CN107576738A - A kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose - Google Patents
A kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose Download PDFInfo
- Publication number
- CN107576738A CN107576738A CN201710804492.3A CN201710804492A CN107576738A CN 107576738 A CN107576738 A CN 107576738A CN 201710804492 A CN201710804492 A CN 201710804492A CN 107576738 A CN107576738 A CN 107576738A
- Authority
- CN
- China
- Prior art keywords
- nano
- cellulose
- sample
- carboxyl
- content
- 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.)
- Pending
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to technical field of analysis and detection, the method for disclosing carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose.Nano-cellulose sample is diluted to water sample, cationic ion-exchange resin is then added and is ultrasonically treated, obtain prepare liquid；Reacted with the hydrochloric acid standard solution and sodium bicarbonate solution of a series of different volumes, caused carbon dioxide is detected with head space gas chromatography, and standard curve is obtained according to the corresponding relation of the added in molar amounts of resulting chromatographic peak area signal value and hydrochloric acid；Then gained prepare liquid is added in ml headspace bottle, head space gas chromatography detection is carried out according to standard curve identical method and Parameter Conditions, the chromatographic peak area signal value of sample is recorded, carboxyl-content in nano-cellulose sample is calculated according to standard curve.Inventive process avoids the serious gelation of nano-cellulose sample and the titration process of complexity, make measurement process quicker, measurement result is more accurate.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular in a kind of headspace gas chromatography detection nano-cellulose
The method of carboxyl-content.
Background technology
In the energy, today of resource scarcity, cellulose and its derived product due to cleaning, recyclability, Ke Yizuo
For the excellent substitute of fossil fuel, production, the various aspects of life have been applied to.Nano-cellulose exists as cellulose
A kind of form of hyperfine structure, many premium properties of cellulose are not only remained, and rely on its high load capability, well
Biocompatibility, degradability, turn into a kind of material of high added value, there is important application in terms of biological medicine.Mesh
Preceding research comparative maturity is base material using nano-cellulose as insoluble drug release material, controls medicine human recycle system's
Release.As a kind of function base, carboxyl has the function that important in nano-cellulose, on the one hand, carboxyl can improve nanometer
The reactivity of cellulose, on the other hand, the stability that nano-cellulose disperses in aqueous can be improved, can also be improved
Its absorption property.Therefore, invention one kind can be quick, the accurate method for detecting carboxyl-content in nano-cellulose, to nanofiber
The development of cellulosic material is significant.
At present, the detection of carboxyl-content is mainly conductometry in nano-cellulose.Nano-cellulose first has to use salt
Acid is pre-processed, it is therefore an objective to the carboxylic acid sodium in nano-cellulose is completely converted into the form of carboxylic acid, then uses sodium hydroxide
Titrated, and the change of titration process electrical conductivity is recorded with conductivity meter, the content of carboxyl is according to titration process electrical conductivity
Change curve can obtain.Subject matter existing for this method is that nano-cellulose suspension can be rolled into a ball in hydrochloric acid preprocessing process
Poly-, caking phenomenon, especially in the higher nano-cellulose suspension of carboxyl-content.Therefore, the Lower result of measurement can be made.
In order to solve the problems, such as to reunite in preprocessing process, lump, the excessive sodium hydroxide dispersion of nanofibers element of back titration is outstanding
Supernatant liquid, then carry out back titration with the hydrochloric acid of standard.However, too high PH can increase the degree of carboxyl dissociation, make nanofiber
Plain suspension pension gelation, titration process become more difficult.Although the influence that gelation is brought can be weakened by diluting,
It is the sensitivity that can reduce detection.Therefore, it is necessary to establish carboxyl-content in a kind of fast and accurately measure nano-cellulose
Method.
The content of the invention
In place of shortcoming and defect existing for above prior art, it is an object of the invention to provide a kind of headspace gas
The method of carboxyl-content in chromatography detection nano-cellulose.
The object of the invention is achieved through the following technical solutions：
The method of carboxyl-content, comprises the following steps in a kind of headspace gas chromatography detection nano-cellulose：
(1) sample pretreatment：Nano-cellulose sample is diluted to water sample, then by the filter equipped with cationic ion-exchange resin
Bag is immersed in above-mentioned water sample, and the filter bag equipped with cationic ion-exchange resin is taken out after supersound process, obtains nano-cellulose sample
Prepare liquid；
(2) foundation of standard curve：A series of hydrochloric acid standard solution of different volumes is added in ml headspace bottle, then noted
Enter sodium bicarbonate solution, be sufficiently mixed sodium bicarbonate solution and hydrochloric acid standard solution after sealing, be subsequently placed in headspace gas color
In the head-space sampler of spectrometer, head-space sampler operating condition and gas chromatograph operating condition are set, carry out headspace gas
Chromatography detects, according to pair of the added in molar amounts of hydrochloric acid in resulting chromatographic peak area signal value and hydrochloric acid standard solution
It should be related to obtain a standard curve；
(3) detection of sample carboxyl-content：Step (1) is obtained into nano-cellulose sample prepare liquid and is added to ml headspace bottle
In, head space gas chromatography detection is carried out according to step (2) identical method and Parameter Conditions, records the chromatographic peak of sample
Area of signal value, carboxyl-content in nano-cellulose sample is then calculated according to the standard curve of step (2).
Preferably, described in step (1) by nano-cellulose sample be diluted to water sample refer to nano-cellulose sample is dilute
It is 0.1%~0.2% to release to solid content.So that resins exchange pretreatment is smoothed out.
The cationic ion-exchange resin is preferably 001x7 type cationic ion-exchange resins.
Preferably, the time being ultrasonically treated described in step (1) is 30~60min.
Preferably, the concentration of hydrochloric acid standard solution described in step (2) is 0.05~1mol/L, and hydrochloric acid standard solution adds
It is 10~1000 μ L to enter amount；The concentration of the sodium bicarbonate solution is 0.01~0.1mol/L.
Preferably, head-space sampler operating condition is described in step (2)：40~80 DEG C of equilibrium temperature, during Sample equilibration
Between 4~40min, carrier gas 10~20s of equilibration time in ml headspace bottle, pipeline 10~20s of inflationtime, pipeline equilibration time 1~
10s, 10~20s of loop balance time.
Preferably, gas chromatograph operating condition is described in step (2)：Chromatographic column temperature is 50~150 DEG C, nitrogen conduct
Carrier gas, nitrogen flow are 2.0~6.0mL/min；150~250 DEG C of TCD detector temperatures.
Relative to prior art, method of the invention has the following advantages that and beneficial effect：
(1) present invention is pre-processed using cationic ion-exchange resin to nano-cellulose sample, pre- compared to existing hydrochloric acid
The mode of processing, the serious gelation of nano-cellulose sample is avoided, makes measurement process quicker, measurement result is more accurate
Really.
(2) method of the invention need not carry out cumbersome titration process to sample, greatly shorten the time of detection.
Brief description of the drawings
Fig. 1 be hydrochloric acid in chromatographic peak area signal value and hydrochloric acid standard solution in the embodiment of the present invention added in molar amounts it
Between corresponding relation canonical plotting.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Instrument and equipment used in following examples and reagent：Headspace autosampler：Thermo HS TriPlus
300, US；Gas chromatograph：Agilent GC 7890A, US；Ultrasound Instrument：KQ2200B；Liquid-transfering gun：100μL、1000μL、5mL
Each one；100 μ L syringes；20mL ml headspace bottles are some.
Sodium acid carbonate (analysis is pure, >=99.5%)；Hydrochloric acid (content 36%-38%)；Deionized water.
Embodiment
(1) sample pretreatment：Nano-cellulose sample is diluted to solid content 0.1~0.2%, takes the sample after dilution
50g is in beaker；Then 001x7 type cationic ion-exchange resins 1g is taken in filter bag, nanometer filter bag being put into after filling dilution
In the beaker of cellulose sample.Above-mentioned sample is put into ultrasonoscope, 30min is ultrasonically treated, then takes out equipped with resin
Filter bag, obtain nano-cellulose sample prepare liquid.
(2) standard curve is established：By the hydrochloric acid standard solution (0.1076mol/ of a series of different amounts of (20~200 μ L)
L) it is added in ml headspace bottle, then the glass tube of one end open is put into ml headspace bottle, 1mL is injected into glass tube
0.06mol/L sodium bicarbonate solution, then covers ml headspace bottle, and teetertottering makes sodium bicarbonate solution and hydrochloric acid standard solution
It is sufficiently mixed, is subsequently placed in the head-space sampler of headspace gas chromatography instrument, head-space sampler operating condition and gas phase is set
Chromatograph operating condition (head-space sampler operating condition：60 DEG C, Sample equilibration time 10min of equilibrium temperature, in headspace sample bottle
Carrier gas equilibration time 12s, pipeline inflationtime 12s, pipeline equilibration time 3s, loop balance time 12s；Gas chromatograph operates
Condition：Chromatographic column temperature is 105 DEG C, and nitrogen (flow 3.1mL/min) is used as carrier gas；200 DEG C of TCD detector temperatures), then carry out
Head space gas chromatography detects, according in resulting chromatographic peak area signal value and hydrochloric acid standard solution hydrochloric acid mole plus
Enter the corresponding relation between amount and obtain a standard curve, as shown in Figure 1.Relationship below is obtained by standard curve：
A=-0.442 (± 0.331)+2057 (± 32.65) n (n=7, R2=0.999) (1)
In formula, A is the peak area signal value of the carbon dioxide of gas Chromatographic Determination, and n is the molal quantity of the hydrochloric acid added
(mmol)。
(3) sample detection：Step (1) is obtained into nano-cellulose sample prepare liquid 8g to be added in ml headspace bottle, according to
Step (2) identical method and Parameter Conditions carry out head space gas chromatography detection, record the chromatographic peak area signal of sample
It is worth (21.5).
(4) result calculates：The carboxyl-content Q of sample is recorded the chromatographic peak area signal value readout sign of sample by step (3)
Corresponding abscissa on directrix curve, then divided by the absolute dry mass of nano-cellulose sample can obtain.Its calculation formula is as follows：
In formula Q be sample carboxyl-content, mmol/g；N is as the carboxyl amount of the sample obtained by standard curve, mmol；M is
The quality of samples taken, g；W% is the solid content of sample.
(5) the quantitative Monitoring lower-cut of method is calculated by below equation：
In formula：A and Δ a is respectively the intercept of standard curve and the error of intercept；S is the slope of standard curve.
The quantitative Monitoring lower-cut (LOQ) that this method can be calculated by formula (1) and formula (3) is 0.1mmol/g.
Using carboxylic in headspace gas chromatography (HS-GC methods) measure tetra- nano-cellulose samples of A, B, C, D of the present invention
The content of base, and compared with traditional conductometry, both relative deviations (RD) are calculated, its data is shown in Table 1.
Table 1
As shown in Table 1, the carboxyl-content in the nano-cellulose measured by the headspace gas chromatography of the present invention is higher than
Conductometry, this is due to the phenomenon that conductometry has gelation in detection process, causes measurement result relatively low.Top
Gas chromatography can be very good solve the problem, quickly measure the carboxyl-content in nano-cellulose sample, greatly
Improve the detection efficiency of experimenter.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. a kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose, it is characterised in that including following step
Suddenly：
(1) sample pretreatment：Nano-cellulose sample is diluted to water sample, then soaked the filter bag equipped with cationic ion-exchange resin
Enter into above-mentioned water sample, the filter bag equipped with cationic ion-exchange resin is taken out after supersound process, it is to be measured to obtain nano-cellulose sample
Liquid；
(2) foundation of standard curve：A series of hydrochloric acid standard solution of different volumes is added in ml headspace bottle, is then injected into carbon
Sodium bicarbonate solution and hydrochloric acid standard solution, are sufficiently mixed by sour hydrogen sodium solution after sealing, are subsequently placed in headspace gas chromatography instrument
Head-space sampler in, head-space sampler operating condition and gas chromatograph operating condition are set, carry out headspace gas chromatography
Analysis detection, the corresponding pass according to resulting chromatographic peak area signal value with the added in molar amounts of hydrochloric acid in hydrochloric acid standard solution
System obtains a standard curve；
(3) detection of sample carboxyl-content：Step (1) is obtained into nano-cellulose sample prepare liquid to be added in ml headspace bottle, pressed
Head space gas chromatography detection is carried out according to step (2) identical method and Parameter Conditions, records the chromatographic peak area of sample
Signal value, carboxyl-content in nano-cellulose sample is then calculated according to the standard curve of step (2).
2. the method for carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose according to claim 1, its
It is characterised by：Nano-cellulose sample is diluted into water sample described in step (1) to refer to nano-cellulose sample being diluted to admittedly
Content is 0.1%~0.2%.
3. the method for carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose according to claim 1, its
It is characterised by：The cationic ion-exchange resin is 001x7 type cationic ion-exchange resins.
4. the method for carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose according to claim 1, its
It is characterised by：The time being ultrasonically treated described in step (1) is 30~60min.
5. the method for carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose according to claim 1, its
It is characterised by：The concentration of hydrochloric acid standard solution is 0.05~1mol/L described in step (2), and the addition of hydrochloric acid standard solution is
10~1000 μ L；The concentration of the sodium bicarbonate solution is 0.01~0.1mol/L.
6. the method for carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose according to claim 1, its
It is characterised by that head-space sampler operating condition is described in step (2)：40~80 DEG C of equilibrium temperature, Sample equilibration time 4~
40min, carrier gas 10~20s of equilibration time, pipeline 10~20s of inflationtime, pipeline 1~10s of equilibration time in ml headspace bottle, loop
10~20s of equilibration time.
7. the method for carboxyl-content in a kind of headspace gas chromatography detection nano-cellulose according to claim 1, its
It is characterised by that gas chromatograph operating condition is described in step (2)：Chromatographic column temperature is 50~150 DEG C, and nitrogen is as carrier gas, nitrogen
Throughput is 2.0~6.0mL/min；150~250 DEG C of TCD detector temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710804492.3A CN107576738A (en) | 2017-09-08 | 2017-09-08 | A kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710804492.3A CN107576738A (en) | 2017-09-08 | 2017-09-08 | A kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107576738A true CN107576738A (en) | 2018-01-12 |
Family
ID=61031473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710804492.3A Pending CN107576738A (en) | 2017-09-08 | 2017-09-08 | A kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107576738A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760900A (en) * | 2018-03-20 | 2018-11-06 | 华南理工大学 | A kind of headspace gas chromatography measuring sodium carboxymethylcellulose degree of substitution |
| CN110208410A (en) * | 2019-06-06 | 2019-09-06 | 华南理工大学 | A kind of automatic headspace gas chromatography method of quick measurement deacetylating degree of chitosan |
| CN111795938A (en) * | 2020-06-15 | 2020-10-20 | 华南理工大学 | Method for measuring carboxyl content of nanocellulose by using multi-wavelength spectrum technology |
| CN112348961A (en) * | 2020-11-30 | 2021-02-09 | 江南大学 | Construction method and application of color fiber three-dimensional color mixing space grid model and grid point array color matrix |
| CN112505241A (en) * | 2020-12-24 | 2021-03-16 | 杭州协合医疗用品有限公司 | Method for measuring carboxyl content in oxidized regenerated cellulose |
| CN113671057A (en) * | 2020-05-15 | 2021-11-19 | 中国科学院理化技术研究所 | Method for detecting aerobic biodegradation performance of high polymer material in marine environment |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931823A (en) * | 2006-09-29 | 2007-03-21 | 广西万山香料有限责任公司 | Process of extracting and separating shikimic acid from aniseed |
-
2017
- 2017-09-08 CN CN201710804492.3A patent/CN107576738A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1931823A (en) * | 2006-09-29 | 2007-03-21 | 广西万山香料有限责任公司 | Process of extracting and separating shikimic acid from aniseed |
Non-Patent Citations (3)
| Title |
|---|
| JIN-FENG ZHONG等: "Determination of degree of substitution in succinic anhydride modified cellulose by headspace gas chromatography", 《JOURNAL OF CHROMATOGRAPHY A》 * |
| JUNHUA ZHANG等: "Microfibrillated cellulose from bamboo pulp and its properties", 《BIOMASS AND BIOENERGY》 * |
| X.-S.CHAI等: "An Improved and Practical Headspace Gas Chromatographic Method for Determination of Carboxyl Acids Content in Wood Fibers", 《IND.ENG.CHEM.RES.》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108760900A (en) * | 2018-03-20 | 2018-11-06 | 华南理工大学 | A kind of headspace gas chromatography measuring sodium carboxymethylcellulose degree of substitution |
| CN110208410A (en) * | 2019-06-06 | 2019-09-06 | 华南理工大学 | A kind of automatic headspace gas chromatography method of quick measurement deacetylating degree of chitosan |
| CN113671057A (en) * | 2020-05-15 | 2021-11-19 | 中国科学院理化技术研究所 | Method for detecting aerobic biodegradation performance of high polymer material in marine environment |
| CN111795938A (en) * | 2020-06-15 | 2020-10-20 | 华南理工大学 | Method for measuring carboxyl content of nanocellulose by using multi-wavelength spectrum technology |
| CN112348961A (en) * | 2020-11-30 | 2021-02-09 | 江南大学 | Construction method and application of color fiber three-dimensional color mixing space grid model and grid point array color matrix |
| CN112348961B (en) * | 2020-11-30 | 2021-08-10 | 江南大学 | Construction and application of color fiber three-dimensional color mixing space grid model and grid point array chromatogram |
| CN112505241A (en) * | 2020-12-24 | 2021-03-16 | 杭州协合医疗用品有限公司 | Method for measuring carboxyl content in oxidized regenerated cellulose |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107576738A (en) | A kind of method of carboxyl-content in headspace gas chromatography detection nano-cellulose | |
| CN101650347B (en) | Method for simultaneously measuring contents of multiple organic acids in feeder acidulant | |
| CN106153769A (en) | A kind of method utilizing headspace gas chromatography Accurate Determining fiber water holding capacity | |
| CN110057878A (en) | A kind of molecular imprinting electrochemical detection method of ketamine drugs | |
| CN105223244A (en) | A kind of preparation method and application detecting the trace electrochemical sensor of vanillic aldehyde | |
| Yan et al. | Rapid determination of degree of deacetylation of chitosan by a headspace analysis based Titrimetric technique | |
| CN103884748A (en) | Preparation method of molecular imprinting electrochemical sensor for detecting serotonins | |
| CN103698437B (en) | Method for quickly detecting starch coated amount in modified calcium carbonate filler through headspace gas chromatography | |
| CN103616447A (en) | Method for quickly measuring content of calcium carbonate in paper through headspace gas chromatography | |
| Zhong et al. | Determination of degree of substitution in succinic anhydride modified cellulose by headspace gas chromatography | |
| CN109298095A (en) | A method of pulp fibres water holding capacity is air-dried using headspace gas chromatography Accurate Determining | |
| CN111024860B (en) | Method for measuring different forms of moisture in sludge by using headspace gas chromatography | |
| CN108760900A (en) | A kind of headspace gas chromatography measuring sodium carboxymethylcellulose degree of substitution | |
| CN1441248A (en) | Detection method of glyoxalic acid, glycolic acid, glyoxal and oxalic acid | |
| CN114609295A (en) | High performance liquid chromatography analysis method for quinic acid content in tala enzymolysis waste liquid | |
| CN105572121B (en) | A kind of detection method of nitrogen content | |
| Zhang et al. | Determination of N-Methyl morpholine in biomass pretreatment solutions by the ammonia-assisted headspace gas chromatography | |
| CN107255678B (en) | Method for accurately determining content of calcium carbonate in paper by utilizing headspace gas chromatography | |
| CN101576539B (en) | Method for measuring impurity A in xylometazoline hydrochloride | |
| CN107727782B (en) | Method for determining effective content of AKD emulsion by ionic liquid-assisted headspace gas chromatography | |
| CN116718650A (en) | Preparation method and application of molecular imprinting electrochemical sensor for detecting aflatoxin B1 | |
| CN110514549A (en) | A kind of rapid detection method of ammonia acetylene mixing Gas content | |
| Yu et al. | Highly selective determination of phenolphthalein by flow injection chemiluminescence method based on a molecular imprinting polymer | |
| CN104749304A (en) | Method for determining concentrations of cyanide ion and sulfide ion in desulphurization solution | |
| CN109001324A (en) | A kind of method of succinic anhydride content in gas chromatographic detection sample |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180112 |
|
| RJ01 | Rejection of invention patent application after publication |