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1.
One‐dimensional (1D) (spherically averaged) powder diffraction diagrams are commonly used to determine the degree of cellulose crystallinity in biomass samples. Here, it is shown using molecular modeling how disorder in cellulose fibrils can lead to considerable uncertainty in conclusions drawn concerning crystallinity based on 1D powder diffraction data alone. For example, cellulose microfibrils that contain both crystalline and noncrystalline segments can lead to powder diffraction diagrams lacking identifiable peaks, while microfibrils without any crystalline segments can lead to such peaks. This leads to false positives, that is, assigning disordered cellulose as crystalline, and false negatives, that is, categorizing fibrils with crystalline segments as amorphous. The reliable determination of the fraction of crystallinity in any given biomass sample will require a more sophisticated approach combining detailed experiment and simulation. © 2014 Wiley Periodicals, Inc. Biopolymers 103: 67–73, 2015. 相似文献
2.
Watanabe Y Kitamura S Kawasaki K Kato T Uegaki K Ogura K Ishikawa K 《Biopolymers》2011,95(12):833-839
Plant cellulose is the most abundant organic compound on earth. Technologies for producing cellulose fiber or improving the enzymatic saccharification of cellulose hold the key to biomass applications. A technology for atomizing biomass without strong acid catalysis remains to be developed. The water jet is a well-known device used in machines (e.g., washing machines, cutters, and mills) that use high-pressure water. In this study, we examined whether a water jet system could be used to atomize crystalline cellulose, which comprises approximately 50% of plant biomass. The Star Burst System manufactured by Sugino Machine Limited (Sugino Machine; Toyama, Japan) is a unique atomization machine that uses a water jet to atomize materials and thereby places lower stress on the environment. After treatment with this system, the crystalline cellulose was converted into a gel-like form. High-angular annular dark-field scanning transmission electron microscopy showed that the cellulose fibers had been converted from a solid crystalline into a matrix of cellulose nanofibers. In addition, our results show that this system can improve the saccharification efficiency of cellulases by more than three-fold. Hence, the Star Burst System provides a new and mild pretreatment system for processing biomass materials. 相似文献
3.
Ping LuYou-Lo Hsieh 《Carbohydrate polymers》2012,87(4):2546-2553
This is the first report on the derivation and structures of cellulose nanocrystals from grape skins. Pure cellulose was isolated from chardonnay grape skins at a 16.4% yield by a process involving organic extraction, acid and base dissolutions, and basic and acidic oxidation. The as-extracted cellulose was 54.9% crystalline and microfibrillar. Acid hydrolysis (64-65% H2SO4 45 °C, 30 min) of grape skin cellulose produced the more crystalline (64.3%) cellulose nanocrystals (CNCs) that appeared mostly as spherical nanoparticles with diameters ranging from 10 to 100 nm and a mean diameter of 48.1 (±14.6) nm as observed by TEM. AFM further disclosed the spherical nanoparticles actually consist of a nano-rod core (seed) surrounded by numerous tiny cellulose fragments as the shell. Interestingly, the spherical core-shell nanoparticles resemble the shape of grape bundles, the starting biomass, may be assembled via interfacial hydrogen bonds. 相似文献
4.
Andersson Seppo Wikberg Hanne Pesonen Erkki Maunu Sirkka Liisa Serimaa Ritva 《Trees - Structure and Function》2004,18(3):346-353
The variation in the mass fraction of crystalline cellulose (crystallinity of wood), the intrinsic crystallinity of cellulose, and the thickness of cellulose crystallites in early wood of Norway spruce [Picea abies (L.) Karst.], and Scots pine (Pinus sylvestris L.) grown in Finland were studied using wide angle X-ray scattering and nuclear magnetic resonance spectroscopy. The mass fraction of crystalline cellulose in wood increased slightly with the distance from the pith and was about 30±4% in mature wood of both species. The crystallinity of cellulose and the thickness of cellulose crystallites were almost constant for both species. The crystallinity of cellulose was 52±3% for both species and the average thickness of the cellulose crystallites was 32±1 Å and 31±1 Å for Norway spruce and Scots pine, respectively. The mass fraction of cellulose in wood, calculated from the crystallinity values, increased with the distance from the pith for both species. 相似文献
5.
The powder and tableting properties of cellulose II powders (MCCII) and (SDCII) were evaluated and compared with common direct compression binders. The cellulose II polymorphs offered more benefits in terms of functionality as compared with cellulose I (Avicel® PH-102) spray dried lactose and starch. Spray dried cellulose II (SDCII) had a better disintegrant ability, but a lower compactibility than microcrystalline cellulose I (Avicel® PH-102). However, when mixed and compressed with acetaminophen, SDCII was as compactable as cellulose I. Further, unprocessed cellulose II has a comparable compressibility to that of cellulose I. SDCII was found to be less friable, less sensitive to magnesium stearate, and possessed better acetaminophen loading capacity than unprocessed cellulose II and comparable to that of cellulose I. The cellulose II materials showed potential for use as a direct compression excipient. 相似文献
6.
Ping LuYou-Lo Hsieh 《Carbohydrate polymers》2012,87(1):564-573
Pure cellulose have been isolated from rice straw at 36% yield and hydrolyzed (64% H2SO4, 8.75 mL/g, 45 °C) for 30 and 45 min to cellulose nanocrystals (CNCs), i.e., CNC30 and CNC45, respectively. CNC45 was smaller (11.2 nm wide, 5.06 nm thick and 117 nm long) than CNC30 (30.7 nm wide, 5.95 nm thick and 270 nm long). Freeze-drying of diluted CNC suspensions showed both assembled into long fibrous structures: ultra-fine fibers (∼400 nm wide) from CNC45 and 1-2 μm wide broad ribbons interspersed with CNC clusters from CNC30. The self-assembled fibers from CNC30 and CNC45 were more highly crystalline (86.0% and 91.2%, respectively) and contained larger crystallites (7.36 nm and 8.33 nm, respectively) than rice straw cellulose (61.8%, 4.42 nm). These self-assembled fibers had essentially nonporous or macroporous structures with the CNCs well aligned along the fiber axis. Furthermore, the self-assembled ultra-fine fibers showed extraordinary structural stability, withstanding vigorous shaking and prolong stirring in water. 相似文献
7.
A. J. Varma 《Carbohydrate polymers》1984,4(6):473-479
The use of X-ray photoelectron spectroscopic techniques (XPS or ESCA) in the characterization of cellulose, starch and their oxidation products is discussed. The ESCA results obtained from these materials in the finely powdered state are presented and compared to the results obtained with celluloses in the fibrous form. A far greater amount of surface impurities were found to be present for the powdered polysaccharides due to their greater surface area. Also, it has been shown that a high full-width at half-maximum (f.w.h.m.) value for the C1s signal is obtained with 100% periodate oxidized maize starch, while a smaller value was found for 11% periodate oxidized cellulose powder. Finally, cellulosic powders seem to produce the O1s signal 0·8 eV downfield (i.e. higher binding energy value) as compared to the starches and this may be related to the rigid, crystalline and linear structure of the cellulose molecule as compared to the more amorphous and branched structure of the starches. 相似文献
8.
Synthesis of cellulose in vitro is expected to afford tailor-made cellulosic materials with highly homogeneous structure compared to natural cellulosic materials. Here we report the enzymatic synthesis of cellulose II with high crystallinity from glucose and α-glucose 1-phosphate (αG1P) by cellodextrin phosphorylase (CDP). Although glucose had been believed not to act as a glucosyl acceptor of CDP, a significant amount of insoluble cellulose was precipitated without accumulation of soluble cello oligosaccharides when glucose was mixed with αG1P and CDP. This phenomenon can be explained in terms of the large difference in acceptor reactivity between glucose and cello oligosaccharides. 1H NMR spectrometric analysis revealed that this insoluble cellulose had an average degree of polymerization (DP) of nine. TEM observation, together with electron and X-ray diffraction studies, indicated that the insoluble cellulose formed platelet-shaped single lamellar crystals of cellulose II, several μm in length and several hundred nm in width; this is large compared to reported cellulose crystals. The thickness of the lamellar crystal is 4.5 nm, which is equivalent to a chain length of a cello oligosaccharide with DP nine and is consistent with the 1H NMR spectroscopic results. These results suggest that cello oligosaccharides having an average DP of nine are synthesized in vitro by CDP when glucose is used as an acceptor, and the product forms highly crystalline cellulose II when it precipitates. 相似文献
9.
Nishiyama Y Okano T Langan P Chanzy H 《International journal of biological macromolecules》1999,26(4):279-283
High-resolution fibre neutron diffraction data were recorded from cellulose samples on a D19 diffractometer at the Institut Laue-Langevin (Grenoble). Highly crystalline cellulose I samples from Cladophora (cellulose I alpha + I beta) or Halocynthia (cellulose I beta) origin were prepared in the form of oriented films. Samples were studied in a hydrogenated form and in a hydrogen-deuterium exchanged deuterated form corresponding to all OH moieties being replaced by ODs. These samples, which diffracted to a resolution of around 0.9 A, gave diffraction diagrams consisting of several hundred independent diffraction spots. Crystalline cellulose II fibres resulting from the mercerization of flax were also studied in a hydrogenated form using NaOH/H2O as mercerizing medium and in a deuterated form using NaOD/D2O. Both of these samples diffracted to around 1.2 A, giving fibre diffraction diagrams slightly less resolved than those of cellulose I, but still consisting of more than one hundred independent diffraction spots. For cellulose I as well as for cellulose II, significant differences between the hydrogenated and deuterated patterns were observed and recorded. These new data should lead to improved structures for cellulose and direct identification of the position of hydrogen atoms involved in hydrogen bonding. 相似文献
10.
Dishun Zhao He LiJuan Zhang Linlin FuMengshuai Liu Jiangtao FuPeibing Ren 《Carbohydrate polymers》2012,87(2):1490-1494
Two kinds of alkylimidazolium salts containing dimethyl phosphate or diethyl phosphate were obtained as room temperature ionic liquids synthesized by one step, and both of them have the ability to dissolve untreated cellulose. Especially, 1-ethyl-3-methylimidazolium diethylphosphonate ([EMIM]DEP) could obtain 4 wt% cellulose solution within 10 min under 90. The effects of dissolution temperature on cellulose dissolution time and degree of polymerization were investigated. As dissolution temperature increased, dissolution time was greatly reduced. Both the original and regenerated cellulose samples were characterized with wide-angle X-ray diffraction, thermogravimetric analysis and scanning electron micrograph. The results showed that the crystalline structure of cellulose was converted to cellulose II from cellulose I in native cellulose. It was also found that the regenerated cellulose had good thermal stability with [EMIM]DEP ionic liquid. 相似文献
11.
Adhesion measurements have been performed with thin cellulose films using continuum contact mechanics with application of the JKR theory. Three different cellulose surfaces were prepared, one crystalline and two surfaces with a lower degree of crystalline order. Adhesion between two cross-linked poly(dimethylsiloxane) (PDMS) caps, as well as the adhesion between PDMS and the various cellulose surfaces, was measured. The work of adhesion (from loading) was found to be similar for all three surfaces, and from contact angle measurement with methylene iodide it was concluded that dispersive interactions dominate. However, the adhesion hysteresis differed significantly, being larger for a less ordered cellulose surface and decreasing with increasing degree of crystalline order. This is suggested to be due to the surface groups' ability to orient themselves and participate in specific or nonspecific interactions, where a surface with a lower degree of crystalline order has a higher possibility for reorientation of the surface groups. The mobility of cellulose chains increases with water uptake, resulting in stronger adhesive joints. These films will hence allow for determination of the contributions of hydrogen bonding and inter-diffusion on the adhesion, determined from the unloading data, as the thermodynamic work of adhesion was found to be independent of the cellulose surface used. 相似文献
12.
Daniel Van OpdenboschPhilipp Maisch Gerhard Fritz-PopovskiOskar Paris Cordt Zollfrank 《Carbohydrate polymers》2012,87(1):257-264
Transparent cellulose sheets were prepared through tape-casting a solution of cellulose. Flexible, luminescent sheets were produced by adding europium trichloride to the casting solution and treating the sheets with an aqueous solution of ammonium fluoride. Scanning electron micrographs of the resulting sheets showed europium trifluoride particles with diameters from 200 nm to 500 nm. These were found by transmission electron microscopy to be agglomerates of crystallites in the size range of 10-20 nm. The structure of supercritically dried sheets was further assessed by small-angle X-ray scattering and suggests a preferred orientation of slightly elongated pores of roughly 12 nm in diameter. Evaluation of the emission characteristics of the sheets showed the band pattern between 580 nm and 700 nm typical for Eu3+ phosphors. Our developed process is a versatile tool for the fabrication of transparent cellulose structures with different shapes and various embedded functional particles. 相似文献
13.
Olga Volfová Olga Suchardová Jan Panoš Vladimír Krumphanzl 《Applied microbiology and biotechnology》1985,22(4):246-248
Summary A wild coculture of obligately thermophilic bacteria, including only a single cellulolytic species Clostridium, ferments 2% crystalline cellulose and produces 4.6–5.1 g·l–1 of ethanol at 55°–60° C; that is, 0.96–1.1 moles of ethanol from 1 mole of glucose equivalent of cellulose degraded. However, the ethanol yield decreases with increasing cellulose concentration. Ethanolacetic acid ratio varies around 1 and cannot be influenced by substrate concentration. However, this ratio can be influenced by changing pH and temperature. For the ethanol production from cellulose, neutral and weekly alkaline media with a pH of 7.0–8.0 and a temperature of 55° C are optimal. Experiments in which the coculture was subjected to high ethanol concentrations showed that higher concentrations of added ethanol (up to 20 g·l–1) suppress cellulose degradation by 50% and inhibit the actual production of ethanol. 相似文献
14.
Takashi Sasaki Takashi Tanaka Noriko Nanbu Yohko Sato Keiji Kainuma 《Biotechnology and bioengineering》1979,21(6):1031-1042
Chemical and physical treatments of cotton cellulose have been studied in order to elucidate the relationship between the degree of crystallinity of cellulose and the susceptibility of cellulose to cellulase. Cotton cellulose powder was treated with the following solvents: 60% H2SO4, Cadoxen, and DMSO-p -formaldehyde. The dissolved celluloses were recovered at high yield of over 97% by addition of nine volumes of cold acetone. X-ray diffraction for measurements of relative crystallinity showed that the crystalline structure of cellulose declined in quantity and perfection by the dissolving treatment and changed to an amorphous form that is highly susceptible to enzymatic hydrolysis. These reprecipitated celluloses were hydrolyzed almost completely within 48 hr by Aspergillus niger cellulase containing mainly 1,4-β-glucan glucanohydrolase (EC 3.2.1.4), without action of 1,4-β-glucan cellobiohydrolase (EC 3.2.1. 91). On the other hand, cryo-milled cellulose (below 250 mesh) still had a crystalline structure, was resistant to cellulase, and gave a low percentage of saccharification. These results indicate that in pure cellulose there are good correlations between x-ray diffractograms and susceptibility to microbial cellulase. 相似文献
15.
Azam Jeihanipour Keikhosro Karimi Mohammad J. Taherzadeh 《Biotechnology and bioengineering》2010,105(3):469-476
Pretreatment of high‐crystalline cellulose with N‐methyl‐morpholine‐N‐oxide (NMO or NMMO) to improve bioethanol and biogas production was investigated. The pretreatments were performed at 90 and 120°C for 0.5–15 h in three different modes, including dissolution (85% NMO), ballooning (79% NMO), and swelling (73% NMO). The pretreated materials were then enzymatically hydrolyzed and fermented to ethanol or anaerobically digested to biogas (methane). The pretreatment at 85% NMO, 120°C and 2.5 h resulted in 100% yield in the subsequent enzymatic hydrolysis and around 150% improvement in the yield of ethanol compared to the untreated and water‐treated material. However, the best results of biogas production were obtained when the cellulose was treated with swelling and ballooning mode, which gave almost complete digestion in 15 days. Thus, the pretreatment resulted in 460 g ethanol or 415 L methane from each kg of cellulose. Analysis of the structure of treated and untreated celluloses showed that the dissolution mode can efficiently convert the crystalline cellulose I to cellulose II. However, it decreases the water swelling capacity of the cellulose. On the other hand, swelling and ballooning modes in NMO treatment were less efficient in both water swelling capacity and cellulose crystallinity. No cellulose loss, ambient pressure, relatively moderate conditions, and high efficiency make the NMO a good alternative for pretreatment of high‐crystalline cellulosic materials. Biotechnol. Bioeng. 2010; 105: 469–476. © 2009 Wiley Periodicals, Inc. 相似文献
16.
This paper reports a homogeneous modification of microcrystalline cellulose (MCC) in ionic liquids via radiation-induced grafting. Thermosensitive poly (N-isopropylacrylamide) (PNIPAAm) was successfully grafted onto MCC in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) ionic liquid using γ-ray irradiation technique at room temperature. The grafting yield (GY) increased with dose up to 40 kGy, while decreased slightly with dose rate from 22 to 102 Gy/min. The results of TGA indicated that cellulose grafted PNIPAAm (cellulose-g-PNIPAAm) had higher thermal stability than that of ungrafted regenerated cellulose (reg-cellulose). The crystalline structure of original MCC was largely destroyed during the dissolution process according to the XRD profiles, and grafting PNIPAAm onto cellulose further decreased the intensity of crystallinity. SEM showed that reg-cellulose and cellulose-g-PNIPAAm films displayed dense and homogeneous morphology. Moreover, the resulting cellulose-g-PNIPAAm exhibited obvious thermal sensitivity with a lower critical solution temperature around 35 °C, which was observed from the swelling behavior in water at different temperatures. 相似文献
17.
Adsorption of a xylanase purified from Pulpzyme HC onto alkali-lignin and crystalline cellulose 总被引:2,自引:0,他引:2
Adsorption of a xylanase purified from a commercial xylanase, Pulpzyme HC, onto two model components of kraft pulp, crystalline cellulose (Avicel) and alkali-lignin (Indulin AT), was studied at 40°C. A considerable amount of the purified xylanase was adsorbed onto alkali-lignin in alkaline solutions. The adsorption of the purified xylanase onto crystalline cellulose was not significant and could be described by the Langmuir-type adsorption isotherm. The adsorption of the purified xylanase onto alkali-lignin was assumed to be caused by physical or van der Waals interaction based on the result that NaCl did not change the adsorption isotherm. © Rapid Science Ltd. 1998 相似文献
18.
A variety of commercially used cellulose derivatives were compared with crystalline cellulose as substrates for induction of cellulase biosynthesis in the actinomycete Thermomonospora curvata. Cellulase induction during growth on uncoated cellophane was as rapid as that on crystalline cellulose, but on coated cellophanes, induction was delayed. Susceptibility to enzymatic attack determined the inductive potential of the substrate. Cellulose acetate was a poor substrate because of its extreme recalcitrance to attack. With other cellulose derivatives, soluble sugar accumulation caused a transient repression of cellulase biosynthesis, but the ratio of cellobiose (a cellulase inducer) to glucose (a cellulase repressor) was not a controlling factor. Crystalline cellulose yielded the lowest inducer/repressor sugar ratio (1.1:1 compared to 3.8–4.0:1 for cellulose derivatives), but supported the highest cellulase production. Glucose could not repress cellulase biosynthesis in the presence of cellobiose due to the strong preference for uptake of the disaccharide even by glucose-grown cells. 相似文献
19.
Summary Quantities of disencrusted sub-elementary cellulose fibrils from the cell wall of rose cells culturedin vitro were prepared. Following an X-ray and electron diffraction analysis, these fibrils gave a cellulose diffraction pattern which presented only two strong equatorial diffraction spacings at 0.409 and 0.572 nm indicating that the fibrils have a crystalline structure resembling that of cellulose IVI. This observation is best explained in terms of a lateral disorganization of the cellulose chains within the fibrils. This disorganization cannot be eliminated and is connected with the small width of the fibrils which contain from 12 to 25 cellulose chains only. In these fibrils, most of the cellulose chains are superficial and not locked with neighboring chains in a tight hydrogen bond system as in thicker cellulose microfibrils. 相似文献
20.
Composite particles of rice starch (RS) and microcrystalline cellulose were fabricated by spray-drying technique to be used
as a directly compressible excipient. Two size fractions of microcry stalline cellulose, sieved (MCS) and jet milled (MCJ),
having volumetric mean diameter (D50) of 13.61 and 40.51 μm, respectively, were used to form composite particles with RS in various mixing ratios. The composite
particles produced were evaluated for their powder and compression properties. Although an increase in the microcrystalline
cellulose proportion imparted greater compressibility of the composite particles, the shape of the particles was typically
less spherical with rougher surface resulting in a decrease in the degree of flowability. Compressibility of composite particles
made from different size fractions of microcrystalline cellulose was not different; however, using MCJ, which had a particle
size range close to the size of RS (D50=13.57 μm), provided more spherical particles than using MCS. Spherical composite particles between RS and MCJ in the ratio
of 7∶3 (RS-MCJ-73) were then evaluated for powder properties and compressibility in comparison with some marketed directly
compressible diluents. Compressibility of RS-MCJ-73 was greater than commercial spray-dried RS (Eratab), coprocessed lactose
and microcrystalline cellulose (Cellactose), and agglomerated lactose (Tablettose), but, as expected, lower than microcrystalline
cellulose (Vivapur 101). Flowability index of RS-MCJ-73 appeared to be slightly lower than Eratab but higher than Vivapur
101, Cellactose, and Tablettose. Tablets of RS-MCJ-73 exhibited low friability and good self-disintegrating property. It was
concluded that these developed composite particles could be introduced as a new coprocessed direct compression excipient. 相似文献