[go: up one dir, main page]

WO2010014018A1 - Procédé de fabrication de nanoparticules luminescentes à partir de glucides - Google Patents

Procédé de fabrication de nanoparticules luminescentes à partir de glucides Download PDF

Info

Publication number
WO2010014018A1
WO2010014018A1 PCT/NZ2009/000149 NZ2009000149W WO2010014018A1 WO 2010014018 A1 WO2010014018 A1 WO 2010014018A1 NZ 2009000149 W NZ2009000149 W NZ 2009000149W WO 2010014018 A1 WO2010014018 A1 WO 2010014018A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
luminescent
nanoparticles
nanoparticle
carbon nanoparticles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NZ2009/000149
Other languages
English (en)
Inventor
Hui Peng
Jadranka Travas-Sejdic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Auckland Uniservices Ltd
Original Assignee
Auckland Uniservices Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Auckland Uniservices Ltd filed Critical Auckland Uniservices Ltd
Publication of WO2010014018A1 publication Critical patent/WO2010014018A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon

Definitions

  • the present invention relates to a method of preparing luminescent carbon nanoparticles and to luminescent carbon nanoparticles prepared by that method.
  • Luminescent quantum dots have become an important photonic tool in the past two decades due to their unique properties, such as high chemical stability, resistance to photodegradation and readily tunable optical properties. They have a wide variety of promising applications in biology, medicine and so on. However, the high price, known toxicity and potential environmental hazard associated with many of these materials may greatly limit their applications.
  • luminescent carbon dots have been discovered. These carbon dots have less toxicity than quantum dots but may have similar applications.
  • the carbon dots are carbon nanoparticles which have been functionalized by oxidation with, for example, nitric acid. In certain cases the carbon dots are then passivated with organic or other molecules. There is variation in the fluorescence and luminescence properties of these carbon dots and this may be due to differences in size, composition, surface charge or type of passivation of different dots.
  • One method for producing carbon dots is the laser ablation of a carbon target, eg [1], [2].
  • a carbon target was ablated by using a Q-switched Nd: YAG laser (1064 run, 10 Hz) in a flow of argon gas carrying water vapor at 900 °C and 75 kPa.
  • the obtained sample was treated in an aqueous nitric acid for 12 h (no detectable fluorescence at this step), followed by surface passivation by attaching organic species to the acid-treated carbon particles.
  • the passivated particles were luminescent.
  • the particles were approximately 5 nm in diameter.
  • the other method is to use the combustion soot of candles as the starting material [3].
  • the collected soot was treated with oxidative acid.
  • the luminescent carbon nanoparticles were separated by using polyacrylamide gel electrophoresis.
  • the present inventors have found a simpler and cheaper alternative method of preparing carbon dots from carbohydrates.
  • the present invention provides a method of preparing luminescent carbon nanoparticles by reacting one or more carbohydrates with sulphuric acid and subsequently oxidising a product of the reaction.
  • the present invention provides method of preparing luminescent carbon nanoparticles by reacting one or more carbohydrates with sulphuric acid to form aggregates of luminescent carbon nanoparticles and subsequently breaking up the aggregates so that the luminescent carbon nanoparticles readily disperse.
  • the present invention also provides luminescent carbon nanoparticle prepared by the methods of the present invention.
  • luminescent carbon nanoparticle prepared from one or more carbohydrates.
  • the present invention further provides a luminescent carbon nanoparticle wherein the emission intensity of the carbon nanoparticle does not decrease by more than 20% after 20 hrs of continuous excitation at 360 nm.
  • the present invention provides for the use of the luminescent carbon nanoparticles of the present invention in diagnostic imaging, in biological markers or drug delivery systems
  • the present invention further provides for the use of luminescent carbon nanoparticles according to the present invention in the preparation of a medicament for use in diagnostic imaging of a patient, in biological markers or drug delivery systems.
  • Figure 4 shows emission spectra of luminescent carbon nanoparticles prepared according to the present invention from glucose before (a) and after (b) passivation
  • Figure 5. shows an image of luminescent carbon nanoparticles prepared according to the present invention under ambient light and UV lamp (365nm)
  • Figure 6 shows an FT-IR spectrum of products obtained by H 2 SO 4 treatment of sucrose.
  • Figure 7 shows a Raman spectrum of products obtained by H 2 SO 4 treatment of sucrose.
  • Figure 8. shows UV and emission spectra of luminescent carbon nanoparticles prepared according to the present invention after reaction with TTDA
  • Figure 9. shows a UV and an emission spectra of luminescent carbon nanoparticles prepared according to the present invention after reaction with poly(ethylene glycol) bis(3-aminopropyl) terminated (PEGI S OON)-
  • Figure 10 shows a UV and an emission spectra of luminescent carbon nanoparticles prepared according to the present invention after reaction with ethylenediamine
  • Figure 11 shows a FT-IR spectrum of products obtained by H 2 SO 4 treatment of starch
  • Figure 12 shows a Raman spectrum of products obtained by H 2 SO 4 treatment of starch
  • Figure 13 shows a UV and an emission spectra of luminescent carbon nanoparticles prepared according to the present invention after reaction with TTDA
  • FIG. 16 Time evolution of emission spectra of aggregated CNPs prepared from glucose measured during different time of nitric acid (2.0 M) treatment. The treatment time is indicated on the figure.
  • FIG. 1 TEM images of TTDA passivated CNPs prepared from glucose.
  • FIG. 20 Emission spectra of TTDA passivated CNP at different excitation wavelength which was progressively increased from 360 nm on the left with a 10 nm increment. CNP were obtained by 12 h of nitric acid (2.0 M) treatment. Inset: normalized emission spectra
  • FIG. 21 Emission spectra of TTDA passivated CNP at different excitation wavelength which was progressively increased from 360 run on the left with a 10 run increment. CNPs were obtained by 4 h of nitric acid (2.0 M) treatment.
  • FIG. 22 Emission spectra of PEGi SOON passivated carbon dots at different excitation wavelength which progressively increased from 350 run, in 20 nm increments. CNPs which were obtained by using glucose as starting materials and 12 h of nitric acid (2.0 M) treatment.
  • Figure 23 Normalized emission intensity of TTDA passivated carbon dots during continuous excitation at 360 nm.
  • FIG. 25 Emission spectra of TTDA passivated carbon dots at different excitation wavelength which progressively increased from 350 nm, in 10 nm increments.
  • CNPs were obtained by using starch as starting material and 12 h of nitric acid (2.0 M) treatment.
  • FIG. 26 Emission spectra of carbon dots passivated with different ligands.
  • CNPs were obtained by using glucose as starting material and 12 h of nitric acid (2.0 M, 50 mL) treatment.
  • Figure 27 Quantum yields of carbon dots passivated with different ligands.
  • Figure 28 Confocal microscopy images of mice heart cell labeled with the carbon dots after incubation for 1 h at 37 0 C. Top left: image of mice heart cell without carbon dots labeling.
  • Figure 29 Confocal microscopy images of mice heart cell labeled with the carbon dots after incubation for 2 h at room temperature. Top left: image of mice heart cell without carbon dots labeling.
  • FIG. 30 SEM image of CNPs prepared form sugar.
  • FIG. 31 Absorbance (A) and emission (B) spectra of TTDA passivated carbon dots at different excitation wavelength which progressively increased from 360 ran, in 10 nm increments.
  • CNPs were obtained by using sugar as starting material and 12 h of nitric acid (2.0 M, 50 mL) treatment.
  • FIG. 32 Absorbance (A) and emission (B) spectra of TTDA passivated carbon dots at different excitation wavelength which progressively increased from 360 nm, in 10 nm increments.
  • CNPs were obtained by using sugar as starting material and 12 h of nitric acid (2.0 M, 25 mL) treatment.
  • FIG. 33 Absorbance (A) and emission (B) spectra of TTDA passivated carbon dots at different excitation wavelength which progressively increased from 360 nm, in 10 nm increments.
  • CNPs were obtained by using sugar as starting material and 12 h of nitric acid (2.0 M, 15 mL) treatment.
  • FIG. 34 Absorbance (A) and emission (B) spectra of TTDA passivated carbon dots at different excitation wavelength which progressively increased from 360 nm, in 10 nm increments.
  • CNPs were obtained by using sugar as starting material and 4 h of nitric acid (2.0 M, 15 mL) treatment.
  • Figure 35 Quantum yield of carbon dots prepared using A: 50 mL; B: 25 mL; C: 15 mL of 2.0 M nitric acid and 12 hrs of the treatment; and D: using 15 mL of 2.0 M nitric acid and 4 hrs of the treatment.
  • Figure 36 Absorbance (A) and emission (B) spectra of ATBA passivated carbon dots at different excitation wavelength which progressively increased from 360 nm, in 10 nm increments. CNPs were obtained by using sugar as starting material and 12 h of nitric acid (2.0 M, 50 mL) treatment. Quantum yield measured: 0.045.
  • Figure 37 Absorbance (A) and emission (B) spectra of ATBA passivated carbon dots at different excitation wavelength which progressively increased from 360 nm, in 10 nm increments. CNPs were obtained by using sugar as starting material and 12 h of nitric acid (2.0 M, 25 mL) treatment. Quantum yield: 0.0279
  • the present invention provides a method of preparing luminescent carbon nanoparticles by reacting one or more carbohydrates with sulphuric acid and subsequently oxidising a product of the reaction.
  • the sulphuric acid is concentrated sulphuric acid.
  • the luminescent carbon nanoparticles can also be termed “carbon dots”.
  • carbon nanoparticles and “CNPs” indicate carbon nanoparticles which may or may not be luminescent.
  • the step of oxidising the nanoparticles serves to introduce hydroxyl and carboxylic acid groups to the surface of the nanoparticles. This breaks up the aggregates and allows the nanoparticles to disperse well in solution.
  • the introduced hydroxyl and carboxylic acid groups allow for attachment of other components to the surface of the groups.
  • the surfaces of the luminescent carbon nanoparticles prepared by the methods of the present invention appear to have relatively few defects. This is supported by the fact that carbon nanoparticles prepared according to the present invention show luminescence after nitric acid treatment whereas carbon nanoparticles prepared by other methods often show luminescence only after a passivation step.
  • the aggregates of nanoparticles formed after reaction of a carbohydrate with sulphuric acid may display luminescence even before nitric acid treatment.
  • the aggregates of nanoparticles formed after the reaction of the carbohydrates with sulphuric acid may be broken up by means other than oxidation such as by sonication and the like.
  • the present invention provides a method of preparing luminescent carbon nanoparticles by reacting one or more carbohydrates with sulphuric acid to form aggregates of luminescent carbon nanoparticles and subsequently breaking up the aggregates so that the luminescent carbon nanoparticles readily disperse.
  • the luminescent carbon nanoparticles may have a diameter of between 1 to 100 nm, preferably 2-50 nanometeres, more preferably 2-10 nanometres. In a preferred from, the carbon nanoparticles are about 5 nm in diameter.
  • the carbohydrate can be any carbohydrate ranging from simple sugars to more complex carbohydrates such as the starches and cyclodextrins.
  • the present inventors have found that different carbohydrates provide luminescent carbon nanoparticles having different properties. For instance, under the same reaction conditions, glucose and sucrose produce luminescent carbon dots having maximum emission wavelengths of 442 nm and 460 nm respectively (see Example 1). This allows the property of the luminescent carbon nanoparticles to be controlled according to the desired application. Further control can be achieved, for example, by varying the length of time that the carbohydrate is exposed to the sulphuric acid, by varying the concentration of the acid and the carbohydrate, and by controlling the temperature of the reaction.
  • the product of the reaction is oxidised by an oxidising agent such as an oxidising acid, KMnO 4 , H 2 O 2 , KCrO 4 , or K 2 Cr 2 O 7 .
  • an oxidising agent such as an oxidising acid, KMnO 4 , H 2 O 2 , KCrO 4 , or K 2 Cr 2 O 7 .
  • the oxidising agent is an oxidising acid. More preferably, the oxidising acid is nitric acid.
  • the concentration of the nitric acid is from IM to 5M, preferably from 2M to 3 M, even more preferably about 2M.
  • the product of the reaction may be oxidised with nitric acid from 1 to 24 hours, preferably from 4 to 12 hours.
  • the carbohydrate is selected from the group consisting of glucose, sugar (sucrose), and starch.
  • the carbohydrate is glucose.
  • reaction step and the subsequent oxidation step are each carried out in solution. More preferably, the reaction step and the subsequent oxidation step are each carried out in aqueous solution.
  • the reaction mixture is neutralised with the addition of base.
  • the oxidising agent is added directly to the neutralised reaction mixture.
  • the luminescent carbon nanoparticles can be isolated by common methods such as precipitation, filtration, extraction and evaporation of solvent. They can be purified by any suitable means, such as by electrophoresis or dialysis.
  • the luminescent carbon nanoparticles prepared by the method of the present invention have luminescent properties, these properties may be improved by passivating the surface of the luminescent carbon dots with a passivating agent. Other properties of the luminescent carbon dots such as stability and ease of handling may also be improved.
  • the method further comprises coupling the luminescent carbon nanoparticles to a passivation agent.
  • Suitable coupling techniques include covalent bonding and physical adsorption.
  • Suitable passivating agents are described, for example, in US 2008/0113448, the disclosure of which is hereby incorporated by reference.
  • a passivation agent can be any material that can bind to a carbon nanoparticle surface and encourage or stabilise the radiative recombination of excitons, which it is theorised in US 2008/0113448 comes about through stabilisation of the excitation energy 'traps' existing at the surface as a result of quantum confinement effects and the large surface area to volume ratio of a nanoparticle.
  • a passivation agent can be polymeric, molecular, biomolecular, or any other material that can passivate a nanoparticle surface.
  • the passivation agent can be synthetic polymer such as poly(lactic acid) (PLA), poly(ethylene glycol) (PEG), poly(propionylethyleneimine-co- ethyleneimine) (PPEI-EI), and polyvinyl alcohol) (PVA).
  • PVA poly(lactic acid)
  • PEG poly(ethylene glycol)
  • PPEI-EI poly(propionylethyleneimine-co- ethyleneimine)
  • PVA polyvinyl alcohol
  • the passivation agent can be a biopolymer, for instance a protein or a peptide.
  • the passivation agent and/or additional materials graft to the core nanoparticle via the passivation agent can provide the luminescent particles with additional desirable characteristics.
  • a hydrophilic passivation agent can be bound to the core carbon nanoparticle to improve the solubility/dispersability of the nanoparticle in water.
  • a passivation agent can be selected so as to improve the solubility of the carbon nanoparticle in an organic solvent.
  • the passivating agent can be an amino-functionalised compound.
  • passivating agents include 4,7,10-triox-l,13-tridecanediamine (TTDA), PEGl 500, poly(ethylene glycol) bis(3-aminopropyl) terminated (eg PEG I5OON ), oleylamine, poly(lactic acid(, poly(propionylethyleneimine-co-ethyleneimine) (PPEI- EI), and poly(vinyl alcohol) (PVA), and ethylenediamine.
  • TTDA 4,7,10-triox-l,13-tridecanediamine
  • PEGl 500 poly(ethylene glycol) bis(3-aminopropyl) terminated
  • PEG I5OON poly(ethylene glycol) bis(3-aminopropyl) terminated
  • PPEI- EI poly(vinyl alcohol)
  • PVA poly(vinyl alcohol)
  • the passivation agent is 4,7,10-triox-l,13-tridecanediamine (TTDA).
  • the environment around the carbon nanotube was sufficiently tight to exclude oxygen from the SWNT surface, resulting in a quantum yield of 20%. Without being bound by theory, it is the view of the present inventors that the photoluminescence of the carbon nanoparticles is also due to the electron transfer between C and N.
  • the luminescent carbon nanoparticles comprise nitrogen.
  • a nitrogen-rich passivating agent is a nitrogen-rich compound such as a flavin.
  • the passivating agents are capping ligands with biotin, such as:
  • the luminescent carbon nanoparticles which are coupled to capping ligands with biotin may be in turn coupled to cell-targeting antibodies for use in targeted cell-imaging.
  • the passivation step greatly improves the luminescence and quantum yield of the luminescent carbon nanoparticles.
  • the present invention provides a luminescent carbon nanoparticle prepared by the methods of the present invention.
  • the luminescent carbon nanoparticle is coupled to a passivation agent.
  • the quantum yields of the luminescent carbon nanoparticles prepared according to the present invention can vary substantially depending on the reaction conditions used to prepare them and whether they are coupled to passivating agents. In one embodiment, if the luminescent carbon nanoparticles are not coupled to a passivating agent, then the quantum yield ranges from 1 to 4%.
  • the quantum yield ranges from 5% to 20%.
  • the product of the reaction comprises sulphur prior to the oxidation step.
  • the carbon nanoparticle comprises greater than 0.1% sulphur. Preferably, greater than 0.2% sulphur. More preferably, greater than 0.5% sulphur.
  • the product of the reaction comprises from 40%-95% carbon and from 5%-50% oxygen prior to the oxidation step. More preferably, from 56%-66% carbon and from 28%-36% oxygen.
  • the present invention provides a luminescent carbon nanoparticle prepared from one or more carbohydrates.
  • the luminescent carbon nanoparticle is coupled to a passivation agent.
  • the process of preparing the luminescent carbon nanoparticle includes the step of reacting one or more carbohydrates with sulphuric acid.
  • the carbon nanoparticles prepared according to the methods of the present invention may comprise trace amounts of sulphur.
  • the present invention provides a carbon nanoparticle comprising sulphur.
  • the carbon nanoparticle comprises greater than 0.1% sulphur. Preferably, greater than 0.2% sulphur. More preferably, greater than 0.5% sulphur.
  • the presence of sulphur in the nanoparticles can be measured by any technique known in the art including elemental analysis and XPS.
  • the carbon nanoparticle further comprises from 56%-66% carbon and from 28%-36% oxygen.
  • the carbon nanoparticle is formed by reacting one or more carbohydrates with sulphuric acid.
  • the carbon nanoparticle comprised sulphur before the addition of a passivating agent or is not coupled to a passivating agent.
  • the carbon nanoparticle is luminescent.
  • the analysis for sulphur is conducted on the carbon nanoparticle before coupling the carbon nanoparticle to a passivation agent.
  • the present invention provides a luminescent carbon nanoparticle wherein the emission intensity of the carbon nanoparticle does not decrease by more than 20% after 20 hrs of continuous excitation at 360 nm.
  • the present invention provides a plurality of luminescent carbon nanoparticles wherein the full width at half maximum of the peak at the maximum emission wavelength of the carbon nanoparticles is less than 125 nm.
  • the maximum emission peak of carbon dots prepared according to the methods of the present invention is much narrower than that of carbon dots prepared using other techniques such as the oxidation of candle soot ( Figure 3) which implies that the size distribution of carbon dots is narrower for the carbon dots prepared in accordance with the present invention.
  • the full width at half maximum of the emission peak of carbon dots prepared at optimized conditions is 76 nm, which is much narrower than those prepared from candle soot where the narrowest emission peak has a full width at half maximum of 125 nm (see table 1 of the supporting data of reference 2).
  • the full width at half maximum of the peak at the maximum emission wavelength is less than 100 nm, more preferably less than 80 nm, even more preferably less than 70 nm.
  • the luminescent carbon nanoparticle of the fifth aspect is prepared by the method of the first aspect.
  • the luminescent carbon nanoparticles of the present invention display luminescence prior to, or without, coupling to a passivating agent.
  • carbon nanoparticles of the present invention can be used in any application in which luminescent nanoparticles are known to be useful. Suitable applications are described for instance in US 2008/0113448, the disclosure of which is hereby incorporated by reference.
  • a carbon nanoparticle can be formed to include a reactive functional chemistry suitable for use in a desired application, eg a tagging or analyte recognition protocol.
  • a passivating agent can include a reactive functionality that can be used directly in a protocol, for example to tag a particular analyte or class of materials that may be found in a sample.
  • Exemplary materials can include, for example, carbohydrate molecules that may conjugate with carbohydrates on an analyte or biological species.
  • a functional chemistry of a passivation agent can be further derivatised with a particular chemistry suitable for a particular application.
  • a reactive functionality of a passivating agent can be further derivatised via a secondary surface chemistry functionalisation to serve as a binding site for a substance.
  • a member of a specific binding pair ie two different molecules where one of the molecules chemically and/or physically binds to the second molecule, such as an antigen or antibody can be bound to a nanoiparticle either directly or indirectly via a functional chemistry of the passivation agent that is retained on the nanoparticle following the passivation of the core carbon nanoparticle.
  • a luminescent carbon nanoparticle can be advantageously utilized to tag, stain or mark materials, including biologically active materials, e.g., drugs, poisons, viruses, antibodies, antigens, proteins, and the like; biological materials themselves, e.g., cells, bacteria, fungi, parasites, etc; as well as environmental materials such as gaseous, liquid, or solid (e.g., particulates) pollutants that may be found in a sample to be analysed.
  • biologically active materials e.g., drugs, poisons, viruses, antibodies, antigens, proteins, and the like
  • biological materials themselves e.g., cells, bacteria, fungi, parasites, etc
  • environmental materials such as gaseous, liquid, or solid (e.g., particulates) pollutants that may be found in a sample to be analysed.
  • the passivating material can include or can be derivatized to include functionality specific for surface receptors of bacteria, such as E.coli and L. monocytogenes, for instance. Upon recognition and binding, the bacteria can be clearly discernable due to the photoluminescent tag bound to the surface.
  • bacteria such as E.coli and L. monocytogenes
  • Suitable reactive functionality particular for targeted materials are generally known to those of skill in the art.
  • suitable ligands for that antibody such as haptens particular to that antibody, complete antigens, epitopes of antigens, and the like can be bound to the polymeric material via the reactive functionality of the passivating material. For instance, via a biotinylated functionality.
  • a nanoparticle can be utilized to tag or mark the presence of a particular substance through the development of the photoluminescent characteristic on the nanomaterials only when the nanoparticle is in the presence of the targeted substance.
  • a carbon nanoparticle can be formed and not subjected to a passivation reaction or optionally only partially passivated, such that the nanoparticle exhibits little or no photoluminescence.
  • a passivating material eg, a targeted substance
  • the luminescence from a passivated, highly luminescent carbon nanoparticle can be quenched in the presence of a particular targeted substance.
  • the visible luminescence can be quenched in the presence of a potentially harmful environmental substance such as a nitro-derivatized benzene, TNT, or a key ingredient in explosives.
  • the luminescent properties of the nanoparticle can be quenched via collision or contact of the quencher molecules (i.e., the detectable substance) with the luminescent carbon nanoparticles that result in electron transfers or other quenching mechanisms as are generally known to those in the art.
  • a photoluminescent nanoparticle can obviously be utilized in many other applications as well, in addition to tagging and recognition protocols such as those described above.
  • the disclosed luminescent nanoparticles can generally be utilized in applications previously described as suitable for photoluminescent silicon nanoparticles.
  • luminescent nanoparticles as herein described can be utilized in applications suitable for luminescent nanoparticles.
  • disclosed luminescent nanoparticles can be utilized in applications such as are common for luminescent quantum dots.
  • Luminescent carbon nanoparticles can be environmentally and biologically compatible.
  • a luminescent carbon nanoparticle can be formed so as to pose little or no environmental or health hazards during use.
  • a luminescent carbon nanoparticle prepared by the methods described herein can be utilized in light emission applications, data storage applications such as optical storage mediums, photo-detection applications, luminescent inks, and optical gratings, filters, switches, and the like, just to name a few possible applications that are generally known to those of skill in the art..
  • the luminescent carbon nanoparticles can emit different colours at different excitation wavelengths, they can be used economically in practical, real-world applications. For instance, in using the nanoparticles of the present invention in labelling applications, detection and/or analysis (for instance through utilization of confocal fluorescence microscopy) can be performed at multiple colours without the need for multiple sets of different luminescent materials.
  • the carbon nanoparticles of the present invention may also find applications in LEDs (light emitting diodes).
  • the present invention provides for the use of the luminescent carbon nanoparticles of the present invention in diagnostic imaging.
  • the present invention provides for the use of luminescent carbon nanoparticles according to the present invention in the preparation of a medicament for use in diagnostic imaging of a patient.
  • the imaging can be of any cells or tissues, such as tumours, organs, and the like.
  • the imaging is imaging of heart tissue.
  • the present invention provides for the use of the carbon nanoparticles of the present invention as markers for cell tagging or in drug delivery systems.
  • D-(+)-glucose, sucrose, starch (potato starch, soluble), 4,7, 10-trioxa- 1,13- tridecanediamine, and poly(ethylene glycol) bis(3-aminopropyl) terminated (PEG ISO O N ) were purchased from Sigma- Aldrich.
  • Spectra/Por DispoDialyzers cellulose ester membranes, MW cut off: 1000 were also obtained from Sigma- Aldrich. The other chemicals used were obtained from local suppliers.
  • UV-vis and emission spectra were recorded by using a Shimadzu UV- 1700 Spectrophotometer and a PerkinElmer LS55 luminescence spectrometer, respectively.
  • Raman spectra were obtained with a Renishaw Raman spectrometer (System 1000) with 785 nm (red) laser excitation.
  • FT-IR spectra were recorded by using FT-IR/FT- FIR spectrometer (Spectrum 400, PerkinElmer).
  • Quantum yield was measured according to established procedure (J. R. Lakowicz, Principles of Fluorescence Spectroscopy, 2 nd Ed., 1999, Kluwer Academic/Plenum Publishers, New York) by using quinine sulfate in 0.10 M H 2 SO 4 solution as the standard. The absorbance was measured on a Shimadzu UV- 1700 Spectrophotometer. Absolute values are calculated according to the following equation:
  • Q is the quantum yield
  • / is the measured integrated emission intensity
  • A is the optical density
  • n is the refractive index (taken here as the refractive index of the respective solvents).
  • the subscript R refers to the reference fluorophore, quinine sulfate.
  • Figure 1 shows the absorption and emission spectra of carbon dots prepared from glucose during the treatment in 5 M of nitric acid.
  • the photoluminescent (PL) intensity increased with the increase in reaction time up to 4 hrs, then followed by a decrease in the PL intensity between 4 -5 hours of treatment and then become stable. This result shows the possibility of preparing luminescent carbon dots from glucose.
  • FIG. 2 shows the normalized photoluminescent spectra of carbon dots prepared from glucose and sugar.
  • the maximum emission wavelengths are 442 and 460 nm for carbon dots prepared from glucose and sugar, respectively.
  • Figure 3 shows the PL spectra of carbon dots prepared from candle soot without electrophoresis purification according to the reference[2].
  • the emission peak of carbon dots prepared from glucose is much narrower than that of carbon dots prepared from candle soot, which implies that the size distribution of carbon dots is narrower for the carbon dots prepared in accordance with the present invention.
  • the surfaces of the carbon dots were functionalized with -OH and -COOH groups, which allows other chemicals to be grafted to, and thus passivate the surface and improve the quantum yield.
  • Figure 8 gives the UV and emission spectra after passivation. The quantum yield was 0.092 after passivation.
  • Figure 9 gives the UV and emission spectra after passivation.
  • the quantum yield was 0.05 after passivation with poly(ethylene glycol) bis(3-aminopropyl) terminated
  • Figure 10 gives the UV and emission spectra after passivation.
  • the quantum yield was 0.032 after passivation.
  • TTDA 4,7,10-trioxa- 1,13- tridecanediamine
  • Figure 22 shows the emission spectra of carbon dots passivated with PEG 1500N. These carbon dots show considerable photostability, with the emission intensity decreasing by only 17 % after 19 h of continuous excitation at 360 nm (see Figure 23). The pH has small effect on the PL intensity of carbon dots (Figure 24).
  • Figure 25 shows the emission spectra of TTDA passivated carbon dots at different excitation wavelength which progressively increased from 350 nm, in 10 nm increments.
  • CNPs were obtained using the technique set out in Example 5 by using starch as starting material and 12 h of nitric acid (2.0 M) treatment.
  • Carbon dots were prepared according to procedure the described in Example 1 with the difference that the purification was carried out by means of dialysis as explained in the Experimental part.
  • the carbon dots were dissolved in PBS buffer solution. 50 ⁇ L of the solution was added to an eppendorf tube containing mice heart cells. The mixture was then incubated for 2 h at either the room temperature or for 1 h at 37 C°. The cells were then imaged with confocal microscopy. The results are shown in Figure 28 and 29.
  • TTDA was added to the CNPs and the mixture was heated to 120 0 C for 72 h under N 2 , followed by removal of water. The CNPs were then again purified via dialysis for two days.
  • Figure 30 shows the SEM image of CNPs obtained by using sugar as the starting material and before the nitric acid treatment.
  • Figure 31 - 33 show the absorbance and emission spectra of carbon dots prepared from CNPs obtained by using 50 mL, 25 mL and 15 mL of nitric acid (2.0 M) treatment for 12 hrs and Figure 34 by using 15 mL of nitric acid (2.0 M) treatment for 4 hrs.
  • Figure 35 provides a summary of quantum yield of carbon dots prepared using 50 mL, 25 mL and 15 mL of 2.0 M nitric acid and 12 hrs of the treatment; and using 15 mL of 2.0 M nitric acid and 4 hrs of the treatment.
  • the conditions for CNP synthesis from sugar have been optimized in terms of the nitric acid volume needed in the reaction and the time of the treatment.
  • a 15 ml of 2 M nitric acid and 12 hrs of treatment were found as the optimum (or alternatively 25 ml of 2 M nitric acid and 4 hrs of the treatment).
  • the maximum quantum yield for CNP obtained from sugar is 7 %.
  • TTDA was added to the CNPs obtained from sugar and the mixture was heated to 120 °C for 72 h under N 2 , after removal of all water. The CNPs were then purified via dialysis for two days.
  • Figure 37 present the absorbance (A) and emission (B) spectra of ATBA passivated carbon dots at different excitation wavelength which progressively increased from 360 nm, in 10 nm increments.
  • CNPs were obtained by using 25 mL of nitric acid 2.0 M for 12 h treatment.
  • Quantum yield 0.0279

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Luminescent Compositions (AREA)

Abstract

La présente invention concerne un procédé de préparation de nanoparticules de carbone luminescentes à partir d’un ou de plusieurs glucides. La présente invention concerne également des nanoparticules de carbone luminescentes préparées par le procédé et leur utilisation dans diverses applications.
PCT/NZ2009/000149 2008-07-28 2009-07-28 Procédé de fabrication de nanoparticules luminescentes à partir de glucides Ceased WO2010014018A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NZ570093A NZ570093A (en) 2008-07-28 2008-07-28 Method of making luminescent nanoparticles from carbohydrates
NZ570093 2008-07-28

Publications (1)

Publication Number Publication Date
WO2010014018A1 true WO2010014018A1 (fr) 2010-02-04

Family

ID=41610572

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/NZ2009/000149 Ceased WO2010014018A1 (fr) 2008-07-28 2009-07-28 Procédé de fabrication de nanoparticules luminescentes à partir de glucides

Country Status (2)

Country Link
NZ (1) NZ570093A (fr)
WO (1) WO2010014018A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787278A (zh) * 2010-03-17 2010-07-28 上海大学 水溶性荧光碳纳米粒子的热解合成方法
WO2012016296A1 (fr) * 2010-08-05 2012-02-09 Curtin University Of Technology Procédés de préparation de nanoparticules à base de carbogène et nanoparticules photoluminescentes à base de carbogène
WO2012035545A3 (fr) * 2010-09-14 2012-05-31 Himadri Bihari Bohidar Nanoparticules de carbone non fonctionnalisées présentant des caractéristiques de fluorescence, leur procédé de préparation et leur utilisation comme agents de bio-imagerie et de détection de solvants
CN102745669A (zh) * 2012-07-18 2012-10-24 中国人民解放军军事医学科学院卫生装备研究所 光致发光碳量子点的制备方法
CN104787742A (zh) * 2014-01-16 2015-07-22 中国药科大学 一种自发反应制备荧光碳纳米粒子的方法
CN113023708A (zh) * 2021-02-24 2021-06-25 云南大学 一种从生物质燃烧烟尘中分离提取碳点及其功能化的方法
CN114456310A (zh) * 2020-10-22 2022-05-10 中国科学院宁波材料技术与工程研究所 纳米凝胶-碳点复合材料、其制备方法及应用
CN119505889A (zh) * 2024-11-01 2025-02-25 安徽师范大学 一种线粒体定位的蓝色发光碳点的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080113448A1 (en) * 2005-10-27 2008-05-15 Clemson University Fluorescent Carbon Nanoparticles
WO2008106629A1 (fr) * 2007-03-01 2008-09-04 Cromoz Inc. Nanotubes de carbone à parois multiples concentriques solubles dans l'eau

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080113448A1 (en) * 2005-10-27 2008-05-15 Clemson University Fluorescent Carbon Nanoparticles
WO2008106629A1 (fr) * 2007-03-01 2008-09-04 Cromoz Inc. Nanotubes de carbone à parois multiples concentriques solubles dans l'eau

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHO, N. ET AL.: "Efficient Photodetection at IR Wavelengths by Incorporation of PbSe-Carbon- Nanotube Conjugates in Polymeric-Nanocomposite", ADV. MATER., vol. 19, 2007, pages 232 - 236 *
DATSYUK, V.: "Chemical Oxidation of Multiwalled Carbon Nanotubes", CARBON, vol. 46, 2008, pages 833 - 840 *
KUCUKAYAN ET AL.: "Use of Saccharides as Solid-State Precursors for the Synthesis of Carbon Nanotubes", MATER. RES. SOC. SYMP. PROC., vol. 1081, pages P05 - P14 *
SHI, D. ET AL.: "Luminescent Carbon Nanotubes by Surface Functionalisation", ADV. MATER., vol. 18, 2006, pages 189 - 193 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101787278A (zh) * 2010-03-17 2010-07-28 上海大学 水溶性荧光碳纳米粒子的热解合成方法
WO2012016296A1 (fr) * 2010-08-05 2012-02-09 Curtin University Of Technology Procédés de préparation de nanoparticules à base de carbogène et nanoparticules photoluminescentes à base de carbogène
WO2012035545A3 (fr) * 2010-09-14 2012-05-31 Himadri Bihari Bohidar Nanoparticules de carbone non fonctionnalisées présentant des caractéristiques de fluorescence, leur procédé de préparation et leur utilisation comme agents de bio-imagerie et de détection de solvants
CN102745669A (zh) * 2012-07-18 2012-10-24 中国人民解放军军事医学科学院卫生装备研究所 光致发光碳量子点的制备方法
CN102745669B (zh) * 2012-07-18 2014-09-10 中国人民解放军军事医学科学院卫生装备研究所 光致发光碳量子点的制备方法
CN104787742A (zh) * 2014-01-16 2015-07-22 中国药科大学 一种自发反应制备荧光碳纳米粒子的方法
CN114456310A (zh) * 2020-10-22 2022-05-10 中国科学院宁波材料技术与工程研究所 纳米凝胶-碳点复合材料、其制备方法及应用
CN113023708A (zh) * 2021-02-24 2021-06-25 云南大学 一种从生物质燃烧烟尘中分离提取碳点及其功能化的方法
CN113023708B (zh) * 2021-02-24 2023-10-27 云南大学 一种从生物质燃烧烟尘中分离提取碳点及其功能化的方法
CN119505889A (zh) * 2024-11-01 2025-02-25 安徽师范大学 一种线粒体定位的蓝色发光碳点的制备方法

Also Published As

Publication number Publication date
NZ570093A (en) 2010-11-26

Similar Documents

Publication Publication Date Title
Das et al. Graphene based emergent nanolights: A short review on the synthesis, properties and application
US8932877B2 (en) Fluorescent carbon nanoparticles
Das et al. Heteroatom doped photoluminescent carbon dots for sensitive detection of acetone in human fluids
WO2010014018A1 (fr) Procédé de fabrication de nanoparticules luminescentes à partir de glucides
Jelinek Carbon quantum dots: synthesis, properties and applications
Shi et al. Fluorescent carbon dots for bioimaging and biosensing applications
Ali et al. Red fluorescent carbon nanoparticle-based cell imaging probe
Bogdan et al. Carbohydrate-coated lanthanide-doped upconverting nanoparticles for lectin recognition
Long et al. Low-temperature rapid synthesis of high-stable carbon dots and its application in biochemical sensing
Xiao et al. Fluorescence origin of nanodiamonds
Azqhandi et al. Encapsulation of methotrexate and cyclophosphamide in interpolymer complexes formed between poly acrylic acid and poly ethylene glycol on multi-walled carbon nanotubes as drug delivery systems
Vithalani et al. Glowing photoluminescene in carbon-based nanodots: current state and future perspectives
CN114574196B (zh) 一种高荧光量子产率的碳量子点制备方法及应用
Li et al. Regulating the properties of carbon dots via a solvent-involved molecule fusion strategy for improved sensing selectivity
CN107903893A (zh) 一种具有近红外吸收和近红外发光特性的改性碳纳米点、其制备方法及其应用
KR20090120994A (ko) 형광특성이 향상된 풀러렌-실리카 나노입자, 이의 제조방법및 이의 용도
Li et al. One-pot synthesis of aqueous soluble and organic soluble carbon dots and their multi-functional applications
US20110189702A1 (en) Photoluminescent materials for multiphoton imaging
Chatterjee et al. What makes carbon nanoparticle a potent material for biological application?
Siddique et al. Facile synthesis and versatile applications of amorphous carbon dot
CN112268882B (zh) 一种高选择性检测谷胱甘肽的碳点-二氧化锰纳米荧光探针的制备方法及其应用
Del Canto et al. Photo-controlled release of zinc metal ions by spiropyran receptors anchored to single-walled carbon nanotubes
Fei et al. The fluorescent interactions between amphiphilic chitosan derivatives and water-soluble quantum dots
Zhang et al. Secondary structure-induced aggregation by hydrogen peroxide: a stimuli-triggered open/close implementation by recombination
Layek et al. Insights into surfactant-Induced aggregation and the production of White Light-Emitting Thin films from Cellulose-Derived Carbon dots

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09803204

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09803204

Country of ref document: EP

Kind code of ref document: A1