CN104458784A - Measuring method for crystallinity and crystalline state structure of tobacco cellulose - Google Patents
Measuring method for crystallinity and crystalline state structure of tobacco cellulose Download PDFInfo
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Abstract
The invention relates to a measuring method for crystallinity and crystalline state structure of tobacco cellulose. The measuring method adopts a CP/MAS <13>C-NMR method to conduct detection on a tobacco sample, and then measures the crystallinity and the crystalline state structure of the cellulose in the tobacco sample. The pretreatment of the tobacco sample is that elution is conducted with an acid washing agent, lignose is eluted without the strong oxidant sub-oxygen acid sodium, alkali and acid treatments are conducted, the pretreatment is simple in process and short in time consumption, and when data processing is adopted, interference of lignose is removed through the manner of respectively deducting corresponding noncellulosic background absorption on various types of tobacco samples. According to the method, research on tobacco cellulose sample fibril structure extracted by an acidic washing agent is realized, and important theoretical bases can be provided for cellulose modification, tobacco processing, low-grade tobacco leaf and tobacco stem treatment and the like.
Description
[technical field]
The invention belongs to tobacco scientific domain, be specifically related to a kind of crystallinity of baccy fiber element and the assay method of crystalline structure.
[background technology]
Cellulose is as the base substance forming tobacco leaf cells tissue and skeleton, and its content has considerable influence to the processing characteristics of tobacco, flammability and sucking quality; In the process of tobacco, the factors such as the change of cellulose macromolecule crystalline structure and crystallinity have important impact for the quality such as swollen moisture pick-up properties and pliability of tobacco.Therefore, strengthen to the research of baccy fiber element, raising Cigarette processing quality being significant.
Cellulose macromolecule is coupled to cellobiose unit by glucosyl group by β-Isosorbide-5-Nitrae glycosidic bond, then form the linear polymeric of homogeneous glycan.The structure of fiber, neither unformed shape completely neither crystalline state completely, is partially crystallizable and partially oriented, by the two-phase system of crystalline region and amorphous region connection.Coupling part between crystalline region is amorphous region, and crystalline region and amorphous region are without obvious boundary, and transition is to each other gradual change.Ratio between crystalline region and amorphous region, the degree of perfection of crystallization with the kind of fiber, the position of fiber and different.In the microtexture of cellulose fibre, crystallinity is the important parameter describing cellulose supramolecular structure, and it represents that in cellulose, crystalline region accounts for the long-pending percent of total fiber.Crystalline portion in aggregated structure and unformed part are all the importances determining cellulose character, and the physicochemical property of fiber all have close relationship with crystallinity.
The assay method of cellulose crystallity comprises X-ray diffraction method (XRD method), infra-red sepectrometry (FTIR method), Raman spectroscopy, cross polarization evil spirit angle nmr spin method (CP/MAS
13c-NMR method) etc., but mainly to concentrate in paper-making fibre ([1] Ma Xiaojuan, Huang Liulian, Chen Lihui, etc. the assay method [J] of cellulose crystallity. Paper Science & Technology, 2012,31 (2): 75-78.
[2]Sunkyu Park,John O Baker,Michael E Himmel,etc.Cellulose crystallinityindex:measurement techniques and their impact on interpreting cellulaseperformance[J].Biotechnology for Biofuels,2010,3:10.
[3]Schenzel K.,Fischer S.NIR FT Raman spectroscopy,a rapid,analytical tool fordetecting the transformation of cellulose polymorphs.Cellulose，2001，8:49-57.)。Wherein with more (the Nicoleta Terinte of XRD method application, Roger Ibbett, Kurt Christian Schuster.OVERVIEWON NATIVE CELLULOSE AND MICROCRYSTALLINECELLULOSE I STRUCTURE STUDIED BY X-RAY DIFFRACTION (WAXD): COMPARISON BETWEENMEASUREMENT TECHNIQUES.Lenzinger Berichte, 2011,89:118-131.), it is advantageous that pre-treatment is simple, but accuracy of measurement is not as good as CP/MAS
13c-NMR method, and can not the cellulosic crystalline structure of quantitative response; FTIR because of interfering material more, measurement result is more obvious than additive method higher; Raman spectrum needs to measure in alkaline solution, and result can be subject to the impact of alkali concn; Combine CP/MAS method
13c-NMR can obtain the full detail of cellulose micromechanism more than first three methods complete and accurate, application is started in paper-making fibre research in recent years, as the people such as Xiao Qing (Xiao Qing, Wan Jinquan, Wang Yan .CP/MAS 13C-NMR technology is to the research [J] of wood pulp cellulose micromechanism. chemical journal, 2009,67 (22): 2629-2634.) research and probe that this method has been carried out Eucalyptus wood chip is applied, have passed through comparatively complicated pretreatment process before the assay, and lignin need be removed just can measure.
Research cellulosic in tobacco is had to the mensuration being only limitted to content of cellulose of report, and report is had no to its structure and crystallinity analysis.And tobacco and Eucalyptus class physical chemical differences are comparatively large, application CP/MAS
13c-NMR method is furtherd investigate baccy fiber element crystallinity and crystalline structure and is still belonged to blank.
[summary of the invention]
[technical matters that will solve]
The object of this invention is to provide a kind of crystallinity of baccy fiber element and the assay method of crystalline structure.
[technical scheme]
The present invention is achieved through the following technical solutions.
The invention provides a kind of crystallinity of baccy fiber element and the assay method of crystalline structure, the method comprises the following steps:
Steps A, reference tobacco sample is obtained neutral detergent fiber content according to the determination step of tobacco business standard YC/T 347-2010 neutral detergent fiber; Choose same reference tobacco sample and obtain acid detergent fiber content according to the determination step of tobacco business standard YC/T 347-2010 acid detergent fiber; The content of cellulose of reference tobacco sample is obtained again according to the neutral detergent fiber content of reference tobacco sample and acid detergent fiber content; Then the determination step of same reference tobacco sample according to tobacco business standard YC/T 347-2010 acid detergent fiber obtains graininess, shallow brown-green baccy fiber element reference standard specimen without muffle furnace ashing is chosen;
Step B, utilize CP/MAS
13c-NMR method measures the baccy fiber element reference standard specimen that cellulose standard specimen and steps A obtain and obtains cellulose standard specimen spectrogram and baccy fiber element reference standard specimen spectrogram respectively, then namely obtains non-cellulose in reference tobacco sample with the cellulose standard specimen spectrogram of baccy fiber element reference standard specimen spectrum stripping same amount and absorbs background spectrogram;
Step C, by tobacco sample to be measured according to tobacco business standard YC/T 347-2010 acid detergent fiber determination step without muffle furnace ashing obtain baccy fiber to be measured element sample, then utilize CP/MAS
13c-NMR method measures to baccy fiber element sample to be measured the spectrogram obtaining baccy fiber to be measured element sample, and the non-cellulose obtained in the spectrum stripping step B of baccy fiber element sample to be measured is absorbed the cellulose spectrogram that namely background spectrogram obtains this tobacco sample to be measured;
The analysis of the crystallinity of step D, baccy fiber element to be measured and calculating:
By crystalline region in δ 80 ~ 92ppm in the cellulose spectrogram of tobacco sample to be measured and noncrystalline domain signal areal calculation crystallinity, computing formula is as follows:
In formula: S
brilliant-be the signal area of δ 86 ~ 92ppm,
S
non--be the signal area of δ 80 ~ 86ppm;
Or, the crystallinity calculating baccy fiber element to be measured is decomposed by the C4 district matching of the cellulose spectrogram δ 80 ~ 92ppm of tobacco sample to be measured, computing method are as follows: utilize mixing Lorentz lorentz and Gaussian function model obtain δ 80 ~ 92ppm signal peak fitted figure by the C4 signal peak matching of DWIN-NMR software fitting technique to the cellulose spectrogram of tobacco sample to be measured, respectively by cellulose I in orderly C4 district (δ 80 ~ 92ppm)
α, cellulose I
alpha+beta, and cellulose I
βthe signal Lorentzian spectral line caused carries out matching; In unordered C4 district (δ 80 ~ 86ppm) respectively by secondary crystalline cellulose PC, can and the signal Gaussian spectral line that causes of base fibril surface AS and unreachable base fibril surface IAS carry out matching; Then following formula is adopted to calculate crystallinity:
X=I
α+ I
alpha+beta+ I
β+ PC, wherein I
α, I
alpha+beta, I
β, PC represents respectively
13cellulose crystal formation I after the C4 district matching of C NMR spectrum δ 80 ~ 92ppm
α, I
alpha+betaand I
βwith the relative content of secondary crystalline cellulose PC;
Step e, the crystal formation of baccy fiber element to be measured and the analysis and calculation of content:
To δ 102 ~ 108ppm signal peak matching in the cellulose spectrogram of tobacco sample to be measured, adopt 4 linear expression different crystal forms of Lorentzian, measure crystalline region cellulose I
α, cellulose I
βand the relative content of secondary crystalline cellulose PC;
The calculating of step F, baccy fiber to be measured element fibrillar size:
The total signal strength I of C4 atom is obtained from δ 80 ~ 92ppm signal peak fitted figure of step D
tot, can and the signal intensity I of base fibril surface
aSwith the signal intensity I of unreachable base fibril surface
iAS, the step calculating base fibril aggregation bunch size is as follows: according to q=I
aS/ I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril aggregation bunch, calculates the value of n, then is the size of corresponding base fibril aggregation bunch according to formula d=0.57 × n, d;
The step calculating base fibrillar size is as follows: according to q=(I
aS+ I
iAS)/I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril, calculates the value of n, then is the size of corresponding base fibril according to formula d=0.57 × n, d.
According to one embodiment of present invention, described CP/MAS
13c-NMR method adopts AVANCEAV 400spectrometer superconduction Fourier digitizing nuclear magnetic resonance spectrometer to measure, test condition parameters is as follows: field intensity 9.40T, 4mm and 7mm evil spirit angle probe, rotating speed 15kHz, pulse width 90 °, cross polarization time 4 μ s, duration of contact 2ms, sampling time 34ms, sampling interval duration 2.0s, scanning times: 1024, spectrum width 300ppm, one-level calibration tetramethylsilane (CH
3)
4si.
The present invention is further illustrated below.
The invention provides a kind of crystallinity of baccy fiber element and the assay method of crystalline structure, the method comprises the following steps:
Steps A, reference tobacco sample is obtained neutral detergent fiber content according to the determination step of tobacco business standard YC/T 347-2010 neutral detergent fiber; Choose same reference tobacco sample and obtain acid detergent fiber content according to the determination step of tobacco business standard YC/T 347-2010 acid detergent fiber; The content of cellulose of reference tobacco sample is obtained again according to the neutral detergent fiber content of reference tobacco sample and acid detergent fiber content; Then the determination step of same reference tobacco sample according to tobacco business standard YC/T 347-2010 acid detergent fiber obtains graininess, shallow brown-green baccy fiber element reference standard specimen without muffle furnace ashing is chosen;
The determination step of the neutral detergent fiber saved according to tobacco business standard YC/T 347-2010 7.2.4 by reference tobacco sample obtains neutral detergent fiber content; The determination step choosing the acid detergent fiber that same reference tobacco sample saves according to tobacco business standard YC/T 347-2010 7.2.5 obtains acid detergent fiber content; The content of cellulose of reference tobacco sample is obtained again according to the neutral detergent fiber content of reference tobacco sample and acid detergent fiber content; Then the determination step of same reference tobacco sample according to tobacco business standard YC/T347-2010 acid detergent fiber obtains graininess, shallow brown-green baccy fiber element reference standard specimen without muffle furnace ashing (namely according to the step process of tobacco business standard YC/T347-2010 7.2.5.1 ~ 7.2.5.4) is chosen;
Step B, utilize CP/MAS
13c-NMR method measures the baccy fiber element reference standard specimen that cellulose standard specimen and steps A obtain and obtains cellulose standard specimen spectrogram and baccy fiber element reference standard specimen spectrogram respectively, then namely obtains non-cellulose in reference tobacco sample with the cellulose standard specimen spectrogram of baccy fiber element reference standard specimen spectrum stripping same amount and absorbs background spectrogram;
The object of steps A obtains a reference standard specimen for the tobacco sample of a certain type, and the NMR non-cellulose then obtaining this type tobacco sample by step B absorbs background spectrogram, detects for tobacco sample to be measured.In an embodiment of the present invention, consider that the NMR non-cellulose of different tobacco type sample absorbs background spectrogram and can there are differences, in steps A, the selection of tobacco sample is determined according to the type of tobacco sample to be measured, if tobacco sample to be measured is a series of flue-cured tobacco sample, then choose one of them flue-cured tobacco sample preparation in step and obtain baccy fiber element reference standard specimen.
Step C, by tobacco sample to be measured according to tobacco business standard YC/T 347-2010 acid detergent fiber determination step without muffle furnace ashing obtain baccy fiber to be measured element sample, then utilize CP/MAS
13c-NMR method measures to baccy fiber element sample to be measured the spectrogram obtaining baccy fiber to be measured element sample, and the non-cellulose obtained in the spectrum stripping step B of baccy fiber element sample to be measured is absorbed the cellulose spectrogram that namely background spectrogram obtains this tobacco sample to be measured;
The present invention gives the detailed step of a specific embodiment step B ~ C, this step is as follows:
A, accurately take cellulose standard model (10-250mg), preparation is corresponding
13c NMR composes, and sets up linear relationship (Fig. 1 (a)) (can be realized by NMR apparatus preparation software) according to spectrogram δ 99-112ppm district's integral area and example weight;
B, prepare baccy fiber element reference standard specimen
13c NMR composes (Fig. 1 (b));
C, the cellulose standard sample spectral selecting baccy fiber element reference sample to deduct concentration suitable (being calculated by content of cellulose in baccy fiber element reference sample) absorb background spectrogram (Fig. 1 (c)) as non-cellulose after absorbing;
D, the poor spectrogram (Fig. 1 (e)) being deducted non-cellulose background absorption (Fig. 1 (c)) gained by the spectrogram (Fig. 1 (d)) of baccy fiber to be measured element sample are the cellulose spectrogram of the plain sample of baccy fiber to be measured.
The analysis of the crystallinity of step D, baccy fiber element to be measured and calculating:
By crystalline region in δ 80 ~ 92ppm in the cellulose spectrogram of tobacco sample to be measured and noncrystalline domain signal areal calculation crystallinity, computing formula is as follows:
In formula: S
brilliant-be the signal area of δ 86 ~ 92ppm,
S
non--be the signal area of δ 80 ~ 86ppm;
Or, the crystallinity calculating baccy fiber element to be measured is decomposed by the C4 district matching of the cellulose spectrogram δ 80 ~ 92ppm of tobacco sample to be measured, computing method are as follows: utilize mixing Lorentz lorentz and Gaussian function model obtain δ 80 ~ 92ppm signal peak fitted figure by the C4 signal peak matching of DWIN-NMR software fitting technique to the cellulose spectrogram of tobacco sample to be measured, respectively by cellulose I in orderly C4 district (δ 80 ~ 92ppm)
α, cellulose I
alpha+beta, and cellulose I
βthe signal Lorentzian spectral line caused carries out matching; In unordered C4 district (δ 80 ~ 86ppm) respectively by secondary crystalline cellulose PC, can and the signal Gaussian spectral line that causes of base fibril surface AS and unreachable base fibril surface IAS carry out matching; Then following formula is adopted to calculate crystallinity:
X=I
α+ I
alpha+beta+ I
β+ PC, wherein I
α, I
alpha+beta, I
β, PC represents respectively
13cellulose crystal formation I after the C4 district matching of C NMR spectrum δ 80 ~ 92ppm
α, I
alpha+betaand I
βwith the relative content of secondary crystalline cellulose PC;
Step e, the crystal formation of baccy fiber element to be measured and the analysis and calculation of content:
To δ 102 ~ 108ppm signal peak matching in the cellulose spectrogram of tobacco sample to be measured, adopt 4 linear expression different crystal forms of Lorentzian, measure crystalline region cellulose I
α, cellulose I
βand the relative content of secondary crystalline cellulose PC;
Cellulose also exists five kinds of crystal modifications in the solid state, and native cellulose exists with cellulose I form, and cellulose I crystal is not exist with single crystal form form, but cellulose I
αand cellulose I
βthe potpourri of two kinds of crystal, and they can transform mutually under certain condition; And secondary crystalline cellulose refers to that expression order is too late but motility is greater than cellulose I
αand I
βcrystalline texture.
The calculating of step F, baccy fiber to be measured element fibrillar size:
The total signal strength I of C4 atom is obtained from δ 80 ~ 92ppm signal peak fitted figure of step D
tot, can and the signal intensity I of base fibril surface
aSwith the signal intensity I of unreachable base fibril surface
iAS, the step calculating base fibril aggregation bunch size is as follows: according to q=I
aS/ I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril aggregation bunch, calculates the value of n, then is the size of corresponding base fibril aggregation bunch according to formula d=0.57 × n, d;
The step calculating base fibrillar size is as follows: according to q=(I
aS+ I
iAS)/I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril, calculates the value of n, then is the size of corresponding base fibril according to formula d=0.57 × n, d.
Base fibril and thread polycrystal are structural units minimum in avicel cellulose.Embodiments of the invention are the lateral dimensions that can obtain base fibril by calculating cellulose crystallite dimension.Supposing that cellulose base fibril forms the direction of aggregation is consistent with the direction of fiber main shaft, and assuming that the signal intensity (δ 83.8 ~ 84.1ppm) of surface to unreachable base fibril surface of base fibril one base fibril contact has Main Function, so calculate horizontal base fibrillar size and base fibril aggregation bunch size (i.e. micro-fibril lateral dimension) by NMR spectrum.And suppose in embodiments of the invention that base fibril and base fibril aggregation bunch have the cross section of squarish, rule of thumb equation:
q＝(4n-4)/n
2
Wherein, n is along the glucose number on base fibril or base fibril aggregation bunch.By calculating wide (0.61nm, monoclinic phase 110 and triclinic system 010) and leptoprosopy (0.54nm, monoclinic phase 110 and triclinic system 100) in the mean value of spacing of cellulose chain obtain conversion coefficient, namely on cellulose chain, a glucose is of a size of 0.57nm, so d=0.57 × n, d are the size of corresponding base fibril or base fibril aggregation bunch.
According to one embodiment of present invention, described CP/MAS
13c-NMR method adopts AVANCEAV 400spectrometer superconduction Fourier digitizing nuclear magnetic resonance spectrometer to measure, test condition parameters is as follows: field intensity 9.40T, 4mm and 7mm evil spirit angle probe, rotating speed 15kHz, pulse width 90 °, cross polarization time 4 μ s, duration of contact 2ms, sampling time 34ms, sampling interval duration 2.0s, scanning times: 1024, spectrum width 300ppm, one-level calibration tetramethylsilane (CH
3)
4si.
[beneficial effect]
The pre-treatment carrying out cellulose correlation analysis for tobacco sample in the present invention carries out wash-out with acid detergent, without the need to strong oxidizer Ya Yangsuan sodium delignification and through alkali and acid treatment, pretreatment process is simple, time-consuming short, but when adopting data processing, dissimilar tobacco sample is deducted respectively to the mode of corresponding non-cellulose background absorption to the interference except delignification.By aforementioned improved, achieve the mensuration of the baccy fiber element sample crystallinity to acid detergent process.
This method achieves the Accurate Determining of different cellulose crystal formation distribution and ratio in the baccy fiber element sample to acid detergent process, compensate for the defect that traditional X-ray RD method cannot quantize different crystal forms content.
This method achieves the research of the baccy fiber element sample fibrillar structure to acid detergent process first.
Aforementioned measurements can be processed for cellulose modified, tobacco and the process etc. of discarded tobacco leaf and offal provides important theoretical foundation.
[accompanying drawing explanation]
Fig. 1 is the non-cellulose absorption background spectrogram of one embodiment of the present of invention and the cellulose spectrogram of baccy fiber element sample;
Fig. 2 is that the C4 signal peak matching of the cellulose spectrogram of the tobacco sample to be measured of one embodiment of the present of invention obtains δ 80 ~ 92ppm signal peak fitted figure;
Fig. 3 is that the C1 signal peak matching of the cellulose spectrogram of the tobacco sample to be measured of one embodiment of the present of invention obtains δ 102 ~ 108ppm signal peak fitted figure.
[embodiment]
The present invention can be understood better by following embodiment.
The crystallinity of baccy fiber element and an assay method for crystalline structure, the method comprises the following steps:
Steps A, the determination step of neutral detergent fiber saved according to tobacco business standard YC/T 347-2010 7.2.4 by reference tobacco sample obtain neutral detergent fiber content; The determination step choosing the acid detergent fiber that same reference tobacco sample saves according to tobacco business standard YC/T 347-2010 7.2.5 obtains acid detergent fiber content; The content of cellulose of reference tobacco sample is obtained again according to the neutral detergent fiber content of reference tobacco sample and acid detergent fiber content; Then the determination step of same reference tobacco sample according to tobacco business standard YC/T347-2010 acid detergent fiber obtains graininess, shallow brown-green baccy fiber element reference standard specimen without muffle furnace ashing (namely according to the step process of tobacco business standard YC/T347-2010 7.2.5.1 ~ 7.2.5.4) is chosen;
Step B, utilize CP/MAS
13c-NMR method measures the baccy fiber element reference standard specimen that cellulose standard specimen and steps A obtain and obtains cellulose standard specimen spectrogram (Fig. 1 (a)) and baccy fiber element reference standard specimen spectrogram (Fig. 1 (b)) respectively, then namely obtains non-cellulose in reference tobacco sample with the cellulose standard specimen spectrogram of baccy fiber element reference standard specimen spectrum stripping same amount and absorbs background spectrogram (Fig. 1 (c)); CP/MAS
13c-NMR method adopts AVANCE AV 400spectrometer superconduction Fourier digitizing nuclear magnetic resonance spectrometer to measure, test condition parameters is as follows: field intensity 9.40T, 4mm and 7mm evil spirit angle probe, rotating speed 15kHz, pulse width 90 °, cross polarization time 4 μ s, duration of contact 2ms, sampling time 34ms, sampling interval duration 2.0s, scanning times: 1024, spectrum width 300ppm, one-level calibration tetramethylsilane (CH
3)
4si;
Step C, by tobacco sample to be measured according to tobacco business standard YC/T 347-2010 acid detergent fiber determination step without muffle furnace ashing obtain baccy fiber to be measured element sample, then utilize CP/MAS
13c-NMR method measures to baccy fiber element sample to be measured the spectrogram (Fig. 1 (d)) obtaining baccy fiber to be measured element sample, and the non-cellulose obtained in the spectrum stripping step B of baccy fiber element sample to be measured is absorbed the cellulose spectrogram (Fig. 1 (e)) that namely background spectrogram obtains this tobacco sample to be measured;
The analysis of the crystallinity of step D, baccy fiber element to be measured and calculating:
By crystalline region and noncrystalline domain signal areal calculation crystallinity in δ 80 ~ 92ppm in the cellulose spectrogram (Fig. 1 (e)) of tobacco sample to be measured, computing formula is as follows:
In formula: S
brilliant-be the signal area of δ 86 ~ 92ppm,
S
non--be the signal area of δ 80 ~ 86ppm;
Or, the crystallinity calculating baccy fiber element to be measured is decomposed by the C4 district matching of the cellulose spectrogram δ 80 ~ 92ppm of tobacco sample to be measured, computing method are as follows: utilize mixing Lorentz lorentz and Gaussian function model obtain δ 80 ~ 92ppm signal peak fitted figure (see Fig. 2) by the C4 signal peak matching of DWIN-NMR software fitting technique to the cellulose spectrogram of tobacco sample to be measured, respectively by cellulose I in orderly C4 district (δ 80 ~ 92ppm)
α, cellulose I
alpha+beta, and cellulose I
βthe signal Lorentzian spectral line caused carries out matching; In unordered C4 district (δ 80 ~ 86ppm) respectively by secondary crystalline cellulose PC, can and the signal Gaussian spectral line that causes of base fibril surface AS and unreachable base fibril surface IAS carry out matching; Then following formula is adopted to calculate crystallinity:
X=I
α+ I
alpha+beta+ I
β+ PC, wherein I
α, I
alpha+beta, I
β, PC represents respectively
13cellulose crystal formation I after the C4 district matching of C NMR spectrum δ 80 ~ 92ppm
α, I
alpha+betaand I
βwith the relative content of secondary crystalline cellulose PC;
Step e, the crystal formation of baccy fiber element to be measured and the analysis and calculation of content:
To δ 102 ~ 108ppm signal peak matching in the cellulose spectrogram of tobacco sample to be measured, adopt 4 linear expression different crystal forms (see Fig. 3) of Lorentzian, measure crystalline region cellulose I
α, cellulose I
βand the relative content of secondary crystalline cellulose PC;
The calculating of step F, baccy fiber to be measured element fibrillar size:
The total signal strength I of C4 atom is obtained from δ 80 ~ 92ppm signal peak fitted figure (Fig. 2) of step D
tot, can and the signal intensity I of base fibril surface
aSwith the signal intensity I of unreachable base fibril surface
iAS, the step calculating base fibril aggregation bunch size is as follows: according to q=I
aS/ I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril aggregation bunch, calculates the value of n, then is the size of corresponding base fibril aggregation bunch according to formula d=0.57 × n, d;
The step calculating base fibrillar size is as follows: according to q=(I
aS+ I
iAS)/I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril, calculates the value of n, then is the size of corresponding base fibril according to formula d=0.57 × n, d.
Embodiment 1:
Choose flue-cured tobacco sample Guizhou C
3f, according to abovementioned steps A process, obtains flue-cured tobacco cellulose reference standard specimen, and to obtain this flue-cured tobacco cellulose reference standard specimen content of cellulose be 9.84%.The non-cellulose obtaining flue-cured tobacco sample according to abovementioned steps B absorbs background spectrogram.Then select flue-cured tobacco sample to be measured to detect according to abovementioned steps C ~ D, and contrast with former XRD method and IR method testing result, the crystallinity of flue-cured tobacco sample to be measured is in table 1.
Table 1: the crystallinity of different flue-cured tobacco sample fiber element
Note: * is the formula gained of NMR method crystalline region and amorphous area areal calculation;
* is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the relative content sum of secondary crystalline cellulose PC.
Analyze according to the cellulose crystal formation content of step e to flue-cured tobacco sample to be measured, the results are shown in Table 2.
Table 2: by
13the crystal formation content results of the different flue-cured tobacco cellulose sample that C CP/MAS NMR spectrum calculates
| Sample | I α(％) | I β1(％) | I β2(％) | I α/I β(％) | PC |
| Guizhou C 3F | 22.11 | 4.90 | 40.64 | 0.49 | 32.35 |
| Guizhou B 2F | 13.77 | 0.82 | 65.99 | 0.21 | 19.43 |
| Guizhou X 2F | 8.92 | 4.24 | 51.40 | 0.16 | 35.43 |
| Flue-cured tobacco offal | 9.15 | 1.44 | 62.66 | 0.14 | 26.90 |
Flue-cured tobacco sample fiber element fibrillar structure is calculated, in table 3 according to step F.
Table 3: the quantitative information of different flue-cured tobacco cellulose sample δ 80 ~ 92ppm districts spectrum simulation
Note: in table, * is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the cellulosic relative content sum of para-crystal.
Embodiment 2:
Choose Hunan Turkish tobaccos sample according to abovementioned steps A process, obtain Turkish tobaccos cellulose reference standard specimen, and to obtain this Turkish tobaccos cellulose reference standard specimen content of cellulose be 11.12%.The non-cellulose obtaining Turkish tobaccos sample according to abovementioned steps B absorbs background spectrogram.Then detected according to abovementioned steps C ~ D by Hunan Turkish tobaccos sample, and contrast with former XRD method and IR method testing result, the crystallinity of Turkish tobaccos sample to be measured is in table 4.
Table 4: the crystallinity of Turkish tobaccos sample fiber element
Note: * is the formula gained of NMR method crystalline region and amorphous area areal calculation;
* is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the relative content sum of secondary crystalline cellulose PC.
Analyze according to the cellulose crystal formation content of step e to Turkish tobaccos sample, the results are shown in Table 5.
Table 5: by
13the crystal formation content results of the Turkish tobaccos cellulose sample that C CP/MAS NMR spectrum calculates
| Sample | I α(％) | I β1(％) | I β2(％) | I α/I β(％) | PC |
| Hunan Turkish tobaccos | 4.06 | 0.39 | 55.89 | 0.07 | 39.65 |
Turkish tobaccos sample fiber element fibrillar structure is calculated, in table 6 according to step F.
Table 6: the quantitative information of Turkish tobaccos cellulose sample δ 80 ~ 92ppm district spectrum simulation
Note: in table, * is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the cellulosic relative content sum of para-crystal.
Embodiment 3:
Choose Burley Tobacco in Hubei Province sample according to abovementioned steps A process, obtain burley tobaccos cellulose reference standard specimen, and to obtain this burley tobaccos cellulose reference standard specimen content of cellulose be 14.95%.The non-cellulose obtaining burley tobaccos sample according to abovementioned steps B absorbs background spectrogram.Then detected according to abovementioned steps C ~ D by Hunan burley tobaccos sample, and contrast with former XRD method and IR method testing result, the crystallinity of burley tobaccos sample to be measured is in table 7.
Table 7: the crystallinity of burley tobaccos sample fiber element
Note: * is the formula gained of NMR method crystalline region and amorphous area areal calculation;
* is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the relative content sum of secondary crystalline cellulose PC.
Analyze according to the cellulose crystal formation content of step e to burley tobaccos sample, the results are shown in Table 8.
Table 8: by
13the crystal formation content results of the burley tobaccos cellulose sample that C CP/MAS NMR spectrum calculates
| Sample | I α(％) | I β1(％) | I β2(％) | I α/I β(％) | PC |
| Burley Tobacco in Hubei Province | 6.10 | 0.98 | 57.20 | 0.11 | 35.95 |
Burley tobaccos sample fiber element fibrillar structure is calculated, in table 9 according to step F.
Table 9: the quantitative information of burley tobaccos cellulose sample δ 80 ~ 92ppm district spectrum simulation
Note: in table, * is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the cellulosic relative content sum of para-crystal.
Embodiment 4:
Choose Guangzhou Lianzhou City Sun cured tobacco sample according to abovementioned steps A process, obtain Sun cured tobacco cellulose reference standard specimen, and to obtain this Sun cured tobacco cellulose reference standard specimen content of cellulose be 13.69%.The non-cellulose obtaining Sun cured tobacco sample according to abovementioned steps B absorbs background spectrogram.Then detected according to abovementioned steps C ~ D by Hunan Sun cured tobacco sample, and contrast with former XRD method and IR method testing result, the crystallinity of Sun cured tobacco sample to be measured is in table 10.
Table 10: the crystallinity of Sun cured tobacco sample fiber element
Note: * is the formula gained of NMR method crystalline region and amorphous area areal calculation;
* is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the relative content sum of secondary crystalline cellulose PC.
Analyze according to the cellulose crystal formation content of step e to Sun cured tobacco sample, the results are shown in Table 11.
Table 11: by
13the crystal formation content results of the Sun cured tobacco cellulose sample that C CP/MAS NMR spectrum calculates
| Sample | I α(％) | I β1(％) | I β2(％) | I α/I β(％) | PC |
| Guangzhou Sun cured tobacco | 4.93 | 0.47 | 68.12 | 0.07 | 26.48 |
Sun cured tobacco sample fiber element fibrillar structure is calculated, in table 12 according to step F.
Table 12: the quantitative information of Sun cured tobacco cellulose sample δ 80 ~ 92ppm district spectrum simulation
Note: in table, * is
13by cellulose crystal formation I after C NMR spectrum simulation
α, I
alpha+betaand I
βcalculate with the cellulosic relative content sum of para-crystal.
Claims (2)
1. the crystallinity of baccy fiber element and an assay method for crystalline structure, is characterized in that the method comprises the following steps:
Steps A, reference tobacco sample is obtained neutral detergent fiber content according to the determination step of tobacco business standard YC/T 347-2010 neutral detergent fiber; Choose same reference tobacco sample and obtain acid detergent fiber content according to the determination step of tobacco business standard YC/T 347-2010 acid detergent fiber; The content of cellulose of reference tobacco sample is obtained again according to the neutral detergent fiber content of reference tobacco sample and acid detergent fiber content; Then the determination step of same reference tobacco sample according to tobacco business standard YC/T347-2010 acid detergent fiber obtains graininess, shallow brown-green baccy fiber element reference standard specimen without muffle furnace ashing is chosen;
Step B, utilize CP/MAS
13c-NMR method measures the baccy fiber element reference standard specimen that cellulose standard specimen and steps A obtain and obtains cellulose standard specimen spectrogram and baccy fiber element reference standard specimen spectrogram respectively, then namely obtains non-cellulose in reference tobacco sample with the cellulose standard specimen spectrogram of baccy fiber element reference standard specimen spectrum stripping same amount and absorbs background spectrogram;
Step C, by tobacco sample to be measured according to tobacco business standard YC/T 347-2010 acid detergent fiber determination step without muffle furnace ashing obtain baccy fiber to be measured element sample, then utilize CP/MAS
13c-NMR method measures to baccy fiber element sample to be measured the spectrogram obtaining baccy fiber to be measured element sample, and the non-cellulose obtained in the spectrum stripping step B of baccy fiber element sample to be measured is absorbed the cellulose spectrogram that namely background spectrogram obtains this tobacco sample to be measured;
The analysis of the crystallinity of step D, baccy fiber element to be measured and calculating:
By crystalline region in δ 80 ~ 92ppm in the cellulose spectrogram of tobacco sample to be measured and noncrystalline domain signal areal calculation crystallinity, computing formula is as follows:
In formula: S
brilliant-be the signal area of δ 86 ~ 92ppm,
S
non--be the signal area of δ 80 ~ 86ppm;
Or, the crystallinity calculating baccy fiber element to be measured is decomposed by the C4 district matching of the cellulose spectrogram δ 80 ~ 92ppm of tobacco sample to be measured, computing method are as follows: utilize mixing Lorentz lorentz and Gaussian function model obtain δ 80 ~ 92ppm signal peak fitted figure, respectively by cellulose I in the C4 district that δ 80 ~ 92ppm is orderly by the C4 signal peak matching of DWIN-NMR software fitting technique to the cellulose spectrogram of tobacco sample to be measured
α, cellulose I
alpha+beta, and cellulose I
βthe signal Lorentzian spectral line caused carries out matching; In the C4 district that δ 80 ~ 86ppm is unordered respectively by secondary crystalline cellulose PC, can and the signal Gaussian spectral line that causes of base fibril surface AS and unreachable base fibril surface IAS carry out matching;
Then following formula is adopted to calculate crystallinity:
X=I
α+ I
alpha+beta+ I
β+ PC, wherein I
α, I
alpha+beta, I
β, PC represents respectively
13cellulose crystal formation I after the C4 district matching of C NMR spectrum δ 80 ~ 92ppm
α, I
alpha+betaand I
βwith the relative content of secondary crystalline cellulose PC;
Step e, the crystal formation of baccy fiber element to be measured and the analysis and calculation of content:
To δ 102 ~ 108ppm signal peak matching in the cellulose spectrogram of tobacco sample to be measured, adopt 4 linear expression different crystal forms of Lorentzian, measure crystalline region cellulose I
α, cellulose I
βand the relative content of secondary crystalline cellulose PC;
The calculating of step F, baccy fiber to be measured element fibrillar size:
The total signal strength I of C4 atom is obtained from δ 80 ~ 92ppm signal peak fitted figure of step D
tot, can and the signal intensity I of base fibril surface
aSwith the signal intensity I of unreachable base fibril surface
iAS, the step calculating base fibril aggregation bunch size is as follows: according to q=I
aS/ I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril aggregation bunch, calculates the value of n, then is the size of corresponding base fibril aggregation bunch according to formula d=0.57 × n, d;
The step calculating base fibrillar size is as follows: according to q=(I
aS+ I
iAS)/I
tot, q=(4n-4)/n simultaneously
2, wherein n is along the glucose number on base fibril, calculates the value of n, then is the size of corresponding base fibril according to formula d=0.57 × n, d.
2. the crystallinity of baccy fiber element according to claim 1 and the assay method of crystalline structure, is characterized in that described CP/MAS
13c-NMR method adopts AVANCE AV 400 spectrometer superconduction Fourier digitizing nuclear magnetic resonance spectrometer to measure, test condition parameters is as follows: field intensity 9.40T, 4mm and 7mm evil spirit angle probe, rotating speed 15kHz, pulse width 90 °, cross polarization time 4 μ s, duration of contact 2ms, sampling time 34ms, sampling interval duration 2.0s, scanning times: 1024, spectrum width 300ppm, one-level calibration tetramethylsilane (CH
3)
4si.
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| CN107202809A (en) * | 2017-05-22 | 2017-09-26 | 中国科学院化学研究所 | A kind of characterizing method of the pore space structure of material of regenerated cellulose |
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| JP2002090321A (en) * | 2000-09-21 | 2002-03-27 | Matsushita Refrig Co Ltd | Method for quantifying physical damage of frozen food |
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| CN106908469B (en) * | 2017-03-21 | 2018-12-21 | 苏州大学 | The quantitative analysis method of constituent content in a kind of polytetrafluoroethylblended blended object |
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Effective date of registration: 20161223 Address after: 610000, Sichuan, Chengdu, Longquanyi economic and Technological Development Zone, Jackie Chan Road, Longquan, No. 2, paragraph Patentee after: CHINA TOBACCO SICHUAN INDUSTRIAL CO., LTD. Patentee after: CHONGQING CHINA TOBACCO INDUSTRIAL CO., LTD. Address before: 610000 Jackie Chan Road, Chengdu economic and Technological Development Zone, Longquanyi District, Sichuan, China, No. 2, No. Patentee before: China Tobacco Chuanyu Industry Co., Ltd. |