FABRICATION OF BLUE-FLUORESCENT AND NON-TOXIC NANODIAMONDS 9NDs) FROM ATMOSPHERIC PARTICULATE MATTERS
20210292172 · 2021-09-23
Inventors
- Binoy K. SAIKIA (Jorhat, IN)
- Nazrul ISLAM (Jorhat, IN)
- Tonkeswar DAS (Jorhat, IN)
- Jatin KALITA (Jorhat, IN)
Cpc classification
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
B82Y40/00
PERFORMING OPERATIONS; TRANSPORTING
Y02W30/50
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B82Y5/00
PERFORMING OPERATIONS; TRANSPORTING
C01P2006/60
CHEMISTRY; METALLURGY
B09B3/40
PERFORMING OPERATIONS; TRANSPORTING
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
C01P2004/64
CHEMISTRY; METALLURGY
International classification
B09B3/00
PERFORMING OPERATIONS; TRANSPORTING
C01B32/28
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a method for fabrication of blue-fluorescent and non-toxic nanodiamonds from atmospheric particulate matters including total solid suspended particulate matter (TSPM) and particulate matter with size less than 10μ (PM.sub.10). Mostly, the present invention provides an efficient mitigation process for particulate pollutant by conversion of these pollutants (PM and TSPM) into non-toxic high-value product such as nanodiamond by using the ultrasonic-assisted chemical oxidation method. This method is environmental friendly, simple, and biocompatible for the production of nanodiamonds from such atmospheric particulate matter.
Claims
1. A method for preparing nanodiamonds from atmospheric pollutants comprising the steps of: a) collecting atmospheric pollutants; b) mixing the atmospheric pollutants obtained in step (a) with hydrogen peroxide to obtain an oxidized particulate matter; c) ultrasonicating the oxidized particulate matter obtained in step (b) to obtain a first mixture; d) filtering the first mixture obtained in step (c) using a polytetrafluoroethylene membrane filter (0.22 μm) to obtain a filtrate; e) centrifuging the filtrate obtained in step (d) to obtain a supernant; f) treating the supernatant obtained in step (e) with HNO.sub.3/H.sub.2SO.sub.4 acid and heating to obtain an extract; g) neutralizing the extract obtained in step (f) by adding ammonia solution drop wise to obtain a second mixture; h) filtering the second mixture obtained in step (g) using an ultrafiltration (1 KDa) to obtain a filtrate solution; and i) concentrating the filtrate solution obtained in step (h) to obtain the nanodiamonds.
2. The method as claimed in claim 1, wherein the atmospheric pollutants comprise Total Suspended Particulate Matter having the particle size less than 100 μm (TSPM) and Particulate Matter having the size of aerodynamic diameter of 2.5-10 μm (PM.sub.10).
3. The method as claimed in claim 1, wherein the atmospheric pollutants are collected using High Volume Sampler or Respirable Dust Sampler on quartz filter papers.
4. The method as claimed in claim 1, wherein the hydrogen peroxide used in step (b) is 30% (v/v).
5. The method as claimed in claim 1, wherein the ultrasonication in step (c) is carried out for 1 hour at room temperature.
6. The method as claimed in claim 1, wherein the centrifugation in step (e) is carried out at 1400 rpm for 1 hour.
7. The method as claimed in claim 1, wherein heating in step (f) is carried out at 55-60° C. for 30 min.
8. A nanodiamond having a diameter in the range of 3-24 nm and a X-ray diffraction pattern showing peaks at the d-spacings listed in Table A: TABLE-US-00005 TABLE A ‘d’ spacing value (Å) 2θ (°) 2.0 43.22 1.26 75.1
9. The nanodiamond as claimed in claim 8 having oxygen-containing hydrophilic functional groups and blue-fluorescence under UV-light.
10. The nanodiamond as claimed in claim 8, wherein said nanodiamond are non-toxic and bio-compatible.
11. The nanodiamond as claimed in claim 8 for use in bio-sensing, biomedical imaging, drug delivery, wear resistant polymer, lubricant additives, and metal coating.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE INVENTION
[0050] The present invention relates to a method for preparation of blue-fluorescent and nontoxic nanodiamonds from atmospheric pollutants (SPM and PM.sub.10) with the help of ultrasonic-assisted chemical oxidation method.
[0051] The present invention is related to use of air pollutants as a source of carbon and conversion of same into value added carbon nanomaterials such as nanodiamonds (NDs). The carbon source is mostly vehicular exhaust diesel particulate matter. The method comprises chemical oxidation with the help of Hydrogen peroxide (30%) which is considered as environment friendly. The formed nanodiamond products are functionalized with a hydroxyl groups, carbonyl group, carboxyl group etc. Therefore, it shows fluorescence properties and the product is non-toxic and biocompatible.
[0052] The present invention provides a method for preparing nanodiamonds from atmospheric pollutants comprising the steps of: [0053] a) collecting atmospheric pollutants; [0054] b) mixing the atmospheric pollutants obtained in step (a) with hydrogen peroxide to obtain an oxidized particulate matter; [0055] c) ultrasonicating the oxidized particulate matter obtained in step (b) to obtain a first mixture; [0056] d) filtering the first mixture obtained in step (c) using a polytetrafluoroethylene membrane filter (0.22 μm) to obtain a filtrate; [0057] e) centrifuging the filtrate obtained in step (d) to obtain a supernant; [0058] f) treating the supernatant obtained in step (e) with HNO.sub.3/H.sub.2SO.sub.4 acid and heating to obtain an extract; [0059] g) neutralizing the extract obtained in step (f) by adding ammonia solution drop wise to obtain a second mixture; [0060] h) filtering the second mixture obtained in step (g) using an ultrafiltration (1 KDa) to obtain a filtrate solution; and [0061] i) concentrating the filtrate solution obtained in step (h) to obtain the nanodiamonds.
[0062] In an embodiment of the present invention, there is provided a method for preparing nanodiamonds from atmospheric pollutants, wherein the atmospheric pollutants comprise Total Suspended Particulate Matter having the particle size less than 100 μm (TSPM) and Particulate Matter having the size of aerodynamic diameter of 2.5-10 μm (PM.sub.10).
[0063] In another embodiment of the present invention, there is provided a method for preparing nanodiamonds from atmospheric pollutants, wherein the atmospheric pollutants are collected using High Volume Sampler or Respirable Dust Sampler on quartz filter papers.
[0064] In yet another embodiment of the present invention, there is provided a method for preparing nanodiamonds from atmospheric pollutants, wherein the hydrogen peroxide used in step (b) is 30%.
[0065] In still another embodiment of the present invention, there is provided a method for preparing nanodiamonds from atmospheric pollutants, wherein the ultrasonication in step (c) is carried out for 1 hour at room temperature.
[0066] In an embodiment of the present invention, there is provided a method for preparing nanodiamonds from atmospheric pollutants, wherein the centrifugation in step (e) is carried out at 1400 rpm for 1 hour.
[0067] In another embodiment of the present invention, there is provided a method for preparing nanodiamonds from atmospheric pollutants, wherein heating in step (f) is carried out at 55-60° C. for 30 minutes.
[0068] An embodiment of the present invention provides nanodiamond prepared by the method of the present invention.
[0069] In another embodiment of the present invention, there is provided nanodiamond having a diameter in the range of 3-24 nm and a X-ray diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE-US-00002 TABLE A ‘d’ spacing value (Å) 2θ (°) 2.0 43.22 1.26 75.1
[0070] In yet another embodiment of the present invention, there is provided nanodiamond having a diameter in the range of 3-6 nm and a X-ray diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE-US-00003 TABLE A ‘d’ spacing value (Å) 2θ (°) 2.0 43.22 1.26 75.1
[0071] In still another embodiment of the present invention, there is provided nanodiamond having a diameter in the range of 10-24 nm and a X-ray diffraction pattern showing peaks at the d-spacings listed in Table A:
TABLE-US-00004 TABLE A ‘d’ spacing value (Å) 2θ (°) 2.0 43.22 1.26 75.1
[0072] In another embodiment of the present invention, there is provided nanodiamond having oxygen-containing hydrophilic functional groups and blue-fluorescence under UV-light.
[0073] In yet another embodiment of the present invention, there is provided nanodiamond, wherein said nanodiamond are non-toxic and bio-compatible.
[0074] Another embodiment of the present invention provides a nanodiamond for use in bio-sensing, biomedical imaging, drug delivery, wear resistant polymer, lubricant additives, and metal coating.
[0075] The present invention provides a method of producing nanodiamonds from a carbon source, such as atmospheric air pollutant (TSPM and PM.sub.10). These air pollutants are collected by using environmental samplers like Respirable Dust Sampler for PM.sub.10 and High volume sampler for Total Suspended Particulate Matter (TSPM) which are illustrated in
[0076] The method of the present application is a feasible technique to remove associated atmospheric contaminants from particulate matter and convert them into nanodiamonds using chemical oxidation (H.sub.2O.sub.2 as an oxidizing agent) followed by ultrasonication process. This method requires less time and helps to separate carbon particles from impurities of Particulate Matters. The derived nanodiamond are confirmed by using different characterization techniques such as High resolution-transmission electron microscopy (HR-TEM; JEOL JEM 2100), X-ray diffraction (XRD; Rigako, Ultima IV), Raman spectroscopy (Horiba Jobin Vyon, Model LabRam HR), Fourier transforms infrared spectroscopy (FT-IR; System-2000, Perkin-Elmer), X-ray Photoelectron Spectrometer (XPS; ESCALAB Xi+), ultraviolet-visible spectroscopy (UV-visible; Analytik Jena, SPECORD200, Germany), fluorescence spectroscopy (FL; Horiba Fluorlolog-3), and Zeta potential (ZETASIZER; Model-Nano ZS, Malvern, UK).
EXAMPLES
Example 1: Fabrication Process of Nanodiamonds (NDs) from Total Suspended Particulate Matter (TSPM) and PM.SUB.10
[0077] The ambient air containing particulate pollutants with the size ranges from 10-100 μm in diameter (TSPM) are used for fabrication of blue fluorescent nanodiamonds. The collected TSPM (5-6 g) was mixed with 100 mL of hydrogen peroxide (20-30%) in a Teflon beaker and the mixture was then ultrasonicated (frequency: 20 kHz) in a microprocessor-based ultrasonicator (Model-Power Sonic) for about 1 hrs at an atmospheric pressure and temperature. Polytetrafluoroethylene membrane filter (˜0.22 μm) was used to filter the resultant mixture. The filterate was then centrifuged at about 1400 rpm for 1 hour. The supernatant was carefully taken and treated with nitric acid to remove the atmospheric contaminants or impurities. The nitric acid treated extract was then neutralized by adding ammonia solution drop wise. This neutral extract was concentrated using ultrafiltration and rotary evaporation and kept in a refrigerator at 4° C. for subsequent analysis (
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[0079] At high-resolutions, electron beam analysis (HRTEM) [JEOL JEM 2100] of nanodiamond prepared from TSPM is illustrated in
[0080] The X-ray diffraction (XRD) [Rigako, Ultima IV] analysis of a nanodiamond prepared from TSPM are shown in
[0081]
[0082] The Raman spectra (Horiba Jobin Vyon, Model LabRam HR) show mainly three absorptions bands for TSPM-derived NDs samples (
[0083] The photo-optical properties of the TSPM-derived ND sample were investigated by using ultraviolet (UV-Vis) spectroscopy and FL spectroscopy (UV-visible; Analytik Jena, SPECORD200, Germany), fluorescence spectroscopy (FL; Horiba Fluorlolog-3).
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[0085] The TSPM-derived NDs samples are found to be blue-fluorescence under UV-light (at 365 nm) with considerable intensity as shown in
Example 2: Fabrication of Nanodiamonds (NDs) from Particulate Matter (PM.SUB.10.)
[0086] The same experiment as outline in Example 1 was conducted with the atmospheric particulate matter (PM.sub.10 having the aerodynamic sizes of 2.5-10 μm) in the same manner.
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[0089] The XRD analysis of PM.sub.10 derived ND sample (
[0090] The FTIR analysis (
[0091] Raman Analysis of ND samples from PM.sub.10 (
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Example 3: Surface Properties of NDs Prepared from Air Pollutants (TSPM and PM.SUB.10.)
[0093] Zeta potential is the electrostatic potential or net charge at the plane of particle-slipping. Zeta potential analysis was carried out (ZETASIZER; Model-Nano ZS, Malvern, UK) to know the stability and surface charge of the PMs-derived NDs. The Zeta potentials of the NDs were found to be in the range of −24 mV to −25 mV (
Example 4: Toxicological Studies of NDs Prepared from Air Pollutants (TSPM and PM.SUB.10.)
[0094] Toxicological Studies:
[0095] As the air pollutants are considered as the most dangerous to human health, hence the toxicity of derived NDs from these C-sources were evaluated to know whether the produced product are toxic or non-toxic. Cells were sustained in RPMI medium improved with 10% Fetal bovine serum (FBS) and antibiotics at 37° C. in culture flasks with 5% CO.sub.2. Confluent monolayers (80%) of human normal kidney epithelial (NKE) cells were subjected to exposure of produced NDs at a dose of 5, 10, 20, 50, 100, 150, and 200 μg/mL for 24 hours.
[0096] Cytotoxicity Analysis and DNA Fragmentation or Genotoxicity Analysis:
[0097] Cytotoxicity was determined by using the Alamar Blue reduction bioassay. This method is based upon Alamar Blue dye reduction by live cells. After treatment with the produced NDs, the treatment medium was aspirated and 200 μL of Alamar Blue solution was added to each well and further incubated for 4 h at 37° C. The optical density of each well was measured by using a microplate reader with absorbance at 570 and 600 nm. Similar conditions were repeated three times and the well without any treatment was taken as a control. The results were expressed as a percentage over control.
[0098] The cytotoxicity analysis was performed to evaluate the toxicity levels of air pollutants (TSPM and PM.sub.10) derived NDs for their further utilization. The results demonstrated that NDs did not cause any change in the cell viability compared to those seen in the control study.
[0099] The extent of genotoxicity or fragmentation of DNA was assayed in genomic DNA samples with the help of electrophoresis technique, isolated from control as well as produced NDs treated cells, on agarose/ethidium bromide gels. After treatment, cells were washed with PBS followed by fixation with paraformaldehyde and mounted with a coverslip using the mounting media containing DAPI. Images were observed by confocal microscopy with an inverted laser scanning confocal microscope (Leica Microsystems, Germany).
[0100] The DNA fragmentation pattern treated in different cells compounds were examined. It was observed that the treatment with different compounds at a dose of 200 μg/mL for 24 hours did not cause DNA fragmentation (see
[0101] In summary, it can be confirmed that the air pollutants derived nanodiamonds are non-toxic for human kidney cell-line and it also even non-toxic at genetic level. This process will lead to the mitigation of atmospheric particulate pollution.
[0102] The main advantages of the present invention are: [0103] 1. By using the process of the present invention, typical blue-fluorescent nanodiamonds can be easily produced as compared to other drastic and tedious physical/chemical methods such as hydrothermal synthesis, ion bombardment, laser bombardment, microwave plasma chemical vapor deposition techniques, ultrasound synthesis, and electrochemical synthesis. [0104] 2. Using the process of the present application, the toxic air pollutants (TSPM and PM.sub.10) are converted into non-toxic high-value nanodiamonds (NDs). [0105] 3. Hydrogen peroxide used as oxidizing agent in the process is environment-friendly as compared to other chemical or acid solutions. [0106] 4. The process of the present invention is less time consuming.