WO2004047568A1 - Poudres inorganiques a selectivite pour le monoxyde de carbone, hcn ou no - Google Patents

Poudres inorganiques a selectivite pour le monoxyde de carbone, hcn ou no Download PDF

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Publication number
WO2004047568A1
WO2004047568A1 PCT/US2003/037627 US0337627W WO2004047568A1 WO 2004047568 A1 WO2004047568 A1 WO 2004047568A1 US 0337627 W US0337627 W US 0337627W WO 2004047568 A1 WO2004047568 A1 WO 2004047568A1
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WO
WIPO (PCT)
Prior art keywords
filter
protein
polymeric matrix
powder
polymeric
Prior art date
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Ceased
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PCT/US2003/037627
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English (en)
Inventor
William DESISTO
Robert CASHON
Benjamin Mccool
Georgios D. Karles
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Philip Morris Products SA
University of Maine System
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Philip Morris Products SA
University of Maine System
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Priority to AU2003293032A priority Critical patent/AU2003293032A1/en
Publication of WO2004047568A1 publication Critical patent/WO2004047568A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES OF CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter tips or filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces of cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES OF CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter tips or filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces of cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
    • A24D3/166—Silicic acid or silicates

Definitions

  • a new filter containing a polymer network having a protein encapsulated in the polymer network The protein is encapsulated within the polymer network and not just precipitated or supported on an active support. The protein is frozen in the polymer network. Chemical additives can also be present to stabilize the protein.
  • the invention also relates to a device that can work as a color change indicator when carbon monoxide("CO") or NO is passed through the device.
  • the invention relates to binding molecules, wherein the protein or other molecules, are responsible for the selective binding of gases.
  • the other molecules preferably contain at least one inorganic element.
  • heme proteins for example, hemoglobin, myoglobin, etc.
  • the heme proteins are well known to bind oxygen, carbon monoxide and nitrous oxide.
  • powders or ultra-thin coatings are required, in order to ensure a high gas flux through the adsorbent.
  • Specific areas of concern for protein encapsulation include protein denaturation during processing. Proteins can denature during poly-condensation reactions occurring as the gel is forming. During thin film and powder formation, the shrinkage and collapse of the pore structure is an additional concern.
  • a freezing process for the formation of silica powders is disclosed in W. Mahler and U. Chowdhry, "Ultrastructure Processing of Ceramics, Glasses and Composites," edited by L. Hench and D. Ulrich, John Wiley and Sons, 1984.
  • US patents 3,693,327 (“ '327 patent”) and 3,982,987 disclose filters suitable for removing carbon monoxide from gasses passed through the filter.
  • the filter can be used as a cigarette filter.
  • the air filter medium in the '327 patent contains amorphous hemoglobin, crystalline hemoglobin, amo ⁇ hous heme or crystalline heme in stoichiometric excess.
  • US patent 4,612,333 discloses filter composition comprising a foamed gypsum material containing carbonaceous material dispersed throughout the foamed gypsum (col. 2, lines 4-48).
  • the carbonaceous material can be an activated carbon, dried blood
  • a filter according to the present invention comprises a polymeric matrix having a protein encapsulated in said polymeric matrix.
  • the filter is preferably a cigarette filter.
  • the polymer matrix can be a polymeric powder or gel. It is preferably a gel such as organic or inorganic gel.
  • the polymeric matrix would have an encapsulated active component inco ⁇ orated in the matrix.
  • a powder can be prepared by the inco ⁇ oration of a protein into a polymeric gel such as silicic acid gel followed by a fast freezing and thawing that preserves the open polymeric network and the activity of the protein. The powder can be used as a selective filter.
  • This active powder could be used in cigarette filters for the removal of carbon monoxide from mainstream smoke.
  • the active powder could be synthesized in a powder form or it could be gelled or precipitated in situ on a filter support or a fibrous support.
  • the dry powder could be used as a color change indicator in the cigarette filters.
  • the powder can be used in a clear filter section as an indicator of reaction with carbon monoxide. It could also be used in a breakable vial or in other similar forms as means to detect the presence of carbon monoxide.
  • Filters prepared in this manner would be important in other applications in other areas where the removal of carbon monoxide is desirable or necessary. It can be used in the automotive industry.
  • An object of the invention is to synthesize an adsorbent material with selectivity towards carbon monoxide (CO), nitric oxide (NO) and/or cyanide (CN).
  • CO carbon monoxide
  • NO nitric oxide
  • CN cyanide
  • FIGURES Figure 1 illustrates UV/Nis spectra of the polymeric gels according to the invention.
  • Figure 2 illustrates the color differences between a) pure SiO 2 powder, b) 83 ⁇ M Mb/SiO 2 , c) 50 ⁇ M Mb/SiO 2 and d) 27 ⁇ M Mb/SiO 2 .
  • Figure 3a illustrates the UN/Vis spectra of oxy and deoxy-myoglobin/SiO 2
  • Figure 3b illustrates the visual bands of deoxy-myoglobin and CO bound deoxy- myoglobin
  • FIG 4 illustrates the stabilization of the Fe2+ state in Mb (myoglobin) with the addition of cysteine.
  • FIG. 5 illustrates the stabilization of the Fe2+ state in Hb (hemoglobin) with the addition of cysteine.
  • Figure 6 illustrates the potential of binding CO in Hb encapsulated powders containing cysteine.
  • Figure 7 illustrates the color difference between deoxy-Mb and CO bound Mb.
  • Figure 8 illustrates the kinetics of CN- binding to metHb.
  • Figure 9 illustrates the kinetics of CO binding to Hb (deoxy).
  • Figure 10 illustrates the relative reductions in the 4th puff for gas phase main stream smoke components.
  • Figure 11 illustrates the relative reductions for the total of 8 puffs for gas phase main stream smoke components.
  • Figure 12 illustrates a UV/visible spectra showing cyanide interaction with hemin-Cl / pyridine entrapped in silicic acid powder.
  • Figure 13 illustrates a UV/visible spectra showing cyanide interaction with cobalt tetraphenylpo ⁇ hyrin / pyridine entrapped in silicic acid powder
  • Figure 14 illustrates UV/visible spectra showing cyanide interaction with cobalt tetraphenylpo ⁇ hyrin / pyridine entrapped in TEOS powder according to the invention.
  • a filter which comprises a polymeric matrix having a protein encapsulated in said polymeric matrix.
  • the protein or other binding molecules are preferably encapsulated in an inorganic or organic polymeric structure such as, but not limited to structures originating from a polymeric gel.
  • the polymeric gel leads to the high surface area of the final powder.
  • the proteins or other binding molecules can be, but are not limited to heme proteins, for example, hemoglobin, myoglobin, simple po ⁇ hyrins or complex chemically modified po ⁇ hyrins with extra functionalities, beta vitamin or chlorophyll etc. These proteins and other binding molecules can bind oxygen, carbon monoxide and
  • Fe When Fe is in the 3 + state, it binds CN-, NO, OH " , H 2 O and pyridine. When Fe is in the 2 + state, it binds O 2 , CO, NO and pyridine.
  • Auto-oxidation occurs in hemes when the pH is low and the O 2 content is high. Auto-oxidation is promoted with an Fe(III) ligand and water. It is preferable to create an environment where auto-oxidation is limited. This can occur by minimizing the amount of H 2 O or the dimerization.
  • There are several possible ways to limit the auto-oxidation one such way is by so ⁇ tion of the heme into a mesoporous material.
  • Another way to limit the auto-oxidation is to anchor the heme onto a silica surface such as, but not limited to covalent grafting.
  • a further way to limit the auto-oxidation is by encapsulating the heme with a functionalized silica gel.
  • the inorganic polymers are preferably those of a silica (SiO ) matrix.
  • organic polymers include, but are not limited to: polyacrylic acid, carboxymethylcellulose and other cellulose derivatives, chitosan, gelatin, carageenan, pullulan, alginates, etc. and their modified analogs or copolymers as crosslinked or uncrosslinked systems.
  • the polymers are preferably not foaming polymer such as the polymeric foams described in US 4,612,333.
  • the freezing technique used to produce the silica matrix can also be used to produce zirconia gels as described in W. Mahler and U. Chowdhry, "Ultrastructure Processing of Ceramics, Glasses and Composites," edited by L. Hench and D. Ulrich, John Wiley and Sons, 1984 ("Mahler”).
  • Silica gels described in Mahler can be prepared from silicic acid.
  • the acid is synthesized by passing a dilute sodium silicate solution containing approximately 6.0 weight percent SiO 2 through an ion exchange column packed with a strong cation exchange resin, for example, Rexyn 101M, R 231 (from Fischer Scientific)
  • a strong cation exchange resin for example, Rexyn 101M, R 231 (from Fischer Scientific)
  • the process exhanges sodium ions for protons, and the effluent from the column is a cear solution of sdium free silicic acid, pH of about 3 containing the 6% by weight SiO 2 .
  • the silicic acid In freshly prepared silicic acid solutions, the silicic acid has a number average molecular weight of about 500 to 1500. As the polysilicic acid ages, the molecular weight increases. With further aging, the solution gels and the molecular weight continues to increase.
  • a gel can be obtained by adjusting the pH of the silicic acid to 5 with l NH 4 OH and letting it age for 30 minutes. It was then frozen unidirectionally by placing in to a -70°C bath at a rate of 4 cm/hr. The frozen mass was then allowed to thaw at room temperature. The product obtained was silica fibers having about 50 ⁇ m in diameter and 15 cm long.
  • organic polymer systems that may gel or precipitate out and form porous solids through either evaporation, freezing, pH changes, precipitation triggering agents may also be used to encapsulate the protein.
  • these polymer candidates include, but are not limited to: polyacrylic acid, carboxymethylcellulose and other cellulose derivatives, chitosan, gelatin, carageenan, pullulan, alginates, etc. and their modified analogs or copolymers as crosslinked or uncrosslinked systems.
  • Volatile additives can be added in the system to provide porosity upon evaporation of the volatile additive.
  • a powder can be made by freezing a polymeric gel at temperatures about 77 K.
  • the cooling temperature can be higher than 77 K as long as the gel freezes (below the freezing point of the aqueous solution). Fast freezing leads to a homogeneous, high surface area powder. Then it is preferable to thaw the frozen polymeric gel.
  • the thaw process can be done at room temperature (23°C) or at a slightly elevated temperature up
  • the thawed product can optionally be filtered and then optionally dried.
  • An active powder is formed.
  • This active powder could be used in cigarette filters for the removal of carbon monoxide and NO from mainstream smoke. It could be synthesized in a powder form or it could be gelled or precipitated in situ on a filter support or a fibrous support. Again, preferably the form is an active powder or an ultra-thin coating. The powder or coating is used to ensure a high gas flux through the adsorbent. Filters prepared in this manner would be important in other applications in other areas where the removal of carbon monoxide is desirable or necessary.
  • the powder could also be combined with a binder and formed into larger granular particles or even extruded in different shapes as may be required by the application (larger particles may be used to address pressure drop limitations).
  • the filters of this invention also work without the use of a foamed gypsum.
  • SiO 2 encapsulated myoglobin powder is made as follows.
  • the protein used was horse heart myoglobin.
  • the protein was incorporated into the SiO 2 matrix in a nondestructive fashion thereby retaining its biological activity.
  • the preparation of such powders involved inco ⁇ oration of the protein into a silicic acid gel followed by a fast freezing technique that preserves the open polymeric gel network in powder form. UV/Nis spectroscopy was used to verify that the myoglobin remained intact in both the gel and powder forms.
  • Silica gels were produced by cation exchange of a 6% wt. sodium silicate solution.
  • the resulting silicic acid solution was adjusted from an acidic pH preferably from about 2.5 to about 6 in order to induce gellation.
  • Gels containing 83, 50 and 27 ⁇ M myoglobin (Mb) were made by adding the appropriate amount of 200 ⁇ M Mb solution to the silicic acid solutions immediately following the pH adjustment. The gels were stirred for 5 minutes then allowed to age undisturbed for 18 hours at room temperature.
  • UV/Nis spectra of the resulting aged gels are presented in Figure 1.
  • the bands located at 500 and 630 nm are the bands corresponding to oxymyoglobin from horse heart.
  • the shoulder on the 500 nm band and the band at 570 nm corresponds to the small amount of deoxy- myoglobin present in the starting myoglobin powder.
  • the spectra compare directly with established literature values. See E. Antonini and M. Brunori, "Hemoglobin and Myoglobin in Their Reactions with Ligands," Elsevier Science, New York USA 1971.
  • the fast freezing technique has been found to produce SiO powders with surface areas as high as 1 ,000 m 2 /g . During the freezing process, the polymeric gel network was trapped in intercrystalline gaps of ice.
  • the freezing technique was believed to preserve the open polymeric structure of the gel leading to the high surface area of the final powder. This freezing technique is described in W. Mahler and U. Chowdhry, in "Ultrastructure Processing of Ceramics, Glasses and Composites,” edited by L. Hench and D. Ulrich, John Wiley and Sons, 1984, in particular pages 207-217, which is inco ⁇ orated by reference in its entirety for all useful pu ⁇ oses.
  • the gels After warming to room temperature, the gels separated into a water phase and a wet gel phase. The water phase was removed by filtration and the wet gel was dried resulting in a SiO 2 powder. The gels made from 6% wt.
  • the BET surface areas of Mb series were 10, 60 and 220 m 2 /g, respectively.
  • the surface area of the Mb loaded powders was drastically reduced indicating successful encapsulation and elimination of the micropores found in the pure SiO 2 powders. Removal of the Mb by heating at 500°C for 3 hours results in white SiO 2 powders with BET surface areas around 550m 2 /g.
  • 100 mg of 83 ⁇ M Mb/SiO 2 was loaded in a cuvette with a small amount of pH 7.4 phosphate buffer. The particles were then suspended in glycerin to prevent settling.
  • the UN Vis spectrum of oxy-myoglobin was recorded from 350 to 700 nm.
  • the oxy-myoglobin/SiO 2 was reduced to deoxy-myoglobin/SiO 2 by adding a small amount of sodium disulfite to the cuvette.
  • Figure 3a presents the UN/Nis spectra of oxy and deoxy-myoglobin/SiO 2 .
  • the shifting in the Soret band of horse heart myoglobin from 410 nm to 430 nm was the classic indication of the shift from oxy to deoxy-myoglobin (see E. Antonini and M. Brunori, "Hemoglobin and Myoglobin in Their Reactions with Ligands," Elsevier Science, New York USA 1971).
  • the band located around 530 nm evidenced the spectrum of the deoxy-myoglobin/SiO2.
  • the broadening and small shoulder on the 530 nm band was attributed to a trace amount of unreduced oxy-myoglobin.
  • the 530 nm band splits into two bands at 540 and 570 nm both exhibiting higher absorbance of light. This shifting and splitting is illustrated in the spectrum labeled CO-bound deoxy-Mb/SiO 2 in Figure 3b.
  • L-cysteine was added in a 2:1 molar ratio to heme groups (four in hemoglobin, one in myoglobin).
  • the L-cysteine stabilized the oxyhemoglobin (CO-active) over methemoglobin (CO-inactive).
  • several SiO2 powders were tested for their removal potential of main stream smoke components.
  • the cigarettes were prepared by creating a cavity containing 50 mg of powder in between cellulose acetate ("CA") plugs in the filter. To create the cavity, the C A plug was removed from the filter tube of a control cigarette. A section of the CA filter was then cut and reinserted in the filter tube. Following, fifty mg of powder were loaded in the filter.
  • CA cellulose acetate
  • the remaining section of the originally removed CA plug was then reinserted in the filter tube to complete the CA/Silica/CA filter configuration.
  • the control cigarette was an industry standard 1R4F cigarette.
  • the gas phase components of the main stream smoke were analyzed using GC- Mass Spectroscopy, while the cigarettes were smoked at FTC conditions (2 second 35 cc puff with one puff taken every minute).
  • Tables I and II show the results for several gas phase components.
  • Table I contains results from the GC-MS analysis of the 4th puff, while Table II contains data from the total of eight puffs per cigarette. The same data are also shown in graphical form in Figure 11. It is known, that porous adsorbents, and silica is one of them, will adsorb gas phase components and that the extent of removal is greater the greater the surface area of the adsorbent. Considering the surface area of silica containing myoglobin is reduced as myoglobin is encapsulated within the silica matrix, the above results demonstrate that myoglobin and specifically its protein component remove gas phase components such as dienes, aromatics, aldehydes, etc.
  • the powders tested in this example were prepared more than three months prior to testing and were used in cigarette testing without any special preconditioning or treatment.
  • the selectivity of the protein towards aldehydes is similar to the selectivity of the amino- propyl silane modified silica, which is another indication that certain compounds of the smoke stream are selectively chemisorbed onto the myoglobin impregnated silica.
  • Another method of inco ⁇ orating the protein into the gel is as follows: The molecule such as the hemin can be dissolved in a basic solution. The base promotes solvation of heme. Pyridine is a good base to use since it also minimizes dimerization.
  • the hemin solution with silica solution prior to complete gelling. This also produces a good gel.
  • the gel is a methyl-terminated silica gel.
  • the trapped hemin within these gels is functionally intact.
  • the hemin contains Fe( ⁇ II) and binds HCN.
  • Powders suitable for gas abso ⁇ tion measurements were prepared and characterized by UV/visible spectrophotometry. The spectra of powders were done
  • Figure 12 illustrates the visible spectra of hemin-pyridine encapsulated using silicic acid.
  • the spectra illustrates the powder before and after addition of cyanide. It can be seen that the peak at 616nm has been significantly shifted to the 642 nm. The change occurred within 2-5 minutes. The color of the powder was changed from a brown- green color to a brown-red color. Another words, powders with cyanide appeared reddish-brown in color while powders without cyanide have a greenish color. Observation of the Soret abso ⁇ tion bands (400- 450 nm) is not possible in these powders.
  • Figure 14 shows the spectral results of binding CN gas to the cobalt- tetraphenylpo ⁇ hyrin-pyridine encapsulated using TEOS. There was no significant color change observed. The Soret peak was shifted slightly from the 430nm to the 432nm and a new peak at 537 nm appeared.
  • the device according to this invention can be used in other applications besides filters where the detection of carbon monoxide, HCN and/or NO is desirable or necessary.
  • the device can be used as a CO, HCN and/or NO detector.
  • the device would contain the dry powder encapsulated with active components as described above used in the filter.
  • the device would contain a clear or transparent section that contains the dry encapsulated powder. This section is preferably transparent, although, translucent would also work. Transparent is defined permitting the complete passage of rays of visible light through. Translucent is defined as permitting the partial passage of rays of visible light. When gas is passed through the device, the powder changes upon reaction with the carbon monoxide gas.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

On prépare une poudre de silice avec des composants actifs encapsulés destinés à une filtration sélective en incorporant une protéine ou une molécule contenant un élément inorganique dans une substance polymère et en congelant rapidement ensuite ce mélange, permettant de préserver le réseau polymère ouvert et l'activité de la protéine ou de la molécule contenant l'élément inorganique. La protéine ou la molécule encapsulée peut être utilisée comme indicateur à changement de couleur pour CO, HCN ou NO
PCT/US2003/037627 2002-11-26 2003-11-24 Poudres inorganiques a selectivite pour le monoxyde de carbone, hcn ou no Ceased WO2004047568A1 (fr)

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AU2003293032A AU2003293032A1 (en) 2002-11-26 2003-11-24 Inorganic powders with selectivity towards carbon monoxide, hcn, or no

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US60/429,207 2002-11-26

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017172882A1 (fr) * 2016-03-29 2017-10-05 The Arizona Board Of Regents On Behalf Of The University Of Arizona Matériaux de filtration de type mousse à base de pyridazine et de pyridazinone pour l'élimination des nucléophiles, des électrophiles, et des métaux
CN107474960A (zh) * 2017-08-29 2017-12-15 上海华宝生物科技有限公司 一种卷烟烟气敏感变色释香颗粒的生产方法
US10619023B2 (en) 2015-08-11 2020-04-14 Arizona Board Of Regents On Behalf Of The University Of Arizona Green chemistry method of synthesizing polymer structures that can function as a built-in antioxidant
US10633517B2 (en) 2017-03-10 2020-04-28 Arizona Board Of Regents On Behalf Of The University Of Arizona Hydrogenated tetrazine-based antioxidants and free radical reaction inhibitors and uses thereof
US10731018B2 (en) 2015-08-11 2020-08-04 Arizona Board Of Regents On Behalf Of The University Of Arizona Antioxidant polydihydropyridazine and polypyridazine foams from 1,2,4,5-tetrazine
US10851192B2 (en) 2015-08-11 2020-12-01 Arizona Board Of Regents On Behalf Of The University Of Arizona Dihydropyridazine-based antioxidants and uses thereof
US11352475B2 (en) 2016-06-29 2022-06-07 Arizona Board Of Regents On Behalf Of The University Of Arizona Method of formation of a robust network of foam through Diels-Alder reaction
CN115753907A (zh) * 2022-10-17 2023-03-07 华南师范大学 一种血晶素纳米球-石墨烯复合材料的制备及其在检测一氧化氮气体中的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3693327A (en) * 1970-12-30 1972-09-26 Israel Herbert Scheinberg Filters and carbon monoxide indicators
US4612333A (en) * 1985-03-22 1986-09-16 Vassileff Neiko I Foamed gypsum filter containing carbonaceous material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3693327A (en) * 1970-12-30 1972-09-26 Israel Herbert Scheinberg Filters and carbon monoxide indicators
US4612333A (en) * 1985-03-22 1986-09-16 Vassileff Neiko I Foamed gypsum filter containing carbonaceous material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10619023B2 (en) 2015-08-11 2020-04-14 Arizona Board Of Regents On Behalf Of The University Of Arizona Green chemistry method of synthesizing polymer structures that can function as a built-in antioxidant
US10731018B2 (en) 2015-08-11 2020-08-04 Arizona Board Of Regents On Behalf Of The University Of Arizona Antioxidant polydihydropyridazine and polypyridazine foams from 1,2,4,5-tetrazine
US10851192B2 (en) 2015-08-11 2020-12-01 Arizona Board Of Regents On Behalf Of The University Of Arizona Dihydropyridazine-based antioxidants and uses thereof
WO2017172882A1 (fr) * 2016-03-29 2017-10-05 The Arizona Board Of Regents On Behalf Of The University Of Arizona Matériaux de filtration de type mousse à base de pyridazine et de pyridazinone pour l'élimination des nucléophiles, des électrophiles, et des métaux
US11352475B2 (en) 2016-06-29 2022-06-07 Arizona Board Of Regents On Behalf Of The University Of Arizona Method of formation of a robust network of foam through Diels-Alder reaction
US10633517B2 (en) 2017-03-10 2020-04-28 Arizona Board Of Regents On Behalf Of The University Of Arizona Hydrogenated tetrazine-based antioxidants and free radical reaction inhibitors and uses thereof
CN107474960A (zh) * 2017-08-29 2017-12-15 上海华宝生物科技有限公司 一种卷烟烟气敏感变色释香颗粒的生产方法
CN115753907A (zh) * 2022-10-17 2023-03-07 华南师范大学 一种血晶素纳米球-石墨烯复合材料的制备及其在检测一氧化氮气体中的应用

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