CN114210348B - Mixed catalyst and application thereof in protein content determination - Google Patents
Mixed catalyst and application thereof in protein content determination Download PDFInfo
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- CN114210348B CN114210348B CN202111342293.8A CN202111342293A CN114210348B CN 114210348 B CN114210348 B CN 114210348B CN 202111342293 A CN202111342293 A CN 202111342293A CN 114210348 B CN114210348 B CN 114210348B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 230000029087 digestion Effects 0.000 claims abstract description 45
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 28
- 238000001514 detection method Methods 0.000 claims abstract description 23
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 14
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004310 lactic acid Substances 0.000 claims abstract description 8
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 46
- 241000208125 Nicotiana Species 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 27
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 11
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 11
- 235000011151 potassium sulphates Nutrition 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 108090000623 proteins and genes Proteins 0.000 claims description 10
- 102000004169 proteins and genes Human genes 0.000 claims description 10
- 239000000413 hydrolysate Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010561 standard procedure Methods 0.000 claims description 7
- 239000011550 stock solution Substances 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 235000019505 tobacco product Nutrition 0.000 claims description 5
- 239000012086 standard solution Substances 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims 1
- JTTXECQCCPZGII-UHFFFAOYSA-M sodium;ethane-1,2-diol;hydroxide Chemical compound [OH-].[Na+].OCCO JTTXECQCCPZGII-UHFFFAOYSA-M 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003814 drug Substances 0.000 description 9
- 229940079593 drug Drugs 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 235000019506 cigar Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 1
- 101000954509 Trichosurus vulpecula Very early lactation protein Proteins 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- XEYBHCRIKKKOSS-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N XEYBHCRIKKKOSS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002331 protein detection Methods 0.000 description 1
- 230000013777 protein digestion Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002133 sample digestion Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940083618 sodium nitroprusside Drugs 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
Abstract
The invention relates to the technical field of detection, in particular to a mixed catalyst and application thereof in protein content determination. The mixed catalyst comprises copper sulfate, selenium powder and a catalytic auxiliary agent, wherein the catalytic auxiliary agent is prepared by taking carbon aerogel as a carrier, loading nano ferroferric oxide on the carrier and then grafting lactic acid, and the mass ratio of the copper sulfate to the selenium powder to the catalytic auxiliary agent is (10-15): 1 (0.1-0.2). The mixed catalyst and the application thereof in protein content determination can improve the catalytic activity of the mixed catalyst by adding the catalytic auxiliary agent, thereby being beneficial to reducing digestion time and improving detection efficiency.
Description
Technical Field
The invention relates to the technical field of detection, in particular to a mixed catalyst and application thereof in protein content determination.
Background
The protein in the tobacco is one of compounds which has important influence on the quality of the tobacco, firstly, the protein is a substance basis for ensuring the activity of organisms in the growth and development process of tobacco plants, and secondly, the protein and other chemical substances in the baking and alcoholizing processes of the tobacco after picking can generate a series of chemical reactions, on one hand, aroma components and the like for improving the smoking quality of the tobacco can be generated, the use value of the tobacco is improved, and on the other hand, substances with irritation and pungency such as ammonia and the like can be generated. Therefore, the protein content in tobacco leaves is controlled to be within a certain range.
At present, most of detection of proteins in the tobacco industry takes red oxidized mercury as a catalyst in digestion reaction, the red oxidized mercury belongs to highly toxic chemicals, and the storage, the use and the waste liquid treatment of the red oxidized mercury need strict supervision and management, so that a large amount of extra manpower is needed for management, environmental pollution is easy to be caused, and in addition, when the red oxidized mercury is used as the catalyst, the digestion time of a sample is long, so that the detection efficiency is greatly reduced.
Disclosure of Invention
In view of the above, the present invention aims to provide a mixed catalyst and an application thereof in protein content measurement, wherein the catalytic activity of the mixed catalyst can be improved by adding a catalytic auxiliary agent, so that the digestion time is reduced, and the detection efficiency is improved.
The invention solves the technical problems by the following technical means:
the mixed catalyst comprises copper sulfate, selenium powder and a catalytic auxiliary agent, wherein the catalytic auxiliary agent is prepared by taking carbon aerogel as a carrier, loading nano ferroferric oxide on the carrier and then grafting lactic acid.
According to the mixed catalyst, the catalytic auxiliary agent is also added, when the mixed catalyst is used, the grafted polylactic acid can destroy alpha-helix and beta-sheet in protein molecules, the high-grade structure of the protein molecules is enabled to be digested more easily and decomposed into ammonia, meanwhile, the carbon aerogel serving as a carrier has a porous structure and has more active vacancies on the surface, when the mixed catalyst is used, the adsorption and activation of the protein are facilitated, the concentration of the protein on the surface is improved, and the catalytic efficiency is improved, but the carbon aerogel is lighter in weight and is not easy to separate from a reaction substrate, so that nano ferroferric oxide loaded on the carbon aerogel can be added into the reaction liquid better on one hand, so that the carrier can be added into the reaction liquid to form a suspension, and on the other hand, the magnetism of the catalytic auxiliary agent can be increased, and the secondary utilization of later separation and recovery is facilitated.
Further, the mass ratio of the copper sulfate to the selenium powder to the catalyst auxiliary agent is (10-15) 1 (0.1-0.2).
Further, the preparation method of the catalyst promoter comprises the following steps:
load: stirring and dissolving ferrous ammonium sulfate into hydrazine hydrate to obtain ferrous ammonium sulfate solution, adding pretreated carbon aerogel powder into ethylene glycol, performing ultrasonic dispersion, adding the ferrous ammonium sulfate solution, continuously stirring for 30-40min at a rotating speed of 1000-1200r/min, adjusting pH to 11-13, heating to boiling reflux for 2-4h, filtering after the reaction is completed, washing a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain a carrier loaded with nano ferroferric oxide;
grafting: adding the prepared carrier loaded with nano ferroferric oxide into tetrahydrofuran, performing ultrasonic dispersion, dropwise adding stannous octoate, dropwise adding lactic acid, performing vacuum pumping after the dropwise adding is finished, stirring at 50-75 ℃ for reaction for 4-6h, adding the reaction product into chloroform, stirring for 20min, centrifuging, and performing vacuum drying to obtain a precipitate to obtain the catalytic auxiliary agent.
Further, in the loading step, 1mol/L sodium hydroxide glycol solution is adopted for pH adjustment.
Further, the preprocessing in the loading step is as follows: adding the carbon aerogel powder into a ball mill, spraying and adding methacryloxy silane hydrolysate, adding agate balls, performing ball milling for 15-18h under the condition of the rotating speed of 150-200r/min, filtering after the ball milling is finished to obtain the carbon aerogel powder, and washing and drying.
Through carrying out wet ball-milling to carbon aerogel powder, can reduce the agglomeration of carbon aerogel powder for it is more dispersed in the in-process of using, simultaneously, adds methacryloxy silane hydrolysate and handles it, can also increase its hydrophilic performance, can promote to a certain extent that it can be better with the contact of reaction liquid, plays better helping catalytic effect.
Further, the solid-to-liquid ratio of the carbon aerogel powder to the methacryloxysilane hydrolysate is 1 (2-20), and the mass ratio of the carbon aerogel powder to the agate beads is 1 (20-50).
In addition, the invention also discloses application of the catalyst in detection of tobacco protein.
Further, when the mixed catalyst is used for digesting the tobacco products, the digestion temperature is 380 ℃ and the digestion time is 1h.
Further, the application specifically comprises the steps of,
s1: preparing a sample treatment solution: preparing a tobacco sample according to YC/T31, measuring the moisture content, accurately weighing the tobacco sample, placing the tobacco sample in a digestion tube, sequentially adding a mixed catalyst, adding potassium sulfate, adding concentrated sulfuric acid, placing the digestion tube in a digester for digestion, taking out the digestion tube after digestion is completed, slightly cooling, slowly adding a small amount of water, shaking uniformly, cooling to room temperature, using water to fix the volume to a scale, and uniformly mixing to obtain a sample treatment solution;
s2: preparation of standard preparation liquid: adding a mixed catalyst into a digestion tube in sequence, adding potassium sulfate, adding concentrated sulfuric acid, putting the digestion tube into a digester for digestion, extracting the digestion tube after digestion is completed, slightly cooling, slowly adding a small amount of water, shaking uniformly, cooling to room temperature, using water to fix the volume to a scale, and mixing uniformly for later use;
s3: preparation of stock solution: weighing ammonium sulfate in a digestion tube, adding a mixed catalyst, adding potassium sulfate, adding sulfuric acid, digesting in a digester, transferring into a volumetric flask after cooling, and shaking uniformly with the standard preparation solution in the step S2 to a constant volume;
s4: preparation of working standard liquid: according to the predicted total nitrogen content of the detected sample, the stock solution prepared in the step S3 is fixed with the standard preparation solution in the step S2, and working standard solutions with the nitrogen content concentration of 0.2%, 0.4%, 0.6%, 0.8% and 1.0% are obtained;
s5: preparation of needle washing liquid: the standard preparation liquid prepared in the step S2 is used as the needle washing liquid;
s6: and (3) result detection: and (3) using a flow analyzer to perform on-machine detection according to the follow-up steps of the standard method of the tobacco industry, and calculating a result.
The invention provides a mixed catalyst, which has the following advantages:
1. the mixed catalyst provided by the invention avoids the use of red mercury oxide, avoids the hidden danger of injury to detection personnel in the use process, and simultaneously omits the problems of storage, waste liquid treatment and the like, and is environment-friendly and safe.
2. According to the mixed catalyst, the catalytic action of the copper sulfate and the selenium powder can be improved through the added catalytic auxiliary agent, so that the catalytic efficiency is improved, the protein digestion time is reduced, the mixed catalyst can be recycled after being used, and the protein detection cost is reduced.
3. The mixed catalyst provided by the invention has no obvious difference with the detection result of the existing standard method when being applied to detecting the protein content in tobacco, has good stability, and the sample digestion treatment time is obviously shorter than that of the existing standard detection method.
Detailed Description
In order that those skilled in the art may better understand the technical solution of the present invention, the following further details of the present invention will be described by way of examples, which should not be construed as limiting the technical solution:
example one preparation of the catalyst 1
Preparation of catalytic promoter
Pretreatment: weighing methacryloxy silane, dropwise adding the methacryloxy silane into 1wt% acetic acid aqueous solution, and stirring until the solution is clear and transparent to obtain methacryloxy silane hydrolysate with the mass fraction of methacryloxy silane of 2wt% for later use; adding carbon aerogel powder into a ball mill, spraying and adding methacryloxy silane hydrolysate, adding agate balls, wherein the solid-to-liquid ratio of the carbon aerogel powder to the methacryloxy silane hydrolysate is 1:5, the mass ratio of the carbon aerogel powder to the agate balls is 1:20, performing ball milling for 16 hours under the condition of the rotating speed of 150r/min, filtering after the ball milling is finished to obtain the carbon aerogel powder, and washing and drying.
Load: stirring and dissolving 1.0g of ferrous ammonium sulfate in 10ml of hydrazine hydrate to obtain ferrous ammonium sulfate solution, adding 0.25g of pretreated carbon aerogel powder into 15ml of ethylene glycol, performing ultrasonic dispersion, adding the ferrous ammonium sulfate solution, continuously stirring for 35min at a rotating speed of 1200r/min, adjusting pH to 11-13, heating to boiling and refluxing for 3h, filtering after the reaction is completed, washing a filter cake with absolute ethyl alcohol and deionized water successively, and drying to obtain a carrier loaded with nano ferroferric oxide;
grafting: adding 0.2g of the prepared carrier loaded with nano ferroferric oxide into 10ml of tetrahydrofuran, dispersing by ultrasonic, dropwise adding 1ml of stannous octoate-ethylene glycol solution, dropwise adding 2g of lactic acid, vacuumizing after the dropwise adding is finished, stirring and reacting for 5 hours at the temperature of 60 ℃, adding the reaction product into chloroform, stirring for 20min, centrifuging, and vacuum drying the obtained precipitate to obtain the catalyst aid.
The mixed catalyst of the embodiment comprises 0.2g of copper sulfate, 0.02g of selenium powder and 2mg of catalyst auxiliary agent.
Example two preparation of catalyst 2
Preparation of catalytic promoter
Pretreatment: weighing methacryloxy silane, dropwise adding the methacryloxy silane into 1wt% acetic acid aqueous solution, and stirring until the solution is clear and transparent to obtain methacryloxy silane hydrolysate with the mass fraction of methacryloxy silane of 1wt% for later use; adding carbon aerogel powder into a ball mill, spraying and adding methacryloxy silane hydrolysate, adding agate balls, wherein the solid-to-liquid ratio of the carbon aerogel powder to the methacryloxy silane hydrolysate is 1:20, the mass ratio of the carbon aerogel powder to the agate balls is 1:50, performing ball milling for 15 hours under the condition of 180r/min, filtering after ball milling is completed to obtain carbon aerogel powder, and washing and drying.
Load: stirring and dissolving 1.2g of ferrous ammonium sulfate in 10ml of hydrazine hydrate to obtain ferrous ammonium sulfate solution, adding 0.2g of pretreated carbon aerogel powder into 15ml of ethylene glycol, performing ultrasonic dispersion, adding the ferrous ammonium sulfate solution, continuously stirring for 30min at a rotating speed of 1000r/min, adjusting pH to 11-13, heating to boiling and refluxing for 2h, filtering after the reaction is completed, washing a filter cake with absolute ethyl alcohol and deionized water successively, and drying to obtain a carrier loaded with nano ferroferric oxide;
grafting: adding 0.2g of the prepared carrier loaded with nano ferroferric oxide into 10ml of tetrahydrofuran, dispersing by ultrasonic, dropwise adding 2ml of stannous octoate-ethylene glycol solution, dropwise adding 2.5g of lactic acid, vacuumizing after the dropwise adding is finished, stirring at 75 ℃ for reacting for 4 hours, adding the reaction product into chloroform, stirring for 20min, centrifuging, and obtaining a precipitate, and drying in vacuum to obtain the catalytic aid.
The mixed catalyst of the embodiment comprises 0.24g of copper sulfate, 0.02g of selenium powder and 3mg of catalyst auxiliary agent.
Example three preparation of catalyst 3
Preparation of catalytic promoter
Pretreatment: weighing methacryloxy silane, dropwise adding the methacryloxy silane into 1wt% acetic acid aqueous solution, and stirring until the solution is clear and transparent to obtain methacryloxy silane hydrolysate with the mass fraction of methacryloxy silane of 1.5wt% for later use; adding carbon aerogel powder into a ball mill, spraying and adding methacryloxy silane hydrolysate, adding agate balls, wherein the solid-to-liquid ratio of the carbon aerogel powder to the methacryloxy silane hydrolysate is 1:12, the mass ratio of the carbon aerogel powder to the agate balls is 1:35, performing ball milling for 15 hours under the condition of 200r/min, filtering after ball milling is completed to obtain carbon aerogel powder, and washing and drying.
Load: 2.0g of ferrous ammonium sulfate is stirred and dissolved in 15ml of hydrazine hydrate to obtain ferrous ammonium sulfate solution, 0.25g of pretreated carbon aerogel powder is added into 15ml of ethylene glycol, after ultrasonic dispersion, the ferrous ammonium sulfate solution is added, stirring is continued for 40min at the rotating speed of 1100r/min, pH is regulated to 11-13, heating is carried out until boiling reflux is carried out for 4h, filtering is carried out after the reaction is finished, filter cakes are washed by absolute ethyl alcohol and deionized water successively, and a carrier loaded with nano ferroferric oxide is obtained after drying;
grafting: adding 0.2g of the prepared carrier loaded with nano ferroferric oxide into 10ml of tetrahydrofuran, dispersing by ultrasonic, dropwise adding 1.5ml of stannous octoate-ethylene glycol solution, dropwise adding 3g of lactic acid, vacuumizing after the dropwise adding is finished, stirring at 50 ℃ for reaction for 6 hours, adding the reaction product into chloroform, stirring for 20min, centrifuging, and obtaining a precipitate, and drying in vacuum to obtain the catalytic aid.
The mixed catalyst of the embodiment comprises 0.3g of copper sulfate, 0.02g of selenium powder and 4mg of catalyst auxiliary agent.
Experiment one
The catalyst prepared in the first to third examples is used for digestion treatment of tobacco products, and meanwhile, the mixed catalyst without adding catalyst auxiliary agent is used as a comparative example, and specifically comprises the following steps:
taking the same tobacco leaf sample (from a Chongqing smoke technology center raw material room), equally dividing the sample into 6 parts, respectively adding the mixed catalysts prepared in the first to third examples into three parts, respectively adding the mixed catalysts obtained in the first to third examples after removing the catalyst auxiliary agent into the other three parts, respectively marking the mixed catalysts as a first comparative example, a second comparative example and a third comparative example, respectively digesting the mixed catalysts at 380 ℃ for 0.5, 1.0, 1.5 and 2.0 hours, and keeping the rest of test conditions unchanged. The test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the mixed catalyst prepared by the method has basically no obvious change in the detection result when the digestion time is about 1h, and has no obvious change in the detection result when no catalyst auxiliary agent is added, so that the catalyst auxiliary agent can be beneficial to improving the catalytic effect of the catalyst.
Experiment two
And (3) testing whether the added catalytic auxiliary agent can interfere with the detection of the protein content in the tobacco, taking 2mg, 3mg, 4mg, 5mg and 6mg of the catalytic auxiliary agent into a 75mL digestion tube, respectively adding 2.0g of potassium sulfate, 0.2g of copper sulfate, 0.02g of selenium powder and 5mL of concentrated sulfuric acid, cooling to a certain volume at 380 ℃ for 1.0h, uniformly shaking to serve as a sample for detection, and finding that no response exists on an instrument, wherein the catalytic auxiliary agent can not interfere with the result when the catalytic auxiliary agent is smaller than 6 mg.
Example IV
The mixed catalyst prepared in the first to third embodiments is used for detecting the protein content in tobacco samples, and meanwhile, the existing YC/T161-2002 standard method is used as a comparison, and the tobacco samples are selected from 10 tobacco samples of different grades, 2 tobacco samples of burley tobacco and cigar, and the specific steps are as follows:
primary reagents, materials and instruments
Laboratory control samples (purchased from the national tobacco quality supervision and inspection center) with total nitrogen labeling values of (2.14.+ -. 0.11)%, respectively, wherein the tobacco leaf samples were all from the Chongqing center of tobacco technology feedstock laboratory.
Red mercuric oxide (AR, copper-kernel mercury chemical reagent factory, guizhou); copper (ii) sulfate pentahydrate (AR, national drug group); selenium powder (BR, national drug group); potassium sulfate (AR, national drug group); polyethoxy lauryl ether solution (30%, SKALAR, netherlands); sodium salicylate (AR, national drug group); sodium nitroprusside (AR, sigma Aldrich, usa); sodium chloride (AR, national drug group); sulfuric acid (AR, national drug group); sodium potassium tartrate (AR, sigma Aldrich, usa); disodium phosphate dodecahydrate (AR, national drug group); sodium hydroxide (AR, national drug group); sodium hypochlorite (AR, national drug group); sodium dichloroisocyanurate (AR, tokyo chemical Co.).
SKALAR SAN ++ Continuous flow analyzer (SKALAR corporation, netherlands); DK20 digester (VELP, italy); AX504 analytical balance (inductance: 0.0001g, METTER TOLEDO Co., switzerland); FD115 electrothermal forced air drying oven (BINDER, germany); 3100 pulverizing mill (PERTEN, sweden); milli-Q Direct 16 water purifier (Millipore Co., U.S.A.).
The specific operation is as follows:
s1: preparing a sample treatment solution: preparing a tobacco sample according to YC/T31, measuring the moisture content, accurately weighing 0.1000 g (accurate to 0.0001 g) of the tobacco sample, placing the tobacco sample in a 75mL digestion tube, sequentially adding 2.0g of potassium sulfate, adding 5mL of concentrated sulfuric acid after the prepared mixed catalyst is prepared, placing the digestion tube in the digestion tube, digesting under the condition of 380 ℃ and 1.0h, extracting the digestion tube after digestion, slightly cooling, slowly adding a small amount of water, shaking uniformly, cooling to room temperature, fixing the volume to 75mL by water, and uniformly mixing to obtain a sample treatment solution.
S2: preparation of standard preparation liquid: adding catalyst into 75mL digestion tube, adding potassium sulfate, adding 5mL concentrated sulfuric acid, placing the digestion tube into a digester, digesting at 380 ℃ for 1.0h, extracting the digestion tube after digestion, slightly cooling, slowly adding a small amount of water, shaking, cooling to room temperature, metering the volume with water to a scale, mixing uniformly, and standing for use.
S3: preparation of stock solution: 1.2g of ammonium sulfate is weighed into a 75mL digestion tube, 2.0g of potassium sulfate and 0.3g of copper sulfate are added, 0.02g of selenium powder is added, 5mL of sulfuric acid is added, digestion is carried out under the condition of 380 ℃ and 1.0h, after cooling, the mixture is transferred into a 250mL volumetric flask, and the standard preparation solution in the step S2 is used for constant volume shaking.
S4: preparation of working standard liquid: and respectively transferring 2mL, 4mL, 6mL, 8mL and 10mL of stock solutions according to the predicted total nitrogen content of the detected sample, and respectively using the stock solutions prepared in the step S3 of the standard preparation solution constant volume in the step S2 as working standard solutions in 5 100mL volumetric flasks to obtain the working standard solutions with nitrogen content concentrations of 0.2%, 0.4%, 0.6%, 0.8% and 1.0% respectively.
S5: preparation of needle washing liquid: the standard preparation liquid prepared in the step S2 is used as the needle washing liquid;
s6: and (3) result detection: and (3) using a flow analyzer to perform on-machine detection according to the follow-up steps of the standard method of the tobacco industry, and calculating a result.
The test results are shown in Table 2:
table 2 experimental results of tobacco samples
| Tobacco sample | The method (%) | Standard method (%) | Relative deviation (%) |
| Flue-cured tobacco 1# | 5.19 | 5.13 | 1.16 |
| 2# of flue-cured tobacco | 4.62 | 4.58 | 0.87 |
| Flue-cured tobacco 3# | 4.72 | 4.73 | 0.21 |
| 4# of flue-cured tobacco | 5.14 | 5.16 | 0.39 |
| Flue-cured tobacco 5# | 4.58 | 4.64 | 1.30 |
| 6# of flue-cured tobacco | 5.69 | 5.7 | 0.18 |
| Flue-cured tobacco 7# | 6.92 | 6.84 | 1.16 |
| 8# of flue-cured tobacco | 6.67 | 6.68 | 0.15 |
| Flue-cured tobacco 9# | 5.49 | 5.5 | 0.18 |
| 10# of flue-cured tobacco | 6.27 | 6.32 | 0.79 |
| Cigar 1# | 8.1 | 8.17 | 0.86 |
| Cigar 2# | 9.24 | 9.12 | 1.30 |
| Burley tobacco 1 #) | 11.56 | 11.67 | 0.95 |
| Burley tobacco 2 #) | 12.62 | 12.53 | 0.72 |
As can be seen from the data in Table 2, the mixed catalyst is used for detecting the protein content in the tobacco product, the detection result has no obvious difference from the result measured by the existing standard method, the stability and the repeatability are good, but the digestion treatment time is reduced, the detection time is shortened, and the production efficiency is improved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention. The technology, shape, and construction parts of the present invention, which are not described in detail, are known in the art.
Claims (7)
1. The mixed catalyst comprises copper sulfate and selenium powder and is characterized by further comprising a catalytic auxiliary agent, wherein the catalytic auxiliary agent is prepared by taking carbon aerogel as a carrier, loading nano ferroferric oxide on the carrier and then grafting lactic acid; the mass ratio of the copper sulfate to the selenium powder to the catalyst auxiliary agent is (10-15) 1 (0.1-0.2); the preparation method of the catalyst auxiliary agent comprises the following steps:
load: stirring and dissolving ferrous ammonium sulfate into hydrazine hydrate to obtain ferrous ammonium sulfate solution, adding pretreated carbon aerogel powder into ethylene glycol, performing ultrasonic dispersion, adding the ferrous ammonium sulfate solution, continuously stirring for 30-40min at a rotating speed of 1000-1200r/min, adjusting pH to 11-13, heating to boiling reflux for 2-4h, filtering after the reaction is completed, flushing a filter cake with absolute ethyl alcohol and deionized water, and drying to obtain a carrier loaded with nano ferroferric oxide;
grafting: adding the prepared carrier loaded with nano ferroferric oxide into tetrahydrofuran, performing ultrasonic dispersion, dropwise adding stannous octoate, dropwise adding lactic acid, performing vacuum pumping after the dropwise adding is finished, stirring at 50-75 ℃ for reaction for 4-6h, adding the reaction product into chloroform, stirring for 20min, centrifuging, and performing vacuum drying to obtain a precipitate to obtain the catalytic auxiliary agent.
2. A mixed catalyst according to claim 1, wherein the pH is adjusted in the loading step using 1mol/L ethylene glycol sodium hydroxide solution.
3. A hybrid catalyst according to claim 2, wherein the pretreatment in the loading step is: adding the carbon aerogel powder into a ball mill, spraying and adding methacryloxy silane hydrolysate, adding agate balls, performing ball milling for 15-18h under the condition of the rotating speed of 150-200r/min, filtering after the ball milling is finished to obtain the carbon aerogel powder, and washing and drying.
4. A mixed catalyst according to claim 3, wherein the solid-to-liquid ratio of the carbon aerogel powder to the methacryloxysilane hydrolysate is 1 (2-20), and the mass ratio of the carbon aerogel powder to the agate beads is 1 (20-50).
5. Use of a mixed catalyst according to any one of claims 1-4 in the detection of tobacco product proteins.
6. The use according to claim 5, wherein the mixed catalyst is used for a digestion time of 1h at a digestion temperature of 380 ℃ when the tobacco product is digested.
7. The use according to claim 6, characterized in that it comprises in particular the steps of,
s1: preparing a sample treatment solution: preparing a tobacco sample according to YC/T31, measuring the moisture content, accurately weighing the tobacco sample, placing the tobacco sample in a digestion tube, sequentially adding a mixed catalyst, adding potassium sulfate, adding concentrated sulfuric acid, placing the digestion tube in a digester for digestion, taking out the digestion tube after digestion is completed, slightly cooling, slowly adding a small amount of water, shaking uniformly, cooling to room temperature, using water to fix the volume to a scale, and uniformly mixing to obtain a sample treatment solution;
s2: preparation of standard preparation liquid: adding a mixed catalyst into a digestion tube in sequence, adding potassium sulfate, adding concentrated sulfuric acid, putting the digestion tube into a digester for digestion, extracting the digestion tube after digestion is completed, slightly cooling, slowly adding a small amount of water, shaking uniformly, cooling to room temperature, using water to fix the volume to a scale, and mixing uniformly for later use;
s3: preparation of stock solution: weighing ammonium sulfate in a digestion tube, adding a mixed catalyst, adding potassium sulfate, adding sulfuric acid, digesting in a digester, transferring into a volumetric flask after cooling, and shaking uniformly with the standard preparation solution in the step S2 to a constant volume;
s4: preparation of working standard liquid: according to the predicted total nitrogen content of the detected sample, the stock solution prepared in the step S3 is fixed with the standard preparation solution in the step S2, and working standard solutions with the nitrogen content concentration of 0.2%, 0.4%, 0.6%, 0.8% and 1.0% are obtained;
s5: preparation of needle washing liquid: the standard preparation liquid prepared in the step S2 is used as the needle washing liquid;
s6: and (3) result detection: and (3) using a flow analyzer to perform on-machine detection according to the follow-up steps of the standard method of the tobacco industry, and calculating a result.
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| US3224981A (en) * | 1961-12-29 | 1965-12-21 | Ethyl Corp | Supported copper oxide and palladium catalyst composition |
| CN101354349A (en) * | 2008-07-24 | 2009-01-28 | 广东中烟工业有限责任公司 | Method for measuring protein nitrogen content in tobacco |
| WO2011126545A1 (en) * | 2010-04-09 | 2011-10-13 | Dow Global Technologies Llc | Catalyst compositions for producing mixed alcohols |
| CN103225097A (en) * | 2013-05-15 | 2013-07-31 | 南京航空航天大学 | Preparation of Cu2O/TNTs (TiO2 nanotubes) heterojunction nano composite material and CO2 photoreduction method |
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| US3224981A (en) * | 1961-12-29 | 1965-12-21 | Ethyl Corp | Supported copper oxide and palladium catalyst composition |
| CN101354349A (en) * | 2008-07-24 | 2009-01-28 | 广东中烟工业有限责任公司 | Method for measuring protein nitrogen content in tobacco |
| WO2011126545A1 (en) * | 2010-04-09 | 2011-10-13 | Dow Global Technologies Llc | Catalyst compositions for producing mixed alcohols |
| CN103225097A (en) * | 2013-05-15 | 2013-07-31 | 南京航空航天大学 | Preparation of Cu2O/TNTs (TiO2 nanotubes) heterojunction nano composite material and CO2 photoreduction method |
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