanolamine (cocamide DEA), cetrimonium bromide (CTAB), inter alia.
  • CHAPS 3-[3-cholamidopropyl)dimethylammonio]-
  • the small, halogenated organic compound may be encapsulated in a lipid, e.g., a lipid that is not a wax.
  • the lipid may be saturated or unsaturated, e.g., monounsaturated or polyunsaturated.
  • the lipid may be an oil at room temperature and atmospheric pressure.
  • the oil is canola oil (rapeseed oil), olive oil, soybean oil, grapeseed oil, palm oil, com oil, peanut oil, sunflower oil, sesame oil, cotton oil, avocado oil, mustard oil, safflower oil, citrus oil, mandarin oil, and rice bran oil.
  • the oil is an essential oil.
  • the lipid may be a fatty acid, a glycerolipid, a fat-soluble vitamin, cholesterol, sphingomyelin, or a phospholipid.
  • the gylcerolipid can be a monoglyceride, a diglyceride, or a triglyceride.
  • the triglyceride can be a medium chain triglyceride, e.g., a Cg-Cn triglyceride.
  • the medium-chain triglyceride can include caproic acid, caprylic acid, capric acid, lauric acid, or a mixture thereof.
  • the fat soluble vitamin may be a vitamin E, e.g., a tocopherol or tocotrienol.
  • the phospholipid may be a phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, phosphatidic acid and the like.
  • the phospholipid may be a natural phospholipid, e.g., lecithin, e.g., soy lecithin, egg lecithin, or sunflower lecithin, or a synthetic phospholipid, e.g., conjugated with a polymer, e.g., a poly(ethylene glycol) (PEG) or a derivative thereof.
  • PEG poly(ethylene glycol)
  • the phospholipid is a PEG-conjugated distearoyl-sn-glycero-3- phosphoethanolamine, e.g., methoxypoly(ethylene glycol) 2000- distearoyl- rc-glycero-3- phosphoethanolamine.
  • the small, halogenated organic compound may be encapsulated in a saccharide.
  • the saccharide may be an oligosaccharide or a polysaccharide.
  • the saccharide has a glycosidic bond, e.g., an a-glycosidic bond, e.g., a 1,4-a-glycosidic bond.
  • the saccharide is a cyclodextrin.
  • Exemplary cyclodextrins include a-cyclodextrin, P-cyclodextrin, 'y-cyclodextrin, and the like.
  • the saccharide may be a gum.
  • Exemplary gums include gum Arabic, alginate, carrageenan, alginic acid, alginate (e g., sodium alginate or calcium alginate), guar gum, locust bean gum, gellan gum, beta-glucan, xanthan gum, and the like.
  • the saccharide may be agar.
  • the small, halogenated organic compound may be encapsulated in a polymer.
  • the polymer may be a natural polymer or a synthetic polymer.
  • the polymer may be a homopolymer or a copolymer, e.g., a random copolymer, a block copolymer, or a graft copolymer.
  • Exemplary polymers polyethylene glycol (PEG), e.g., methoxy polyethylene glycol (mPEG), e.g., 1,2- distearoyl-.s77-glycero-3-phosphoethanolamine-N-methoxy(polyethylene glycol)-2,000 (mPEG- 2,000-DSPE), poly caprolactone (PCL), polylactic acid (PLA), poly(lactic-co-glycolic) acid (PLGA), poloxamer, e.g., poloxamer 407 or Pluronic F-127, hyaluronic acid (HA), and the like.
  • PEG polyethylene glycol
  • mPEG methoxy polyethylene glycol
  • mPEG 1,2- distearoyl-.s77-glycero-3-phosphoethanolamine-N-methoxy(polyethylene glycol)-2,000
  • PCL poly caprolactone
  • PLA polylactic acid
  • PLA poly(lactic-co-glycolic) acid
  • poloxamer
  • the encapsulating agent is an emulsifier, extractant, thickening agent, a setting agent, or a stabilizer.
  • the stabilizer is a polypeptide, e.g., casein derived from cow’s milk.
  • the composition comprising the encapsulating agent and the small, halogenated organic compound is lyophilized, freeze-dried, or spray dried, optionally with a lyoprotectant, to extend the shelflife of the encapsulated, small halogenate organic compound.
  • a lyoprotectant known to the person of ordinary skill in the art may be used, including trehalose, sucrose, glycerol, dimethyl sulfoxide, formamide, propylene glycol, ethylene glycol, 2-methyl-2,4-pentanediol, and the like.
  • Example 1 Monitoring reaction extent of the halogenation reaction for reducing reactant concentrations
  • the PAA and KBr concentrations in the halogenation reaction were each systematically reduced to elucidate critical reaction parameters to ensure similar bromoform production and stability. Further, the container material in which the reaction is disposed was investigated to maximize bromoform stability. A set of four 75-mL glass containers and four 100-mL plastic containers were employed to investigate bromoform production parameters and stability.
  • Set 1 contained 10 mM PAA and 100 mM KBr
  • Set 2 contained 5 mM PAA and 50 mM KBr
  • Set 3 contained 10 mM PAA and 50 mM KBr
  • Set 4 contained 5 mM PAA and 50 mM KBr.
  • FIG. l is a graph of the reaction pH of the glass and plastic samples measured 10 min, 1 day, 4, days, 6, days, and 8 days after reaction initiation.
  • the ideal liquid:mass ratio was investigated to ascertain the optimum conditions for bromoform production and scalability.
  • 1 g of Saccharina latissima seaweed was thawed at room temperature, blanched at 80°C for 2 min, weighed into 5 mL tubes, and combined with varied volumes of 10 mM PAA, and 100 mM KBr.
  • the samples were briefly vortexed and centrifuged to homogenize the tissue, and the reaction was allowed to proceed for 30 minutes. The reaction was quenched by flash freezing with liquid nitrogen, and the samples were subsequently stored at -80°C.
  • the samples were subjected to liquid extraction with hexane to quantify bromoform production by GC/MS.
  • the tubes were thawed and centrifuged at 3220 g for 5 min.
  • the supernatant was decanted and combined with 1 mL hexane extractant for each vial.
  • the samples were subsequently vortexed for 30 s to 1 min and centrifuged at 2000g for 3 min. 100 pl of the top layer of liquid was removed and diluted 1 : 10 with 900 pl hexane for GC/MS analysis.
  • FIG. 2 shows the amount of bromoform (pg bromoform/g seaweed) as a function of the amount of PAA and KBr (ml of 10 mm PAA + 100 mM KBr added to 1 g seaweed). It is apparent from the graph that bromoform amount increases concomitantly with increasing liquid and hence total amounts of PAA and KBr.
  • the PAA concentration was optimized for maximal bromoform production.
  • thawed, shredded Saccharina latissima seaweed samples were subjected to the following pretreatment steps: (1) unblanched, (2) 60°C blanching, and (3) 80°C blanching.
  • 1 g (wet weight) seaweed was weighed into 5 ml plastic tubes.
  • lOOpl KBr was then added and mixed, followed by 100 pl PAA containing the following concentrations: 0.13, 0.26, 0.52, 1.05, 2.10, and 4.2 millimoles, stirred with a metal stirrer, and briefly centrifuged. The reaction was allowed to proceed for 1 h, then quenched by flash freezing with liquid nitrogen, and finally lyophilized overnight.
  • the samples were subjected to liquid extraction with methanol extractant and analyzed for the presence of bromoform. Briefly, the lyophilized samples were homogenized by grinding with a mortar and pestle and liquid nitrogen. 0.2 mm beads were combined with 0.8 g seaweed tissue, 1 ml methanol was then added, and the samples were centrifuged at 21,000g for 5 min. The supernatant was subsequently analyzed by GC/MS for the presence of bromoform as a function of the amount of PAA added, as shown in both FIG. 3. This data suggests that decreasing PAA addition generally results in decreased bromoform production, but the relationship is non-linear. It also demonstrates that blanching seaweed, particularly at 60°C, enhances bromoform yields, particularly at lower PAA concentrations.
  • the reactant order-of-addition was investigated in order to optimize the yield of the small, halogenated organic compound in the halogenation reaction.
  • the objective was to confine the concentration of the halogenating agent KBr to 5 mM and drive bromoform production to 110 pg/g seaweed.
  • the dependence of PAA on the production of bromoform at low concentrations of KBr using the established order-of-addition protocol i.e., adding the PAA subsequent to the KBr was explored.
  • Three reaction conditions at 10 mM PAA and 5 mM KBr, 15 mM KBr and 20 mM KBr, and 20 mM PAA were thus investigated, and the results, shown in triplicate, are shown in FIG. 4A.
  • the KBr concentration was decreased to allow for the optimal production of bromoform in the halogenation reaction.
  • Typical sea water contains 0.8 mM; as such, it is desirable to decrease the KBr concentration to the extent possible and as close to the natural levels found in sea water.
  • samples for the halogen reaction were prepared according to following procedure: to 500 pl total liquid, 100 mM PAA final concentration was added at 0, 1, 5, 10, 20 and 100 mM final KBr concentrations and combined with thawed seaweed. The reaction was quenched after 30 min with liquid nitrogen. The samples were then subjected to liquid extraction with hexane as the liquid extractant and later analyzed for the presence of bromoform in the seaweed tissue by GC/MS.
  • FIG 5 shows the concentration of bromoform in the liquid extractant (pg bromoform/g seaweed calculated back to the seaweed concentration) plotted as a function of KBr concentration. As is apparent from the figure, the bromoform yield increases monotonically with KBr concentration.
  • the reaction time was varied to further maximize production of the small, halogenated organic compound.
  • the thawed, shredded seaweed samples were subjected to the following pretreatment steps: (1) unblanched, (2) 60°C blanching, and (3) 80°C blanching. 1 g (wet weight) seaweed was weighed into 5 ml plastic tubes. In order to remove any confounding factor from differential liquid:mass ratio, the unblanched sample was drained of excess water so that it similar to the two blanched samples. Maximum amounts of KBr and PAA were used.
  • the reactions were quenched at 2 min, 1 h, 2 h, 4 h, 6 h, and 24 h using liquid nitrogen.
  • the samples were subsequently subjected to liquid extraction and analyzed for the presence of bromoform and other by products by GC/MS as previously described.
  • the halogenation reaction as shown in FIG. 6 occurs nearly immediately. Unblanched and blanched treatment samples appear to produce similar levels of bromoform. Bromoform levels are also consistent with Experiment 3 designed to optimize the PAA concentration. The presence of other small, halogenated byproducts was also monitored throughout the course of the reaction. Bromochloromethane, bromochloroacetic acid, chloroacetic acid, dibromoacetic acid, and l,3-dichloro-2-propanone levels continued to increase as the reaction proceeded. The unblanched sample tended to have higher levels of byproducts.
  • the halogenation reaction of PAA with KBr was scaled up following the procedure delineated in the example below. Briefly, the Saccharina latissima seaweed was thawed and aliquoted into 200 g batches. The aliquots were shredded in a food processor, blanched for 2 min at 80°C, drained, transferred to cold water, and dripped dry for at least 15 min. The pretreated seaweed samples were then stored in plastic containers for later use.
  • the aliquots were divided into the treatment groups as shown in Table 2 for scale-up of the halogenation reaction. Briefly, the initial pH of the seaweed was measured after combining 30 ml of MilliQ water and 6 g of seaweed and stirring for 5 min. 200 g of each seaweed aliquot was mixed with 100 ml liquid, which contained MilliQ water to volume, 100 mM KBr, and 1 mM or 10 mM PAA. The KBr and PAA were premixed, and the seaweed was added in increments with thorough mixing until all of the seaweed was added. The pH was measured again after all of the seaweed had been combined with the liquid portion and thoroughly mixed. The reaction was subsequently allowed to proceed for 25 min and then stopped by freezing with liquid nitrogen. Samples were taken for GC/MS analysis for bromoform detection before freezing. The samples were finally subjected to liquid extraction and analyzed by GC/MS to quantify bromoform concentration.
  • the seaweed reactions were later inoculated and subjected to anaerobic fermentation in the presence of lactic acid (ensilation) or absence of lactic acid (pickling) after thawing.
  • 100 mg of silage inoculant was added to a 100 ml spray bottle (le8 CFU/ml) and approximately 2 ml inoculant aerosol was sprayed into each sample for a target of le8 CFU/ml, and the samples were placed in an anaerobic hood.
  • the halogenation reaction between PAA and KBr was scaled up employing an alternative procedure.
  • Saccharina latissima seaweed was thawed in filtered sea water, rinsed in tap water, chopped briefly in a food processor, blanched at 80°C, sprayed with ice-cold water, and then shredded in a food processor.
  • the added liquid was reduced 50% from Example 7 in an effort to equalize the liquid:mass ratio between the blanched and unblanched samples.
  • the unblanched pretreated samples also underwent the same soaking and spraying pretreatment steps.
  • the seaweed reactions were later inoculated and subjected to anaerobic fermentation in the presence of lactic acid (ensilation) or absence of lactic acid (pickling) after thawing.
  • 100 mg of silage inoculant was added to a 100 ml spray bottle (le8 CFU/ml) and approximately 2 ml inoculant aerosol was sprayed into each sample for a target of le8 CFU/ml, and the samples were placed in an anaerobic hood.
  • FIG. 8 shows the pH of the scale-up reactions during the halogenation reaction and postinoculation for a total duration of 30 days.
  • FIG. 9 is a graph of the bromoform peak areas versus time for the first and second scale-up halogenation reactions. The halogenation reaction occurred on day 0. Samples were taken on day 0, 7, and 21.
  • bromoform peak area on day 0 was determined by methanol extraction, whereas on days 7 and 21 the bromoform peak area was determined by hexane extraction.
  • a further conclusion that may be drawn is that bromoform concentration decreases rapidly within seven days, even under anaerobic conditions.
  • Example 9 Trial-Scale, long-term stability of halocarbons at low pH in the presence of ensiling microbes The long-term stability of bromoform was assessed under the low pH conditions postinoculation. 25 lbs. of Saccharina latissima seaweed was combined with 10 mM PAA and 100 mM KBr. The KBr was added first and then the seaweed and KBr mixture was drill mixed to ensure uniformity. The PAA was later added to the slurried seaweed and mixed again with a drill mixer. Total liquid added was approximately 5% of the seaweed mass.
  • FIG. 10A is a graph of the pH of the third scaled-up halogenation reaction during the halogenation reaction and post-inoculation for a total duration of 12 days after reaction. Data is given as the mean +/-S.D. The pH decreases with the addition of PAA and lactic acid and then remains stable at -pH 5 for the next 12 days.
  • FIG. 10B shows the bromoform concentration (pg bromoform/g dry weight seaweed) over a period of 13 days post-reaction (the halogenation reaction occurred on day 0). Bromoform is produced rapidly and peaks at 340pg/g upon reaction completion, then begins to decrease before reaching an inflection on day 2 at ⁇ 207pg/g and plateauing for the remainder of the measurement period. Bromoform concentration is given as the mean +/-S.D. These data suggest the bromoform is produced rapidly upon addition of KBr to PAA and gradually degrades over several days.
  • the example set forth below describes the production of bromoform in the presence of seaweed and non-seaweed organic matter.
  • Exemplary halogenation reactions described below produced bromoform with various species of Gracilaria seaweeds and other potential agricultural feedstocks, including Western Timothy hay. Briefly, 23g of Gracilaria spp. macroalgae and 5.4g of Western Timothy hay were each added, respectively, to 100 mb unbuffered reverse-osmosis water and combined with aqueous potassium bromide. The reactions were initiated with 10 mM PAA, and the resulting reaction mixtures was incubated for 1 h. The reactions were quenched by extracting with 2 m of hexane and analyzed on GC/MS for detecting and characterizing small, halogenated organic compounds, as shown in FIG. 11.
  • haloperoxidase enzymes are present in various Saccharina latissima tissues under a variety of reaction conditions.
  • Haloperoxidase enzymes are the catalyst for the natural production of bromoform and other halogenated compounds synthesized by seaweeds.
  • haloperoxidase activity varies substantially in Saccharina lastissima tissue subjected to a variety of conditions.
  • Initial haloperoxidase activity approaches 8 muN and is comparable to uninoculated seaweed tissue.
  • seaweed tissue inoculated with silage inoculant; inoculated and combined with hydrogen peroxide; and inoculated and combined with hydrogen peroxide, potassium bromide, and sodium orthovanadate all have significantly reduced haloperoxidase activity, demonstrating that the ensiling process hinders catalytic activity of vanadium haloperoxidase.

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Abstract

La présente invention concerne des procédés de production de petits composés organiques halogénés à partir d'un produit organique (par exemple d'une charge d'alimentation agricole ou de macroalgues) par l'intermédiaire d'une réaction d'halogénation, et leurs utilisations associées.
PCT/US2024/053142 2023-10-26 2024-10-26 Traitement de produits organiques pour la production de petits composés organiques halogénés Pending WO2025090983A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090312586A1 (en) * 2008-06-13 2009-12-17 Marathon Gtf Technology, Ltd. Hydrogenation of multi-brominated alkanes
US8729494B2 (en) * 2008-07-16 2014-05-20 Micromas Uk Limited Ion source with device for oxidising a sample
US20160090614A1 (en) * 2008-04-30 2016-03-31 Xyleco, Inc. Processing biomass
US9371407B2 (en) * 2012-12-06 2016-06-21 Chevron Phillips Chemical Company Lp Catalyst system with three metallocenes for producing broad molecular weight distribution polymers
US20190127311A1 (en) * 2011-08-19 2019-05-02 The Trustees Of Princeton University C-halogen bond formation
US20220274090A1 (en) * 2014-10-24 2022-09-01 Carbon Technology Holdings, LLC Halogenated activated carbon compositions and methods of making and using same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160090614A1 (en) * 2008-04-30 2016-03-31 Xyleco, Inc. Processing biomass
US20090312586A1 (en) * 2008-06-13 2009-12-17 Marathon Gtf Technology, Ltd. Hydrogenation of multi-brominated alkanes
US8729494B2 (en) * 2008-07-16 2014-05-20 Micromas Uk Limited Ion source with device for oxidising a sample
US20190127311A1 (en) * 2011-08-19 2019-05-02 The Trustees Of Princeton University C-halogen bond formation
US9371407B2 (en) * 2012-12-06 2016-06-21 Chevron Phillips Chemical Company Lp Catalyst system with three metallocenes for producing broad molecular weight distribution polymers
US20220274090A1 (en) * 2014-10-24 2022-09-01 Carbon Technology Holdings, LLC Halogenated activated carbon compositions and methods of making and using same

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