Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

• SPME Solid phase microextraction
• SPME uses a fiber that is coated with a stationary phase material, such as a liquid polymer, solid sorbent, or a mixture of both. Equilibrium is established between an analyte and the coating material when the fiber is exposed to a solution, which allows the technique to be applied to both headspace and direct-immersion sampling.
• a stationary phase material such as a liquid polymer, solid sorbent, or a mixture of both.
• Equilibrium is established between an analyte and the coating material when the fiber is exposed to a solution, which allows the technique to be applied to both headspace and direct-immersion sampling.
• GC gas chromatography
• the coating should be thermally stable to avoid excessive losses during the high temperature desorption step, while also maintaining physical integrity of the film.
• structural tunability is a desirable means of modulating specific properties of the coating material while retaining others.
• Solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE) are two solvent- free sampling techniques in which sampling and sample preparation are combined into one single step.
• SPME generally uses a fused silica fiber that is coated with an absorbent or adsorbent coating material, typically polydimethylsiloxane (PDMS), polyacrylate, or carbowax divinylbenzene.
• an absorbent or adsorbent coating material typically polydimethylsiloxane (PDMS), polyacrylate, or carbowax divinylbenzene.
• the analytes are sampled due to their partitioning to the coating material, typically under equilibrium conditions.
• the analytes are desorbed from the fiber using either thermal desorption (i.e., injection port of a gas chromatograph) or by solvent desorption (i.e., solvent chamber coupled to a high performance liquid chromatography).
• SBSE operates in a similar manner to SPME but differs in the type of support and the amount of coating material employed in the extraction.
• the analytes are extracted into a thick polymer coating on a magnetic stir bar.
• the amount of coating material in SBSE is -50-250 times larger than SPME, which produces a distinct sensitivity enhancement.
• Ionic Liquids ILs
• Ionic liquids are a class of compounds that can be tailor synthesized to exhibit unique solvent properties while retaining many green characteristics.
• Ionic liquids (IL) and their polymerized analogs constitute a class of non-molecular, ionic solvents with low melting points. Also known as liquid organic, molten, or fused salts, most ILs possess melting points lower than 100°C.
• Many ILs are comprised of bulky, asymmetric N-containing organic cations (e.g., imidazole, pyrrolidine, pyridine) in combination with any wide variety of anions, ranging from simple inorganic ions (e.g., halides) to more complex organic species (e.g., triflate).
• ILs have negligible vapor pressures at room temperature, possess a wide range of viscosities, can be custom-synthesized to be miscible or immiscible with water and organic solvents, often have high thermal stability, and are capable of undergoing multiple solvation interactions with many types of molecules.
• an IL can be polymerized by reaction of at least one free silanol group on the surface of a fused silica support with at least one vinyl-terminated organoalkoxysilane.
• the IL comprises one or more of: vinyl- substituted IL monomers and/or cross-linkers, coated on the support with an initiator and heated to induce free radical polymerization.
• the initiator comprises 2,2'-azo- bis(isobutyronitrile) (AIBN).
• the present invention is based, at least in part, on an efficient method for making a coated support.
• the method includes mixing a monomer with a photo-initiator, and, optionally, a crosslinker (to make the polymer more rigid), to form a monomer solution.
• the monomer solution is coated onto a support (such as fibers) and the coated support is exposed to UV radiation.
• a polymerization reaction occurs where a photo-initiated polymeric ionic liquid (P-PIL) is formed without the use of solvent in a very quick process.
• the P-PIL coated support can be conditioned using, for example, high temperatures. Thereafter, the final support can be used in any end-use reaction.
• the patent or application file may contain at least one photograph and/or one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) and/or photograph(s) will be provided by the Office upon request and payment of the necessary fee.
• Prior Art Figure 1 Schematic illustration of a polymerization route.
• Figure 2 Schematic illustration of a photo-polymerization route.
• FIG. 3 Schematic illustration of synthesis of Poly ([VHIM] [CI]).
• Figure 4A Outline of step 1 in fiber surface modification.
• Figure 4B SEM photographs of fiber surface: etched (left), and unetched (right).
• Figure 5A Outline of step 2 - vinyl silanization.
• Figure 5B Schematic illustration of step 3 - polymerization using UV light.
• Figure 5C Schematic illustration of crosslinkers.
• Figure 6 SEM photograph of etched fiber.
• Figure 7 SEM photograph of etched and derivatized fiber.
• Figure 8 SEM photograph of etched and derivatized fiber smeared with monomer.
• Figure 9 SEM photograph of etched and derivatized fiber smeared with UV -initiated polymeric ionic liquid (P-PIL).
• Figure 10 SEM photograph of etched and derivatized fiber with 5 C8 cross-linker photo- initiated polymeric ionic liquid (P-PIL) (smear coating using 4 hr oven-dried coating solution).
• P-PIL polymeric ionic liquid
• Figure 11 SEM photograph of etched and derivatized fiber with 5 C8 cross-linker P-PIL (dip coating using 4 hr oven-dried coating solution).
• Figure 12 SEM photograph of etched and derivatized fiber with 15 C8 cross-linker P-PIL (smear coating using 4 hr oven -dried coating solution).
• Figure 13 SEM photograph of etched and derivatized fiber with 15 C8 cross-linker P-PIL (dip coating using 4 hr oven-dried coating solution).
• Figure 14 Comparison of the extraction efficiency for selected sorbent coatings in headspace SPME mode.
• Figures 15A-F Sorption time profile for naphthalene and 1-octanol at 10 ⁇ g L 1 and 100 ⁇ g L "1 , respectively. Rectangles indicate the sorption time chosen for subsequent competitive inhibition studies.
• Figures 16A-B Calibration curves for 1-octanol using (A) the PDMS/DVB coating, and (B) the PA coating.
• Figures 17A-B Calibration curves for 1-octanol using (A) Fiber PIL 1, and (B) Fiber PIL 2.
• Figures 18A-B Curves showing the linear range, sensitivity, and amount of 1-octanol extracted using (A) Fiber PIL 3, and (B) Fiber PIL 4.
• the methods described herein overcome these problems by mixing a monomer and, optionally, a crosslinker with a photo- initiator, and coating the mixture as a thin film without any organic solvent.
• the exposure to UV light allows for the monomer to polymerize and cure on, for example, a fused silica fiber.
• the resulting sorbent coating exhibits sufficiently high structural integrity, can be highly crosslinked, and allows for the direct immersion sampling of various analytical matrices without the loss of coating.
• the methods described herein can be practiced with a wide variety of polymer matrices in terms of the structure, composition, and chemical make-up of the corresponding cations and anions in the matrix.
• the products synthesized from the methods described are highly versatile in that they can be used in sampling for a variety of complex matrices.
• the P-PIL coated supports made from the methods described herein can be used to sample analyte and matrix types such as acrylamide in coffee, polychlorinated biphenyls in milk, and genotoxic impurities in active pharmaceutical ingredients.
• the methods described herein involve making a photo-initiated polymeric ionic liquid (P-PIL) coated support.
• the method includes: i) mixing at least one ionic liquid monomer (IL) with at least one photo-initiator; ii) at least partially coating a support with the mixture of step i); and, iii) exposing the coated support of step ii) to UV light to form a photo- initiated polymeric ionic liquid (P-PIL) coated support.
• the method further includes adding at least one cross-linker to the mixture of step i).
• the method involves using dicationic IL crosslinkers and monocationic IL monomers containing halide anions. Cross-linking generally enhances the rigidity and stability of the PIL.
• At least a portion of a surface of the support is functionalized prior to coating with the IL monomer mixture.
• the portion of the surface can be functionalized by etching prior to coating with the IL monomer mixture.
• the portion of the surface can be functionalized by etching with a vinyl substituent prior to coating with the IL monomer mixture. Functionalization of the surface promotes copolymerization.
• the method further includes heating the IL monomer mixture at a temperature of between about 35 to about 45°C.
• the IL monomer mixture can be heated at a temperature of about 40°C.
• the photo-initiator is added at about 0.5% to about 5% (m/v).
• the photo-initiator can be added: at about 2% to about 4% (m/v); and, in certain
• the photo-initiator is added at from about 1% to about 3% w/w of the IL monomer.
• Non-limiting examples of suitable photo-initiators include: 2-hydroxy-2- methylpropiophenone (HMPP); 2,2'-azo-bis(isobutyronitrile) (AIBN); hydroxycyclohexylphenyl ketones; 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2 -propyl) ketone; benzoins; benzoin alkyl ethers; benzophenones such as 2,4,6-trimethylbenzophenone and 4-methylbenzophenone;
• HMPP 2-hydroxy-2- methylpropiophenone
• AIBN 2,2'-azo-bis(isobutyronitrile)
• hydroxycyclohexylphenyl ketones 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2 -propyl) ketone
• benzoins benzoin alkyl ethers
• benzophenones such as 2,4,6-trimethylbenzophenone and 4-methylbenzophenone
• trimethylbenzoylphenylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide or phenylbis(2,4,6-trimethylvbenzyoyl) phosphine oxide (BAPO); azo compounds; anthraquinones and substituted anthraquinones, such as, for example, alkyl substituted or halo substituted anthraquinones; other substituted or unsubstituted polynuclear quinines; acetophenones, thioxanthones; ketals;
• acylphosphines 2-hydroxy-2-methyl-l -phenyl -propan-1 -one; 2-isopropyl-9H-thioxanthen-9-one; and mixtures and derivatives thereof.
• the coated support of step ii) is exposed to UV light in the range of about Ultraviolet C, UVC 280 - 100 nm, 4.43 - 12.4 eV.
• the coated support can be exposed to UV light in the range of about 250 - 240 nm.
• the coated support can be exposed to UV light in the range of about 255-253 nm.
• the coated support is exposed to UV light for a time period ranging from about 0.5 to about 3 hours.
• the coated support can be exposed to UV light for a time period ranging from about 1.5 to about 2.5 hours.
• the coated support can be exposed to UV light for a time period of about 2 hours. The skilled practitioner will recognize that other durations of time are possible.
• the P-PIL is synthesized by a polymerization reaction involving one or more functional groups attached to an aromatic ring of a cationic component.
• the P-PIL can be synthesized using a cross-linking reaction.
• the degree of cross-linking can be modified to control the consistency of the formed polymer with lower degrees of cross-linking resulting in a gel-like material.
• the degree of cross-linking can be modified to control the consistency of the formed polymer with greater degrees of cross-linking resulting in a more rigid, plastic-like coating.
• the degree of cross-linking can be modified to influence one or more of: the mechanism of partitioning, including adsorption versus absorption, and overall selectivity for targeted analyte molecules.
• the P-PIL has a solid/liquid transition temperature of about 400°C or less.
• the polymerization reaction includes one or more of: cationic and anionic chain growth polymerization reactions, Ziegler-Natta catalytic polymerization, and step- reaction polymerization; use of two different monomers to form copolymers through addition and/or block copolymerization.
• the IL monomer mixture is polymerized by reaction of at least one free silanol group on the surface of a fused silica support with at least one vinyl-terminated organoalkoxysilane.
• the IL monomer mixture comprises one or more of: vinyl-substituted IL monomers, initiators and/or cross-linkers. It is to be understood that P-PIL coated support can be polymerized to form linear polymers and/or cross-linked using varying ratios of monocationic/dicationic/tricationic/multicationic crosslinking molecules.
• the photo-initiated polymeric ionic liquid comprises: a) at least one cationic component comprised of an ionic liquid (IL); and, b) one or more anionic components, wherein the anionic components can be the same or different.
• the P-PIL comprises a cationic photo-initiated polymeric ionic liquid (c-P-PIL) comprised of: a) at least one ionic component comprised of anionic liquid (IL): and, b) one or more mobile cationic components, wherein the cationic components can be the same or different.
• c-P-PIL cationic photo-initiated polymeric ionic liquid
• the cationic component can be one or more of: monocationic components, dicationic components, tricationic components, other multicationic components, and mixtures thereof. Also, in certain embodiments, the cationic component can be an IL monomer modified through one or more of: incorporation of longer alkyl chains, aromatic components, and/or hydroxyl -functionality.
• Non-limiting examples of the cationic component include at least one or more: quaternary ammonium, protonated tertiary amine, thionium, phosphonium, arsonium, carboxylate, sulfate or sulfonate groups which may be substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic.
• the cationic component can be described by the general formula of—X + RR'R", where X is selected from the group consisting of N, P, and As, and where each of R, R', R" is selected from the group consisting of a proton, aliphatic group, cyclic group and aromatic group.
• the cationic component can be described by the formula of (— X(R) 3 ) + , wherein R is selected from the group consisting of a proton, aliphatic group (e.g., propyl, butyl), cyclic group (e.g., cyclohexane) and aromatic group (e.g., vinyl, phenyl).
• the R, R' and R" are different from each other.
• the cationic component can include one or more amine functional groups within the cation.
• the cationic component can comprise one or more of: imidazolium-based monomers including functionalized imidazolium, pyridinium, triazolium, pyrrolidinium, ammonium.
• the cationic component can comprises: a quaternary ammonium, a protonated tertiary amine, imidazolium (IM) or substituted IM, pyrrolidinium or substituted pyrrolidinium, or pyridinium or substituted pyridinium, thiophene, N-methyl-D-glucaminium cations and related structures.
• IM imidazolium
• IM imidazolium
• substituted IM imidazolium
• pyrrolidinium or substituted pyrrolidinium or pyridinium or substituted pyridinium
• thiophene N-methyl-D-glucaminium cations and related structures.
• Non-limiting specific examples of suitable cationic components include one or more of:
• the P-PIL can include one or more of: poly(VHIM + NTf 2 ); poly(VDDIM + NTf 2 " ), poly(VHDIM + NTf 2 " ), poly(BBIM + NTf 2 " ), poly(BBIM + taurate “ ), or poly(BBIM + A " ).
• the anionic component is exchanged through biphasic anion metathesis with one or more of the cationic components.
• P-PIL coated support can include anionic components comprised or one or more of: carboxylate, sulfate or sulfonate groups which may be substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic.
• the anionic group can be comprised of an amino acid component, bis[(trifluoromethyl)sulfonyl]imide, or any anion containing i) fluorine groups and ii) primary, secondary, or tertiary amine groups. Also, in certain embodiments, the anionic group comprises a taurate component.
• Non-limiting examples of anionic component include one or more of: CI “ , Br “ , I “ ,
• the P-PIL coated support can be synthesized by free radical polymerization of one or more of: l-vinyl-3- hexylimidazolium chloride, l-vinyl-3-dodecylimidazolium bromide, and l-vinyl-3- hexadecylimidazolium bromide.
• devices that include a P-PIL coated support that is one or more of: a solid fused silica support, a stir bar, a fiber, a film, a membrane, a fibrous mat, a woven or non-woven material.
• the P-PIL coated support can comprise one or more walls of fused silica capillaries.
• the P-PIL coated support can comprise small inner diameter fused silica supports.
• the methods described herein can be performed in air at room temperature and consolidated to two primary steps: dynamic dip coating, and exposure to UV radiation. Compared to other PIL coating methods, the methods described herein require fewer steps and eliminate the need for applied heat, dispersive organic solvents, and an inert N 2 atmosphere. The etching of the support allows for a higher surface area and a more rigid surface morphology.
• Derivatizing the surface with VTMS to impart vinyl functionality to the fiber allows the copolymer matrix to be covalently bonded to the support. Immobilization of the cross-linked PIL-based sorbent coating to the silica support also hinders the sloughing off of the coating during direct immersion SPME, particularly in well agitated samples.
• the methods described herein eliminate the need for organic solvents, produce a covalently linked and mechanically stable coating capable of enduring high shear forces, and exhibit lower bleed, lower backgrounds, and lower limits of detection.
• the resulting coatings are nonetheless stable in the presence of different organic solvents and aqueous matrices, and are thus rather versatile.
• Non-limiting uses of the P-PIL coated supports and devices include a chemical separation or analysis device.
• the P-PILs in the device can be functionalized to: 1) selectively extract one or more analytes of interest and to allow all other analytes to be removed so that one or more pre- concentrated analytes can be separated, identified and/or quantified; and/or 2) selectively extract all other molecules so that the analyte(s) of interest can be removed from other molecules thereby allowing them to be separated, identified, and/or quantified.
• One example is a separation device having a support at least partially coated with one or more photo-initiated polymeric ionic liquids (P-PILs).
• the separation device can be one or more of:
• the separation device can be coupled to gas chromatography (GC) in which one or more analytes are thermally desorbed in a GC injection port.
• GC gas chromatography
• HPLC HPLC mobile phase or buffered component is used to desorb molecules from the support.
• CE capillary electrophoresis
• separation devices described herein are useful where one or more analytes to be separated exist as any one of forms of solids, liquids and gases, and are any one of chemical component comprising: small molecules, ions, synthetic or natural polymers,
• the extraction device can be one or more of: liquid-phase microextraction and single drop microextraction devices.
• the extraction device can include the P-PIL coated support packed in a chromatographic column.
• the P-PIL coated support can be a capillary column of a gas chromatography device.
• the extraction device can be a solid phase microextraction (SPME) device.
• the device can be a high performance liquid chromatography column (HPLC).
• the P-PIL is adaptable to desorption after exposure to one or more analytes.
• the extraction device is useful for extracting one or more of DNA, RNA, protein, nucleic acids, peptides, amino acids, cellular extracts and portions thereof, comprising at least one P-PIL coated support.
• the method for capturing C0 2 can include exposing an environment containing C0 2 to at least one P-PIL coated support. Also, in certain embodiments, the P-PIL coated support can be heated to temperatures around 70-110°C to release C0 2 from the P-PIL support. Also, it is to be understood that in a carbon sequestration method, at least one of a reactant gas mixture including C0 2 can be brought into contact with P-PIL carbon sequestration catalyst at a temperature wherein a solid carbon deposit is formed at the surface of the P-PIL carbon sequestration catalyst. Also, in certain embodiments, the method can further include recapturing sequestered C0 2 and reusing the P-PIL carbon sequestration catalyst.
• Yet another example is a method of separating at least one chemical from a mixture of chemicals comprising: providing a mixture containing the at least one chemical; exposing the mixture to at least one solid support including at least one P-PIL adsorbed, absorbed or immobilized thereon; and, retaining at least a portion of the at least one chemical on the solid support for a period of time.
• the solid support is a column, and the method further comprises passing the mixture through the column such that elution of the at least one chemical is prevented or delayed.
• the extraction additives or phase modifiers comprise one or more of: micelles, monomer surfactants, cyclodextrins, nanoparticles, synthetic macrocycles, or other polymer aggregates.
• the support comprises one or more of: fibers at least partially coated with at least one P-PIL; stir bar supports; walls of fused silica capillaries; small inner diameter fused silica supports.
• a stationary phase niicroextraction material for solid phase niicroextraction comprising one or more P-PILs.
• the solid phase niicroextraction material can further include one or more of: a support at least partially coated with the polymeric ionic liquid; fibers at least partially coated with the polymeric ionic liquid; fibers that comprise small inner diameter fused silica fibers.
• the photo-initiated polymeric ionic liquids are generally comprised of: i) a cationic component comprised of an ionic liquid (IL) that is polymerized, and ii) one or more anionic components, wherein the anionic components can be the same or different.
• the cationic component comprises at least one or more: quaternary ammonium, protonated tertiary amine, thionium, phosphonium, arsonium, carboxylate, sulfate or sulfonate groups which may be substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic.
• the cationic component is described by the general formula of—X + RR'R", where X is N, P, or As, and where each of R, R', R" is selected from the group consisting of a proton, aliphatic group, cyclic group, and aromatic group.
• the cationic component is described by the formula of (— X(R) 3 ) + , wherein R is a proton, aliphatic group (e.g., propyl, butyl), cyclic group (e.g., cyclohexane), or aromatic group (e.g., vinyl, phenyl).
• R is a proton, aliphatic group (e.g., propyl, butyl), cyclic group (e.g., cyclohexane), or aromatic group (e.g., vinyl, phenyl).
• R is a proton, aliphatic group (e.g., propyl, butyl), cyclic group (e.g., cyclohexane), or aromatic group (e.g., vinyl, phenyl).
• the R, R', and R" are different from each other.
• Non-limiting examples include where the cation comprises one or more of: imidazolium- based monomers including functionalized imidazolium, pyridinium, triazolium, pyrrolidinium, ammonium.
• the anion comprises one or more of: CI “ , Br “ , ⁇ , bis[(trifluoromethyl)sulfonyl]imide, PF 6 " , BF 4 , CN “ , SCN “ , taurate, and/or other amino acid groups.
• the P-PIL is substantially free of residual halides following anion metathesis.
• the P-PIL comprises one or more of: l-vinyl-3-hexylimidazolium chloride; l-vinyl-3dodecylimidazolium bromide, and l-vinyl-3-hexadecylimidazolium bromide.
• the cationic component comprises: a quaternary ammonium, a protonated tertiary amine, imidazolium (IM) or substituted IM, pyrrolidinium or substituted pyrrolidinium, or pyridinium or substituted pyridinium.
• the cationic component includes one or more amine functional groups within the cation.
• the P-PIL is polymerized to form linear polymers and/or cross-linked using varying ratios of monocationic/dicationic/tricationic/multicationic crosslinking molecules.
• the cationic component comprises one or more of: monocationic components, dicationic components, tricationic components, other multicationic components, and mixtures thereof.
• the cationic component comprises an IL monomer modified through one or more of: incorporation of longer alkyl chains, aromatic components, and/or hydroxyl- functionality.
• Non-limiting examples include wherein the cationic component comprises one or more of: VHIM + ; VDDIM + , VHDEVf, and BBEVf.
• the P-PIL includes one or more of: poly(VHIM + NTf 2 ); poly(VDDIM + NTf 2 " ), poly(VHDIM + NTf 2 " ), poly(BBIM + NTf 2 " ), poly(BBIM + taurate “ ), poly(BBIM + A “ ).
• the anionic component comprises one or more of: carboxylate, sulfate or sulfonate groups which may be substituted or unsubstituted, saturated or unsaturated, linear, branched, cyclic or aromatic.
• the anionic component comprises an amino acid component, bis[(trifluoromethyl)sulfonyl]imide, or any anion containing i) fluorine groups and ii) primary, secondary, or tertiary amine groups.
• the anionic group comprises a taurate component.
• the structural design of the P-PIL is selected in order to achieve high thermal stability.
• the P-PILs have a solid/liquid transition temperature of about 400°C or less.
• the P-PIL comprises one or more of non-molecular ionic solvents, the solvent being comprised of at least one asymmetric cation paired with at least one anion.
• the anionic component is exchanged through biphasic anion metathesis with one or more of the cationic components.
• a "diionic salt” or “DIS” is a salt formed between a dication and a dianion or two anions or between a dianion as described herein and a dication or two cations. This term is not meant to embrace a single species that has a +2 or -2 charge such as Mg +2 or S0 4 "2 . Rather, it contemplates a single molecule with two discreet mono-ionic groups, usually separated by a bridging group. The two ionic species are of the same charge. They may be different types of groups or the diionic liquid salts may be "geminal" which means both ionic groups are not only the same charge, but also the same structure. The counterions need not be identical either.
• either the diion or the salt forming species is chiral, having at least one stereogenic center.
• the diionic liquid salts may be racemic (or in the case of diastereomers, each pair of enantiomers is present in equal amounts) or they may be optically enhanced. "Optically enhanced" in the case of enantiomers means that one enantiomer is present in an amount which is greater than the other. In the case of diastereomers, at least one pair of enantiomers is present in a ratio of other than 1 :1.
• the diionic liquid salts may be "substantially optically pure" in which one enantiomer or, if more than one stereogenic center is present, at least one of the pairs of enantiomers, is present in an amount of at least about 90% relative to the other enantiomer.
• the diionic liquid salts of the invention may also be optically pure, i.e., at least about 98% of one enantiomer relative to the other.
• diionic salt is used to describe a salt molecule, although, it may be used
• DIL diionic liquid
• DILS diiionic liquid salt
• a “diionic liquid” or “DIL” is a liquid comprised of diionic salts. Thus, sufficient DS molecules are present such that they exist in liquid form at the temperatures indicated herein. This presumes that a single DS molecule is not a liquid.
• a DL is either a dicationic ionic liquid or a dianionic ionic liquid (a liquid comprising either dicationic salts or dianionic salts as described herein).
• a “dicationic ionic liquid” (used synonymously with “liquid salts of a dication”) is a liquid comprised of molecules which are salts of dicationic species.
• the salt forming counter-anions may be mono-ionic such as, for example only, Br-, or dianionic, such as, again for example only, succinic acid.
• Any dicationic ionic liquid which is stable and has a solid/liquid transformation temperature of 400°C or less is contemplated.
• dianionic ionic liquids also known as “liquid salts of a dianion,” except the charges are reversed.
• Dicationic liquids and dianionic liquids can also be referred to herein as diionic liquid salts ("DILS" or “DCLS” and “DALS" depending upon charge).
• a dicationic ionic liquid and/or dianionic ionic liquid will not substantially decompose or volatilize (or remain substantially non-volatile) as measured by being immobilized as a thin film in a fused silica capillary or on a silica solid support as described herein, at a temperature of 200°C or less. "Substantially” in this context means less than about 10% by weight will decompose or volatilize at 200°C inside a capillary over the course of about one hour.
• the dicationic ionic liquid will preferably have either a solid/liquid transformation temperature at about 100°C or less or a liquid range (the range of temperatures over which it is in a liquid form without burning or decomposing) of at least 200°C.
• these dicationic ionic liquids will have both a solid/liquid
• a dicationic ionic liquid will not substantially volatilize
• the dicationic ionic liquids will preferably have either a solid/liquid transformation temperature at 25°C or less. In another embodiment, the dicationic ionic liquids will also have a liquid range of at least 200°C. In another embodiment, the liquid range will be 300°C or above.
• the diionic liquids either dicationic ionic liquids or dianionic ionic liquids will be stable, that is not substantially volatilized or decomposed, as discussed herein, at a temperature of less than about 300°C and will have a solid/liquid transformation temperature at about 25°C or less.
• the diionic liquids will have a liquid range of at least 200°C, and even more preferably at least 300° C. Any diionic compound which can form a stable liquid salt that meets the broadest parameters is contemplated.
• the present invention provides a stable diionic liquid comprising at least one liquid salt of dianionic molecule or dicationic molecule of the structure of formula I or II: C- A-B-A' (I) or C'-A-B-A'-C" (II) wherein A and A' are either both anions or both cations, or are both groups which overall have an anionic or cationic charge and which may be the same or different, so long as they both have the same charge (positive or negative); B is a bridging group (also referred to as a chain or bridging moiety) that may be substituted or unsubstituted, saturated or unsaturated, aliphatic, including straight or branched chains, cyclic or aromatic, and which may contain, in addition to carbon atoms and hydrogen, N, O, S and Si atoms; and C, C and C" are counter ions having a charge which is opposite that of A and A'.
• a and A' are either both anions or both cations, or
• C and C" are ether both mono-anionic or mono- cationic or groups which have a single anionic or cationic charge and may be the same or different so long as they both have the same charge (positive or negative) and C is ether dianionic or dicationic or contains two groups which each have a single anionic or cationic charge.
• a and A' are cationic and are, without limitation, substituted or unsubstituted, saturated or unsaturated, aliphatic including straight or branched chain, cyclic or aromatic, quaternary ammonium, protonated tertiary amine, phosphonium or arsonium groups.
• C and C" are anionic counterions which, without limitation, include halogens, mono-carboxylates, mono-sulfonates, mono-sulphates, NTf 2 -, BF 4 , trifilates or PF 6
• C is a dianionic molecule having two anionic groups each selected from, without limitation, carboxylate, sulfate or sulfonate groups.
• a and A' are anionic and are, without limitation, substituted or unsubstituted, saturated or unsaturated, aliphatic including straight or branched chain, cyclic or aromatic, carboxylates, sulfonates, and sulphates.
• C and C" are cationic counterions which, without limitation, include quaternary ammonium, protonated tertiary amine, phosphonium or arsonium groups.
• C is a dicationic molecule which can be, without limitation, a compound having two cationic groups each selected from quaternary ammonium, protonated tertiary amine, phosphonium or arsonium groups.
• these dianionic ionic liquids will have both a temperature of solid/liquid transformation of about 100°C or less and a liquid range of at least 200°C.
• these liquid salts of formula I or II have a solid/liquid transition temperature of from about 100°C or less and/or a liquid range of 200°C or more and/or are substantially non-volatile and non-decomposable at temperatures below 200°C.
• the structural considerations for diionic liquids are the same whether they are dianionic ionic liquids or dicationic ionic liquids.
• the diionic liquids will include a diionic species, either a dianionic or a dicationic molecule.
• the ionic species are normally separated by a chain or bridging moiety or group as discussed herein. Any anion or cation which can provide a dianionic ionic liquid or dicationic ionic liquid is contemplated. These include those that are identified above as A and A'.
• Possible cations include, without limitation, quaternary ammonium (— N(R) 4 ) + , protonated tertiary amines (— N(R) 3 H) + , phosphonium and arsonium groups. These groups can be aliphatic, cyclic, or aromatic.
• Anions may include, for example, carboxylates, sulphonates, or sulphonates.
• Examples of a dicarboxylic acid dianion include, without limitation, succinic acid, nonanedioic acid, and
• dodecanedioic acid dodecanedioic acid.
• diionic species include:
• n is discussed in connection with the length of the bridging group.
• hybrid dianions and dications are contemplated.
• a dication can be composed of a quaternary ammonium group and an arsonium group and a dianion can be composed of a carboxylate group and a sulphonate.
• the counter ions may also be different from each other.
• the bridging group or chain interposed between the two ionic species can be any length or any composition which affords a diionic liquid of suitable properties. These include the groups identified as B above. There are certain factors that should be considered in selecting such a chain or bridging moiety. First, the larger the diionic molecule in general, the greater the chance that the melting point or temperature of solid/liquid transformation will be elevated. This may be less of a concern where the liquid range need not be extensive and the temperature of solid/liquid transformation need not be incredibly low. If, however, one desires a liquid range of about 200°C or more and/or a solid/liquid transformation temperature at 100°C or less, the size of the overall molecule can become a larger and larger factor. Second, the chain should have some flexibility.
• the chain or bridging group may be aliphatic, cyclic, or aromatic, or a mixture thereof. It may contain saturated or unsaturated carbon atoms or a mixture of same with, for example, alkoxy groups (ethoxy, propoxy, isopropoxy, butoxy, and the like). It may also include or be made completely from alkoxy groups, glycerides, glycerols, and glycols.
• the chain may contain hetero- atoms such as O, N, S, or Si and derivatives such as siloxanes, non-protonated tertiary amines and the like.
• the chain may be made from one or more cyclic or aromatic groups such as a cyclohexane, an immidazole, a benzene, a diphenol, a toluene, or a xylene group or from more complex ring- containing groups such as a bisphenol or a benzidine.
• cyclic or aromatic groups such as a cyclohexane, an immidazole, a benzene, a diphenol, a toluene, or a xylene group or from more complex ring- containing groups such as a bisphenol or a benzidine.
• the diionic liquids are generally salts, although they may exist as ions (+1, -1, +2, -2) in certain circumstances. Thus, in most instances, each ion should have a counterion, one for each anion or cation. Charge should be preserved. In the case of a dianionic ionic liquid, two cations (including those identified as C or C") (or one dication) (including those identified as C) are required and in the case of a dicationic ionic liquid, two anions (including those identified as C or C") (or one dianion) (including those identified as C) are required. The choice of anion can have an effect of the properties of the resulting compound and its utility as a solvent.
• anions and cations will be described in the context of a single species used, it is possible to use a mixture of cations to form salts with a dianionic species to form a dianionic ionic liquid. The reverse is true for dications.
• the salt-forming ions will be referred to as counterions herein.
• Cationic counterions can include any of the dicationic compounds previously identified for use in the production of dicationic ionic liquids. In addition, monoionic counterparts of these may be used. Thus, for example, quaternary ammonium, protonated tertiary amines, phosphonium, and arsonium groups are useful as cationic counterions for dianionic molecules to form dianionic ionic liquids.
• anionic counterions can be selected from any of the dianionic molecules discussed herein useful in the creation of dianionic ionic liquids. These include dicarboxylates, disulphonates, and disulphates. The corresponding monoionic compounds may also be used including carboxylates, sulphonates, sulphates and phosphonates. Halogens may be used as can triflate, NTf 2 " , PF 6 , BF 4 " and the like. The counterions should be selected such that the diionic liquids have good thermal and/or chemical stability and have a solid/liquid transformation temperature and/or a liquid range as described herein.
• the ionic groups can be substituted or unsubstituted. They may be substituted with halogens, with alkoxy groups, with aliphatic, aromatic, or cyclic groups, with nitrogen-containing species, silicon-containing species, with oxygen-containing species, and with sulphur-containing species.
• the degree of substitution and the selection of substituents can influence the properties of the resulting material as previously described in discussing the nature of the bridge or chain. Thus, in certain embodiments, care should be taken to ensure that excessive steric hindrance and excessive molecular weight are avoided, that resulting materials does not lose its overall flexibility and that nothing will interfere with the ionic nature of the two ionic species.
• the diionic liquids can be used in pure or in substantially pure form as carriers or as solvents. "Substantially” in this context means no more than about 10% of undesirable impurities. Such impurities can be either other undesired diionic salts, reaction by-products, contaminants or the like as the context suggests. In an intended mixture of two or more DILS, neither would be considered an impurity. Because they are non-volatile and stable, they can be recovered and recycled and pose few of the disadvantages of volatile organic solvents. Because of their stability over a wide liquid range, in some instances over 400°C, they can be used in chemical syntheses that require both heating and cooling. Indeed, these solvents may accommodate all of the multiple reaction steps of certain chemical syntheses.
• diionic liquids may be used in solvent systems with cosolvents and gradient solvents and these solvents can include, without limitation, chiral ionic liquids, chiral non- ionic liquids, volatile organic solvents, non-volatile organic solvents, inorganic solvents, water, oils, etc. It is also possible to prepare solutions, suspensions, emulsions, colloids, gels and dispersions using the diionic liquids.
• Polymers may include the diionic salts within the backbone or as pendant groups and they may be cross-linked or non-cross-linked.
• the dianionic liquids can be used to perform separations as, for example, the stationary phase for gas-liquid chromatography.
• Dicationic ionic liquid salts which may be used for exemplification include: (1) two vinyl imidazolium or pyrrolidinium dications separated by an alkyl linkage chain (of various length) or (2) one vinyl imidazolium or pyrrolidinium cation separated an alkyl linkage chain (of various length) and connected to a methyl, ethyl, propyl, or buylimidazolium cation or a methyl, ethyl, propyl, or butylpyrrolidinium cation.
• the presence of unsaturated groups facilitates cross-linking and/or immobilization.
• Dianionic anions can also be used with either monocations or dications to form a variety of different ionic liquid combinations. When a dication is used, anyone is used as charge balance must be preserved.
• the dianionic anions can be of the dicarboxylic acid type (i.e., succinic acid, nonanedioic acid, dodecanedioic acid etc), as shown below.
• Diionic liquid salts can be coated on a capillary (or solid support) and optionally,
• dicationic ionic liquids include, without limitation, trifilates, carboxylates, sulfonates and sulfates (both mono- and poly-anionic species).
• Dianionic ionic liquids can be produced from any dianion which can form a stable salt, preferably which has a melting point below 400°C, more preferably at or below 100°C, most preferably at or below room temperature (25°C). These include dicarboxylate, disulfonate and disulfates.
• Mixed dianions one made from, for example, a dicarboxylate and a disulfate, are also desirable. Cations or counterions for these include, again without limitation, the dications, as well as their monocationic counterparts.
• Various monoionic liquid or diionic liquid salt may be used.
• Diionic liquids such as those shown immediately below can be absorbed or adsorbed onto a solid support.
• ionic liquids both monoionic and diionic liquid salts can be immobilized by being bound or cross-linked to themselves and to a solid support as previously discussed in connection with manufacturing capillary GC columns. To do so, however, the species used should have at least one unsaturated group disposed to allow reaction resulting in immobilization. See for example the monocationic and dicationic species immediately below.
• SPME task specific SPME
• TSSPME Task specific SPME
• ionic liquids or diionic liquids used are further modified such that they will specifically interact with a particular species. Those shown below, for example, may be used in the detection of cadmium and mercury (Cd 2+ or Hg 2+ ).
• the first monocationic material can be coated, absorbed or adsorbed onto a fiber as previously discussed.
• a diionic liquid salt can also be absorbed or adsorbed in known fashion.
• the second and third ionic liquid materials illustrated below, the first monoionic and the second dicationic, by virtue of the presence of unsaturated groups, can be more easily immobilized on a solid support using techniques analogous to those described previously with regard to cross-linking in connection with manufacturing capillary GC columns.
• a particular sample can be suspended in a matrix that includes ionic liquids and preferably diionic liquid salts in accordance with the present invention.
• This matrix can be loaded or immobilized on the fiber of an SPME syringe as described above and then injected into a mass spectrometer to practice a technique known as SPME/MALDI mass spectrometry.
• the matrix is exposed to a UV laser. This causes the volatilization or release of the sample much as heat does in a GC. This allows the sample to enter mass spectrometer where it can be analyzed.
• Ionic materials which can be used as a matrix. Non-limiting examples include
• boron selective ionic liquids are used.
• a boron selective IL can be comprised of: i) at least one cationic component having at least one functionalized group capable of chelating boron; and, ii) one or more anionic components.
• the functionalized group comprises one or more hydroxyl groups. In other certain embodiments, the functionalized group comprises one or more -(OCH 3 ) hydroxyl groups.
• the cationic component is polymerized to form a polymeric ionic liquid (PIL).
• PIL polymeric ionic liquid
• the boron selective ionic liquid IL can include more than one type of ionic component.
• the boron selective ionic liquid (IL) can be comprised of at least one saccharide cationic component and one or more anionic components.
• the saccharide cationic component comprises one or more of: polyglycols, monosaccharides, disaccharides, oligosaccharides and polysaccharides, including sugars, starches, cellulose, and related compounds.
• the cationic component comprises N-methyl-D-glucamine.
• the cationic component is polymerized to form a polymeric ionic liquid (PIL).
• PIL polymeric ionic liquid
• a selective polymeric ionic liquid comprised of: i) at least one polymerized cationic component having at least one functionalize group capable of chelating boron; and, ii) one or more anionic components.
• the boron selective IL and/or PIL is doped with one or more of: non-boron selective ILs and/or PILs, polymeric materials, and solvents.
• a boron ionic liquid formed from N- methyl-D-glucamine by the quaternization of an amine using a double nucleophilic substitution with an alkyl halide.
• Non-limiting examples of boron selective ILs include:
• a device useful in chemical separation or analysis comprising: a support and at least one P-PIL adsorbed, absorbed or immobilized thereon.
• a device comprising one or more P-PILs functionalized to: (1) selectively extract one or more analytes of interest and to allow all other analytes to be removed so that one or more pre-concentrated analytes can be separated, identified and/or quantified; and/or (2) to selectively extract all other molecules so that the analyte(s) of interest can be removed from other molecules thereby allowing them to be separated, identified, and/or quantified.
• a device comprising coated or immobilized P-PILs for solid phase microextraction (SPME), wherein one or more P-PILs are used in neat polymeric form, or mixed with other ILs or P-PILs, solvents, other polymers, including but not limited to PDMS, PEG, silicone oils, or other chromatographic adsorbent materials.
• SPME solid phase microextraction
• a separation device comprising a support at least partially coated with one or more P-PILs.
• the separation device in one or more of: headspace extraction, direct-immersion extraction, or membrane protected SPME extraction.
• One non-limiting example includes where the separation device can be coupled to gas chromatography (GC) in which one or more analytes are thermally desorbed in a GC injection port.
• GC gas chromatography
• separation device can be coupled to HPLC in which a HPLC mobile phase or buffered component is used to desorb molecules from the support.
• Another non-limiting example includes where the separation device can be coupled to capillary electrophoresis (CE) in which a running buffer from the CE is used to remove analytes from the support.
• CE capillary electrophoresis
• analytes to be separated can exist in any forms of matter (solids, liquids, and gases) and can be of any chemical component (small molecules, ions, synthetic or natural polymers, macromolecules, biomolecules).
• Another non-limiting example includes where the separation device can be used for
• Non-limiting examples include one or more of the following: the solid support is packed in a chromatographic column; the solid support is a capillary column useful in gas chromatography; the device is use in solid phase microextraction (SPME).
• SPME solid phase microextraction
• the device configured for thermally desorbing analytes from the support.
• the device comprises a solvent desorption device coupled to a high performance liquid chromatography column (HPLC).
• HPLC high performance liquid chromatography column
• the separation device can comprise one or more of the following: a stationary phase coating on the support; a stationary phase coating coatings for useful for microextractions; a coating for solid phase microextraction (SPME); a support comprising one or more of: a solid fused silica support, a stir bar, a fiber, a film, a membrane, a fibrous mat, a woven or non-woven material.
• a stationary phase coating on the support a stationary phase coating coatings for useful for microextractions
• SPME solid phase microextraction
• a support comprising one or more of: a solid fused silica support, a stir bar, a fiber, a film, a membrane, a fibrous mat, a woven or non-woven material.
• a method comprising mixing one or more P- PILs with one or more solvents to vary the viscosity and surface tension of the P-PIL.
• the method can further include allowing the P-PIL to be suspended from a microsyringe configured for sampling of one or more analytes.
• at least one suspended drop is used to sample an analyte matrix (liquid, solid, or gas) and wherein the P-PIL is directly injected into a GC, HPLC, or CE or mixed with a solvent and then directly injected into GC, HPLC, or CE.
• the analytes to be separated can exist in any forms of matter (solids, liquids, and gases) and can be of any chemical component, including, but not limited to small molecules, ions, synthetic or natural polymers, macromolecules, biomolecules.
• a device for selective C0 2 absorbance comprising at least one P-PIL on a support.
• the process can include being reversible by heating the P-PIL to temperatures around 70-110°C.
• a device comprising at least one P-PIL on a support, and capable of an on-support metathesis exchange of anions from an immobilized P-PIL absorbent material.
• a carbon sequestration method comprising bringing at least one of a reactant gas mixture including carbon dioxide contact with a P-PIL carbon sequestration catalyst at a temperature wherein a solid carbon deposit is formed at the surface of the
• the method further includes recapturing sequestered C0 2 and reusing the P-PIL carbon sequestration catalyst.
• the method can further include tuning one or more of chemical and physical properties of the P-PIL through one or more of: i) choice of the anion, and ii) modification of the cation structure.
• the method can further include tuning one or more of chemical and physical properties of the P-PIL through one or more of: i) choice of the cation, and ii) modification of the ion structure.
• the method can further include forming a mixture of P-PIL and one or more extraction additives or phase modifiers that aid in selectively increasing extraction efficiency or promoting wetting of glass or metal substrates.
• the solid phase microextr action material can include ionic liquids that are comprised of one or more of non-molecular ionic solvents comprised of bulky, asymmetric cations paired with one or more types of anions.
• one or more of chemical and physical properties of the P-PILs are capable of being tunable through choice of anion and/or modification of the cation structure.
• TSILs task-specific ionic liquids
• a composite semipermeable device comprising: a porous substrate comprised of at least one P-PIL on a support; and a separating functional IL material layer formed on the substrate film, wherein the IL that forms the separating functional layer contains a boron selective IL and/or PIL.
• a semipermeable membrane element comprising the separation device described herein as a separation membrane.
• a fluid separation system comprising the separation device described herein as a fluid separation element.
• a water treatment method comprising subjecting water to a permeation process using the separation device described herein.
• a method of purifying water comprising: providing a feed water to a filtration device comprised of the separation device described herein.
• the feed water is seawater, brackish water or oil field recovery water.
• the method can further include reducing boron content in the feed water to less than about 0.5 mg/L.
• the separation coefficient of boric acid between water and the boron compounds described herein can be done by liquid-phase extraction coupled with spectrophotometry or atomic spectroscopy, as well as the possibility to regenerate the ionic liquid by rinsing with an acidic or basic aqueous solution or by subjecting the IL/PIL material to electrodialysis.
• step i) mixing at least one ionic liquid monomer (IL) with at least one photo-initiator, ii) at least partially coating a support with the mixture of step i), and
• step iii) exposing the coated support of step ii) to UV light to form a cationic photo-initiated polymeric ionic liquid (c -P-PIL) coated support,
• c-P-PIL comprises:
• At least one ionic component comprised of anionic liquid (IL), and one or more mobile cationic components, wherein the cationic components can be the same or different.
• IL anionic liquid
• the c-P-PIL can be formed by one or more of polymerization reactions that include one or more of: cationic and anionic chain growth polymerization reactions, Ziegler-Natta catalytic polymerization, and step-reaction polymerization; use of two different monomers to form copolymers through addition and/or block copolymerization.
• the method can further include adding at least one cross-linker to the mixture of step i).
• At least a portion of a surface of the support is functionalized prior to coating with the IL monomer mixture.
• at least a portion of a surface of the support is functionalized by etching prior to coating with the IL monomer mixture, ad described herein.
• polymeric anion generally refers to a polymer which has a negative ionic charge.
• Non-limiting examples of polymeric anions can include: anions of polymeric carboxylic acids, such as poly acrylic acids, polymethacrylic acids or polymaleic acids, or polymeric sulfonic acids, such as polystyrene sulfonic acids and polyvinyl sulfonic acids.
• the polycarboxylic and - sulfonic acids can also be copolymers of and vinyl sulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
• Non-limiting specific examples can include: polyacrylate, polymethacrylate, dextran, sulfate, sulfated glycosaminoglycans, polyglutamate, polyaspartate, carboxymethyl-cellulose, -dextran, or - agarose, sulfoethyl- or sulfopropyl-cellulose, -dextran, or -agarose, polyphosphate, polyanethole sulfonate, or any other suitable negatively charged polymer.
• polymeric anions can include: anions of polymeric carboxylic acids (e.g., polyacrylic acids, polymethacrylic acid, polymaleic acids, etc.); polymeric sulfonic acids (e.g., polystyrene sulfonic acids ("PSS"), polyvinyl sulfonic acids, etc.); and the like.
• the acids may also be copolymers, such as copolymers of vinyl carboxylic and vinyl sulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
• Non-limiting examples of monomeric anions include, for example, anions of Ci to C 2 o alkane sulfonic acids (e.g., dodecane sulfonic acid); aliphatic perfluorosulfonic acids (e.g., trifluoromethane sulfonic acid, perfluorobutane sulfonic acid or perfluorooctane sulfonic acid); aliphatic Ci to C 2 o carboxylic acids (e.g., 2-ethyl-hexylcarboxylic acid); aliphatic perfluorocarboxylic acids (e.g., trifluoroacetic acid or perfluorooctanoic acid); aromatic sulfonic acids optionally substituted by Q to C 2 o alkyl groups (e.g., benzene sulfonic acid, o-toluene sulfonic acid, p-toluene sulfonic acid or
• the polymeric anions can be one or more of: a polymeric carboxylic or sulfonic acid (e.g., polystyrene sulfonic acid ("PSS"); for example, where the molecular weight of such polymeric anions typically ranges from about 1,000 to about 2,000,000, and in some embodiments, from about 2,000 to about 500,000.
• PSS polystyrene sulfonic acid
• VTMS vinyltrimethoxysilane
• AIBN 2,2'-azobisisobutyronitrile
• 1-chlorohexane ammonium hydrogen difluoride
• 2-hydroxy-2-methylpropiophenone HMPP were purchased from Sigma- Aldrich (Milwaukee, WI, USA).
• Analytes chosen including 2-methyl-l-butanol, cyclohexanol, octanol, furfural, benzaldehyde, 1 -phenyl- 1-propanol, ethyl propionate, ethyl hexanoate, ethyl valerate, furfural pentanoate, and furfural propionate were purchased from Sigma-Aldrich.
• Acetonitrile, acetone, chloroform, methanol, n-hexane, isopropanol, dichloromethane, and ethyl acetate were purchased from Fisher Scientific (Fair Lawn, NJ, USA).
• Ultrapure water (18.2 ⁇ /cm) was obtained from a Milli-Q water purification system (Millipore, Bedford, MA, USA) and was used for the preparation of all aqueous solutions.
• Homemade SPME fibers consisting of untreated fused silica capillary tubing (0.5 mm I.D) and a 10 Hamilton syringe were purchased from Supelco (Bellefonte, PA) and Hamilton (Reno, NV, USA), respectively.
• Amber glass vials (20 mL) with PTFE/Butyl septa caps were purchased from Supelco.
• the RPR- 100 UV reactor was purchased from Southern New England Ultraviolet Company (Bradford, Connecticut).
• [DiVDDIM] [Br 2 ]) were carried out.
• [DiVOIM] [Br 2 ] was synthesized by reacting 2 molar equivalence of 1-vinylimidazole with 1 molar equivalence of 1,8-dibromooctane in 5 mL of isopropanol at 50 °C for 36 hr in a dark environment.
• the di-cationic product was then purified by water and ethyl acetate, and was dried under vacuum at 50°C for 2 days.
• the support comprised fibers.
• a series of fiber modification steps were employed prior to coating the [VHIM] [CI] monomer, cross-linker, and initiator mixture in order to establish a stable film of this mixture on the fiber surface.
• the bare fiber was etched (See Fig. 6).
• the 1 cm bare silica portion was immersed into a 5 % (w/v) ammonium hydrogen difluoride solution in methanol for 5 min, air dried for 30 min, and conditioned in a GC injector at 250 °C for 1 hr.
• the fiber was then washed thoroughly with water to remove excess salt and conditioned in a GC injector at 250 °C for 5 min.
• the etched fiber was immersed into 10 mL of a VTMS solution to functionalize the surface with a vinyl substituent prior to coating. (See Fig. 7).
• Characterization of the etched and functionalized fiber was performed using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX).
• the [DiVOIM] [Br 2 ] cross-linker possessed higher solubility, compared to its longer-chained counterpart, in the [VHIM] [CI] monomer and can be fully-dissolved at room temperature.
• VAAEs volatile alcohol, aldehydes, and esters
• a stock solution was prepared from the individual stock solutions by combining all analytes at various concentrations and diluting with acetonitrile.
• a working standard with analyte concentrations ranging from 10 to 500 ppb was prepared by spiking a specific volume of the standard stock solution into a 20 mL amber sampling vial filled with 15 mL of a 30 % NaCl (w/v) aqueous solution.
• Extractions in headspace mode were performed by exposing the fiber coating to the headspace of the sampling vial capped with a PTFE/Butyl self-sealing septa screw cap at room temperature. Agitation was performed at 750 RPM using a magnetic stir bar.
• the analytes were desorbed into the GC-MS by exposing the fiber to the GC injector at 175°C for 5 min.
• Direct immersion studies were also performed in a similar manner; however, 20 mL of a de-ionized water solution was used as a sample matrix. Used sampling vials and stir bars were cleaned by sonication in a detergent solution, followed by de-ionized water and acetone for 1 hr each. Carryover was monitored regularly and deemed to be less than 5 %.
• Fiber bleeding, precision, and extraction efficiency tests for all fiber coatings were performed using an Agilent 7890 gas chromatograph coupled to a 5975 mass spectrometer (GC-MS). Detection of all analytes via single ion monitoring (SIM) mode were established by monitoring 2 to 3 relevant m/z fragments for each analyte.
• Helium was used as a carrier gas with a flow rate of 1 mL min "1 while a HP5-MS (30 m x 250 ⁇ x 0.25 ⁇ ) GC column was employed for all studies.
• the thermal desorption of analytes as well as the bleed-monitoring were performed in splitless mode.
• Thermal stability of sorbent coatings should be investigated to determine the appropriate desorption temperature for purposes of maximizing the fiber lifetime.
• thermal stability is governed by their susceptibility to undergo nucleophilic substitution at high temperatures.
• Thermal stabilities of the copolymers synthesized in this example were monitored by thermal gravimetric analysis (TGA).
• TGA thermal gravimetric analysis
• the TGA curves for copolymers derived from the monocationic [VMM] [CI] IL containing different amounts of the [(VIM) 2 Ci 2 ] 2[Br] dicationic IL cross-linker are compared to the linear poly([VHIM][Cl]) PIL prepared by AIBN- initiated polymerization containing no cross-linker.
• the cross-linked PILs produced by UV polymerization exhibited slightly higher stability than the AIBN-initiated PIL sorbent coating. As the extent of cross-linking was increased, the thermal stability also increased. Without wishing to be bound by theory, the enhancement in the copolymer thermal stability is believed to be the result of adding cross-linkers containing the less thermally labile bromide anion.
• a noncross-linked UV- initiated poly([VHIM][Cl]) PIL coating was also examined, wherein this coating exhibited lower thermal stability compared to its AIBN-initiated counterpart.
• Sorption-time profiles were generated for Fiber 6 and Fiber 12 (see Table 1) in headspace mode and Fiber 12 in the direct immersion mode.
• the profiles were obtained by exposing the fiber for different time intervals to the headspace of the sample solution containing the selected analytes in a 30% NaCl (w/v) solution at varying concentrations.
• equilibration was achieved at approximately 45 min except for 1-octanol and a-ethyl benzene methanol in which equilibration was achieved in approximately 60 min.
• equilibration times were also reached at approximately 45 min for most analytes.
• Sorption time optimization for direct immersion studies was performed by immersing Fiber 12 in a deionized water sample solution at various time intervals and analyte concentrations. Most analytes achieved equilibration at approximately 45 min.
• Fig. 9 shows a SEM photograph of etched and derivatized fiber smeared with UV-initiated polymeric ionic liquid (P-PIL).
• Fig. 10 shows a SEM photograph of etched and derivatized fiber with 5%C8 cross-linker P- PIL (smear coating using 4 hr oven-dried coating solution).
• Fig. 11 shows a SEM photograph of etched and derivatized fiber with 5%C8 cross-linker P- PIL (dip coating using 4 hr oven -dried coating solution).
• Fig. 12 shows a SEM photograph of etched and derivatized fiber with 15%C8 cross-linker P- PIL (smear coating using 4 hr oven-dried coating solution).
• Fig. 13 shows a SEM photograph of etched and derivatized fiber with 15%C8 cross-linker P- PIL (dip coating using 4 hr oven -dried coating solution).
• Fig. 14 displays the extraction efficiency for all fourteen fibers prepared in this example in headspace SPME mode.
• Coatings with varying amounts of cross-linker to monomer (15, 30, and 50% w/w), cross-linker type [(VIM) 2 C 8 ] 2[Br] and [(VIM) 2 Ci 2 ] 2[Br]), and initiator content (1 or 3% w/w relative to the [(VHIM)] [CI] IL monomer) were prepared and subjected to headspace extraction of chosen analytes.
• the PIL-based coatings containing [(VIM) 2 C 8 ] 2[Br] cross-linker revealed a few general trends.
• Fiber 7 (containing 1% (w/w) initiator) exhibited higher extraction efficiency for all analytes compared to Fiber 8, which contained 3% (w/w) initiator).
• amount of cross-linker was increased to 30% and 50%, higher peak areas were observed for coatings consisting of 3% (w/w) initiator relative to 1%.
• Fiber 12 consisting of a 50% (w/w) [(VIM) 2 Ci 2 ] 2[Br] cross-linker, outperformed Fiber 6, for all analytes especially 1-octanol, in which 3-fold higher peak areas were observed.
• (w/w) cross-linker were lower than or equal to those of Fiber 10, except for furfuryl propionate.
• the LODs ranged from 0.01 to 2.5 ⁇ g L -1 and 0.01 to 0.5 ⁇ g L -1 for Fiber 10 and Fiber 12, respectively.
• Fiber AIBN and UV were also performed using Fiber AIBN and UV in order to study the effects of linear (i.e., noncross-linked) coatings on sensitivity and precision.
• Fiber AIBN exhibited higher sensitivity for all studied analytes in comparison to Fiber UV.
• the LOD of Fiber UV was observed to be lower for some analytes due to higher sorbent coating bleed for Fiber AIBN. This resulted in an elevated background and a higher detection limit.
• the overall LODs ranged from 0.01 to 2.5 ⁇ g L -1 for both fibers with precision ranging from 2.1 to 13.3% and 1.1 to 12.0% for Fibers AIBN and UV, respectively.
• Fibers 10 and 12 which contained the more hydrophobic [(VIM) 2 C 12 ] 2[Br] cross-linker, were selected to explore the feasibility of the cross-linked PIL sorbent coatings.
• Polar analytes possessing low volatility were chosen as targets to examine sorbent coatings for direct immersion SPME in aqueous solutions, which requires coatings that exhibit significantly low solubility in water.
• Calibration curves were obtained by decreasing analyte concentrations from 75 to 0.01 ⁇ g L -1 while using a minimum of seven calibration levels.
• Direct immersion extractions were performed in deionized water at room temperature with an extraction time of 45 min under agitation. Table 3 below lists the figures of merit for the extraction of these analytes using the two coatings:
• LODs ranged from 0.001 to 0.1 ⁇ g L 1 and 0.001 to 0.5 ⁇ g L 1 for Fibers 10 and 12, respectively.
• Fiber AIBN and Fiber UV were also compared.
• the coating dissolved almost immediately after being immersed into the sample solution. Therefore, Fiber AIBN is not suitable for direct immersion SPME.
• Fiber 12 was selected for analysis of select analytes from deionized, well, and river water.
• the experiments were performed by spiking 2.5 ⁇ g L 1 of analyte into the water sample and immersing the coating into the sample solution for 45 min under agitation.
• the relative recoveries ranged from 88.9 ⁇ 2.0 to 112.5 ⁇ 10.3% for deionized water.
• the relative recoveries for well and river water ranged from 58.0 ⁇ 4.1 to 116.0 ⁇ 11.2% and 70.9 ⁇ 3.2 to 135.8 ⁇ 13.8%, respectively.
• the sorbent coating was capable of withstanding the complex matrix environment to extract analytes at trace -level concentrations, further demonstrating the durability and stability of the cross-linked PIL -based sorbent coatings for direct immersion studies.
• particulate matter within the complex sample matrix may have affected the morphology of the fiber, particularly true since the only sample preparation performed on the river water sample was to filter particulate matter through a syringe filter. Nevertheless, no discernible loss in analyte extraction efficiency or precision was observed for the fiber coating up until the time it was sacrificed for SEM imaging.
• Naphthalene and 1-octanol were purchased from Sigma-Aldrich (Milwaukee, WI).
• 1- vinylimidazole, 1,8-dibromooctane, 1,12-dibromododecane, vinyltrimethoxysilane (VTMS), 2,2'- azobis(2-methylpropionitrile) (AIBN), 1-chlorohexane, ammonium hydrogen difluoride, and 2- hydroxy-2-methylpropiophenone (DAROCUR 1173) were purchased from Sigma-Aldrich.
• Lithium bis[(trifluoromethyl) sulfonyl]imide (LiNTf 2 ) was purchased from SynQuest Labs (Alachua, FL). Acetone and isopropanol were purchased from Fisher Scientific (Fair Lawn, NJ). Deionized water (18.2 ⁇ /cm) was obtained from a Milli-Q water purification system (Millipore, Bedford, MA) and was used for the preparation of all aqueous solutions.
• AIBN-initiated poly([VBHDIM] [NTf 2 ]) PIL-based fiber was fabricated according to the procedure described in Example 1 above, except an etched bare silica support was used to enhance the overall mechanical stability of the coated fiber.
• Fiber surface derivatization using a VTMS solution was employed for UV -initiated PIL-based coatings, namely, poly (1 -vinyl - 3hexylimidazolium) chloride (poly([VHIM][Cl])) (Fiber PIL 2), poly [l,12-di(3- vinylimidazolium)dodecane] dibromide(poly ⁇ [(VIM) 2 C 12 ] ⁇ 2[Br] in poly([VHIM][Cl] (Fiber PIL 3), and poly[l,12-di(3-vinylimidazolium)dodecane] di ⁇ bis[(trifluoromethyl)sulfonyl]imide ⁇
• the coatings synthesized through AIBN-initiated polymerization are linear polymers, whereas the coatings synthesized through the UV-initiated polymerization are crosslinked copolymeric coatings.
• SPME experiments were performed at room temperature by exposing a coated fiber to the headspace of a 20 mL amber glass sampling vial (Supelco) containing a specific concentration of 1- octanol and naphthalene. Agitation of the sample solution was achieved by stirring the solution at 750 RPM via a magnetic stir bar. The extraction time was adjusted for equilibration of both analytes. Following extraction, the analytes were desorbed in the GC injector at 175 °C for 5 min. Analyte carryover was monitored for all fibers and was found to be ⁇ 5%.
• the calibration curves for 1 -octanol using the PDMS/DVB coating are shown in Fig. 16.
• the linear range of 1-octanol at a 10: 1 (1 -octanol: naphthalene) ratio rang ed from 1 to 500 ⁇ g L "1 .
• the upper limit of the linear range decreased to approximately 250 ⁇ g L "1 .
• the amount of 1-octanol extracted at every concentration studied is significantly lower than the 10: 1 (l-octanol:naphthalene) ratio.
• Fiber PIL 2 was studied to investigate the effect of UV -initiated on-fiber polymerization. The results shown in Fig. 17B for Fiber PIL 2 are similar to Fiber PIL 1 and the PA coating; only negligible changes in the linear range, sensitivity, and amount of 1-octanol extracted were observed.

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• 2013
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