CN105037122B - A kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof - Google Patents
A kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof Download PDFInfo
- Publication number
- CN105037122B CN105037122B CN201510373903.9A CN201510373903A CN105037122B CN 105037122 B CN105037122 B CN 105037122B CN 201510373903 A CN201510373903 A CN 201510373903A CN 105037122 B CN105037122 B CN 105037122B
- Authority
- CN
- China
- Prior art keywords
- compound
- present
- acid
- solution
- yellow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/647—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring
- C07C49/653—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring polycyclic
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/80—Indicating pH value
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention provides a kind of compound extracting isolated from Exocarpium Juglandis Immaturus, and its acid structure is as follows:.The present invention also provides for the application in preparing acid-base indicator of this compound.The compound of the present invention, in aqueous in yellow transparent solution, shows faintly acid；When pH value 89, the secondary colour for yellow and pink colour is interval；In the aqueous solution of pH >=9, solution becomes pink colour clear solution；The highest color of pH value is the deepest, to aubergine clear solution.This compound i.e. can be as the pH indicator of instruction soda acid change.The compounds of this invention does not reacts with the water in air, oxygen and carbon dioxide, good stability；Sensitivity is 1 × 10‑5Mol/L, sensitivity is high.
Description
Technical field
The present invention relates to a kind of compound extracting isolated from Exocarpium Juglandis Immaturus.
Background technology
Semen Juglandis also known as Semen Juglandis, Juglandales (Juglandales), Juglandaceae (Juglandaceae), Juglans (Juglans L.),
Semen Juglandis (Juglans regia L.).Originate in North China, northwest, southwest, Central China, south China and East China.It is distributed in the Central Asia, west
Asia, South Asia and Europe.It is born in hillside and the hilly country of height above sea level 400-1800 rice, the common cultivation in China Plain and knob
Training, likes fertile moistening sandy loam, is common in the place that both sides, river valley, mountain area soil layer is deep.Kernel oil content is high, contains
Abundant nutrient substance, can eat raw, be a kind of nut useful to human body, have the effects such as strong brain；Also can extract oil edible；
Timber is solid, is good hardwood material.
Exocarpium Juglandis Immaturus refers to the green-skinned of the fruit of Semen Juglandis, i.e. peel, is a kind of Chinese medicine, is referred to as Exocarpium Juglandis Immaturum.Exist every year
The Semen Juglandis harvest season, substantial amounts of Exocarpium Juglandis Immaturus can be produced.Owing to Pericarpium Citri Reticulatae Viride alkalescence is stronger, it is impossible to edible, can not be directly as
Agro-farming fertilizer, can cause certain pollution if directly abandoning to environment.So using Exocarpium Juglandis Immaturus as research material, i.e. realizing
Twice laid, can expand new content in field of natural product chemistry the most again.
Acid-base reaction, is a modal class reaction, generally for determining reaction end, can introduce acid-base indicator and help really
Determine terminal.Acid-base indicator, is to utilize the specific color reaction of some materials, when solution ph changes, and itself knot
Structure changes and causes color to change.It is class organic monoacid or an organic weak base, and they can become in the solution in partial ionization
The ion of indicator and hydrion (or hydroxide ion), and due to the change in structure, their molecule and ion tool
There is different colors, thus in the solution that pH is different, present different colors.
Containing plant pigment in the flower of some plant, stem, leaf, root and fruit in nature, therefore, it can use certain method
These plant pigment are separated, can be used as acid-base indicator and apply.The most common litmus reagent, it is simply that from stone
Stamen lichen extracts.Additionally, in the plants such as sun lotus, Pericarpium Vitis viniferae, purple cabbage, Calyx Hibisci Sabdariffae, all there are and can refer to
Show the pigment of Acidity of Aikalinity.
Summary of the invention
The invention provides a kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof.
The present invention provides a kind of noval chemical compound, and its acid structure is as follows:
The present invention also provides for the application in preparing acid-base indicator of the above-mentioned noval chemical compound.
Third object of the present invention is to provide a kind of acid-base indicator, and it is the noval chemical compound described in claim 1.
The present invention extracts isolated one noval chemical compound: 4,8-dimethylenenaphthalene-1,5 (4 from Exocarpium Juglandis Immaturus
H, 8H)-dione, Chinese is: 4,8-bis-methyl naphthalene alkene-1,5-diketone, is called for short NEO-Z.Owing to this compound is tied
Structure symmetry is strong, easily distils, volatile.Therefore the applicant utilizes this feature, it is vaporized altogether with water, decompression distillation,
Rapidly compound is separated.Qualification result shows, this compound is first time isolated.Pass through1H-NMR with
And the result of HMBC can deduce the acid structure of compound and have the resonant structure of naphthalenone and naphthols.It indicates acid-base value
The phenomenon of the color reaction of change is: acid is yellow solution, and alkali formula is pink colour or lilac solution.By its color reaction
Understanding, its alkali formula structure is bigger than the conjugated degree of acid structure；But owing to alkali formula structure is not sufficiently stable, the most for a long time
Put its alkali formula structure can change, be difficult to characterize alkali formula structure.What the present invention was given is acid structure.
Accompanying drawing explanation
Accompanying drawing is for providing a further understanding of the present invention, and constitutes a part for description, with embodiments of the invention
It is used for together explaining the present invention, is not intended that limitation of the present invention.In the accompanying drawings:
Fig. 1 is the infrared spectrogram of the compound of the present invention；
Fig. 2 is the mass spectrum of the compound of the present invention；
Fig. 3 is the ultraviolet-visible light spectrogram of the compound of the present invention；
Fig. 4 is the compound of the present invention1H-NMR schemes；
Fig. 5 is the compound of the present invention13CNMR schemes；
Fig. 6 is the HMBC figure of the compound of the present invention；
Fig. 7 is the HMQC figure of the compound of the present invention；
Fig. 8 is yellow needle-like crystals compound monocrystal diffraction patterns；
Fig. 9 is Gaussian quantum calculation model；
Figure 10 is the compound of present invention ultraviolet-visible light spectrogram in different pH value.
Detailed description of the invention
Below example facilitates a better understanding of the present invention, but does not limit the present invention.Experimental technique in following embodiment,
If no special instructions, it is conventional method.Test material used in following embodiment, if no special instructions, is from often
Rule biochemical reagents shop is commercially available.
Instrument and reagent are as follows:
Germany's Heidolph Rotary Evaporators；Germany's Greiffenberger Antriebstechnik vacuum pump；Shanghai
EYELA cooling water circulating device, model C A-1111；Column chromatography silica gel (200-300mesh) and tlc silica gel
(GF254) it is Haiyang Chemical Plant, Qingdao to produce；Petroleum ether, chloroform, ethyl acetate are industry and heavily steam；Thin plate detects
Using 254nm uviol lamp, sulphuric acid-ethanol (5%) submergence is heated.
The preparation method of the compound of the present invention is as follows:
(1) weighing 1kg Exocarpium Juglandis Immaturus, put in water, Exocarpium Juglandis Immaturus is 1:2-1:10 with the weight ratio of water；
(2) soak extraction 20-50 minute under room temperature environment；Immersion can be soaked, so by ultrasound wave or microwave-assisted
Soak time can more common soak time short.
(3) aqueous phase after extraction is moved in round-bottomed flask, be placed on Rotary Evaporators, be evaporated under reduced pressure to water in round-bottomed flask
Solution is almost colourless；During decompression distillation, controlling bath temperature is 50 DEG C-70 DEG C, and vacuum is 0.06-0.08MPa.Now,
Yellow transparent aqueous solution in receiving bottle, is the aqueous solution containing the compounds of this invention.
(4) aqueous solution in receiving bottle is taken out, add petroleum ether, be repeated that to be extracted to aqueous phase colourless, take petroleum ether phase, abandon
Remove aqueous phase.
(5) by the petroleum ether phase of extraction gained, it is placed on Rotary Evaporators, under conditions of bath temperature is less than 35 DEG C,
Decompression distillation, obtains yellow crude extract, weighs about 500mg.
(6) mix with 0.5g silica gel (200-300 mesh) after crude extract being dissolved with a small amount of solvent, then with the identical silicon of 50g
Glue carries out filling post, with petroleum ether: chloroform (v:v) 2:1-1:2 carries out eluting, obtains the component of yellow substance.Silica gel is also
Can substitute with magnesium oxide or aluminium oxide.
Below in conjunction with embodiment, the extracting method of the compounds of this invention is described in detail.
Embodiment 1
(1) fresh for 1kg Exocarpium Juglandis Immaturus is put in the water of 2L；
(2) under room temperature environment, 30min is soaked；
(3) aqueous phase after extraction is moved in round-bottomed flask, be placed on Rotary Evaporators decompression distillation to water in round-bottomed flask
Solution is almost colourless, used time 30min；During decompression distillation, controlling bath temperature is 60 DEG C, and vacuum is 0.07MPa.This
Time, the yellow transparent aqueous solution in receiving bottle, it is the aqueous solution containing the compounds of this invention.
(4) aqueous solution in receiving bottle is taken out, add 1L petroleum ether in three times and extract, take petroleum ether phase, discard water
Phase.
(5) by the petroleum ether phase of extraction gained, it is placed on Rotary Evaporators, under conditions of bath temperature is less than 30 DEG C,
Decompression distillation, obtains yellow crude extract, weighs about 500mg；Vacuum does not has specific requirement herein, as long as can distilling off solvent
?；
(6) crude extract (as long as the solvent of this compound can be dissolved, can be used with a small amount of solvent；Such as
Solvent is petroleum ether) dissolve after mix with 0.5g silica gel (200-300 mesh), then with the identical silica gel of 50g carry out fill post, use stone
Oil ether: chloroform (v:v) 1:1 carries out eluting, obtains yellow substance, and decompression i.e. obtains the present invention extracted after solvent is distilled off
Compound, crystal weighs about 20mg；Distillation condition is: bath temperature is less than 30 DEG C, and vacuum does not has specific requirement,
As long as can distilling off solvent.
Embodiment 2
(1) fresh for 200g Exocarpium Juglandis Immaturus is added in the water of 1L；
(2) under room temperature environment, 20min is soaked；
(3) aqueous phase after extraction is moved in round-bottomed flask, be placed on Rotary Evaporators, 20min is evaporated under reduced pressure, now
In round-bottomed flask, aqueous solution is almost colourless；During decompression distillation, controlling bath temperature is 70 DEG C, and vacuum is 0.065MPa.
Now, the yellow transparent aqueous solution in receiving bottle, it is the aqueous solution containing the compounds of this invention.
(4) aqueous solution in receiving bottle is taken out, add 0.5L petroleum ether in three times and extract, take petroleum ether phase, discard
Aqueous phase.
(5) by the petroleum ether phase of extraction gained, it is placed on Rotary Evaporators, under conditions of bath temperature is less than 25 DEG C,
Decompression distillation, obtains yellow crude extract, weighs about 110mg；Vacuum does not has specific requirement herein, as long as can distilling off solvent
?；
(6) crude extract (as long as the solvent of this compound can be dissolved, can be used with a small amount of solvent；Such as
Solvent is petroleum ether) dissolve after mix with 0.1g silica gel (200-300 mesh), then with the identical silica gel of 20g carry out fill post, use stone
Oil ether: chloroform (v:v) 1:2 carries out eluting, obtains yellow substance, and decompression i.e. obtains the present invention extracted after solvent is distilled off
Compound, crystal weighs about 8mg；Distillation condition is: bath temperature is less than 30 DEG C, and vacuum does not has specific requirement, only
Can distilling off solvent.
Embodiment 3
(1) fresh for 1kg Exocarpium Juglandis Immaturus is put in the water of 10L；
(2) under room temperature environment, 50min is soaked；
(3) aqueous phase after extraction is moved in round-bottomed flask, be placed on Rotary Evaporators decompression distillation to water in round-bottomed flask
Solution is almost colourless, used time 30min；During decompression distillation, controlling bath temperature is 50 DEG C, and vacuum is 0.08MPa.This
Time, the yellow transparent aqueous solution in receiving bottle, it is the aqueous solution containing the compounds of this invention.
(4) aqueous solution in receiving bottle is taken out, add 1L petroleum ether in three times and extract, take petroleum ether phase, discard water
Phase.
(5) by the petroleum ether phase of extraction gained, it is placed on Rotary Evaporators, under conditions of bath temperature is less than 30 DEG C,
Decompression distillation, obtains yellow crude extract, weighs about 1150mg；Vacuum does not has specific requirement herein, as long as can distill out molten
Agent；
(6) crude extract (as long as the solvent of this compound can be dissolved, can be used with a small amount of solvent；Such as
Solvent is petroleum ether) dissolve after mix with 0.5g magnesium oxide, then with the identical magnesium oxide of 50g carry out fill post, with petroleum ether: chloroform
(v:v) 2:1 carries out eluting, obtains yellow substance, and decompression i.e. obtains the compound of the present invention extracted after solvent is distilled off,
Crystal weighs about 50mg；Distillation condition is: bath temperature is less than 30 DEG C, and vacuum does not has specific requirement, as long as can distill
Go out solvent.
Embodiment 4
1, Spectrum Analysis result
Embodiment 1 and 2 is extracted the compound obtained and is identified by the applicant, is 4,8-dimethylenenaphth
Alene-1,5 (4H, 8H)-dione, Chinese is: 4,8-bis-methyl naphthalene alkene-1,5-diketone.Its structure is as follows.
Concrete qualification process is as follows:
(1) this compound is yellow needle-like crystals, under the uviol lamp of 254nm wavelength, fluorescence detected, sulphuric acid-
Ethanol (5%, v:v) colour developing is yellow.
(2) the applicant combine Modern spectroscopy means (IR, MS,1H-NMR,13C-NMR, HMBC, HMQC, ultraviolet-can
Seeing spectrum, X-ray single crystal diffraction is analyzed) determine its structure.Its nuclear magnetic resonance, NMR, infrared, ultraviolet and mass spectrogram
It is analyzed as follows:
1H-NMR spectrum shows this compound, at displacement δH=11.9 unimodal identical with the result of Gaussian quantum calculation,
It is the peak of the hydrogen of hydrogen bond.
13C-NMR spectrum shows this compound, has 10 C, wherein 5 quaternary carbons.
Can analyze from HMBC spectrogram and HMQC spectrogram, this compound is at CDCl3In may have tautomer.
Infrared spectrum shows, the broad peak of wave number 3435 is intramolecular hydrogen bond, and 3076 are probably intermolecular hydrogen bond, and 1643 are
Carbonyl peak, 1290 is the peak of the tertiary alcohol.Molecule can be deduced and there is the phenomenon that carbonyl converts to enol form.
Ultraviolet-visible spectrum shows, this compound has absworption peak at 230nm-280nm and 360nm-500nm.
Determine that compound is Fig. 7 structure according to single crystal diffraction.
2, the explanation of Gaussian quantum calculation result
By said structure, Gaussian 09 quantum chemistry software is used to calculate.Result of calculation shows,1H-NMR
In spectrum, the chemical shift δ of these No. 20 and No. 21 hydrogen atoms of compoundH=10.77, this explains at the 20 of methylene
Number between hydrogen atom and No. 12 oxygen atoms, there is hydrogen bond；In like manner, there is also hydrogen between No. 21 hydrogen atoms and No. 14 oxygen atoms
Key.Fig. 8 is Gaussian quantum calculation model.
The character of the compound of embodiment 5 present invention and application
Because the compound of the present invention is to be in the news out for the first time, the parameter relevant in order to improve its physicochemical property, the most also
In order to probe into the character of this compound further, its physicochemical property is further studied by the applicant.
The molecular weight of the compounds of this invention is 184, [M+H]+Molecular weight be 185.059, can be dissolved in chloroform, petroleum ether,
Acetone, methanol and water equal solvent；The compound of the present invention, in aqueous in yellow transparent solution, shows faintly acid；?
During pH value 8-9, the secondary colour for yellow and pink colour is interval；In the aqueous solution of pH >=9, it is transparent molten that solution becomes pink colour
Liquid；The highest color of pH value is the deepest, to aubergine clear solution.This compound i.e. can refer to as the pH of instruction soda acid change
Show agent.
The common method measuring acid-base indicator pK value, has spectrophotometry method and potentiometric titration.The application adopts
With the acid dissociation constant pKa of spectrophotometry compound, result obtains the theoretical color transition point of the compound of the present invention and is
PH=8.87.8.87 refer to yellow becomes the color transition point of pink colour, and pink colour causes to aubergine due to color burn, not
It it is second time variable color.
By experiment, find that the concentration at this compound is 1 × 10-5During mol/L, close to the limit of human eye observation；The present invention
Compound does not reacts with the water in air, oxygen and carbon dioxide, good stability.
Finally it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, to the greatest extent
The present invention has been described in detail by pipe with reference to previous embodiment, and for a person skilled in the art, it is the most permissible
Technical scheme described in foregoing embodiments is modified, or wherein portion of techniques feature is carried out equivalent.All
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included in the present invention's
Within protection domain.
Claims (3)
1. a compound, its structural formula is:
。
2. the application in preparing acid-base indicator of the compound described in claim 1.
3. an acid-base indicator, it is the compound described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510373903.9A CN105037122B (en) | 2015-06-30 | 2015-06-30 | A kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510373903.9A CN105037122B (en) | 2015-06-30 | 2015-06-30 | A kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105037122A CN105037122A (en) | 2015-11-11 |
| CN105037122B true CN105037122B (en) | 2016-11-30 |
Family
ID=54444171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510373903.9A Expired - Fee Related CN105037122B (en) | 2015-06-30 | 2015-06-30 | A kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105037122B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328114B (en) * | 2007-06-23 | 2010-09-15 | 中国科学院兰州化学物理研究所 | Method for extracting walnuts ketone from walnut green husk |
| CN104292092B (en) * | 2014-09-26 | 2016-05-25 | 浙江大学宁波理工学院 | Separation and purification 4 from hickory nut epicarp, the method for 8-DHT and 4,8-DHT application |
| CN104458740A (en) * | 2014-11-24 | 2015-03-25 | 苏州东辰林达检测技术有限公司 | Preparation method for carrot pigment acid-base detection indicator |
-
2015
- 2015-06-30 CN CN201510373903.9A patent/CN105037122B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105037122A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | Determination of metabolites by 1H NMR and GC: analysis for organic osmolytes in crude tissue extracts | |
| CN104897843B (en) | Method for measuring content of endogenous hormones of burgeons of tea tree | |
| CN109369344A (en) | A method of the separation and Extraction cannabidiol from industrial hemp plant | |
| Tan et al. | DES-Fe3O4 composite for rapid extraction of residual plant growth regulators in edible vegetable oil | |
| CN101206199A (en) | Sparklet testing method of soya-bean fatty acid | |
| CN105037122B (en) | A kind of compound extracting isolated from Exocarpium Juglandis Immaturus and application thereof | |
| CN107007585B (en) | Beans ascidian anti-oxidizing compounds and extracting method and purposes | |
| CN107759475A (en) | Dehydroabietylamine derivatives and its preparation method and application | |
| CN105037121B (en) | A kind of method extracting separation bis-methyl naphthalene alkene-1,5-diketone of 4,8-from Exocarpium Juglandis Immaturus | |
| Chen et al. | Characteristics of chemical components in the trunk xylem sap of pine trees by means of a centrifugation collection method | |
| CN103109813B (en) | 4-H-Celastrus angulatus original medicine and preparation method and quality detection method thereof | |
| MacLean et al. | Analytical method for thujaplicins | |
| Adam et al. | Headspace single‐drop microextraction of herbal essential oils | |
| Yao et al. | Hydrogen isotopic composition of plant leaf wax in response to soil moisture in an arid ecosystem of the northeast Qinghai-Tibetan Plateau, China | |
| CN104910125B (en) | Pest-resistant component separated from Glycosmis parviflora | |
| Angst et al. | Performance of base hydrolysis methods in extracting bound lipids from plant material, soils, and sediments | |
| CN104478687B (en) | The compounds and methods of extraction and isolation and application from shizandra berry | |
| CN106946830A (en) | The extraction separation of flavone compound and Histochemical localization method in seven color bamboo stalks | |
| CA2727891A1 (en) | Method for measuring total content of natural brassinosteroids using chromatography apparatus | |
| Mosleh et al. | Quality control of Rosa× damascena flowers from Layzangan of Fars province in Iran | |
| Rahman et al. | Chemical constituents of essential oil of petals and corolla tubes of Nyctanthes Arbor-Tristis Linn flower | |
| CN104833760A (en) | Method for using high-performance liquid chromatography to measure greenhouse tomato soil low-molecular-weight organic acids | |
| CN105116139A (en) | Enzyme linked immunosorbent assay kit for detecting atrazine residuals and preparation method thereof | |
| CN105628843A (en) | Solid-phase membrane extraction-gas chromatography electron capture detection method for eight pyrethroid pesticides in water body | |
| Schultz et al. | Measurements of phytol in estuarine suspended organic matter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161130 Termination date: 20180630 |