CN104458939A - Method for detecting camellia nitidissima chi oil type volatile ingredients - Google Patents
Method for detecting camellia nitidissima chi oil type volatile ingredients Download PDFInfo
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Abstract
The invention relates to the field of a solid phase extraction-gas chromatography-mass spectrometry combined technology and provides a method for detecting camellia nitidissima chi oil type volatile ingredients. The method comprises the following steps: detecting the camellia nitidissima chi oil type volatile ingredients by a solid phase extraction adsorption-gas chromatography-mass spectrometry combined process, wherein the solid phase extraction is headspace stir bar solid phase adsorption extraction, and a stir bar is coated with a two-dimensional or three-dimensional graphene-polymer coating; the materials of the graphene-polymer coating include graphene and graphene modified materials, and the graphene modified materials include graphene oxide, graphene-polyethylene glycol dimethacrylate, graphene-polypyrrole, graphene-polymethyltrimethoxy silane and a graphene nanomaterial. The method has the characteristics of accurate detection, high sensitivity, good selective adsorption effect and long service life.
Description
Technical field
The present invention relates to organophosphorous pesticides-mass spectrometric hyphenated technique field, particularly a kind of detection method being applied in Camellia nitidissima oils volatile ingredient.
Background technology
Camellia nitidissima belongs to Theaceae, Camellia, is twin sisters with tea, camellia, South Mountain tea, oil tea, tea plum etc.Camellia nitidissima spend golden yellow, dazzling brilliant, be coated with coating of wax seemingly, sparkling and crystal-clear and glossy, seemingly have translucent sense.Camellia nitidissima is singly born in axil, when the flowers are in blossom, have cup-shaped, gyalectiform or bowl-shape, delicate and charming colourful, beautiful grace.In the past, people did not see the golden yellow kind of pattern.Nineteen sixty, Chinese science worker has found a kind of flavous camellia at Nanning one band first, is named as Camellia nitidissima.Be referred to as magical " Dongfang " magic tea abroad, be described as " plantage giant panda ", " tea race queen ", be one of country eight kinds of first class of protection plants, the ground such as MeiZhou,GuangDong, Guangxi Fangcheng Port also has manually introduces a fine variety.
About Camellia nitidissima, Compendium of Material Medica has carries: " camellia produces south ... have again the names such as a sth. made by twisting is red, and Chiba is red, Chiba is white, or cloud also has yellow person "; Guangxi " local chronicle " is also on the books: " Camellia nitidissima, evergreen shrubs grow in barren hill "; " Ye Hehua of Camellia nitidissima, famous and precious heat-clearing can be done through processing, control dysentery, fat removing and decompression ".Among the people in area, Guangdong and Guangxi Provinces, the Camellia nitidissima of common people's widespread use over the past thousands of years make tea or Baoshang with clearing heat and detoxicating, blood lipid-reducing blood sugar-decreasing, diuresis dry, step-down and improve immunity etc.
Research finds, golden camellia tea and be rich in Tea Polyphenols in spending, cupreol, the trace elements such as anthocyanidin, general flavone (isoflavones, biflavone, flavanols, chalcone, aurones, anthocyanin, two hydrogen Huang (alcohol) and neoflavonoid etc.), several amino acids, oleanolic acid, soluble sugar, natural VE, 18 carbonic acid, phthalic acid list (ethylhexyl) active skull cap components such as ester, Kaempferol and selenium, manganese, iron, zinc.
In the composition of Camellia nitidissima, oiliness volatile ingredient mainly comprises arbricolin, 1,2-epoxy octadecane, 1,2-Disparmone, irisone, phytol, linoleic acid, methyl linoleate, ethyl linoleate etc., such oiliness volatile ingredient has nti-freckle, effect such as desalination scar and striae of pregnancy etc., has application prospect widely.
Because oiliness volatile ingredient content in Camellia nitidissima is lower, existing research mostly concentrates on the higher Camellia nitidissima active component of some content abundance such as camellia chrysantha polysaccharide, Tea Polyphenols, general flavone etc. and is separated context of detection, and the oiliness volatile ingredient be directed in Camellia nitidissima active component does not have too much relating to.。
Solid phase micro-extraction technique is proposed by Pawliszyn in nineteen ninety as a kind of novel Sample Pretreatment Technique Used, because it saves solvent and fast simple to operate, is therefore widely used.Stir Bar Sorptive Extraction is a kind of novel solid-phase microextraction Sample Pretreatment Technique, have that stationary phase volume is large, loading capacity is high, without the need to additional stirrer, competitive adsorption can be avoided, the advantages such as extracting and enriching can be realized while self stirs, be widely used in food, pre-treatment that medicine, environmental and biological samples are analyzed.At present, the general direct Stir Bar Sorptive Extraction of solid phase micro-extraction technique: the extraction being generally applicable to non-volatility or the more weak material of volatility, Tea Polyphenols as more weak in volatility in Camellia nitidissima, general flavone, saponins material etc., if directly apply to oiliness volatile ingredient to detect, oil components can directly volatilize, and has a strong impact on the order of accuarcy of detection accordingly.
Stir Bar Sorptive Extraction is a kind of technology being applicable to very much low concentration sample enrichment, magnetic-adsorption stirring rod outer wall being wrapped in sorbing material is only needed to put into the cup or bottle that sample solution is housed, start magnetic stirrer a few minutes by more than ten minutes, the active ingredients after enrichment will be adsorbed in stirring rod by enrichment.By extracting the enrichment of stirring rod, can have and analyze the ability of multiple concentration lower than the compound of ppb.
Stir Bar Sorptive Extraction does not need a large amount of solvent extractions, bioaccumulation efficiency is higher than solid-phase microextraction, because dynamic agitation enrichment, repeatability is also good than Solid-Phase Extraction, easy to use, is applicable to Camellia nitidissima Active Components, particularly half volatilization or nonvolatile Tea Polyphenols, total flavonoid composition, general stripping trapping technique or headspace analysis techniques are difficult to analyze, but application solid phase extraction techniques is analyzed said components and had good effect.This technology often realizes the synchronous detection to effective constituent with the coupling such as high performance liquid chromatography, liquid chromatography-mass spectrography, gas chromatography-mass spectrum, Capillary Electrophoresis.
But although stirring rod solid phase extraction techniques is with the obvious advantage, its performance largely depends on the performance of its coating material.Traditional stirring rod solid-phase microextraction thin layer adsorbed polymer material of scribbling of extracting fiber stirring rod surface used mostly is perfluorinated resin, polypyrrole, methyl vinyl silicone, epoxy-dimethyl silicone polymer etc., these materials often price are higher and fragile, need to ensure absorption property by thickening coating in reality processing, the thickening of coating can cause and both can reduce detection sensitivity, the probability that stirring rod coating occurs to rupture in actual mechanical process can be improved again, also there will be sample when analyzing Cucumber such as active components of plants and leave over phenomenon or matrix interference phenomenon at Solid-Phase Extraction coating material, have a strong impact on the accuracy of detection.
Summary of the invention
The present invention is directed to prior art Problems existing, in conjunction with the present situation that Camellia nitidissima oiliness volatile ingredient detects, for stirring rod Solid-Phase Extraction detection technique Problems existing, define a kind of Camellia nitidissima oils volatile ingredient detection method, have detect accurate, highly sensitive, selective adsorption is effective and the feature of long service life.
Content of the present invention is:
A kind of Camellia nitidissima oils volatile ingredient detection method, comprises Solid-Phase Extraction absorption-gas chromatography-mass spectrography and detects, and described Solid-Phase Extraction is the extraction of head space stirring rod solid phase adsorption, and described stirring rod scribbles based on two dimension or three-dimensional graphene-polymer coating.
By selecting Graphene as the coating material of stirring rod, mechanical property, the quality that can make full use of the excellence that Graphene has are light, specific surface area is large, Young modulus and the feature such as fracture strength is large, its machinery, mechanics, chemistry, electric property can be utilized again excellent, and the advantage that raw material is easy to get.Therefore, adopt Graphene class nano material to substitute and traditional be applied in the coating materials such as the perfluorinated resin of stirring rod solid phase extraction techniques, the theoretical specific surface area that can play Graphene is the advantage of 2630 m2/g, effectively increases stirring rod Solid-Phase Extraction coating super large specific surface.Meanwhile, there is stronger π-π between graphene-polymer coating material and oiliness volatile ingredient and interact, thus to such material in Camellia nitidissima, there is good selective extraction adsorption effect.Due to graphene-polymer coating machine excellent performance, make above-mentioned material outstanding in High Rotation Speed extraction wearing quality, young modulus of material and fracture strength greatly, can make stirring rod greatly extend serviceable life, thus greatly be conducive to the reappearance of Camellia nitidissima oiliness volatile ingredient testing result.By adopting headspace absorption extraction, effectively can avoid the error caused at sample feeding, improving the accuracy of Solid-Phase Extraction, ensure the accuracy of testing result further.
Further, the material of described graphene-polymer coating comprises Graphene and Graphene is material modified, and described Graphene is material modified comprises graphene oxide, Graphene-polyethylene glycol dimethacrylate, graphene-polypyrrole, Graphene-poly-methyltrimethoxy silane and Graphene class nano material.
Further, the material of described graphene-polymer coating is that the acticarbon prepared with renewable resource carbonization is synthesized by modified Hummers method and reversible addion-fragmentation chain transfer polymerization.
Further, described graphene-polymer coating is nano coating.Single-layer graphene often only has 0.7-1.2nm thick, multi-layer graphene-polymer coating also only has several nanometer thickness, materials theory specific surface area is 2630 m2/g, actual specific surface 400-800m2/g, thus can obtain higher extraction quantity, lower detection limit and better reappearance based on the solid phase stirring rod extraction absorbing process of Graphene, can realize detecting highly sensitive, the wide region of the medium oil volatile ingredient of Camellia nitidissima and good reproduction.
Further, the acticarbon prepared of described renewable resource carbonization raw material comprise straw, bagasse and cornstalk.
Further, described Camellia nitidissima oiliness volatile ingredient comes from the blade of Camellia nitidissima, fruit, fruit stone, pollen, petal and/or pistil.
Further, described oiliness volatile ingredient comprises arbricolin, 1,2-epoxy octadecane, 1,2-Disparmone, irisone, phytol, linoleic acid, methyl linoleate and ethyl linoleate.
Further, described organophosphorous pesticides-mass spectrometry is detected as selective enumeration method.
The invention has the beneficial effects as follows:
The first, detecting accurately, by selecting Graphene as stirring rod coating material, adopting selective adsorption to replace competitive adsorption, adopt the extraction of head space stirring rod solid phase adsorption to replace directly stirring extraction, effectively improve the order of accuarcy detected;
The second, highly sensitive, grapheme material is nano level layer material, can enlarge markedly adsorption surface area, reduces the thickness of coating, significantly improves the sensitivity of detection;
Three, selective adsorption is effective, and the selective adsorption of grapheme material is based on π-pi-conjugated key effect, and selectivity is strong, good separating effect;
Four, long service life, the mechanical property of grapheme material, excellent in mechanical performance, abrasive resistance is strong, can extend the serviceable life of stirring rod;
Five, maintenance cost is low, directly carries out selective adsorption, reduces conventional contention and adsorbs loaded down with trivial details separating step, do not have separation costs, greatly save the testing cost of routine use and maintenance.
Embodiment
In order to understand content of the present invention further, be specifically described with regard to summary of the invention and specific embodiment below:
A kind of Camellia nitidissima oils volatile ingredient detection method, comprise Solid-Phase Extraction absorption-gas chromatography-mass spectrography and detect, described stirring rod scribbles based on two dimension or three-dimensional graphene-polymer coating.The material of described graphene-polymer coating comprises Graphene and Graphene is material modified, and described Graphene is material modified comprises graphene oxide, Graphene-polyethylene glycol dimethacrylate, graphene-polypyrrole, Graphene-poly-methyltrimethoxy silane and Graphene class nano material.Described graphene-polymer coating is nano coating.
In the concrete preparation of graphene-polymer coating material, can carry out as follows:
The first step, renewable resource carbonization is utilized to prepare acticarbon: to select renewable resource to comprise straw, bagasse and cornstalk, take straw dry after preferably cleaning, bagasse or cornstalk, segment is pulverized, cross 30 mesh sieves, put into porcelain crucible, add substance withdrawl syndrome be the liquor zinci chloridi of 0.05 mol/L as activator, stir and evenly mix, the feed liquid of mixing at room temperature flooded 12 h.Subsequently the feed liquid of having flooded is put into muffle furnace, be that 10 DEG C/min rises to 900 DEG C with heating rate from room temperature, after held for some time, the sample activated is taken out from muffle furnace, immediately sample is poured in certain density aqueous hydrochloric acid solution, then sample to be washed with water to pH value be 7.Again the sample washed is put into electric heating convection oven, dry 4 h for 110 DEG C, in exsiccator, leave standstill cooling.Finally sample is pulverized 300 mesh sieves, namely obtain straw source activity charcoal crude product.Above-mentioned crude product adopts the Cellu.sep bag filter of specification 6000-8000, is dialyse in the deionized water of 7.38 about one week, namely obtains activated charcoal pure sample after vacuum drying at pH.
Second step, modified Hummers legal system are for graphene oxide: the activated charcoal that the first step is obtained sieves, sieve mesh is 300 orders, take and join in the potpourri of dense H2SO4, K2S2O8 and P2O5, heat above-mentioned mixed system to 80 DEG C, keep this temperature, magnetic agitation 5 hours.Cooling reaction system is to room temperature subsequently, by potpourri impouring 500mL deionized water, is filtered by above-mentioned standing thing after hold over night through 0.2 micron membrane filter, and washing is also dried naturally, obtains pre-oxidation graphite.The graphite of this pre-oxidation is joined in the dense H2SO4 of the 120ml of 0 DEG C, subsequently, slowly add KMnO4, and control temperature of reaction 20 DEG C of stirrings.Potassium permanganate finishes, and controls reaction system and stirs 4 hours at 35 DEG C, subsequently, add deionized water, and by peripheral ice bath control temperature below 50 DEG C.Stir after 1.5 hours, then add deionized water, after half an hour, dropwise instill the H2O2 of 30%, reaction system changes brown color into by brown rapidly.Removing stirring apparatus, filter this pale brown potpourri, is that the HCl washing of 1:10 is to remove metallic ion by volume ratio, use deionized water cyclic washing more subsequently, obtain brown solid, after drying at room temperature, above-mentioned brown solid is made the aqueous dispersions that mass concentration is 0.5%, continuous dialysis one week, finally filters, washing, again ultrasonic 1 hour is disperseed, filter, 60 DEG C of vacuum drying 24 hours, can prepare graphene oxide nanometer sheet.Above-mentioned graphene oxide nanometer sheet be again scattered in water, add appropriate hydrazine hydrate after ultrasonic 30 minutes, 100 DEG C of backflows 24 hours, filter, 60 DEG C of vacuum drying 24 hours, can prepare graphene oxide.
The preparation of the 3rd step, graphene-polymer: activation interpolation pipe.Accurately measure the ethylene glycol dimethacrylate of certain mass, Macrogol 6000, dimethyl formamide azoisobutyronitrile, ultrasonic vortex is to the solution obtaining clarifying.Graphene is added above-mentioned solution, and make its concentration be 1.0 mg/mL, then in recirculated water, namely ultrasonic 30 min obtain finely dispersed solution, get that above-mentioned pre-polymerization liquid is some to be poured in 0.6 mL centrifuge tube, insert interpolation pipe, discharge the bubble in solution.After its upper end is sealed with sealing compound and polytetrafluoroethylraw raw material band successively, can react in micro-wave oven, microwave reaction terminates rear Medical forceps and carefully cated for bonding stirring rod is taken out, be methanol/water solution and acetone coating cleaning on 60 DEG C of shaking tables of 1:1 successively by volume ratio, be stored in three water for subsequent use after coating cleaning.
The operation steps of described extraction is: pluck fresh golden flower prophyll in spring, adopts electronic scale weighing; The fresh golden flower prophyll in spring plucked is screened, selects the freshest and the tenderest, optimum blade, remove second-rate blade; The golden flower prophyll raw material optimized must meet the Pharmacopoeia of the People's Republic of China (version in 2010) requirement, and nothing is gone mouldy, free from extraneous odour, inclusion-free; To optimize Camellia nitidissima prophyll clean after, with medicinal herb grinder pulverize, by pulverize after Camellia nitidissima raw material; Get the blade of the Camellia nitidissima after a certain amount of pulverizing, fruit, fruit stone, pollen, petal and/or pistil, cross 120 mesh sieves, the powder after sieving is placed in ml headspace bottle; Then the stainless steel hook of non-activity is adopted to be butchered by Camellia nitidissima powder in the stirring rod of porous graphene-polymer coating, stirring rod is placed in bottle apart from bottom about 2/3 place, finally with teflon rubber cushion bottle cap sealing lid, ml headspace bottle is sealed, (adopt bottom electrical heating mantle heats) at 60 DEG C of temperature and extract 40 minutes.
Detect at the organophosphorous pesticides-mass spectrometry being applied in the detection of Camellia nitidissima oiliness volatile ingredient, described organophosphorous pesticides-mass spectrometry is detected as selective enumeration method, and described Camellia nitidissima oiliness volatile ingredient comes from the blade of Camellia nitidissima, fruit, fruit stone, pollen, petal and/or pistil.Described oiliness volatile ingredient comprises arbricolin, 1,2-epoxy octadecane, 1,2-Disparmone, irisone, phytol, linoleic acid, methyl linoleate and ethyl linoleate.
After extraction, the stirring rod based on porous graphene-polymer coating extracted is put in sample sleeve pipe, finally sample sleeve pipe is put into, in Agilent CDS5200 cracker, carry out thermal desorption.Instrument: the instrument U.S. Agilent6890-5973 type gas chromatography coupling instrument selected, setting heating schedule is: be warmed up to 85 DEG C from room temperature 25 DEG C with 10 DEG C/min, be warmed up to 180 DEG C with 10 DEG C/min again, be finally warmed up to 250 DEG C with 5 DEG C/min and keep 5 minutes; Setting injection port and detector temperature are 250 DEG C; Split ratio is 30:1; Post flow: 1 mL/min, carrier gas is high pure nitrogen; Mass Spectrometry Conditions is " high-purity helium, EI ion gun, ionization voltage 70eV; Ion source temperature is 250 DEG C, transmission line temperature: 250 DEG C; Sweep limit: 40-500 amu.Finally testing result mass spectrum java standard library Nist spectrogram storehouse is contrasted.
The above, be only preferred embodiment of the present invention, not does any pro forma restriction to the present invention; The those of ordinary skill of all industry all can shown in by specification and the above and implement the present invention swimmingly; But all those skilled in the art are not departing within the scope of technical solution of the present invention, disclosed above technology contents can be utilized and make a little change, modify with differentiation equivalent variations, be Equivalent embodiments of the present invention; Meanwhile, all according to substantial technological of the present invention to the change of any equivalent variations that above embodiment is done, modify and differentiation etc., within the protection domain all still belonging to technical scheme of the present invention.
Claims (8)
1. a Camellia nitidissima oils volatile ingredient detection method, comprise organophosphorous pesticides-mass spectrometry to detect, it is characterized in that: described Solid-Phase Extraction is the extraction of head space stirring rod solid phase adsorption, and described stirring rod scribbles based on two dimension or three-dimensional graphene-polymer coating.
2. Camellia nitidissima oils volatile ingredient detection method according to claim 1, it is characterized in that: the material of described graphene-polymer coating comprises Graphene and Graphene is material modified, described Graphene is material modified comprises graphene oxide, Graphene-polyethylene glycol dimethacrylate, graphene-polypyrrole, Graphene-poly-methyltrimethoxy silane and Graphene class nano material.
3. Camellia nitidissima oils volatile ingredient detection method according to claim 2, is characterized in that: the material of described graphene-polymer coating is that the acticarbon prepared with renewable resource carbonization is synthesized by modified Hummers method and reversible addion-fragmentation chain transfer polymerization.
4. Camellia nitidissima oils volatile ingredient detection method according to claim 3, is characterized in that: described graphene-polymer coating is nano coating.
5. Camellia nitidissima oils volatile ingredient detection method according to claim 4, is characterized in that: the raw material of acticarbon prepared by described renewable resource carbonization comprises straw, bagasse and cornstalk.
6. ask described Camellia nitidissima oils volatile ingredient detection method according to claim 5, it is characterized in that: described oiliness volatile ingredient comprises arbricolin, 1,2-epoxy octadecane, 1,2-Disparmone, irisone, phytol, linoleic acid, methyl linoleate and ethyl linoleate.
7. Camellia nitidissima oils volatile ingredient detection method according to claim 6, is characterized in that: described Camellia nitidissima oiliness volatile ingredient comes from the blade of Camellia nitidissima, fruit, fruit stone, pollen, petal and/or pistil.
8. Camellia nitidissima oils volatile ingredient detection method according to claim 7, is characterized in that: described organophosphorous pesticides-mass spectrometry is detected as selective enumeration method.
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Effective date of registration: 20220309 Address after: 518109 No. 1216, 12 / F, Hongyu building, Longguan Road, Shitouling, Yucui community, Longhua street, Longhua District, Shenzhen, Guangdong Patentee after: Shenzhen Xihan health Co.,Ltd. Address before: 310000 No. 548 binwen Road, Puyan street, Binjiang District, Hangzhou City, Zhejiang Province Patentee before: Cheng Jinsheng |
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