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Sample records for decrease cellulose crystallinity

  1. KORRIGAN1 and its aspen homolog PttCel9A1 decrease cellulose crystallinity in Arabidopsis stems.

    PubMed

    Takahashi, Junko; Rudsander, Ulla J; Hedenström, Mattias; Banasiak, Alicja; Harholt, Jesper; Amelot, Nicolas; Immerzeel, Peter; Ryden, Peter; Endo, Satoshi; Ibatullin, Farid M; Brumer, Harry; del Campillo, Elena; Master, Emma R; Scheller, Henrik Vibe; Sundberg, Björn; Teeri, Tuula T; Mellerowicz, Ewa J

    2009-06-01

    KORRIGAN1 (KOR1) is a membrane-bound cellulase implicated in cellulose biosynthesis. PttCel9A1 from hybrid aspen (Populus tremula L. x tremuloides Michx.) has high sequence similarity to KOR1 and we demonstrate here that it complements kor1-1 mutants, indicating that it is a KOR1 ortholog. We investigated the function of PttCel9A1/KOR1 in Arabidopsis secondary growth using transgenic lines expressing 35S::PttCel9A1 and the KOR1 mutant line irx2-2. The presence of elevated levels of PttCel9A1/KOR1 in secondary walls of 35S::PttCel9A1 lines was confirmed by in muro visualization of cellulase activity. Compared with the wild type, 35S::PttCel9A1 lines had higher trifluoroacetic acid (TFA)-hydrolyzable glucan contents, similar Updegraff cellulose contents and lower cellulose crystallinity indices, as determined by (13)C solid-state nuclear magnetic resonance (NMR) spectroscopy. irx2-2 mutants had wild-type TFA-hydrolyzable glucan contents, but reduced Updegraff cellulose contents and higher than wild-type cellulose crystallinity indices. The data support the hypothesis that PttCel9A1/KOR1 activity is present in cell walls, where it facilitates cellulose biosynthesis in a way that increases the amount of non-crystalline cellulose.

  2. Highly ordered cellulose II crystalline regenerated from cellulose hydrolyzed by 1-butyl-3-methylimidazolium chloride.

    PubMed

    Ahn, Yongjun; Song, Younghan; Kwak, Seung-Yeop; Kim, Hyungsup

    2016-02-10

    This research focused on the preparation of highly ordered cellulose II crystalline by cellulose hydrolysis in ionic liquid, and the influence of molecular mobility on recrystallization of cellulose. The molar mass of cellulose was controlled by hydrolysis using 1-butyl-3-methylimidazolium chloride (BmimCl). The molecular mobility of cellulose dissolved in BmimCl was characterized by rheological properties. After characterization of cellulose solution and regeneration, change of molar mass and conversion to crystalline were monitored using gel-permeation chromatography and powder X-ray diffraction, respectively. The molar mass of the cellulose in BmimCl was remarkably decreased with an increase in duration time, resulting in better mobility and a lower conformational constraint below critical molar mass. The decrease in molar mass surprisingly increased the crystallinity up to ∼ 85%, suggesting a recrystallization rate dependence of the mobility. The correlation between the mobility and recrystallization rate represented quit different behavior above and below a critical molar mass, which strongly demonstrated to the effect of mobility on the conversion of amorphous state to crystalline structure.

  3. Reactive Liftoff of Crystalline Cellulose Particles

    PubMed Central

    Teixeira, Andrew R.; Krumm, Christoph; Vinter, Katherine P.; Paulsen, Alex D.; Zhu, Cheng; Maduskar, Saurabh; Joseph, Kristeen E.; Greco, Katharine; Stelatto, Michael; Davis, Eric; Vincent, Brendon; Hermann, Richard; Suszynski, Wieslaw; Schmidt, Lanny D.; Fan, Wei; Rothstein, Jonathan P.; Dauenhauer, Paul J.

    2015-01-01

    The condition of heat transfer to lignocellulosic biomass particles during thermal processing at high temperature (>400 °C) dramatically alters the yield and quality of renewable energy and fuels. In this work, crystalline cellulose particles were discovered to lift off heated surfaces by high speed photography similar to the Leidenfrost effect in hot, volatile liquids. Order of magnitude variation in heat transfer rates and cellulose particle lifetimes was observed as intermediate liquid cellulose droplets transitioned from low temperature wetting (500–600 °C) to fully de-wetted, skittering droplets on polished surfaces (>700 °C). Introduction of macroporosity to the heated surface was shown to completely inhibit the cellulose Leidenfrost effect, providing a tunable design parameter to control particle heat transfer rates in industrial biomass reactors. PMID:26057818

  4. Reactive Liftoff of Crystalline Cellulose Particles

    NASA Astrophysics Data System (ADS)

    Teixeira, Andrew R.; Krumm, Christoph; Vinter, Katherine P.; Paulsen, Alex D.; Zhu, Cheng; Maduskar, Saurabh; Joseph, Kristeen E.; Greco, Katharine; Stelatto, Michael; Davis, Eric; Vincent, Brendon; Hermann, Richard; Suszynski, Wieslaw; Schmidt, Lanny D.; Fan, Wei; Rothstein, Jonathan P.; Dauenhauer, Paul J.

    2015-06-01

    The condition of heat transfer to lignocellulosic biomass particles during thermal processing at high temperature (>400 °C) dramatically alters the yield and quality of renewable energy and fuels. In this work, crystalline cellulose particles were discovered to lift off heated surfaces by high speed photography similar to the Leidenfrost effect in hot, volatile liquids. Order of magnitude variation in heat transfer rates and cellulose particle lifetimes was observed as intermediate liquid cellulose droplets transitioned from low temperature wetting (500-600 °C) to fully de-wetted, skittering droplets on polished surfaces (>700 °C). Introduction of macroporosity to the heated surface was shown to completely inhibit the cellulose Leidenfrost effect, providing a tunable design parameter to control particle heat transfer rates in industrial biomass reactors.

  5. A single molecule study of cellulase hydrolysis of crystalline cellulose

    NASA Astrophysics Data System (ADS)

    Liu, Yu-San; Luo, Yonghua; Baker, John O.; Zeng, Yining; Himmel, Michael E.; Smith, Steve; Ding, Shi-You

    2010-02-01

    Cellobiohydrolase-I (CBH I), a processive exoglucanase secreted by Trichoderma reesei, is one of the key enzyme components in a commercial cellulase mixture currently used for processing biomass to biofuels. CBH I contains a family 7 glycoside hydrolase catalytic module, a family 1 carbohydrate-binding module (CBM), and a highlyglycosylated linker peptide. It has been proposed that the CBH I cellulase initiates the hydrolysis from the reducing end of one cellulose chain and successively cleaves alternate β-1,4-glycosidic bonds to release cellobiose as its principal end product. The role each module of CBH I plays in the processive hydrolysis of crystalline cellulose has yet to be convincingly elucidated. In this report, we use a single-molecule approach that combines optical (Total Internal Reflection Fluorescence microscopy, or TIRF-M) and non-optical (Atomic Force Microscopy, or AFM) imaging techniques to analyze the molecular motion of CBM tagged with green fluorescence protein (GFP), and to investigate the surface structure of crystalline cellulose and changes made in the structure by CBM and CBH I. The preliminary results have revealed a confined nanometer-scale movement of the TrCBM1-GFP bound to cellulose, and decreases in cellulose crystal size as well as increases in surface roughness during CBH I hydrolysis of crystalline cellulose.

  6. Single Molecule Study of Cellulase Hydrolysis of Crystalline Cellulose

    SciTech Connect

    Liu, Y.-S.; Luo, Y.; Baker, J. O.; Zeng, Y.; Himmel, M. E.; Smith, S.; Ding, S.-Y.

    2009-12-01

    This report seeks to elucidate the role of cellobiohydrolase-I (CBH I) in the hydrolysis of crystalline cellulose. A single-molecule approach uses various imaging techniques to investigate the surface structure of crystalline cellulose and changes made in the structure by CBH I.

  7. Impact of ionic liquid pretreatment conditions on cellulose crystalline structure using 1-ethyl-3-methylimidazolium acetate.

    PubMed

    Cheng, Gang; Varanasi, Patanjali; Arora, Rohit; Stavila, Vitalie; Simmons, Blake A; Kent, Michael S; Singh, Seema

    2012-08-23

    Ionic liquids (ILs) have been shown to affect cellulose crystalline structure in lignocellulosic biomass during pretreatment. A systematic investigation of the swelling and dissolution processes associated with IL pretreatment is needed to better understand cellulose structural transformation. In this work, 3-20 wt % microcrystalline cellulose (Avicel) solutions were treated with 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) and a mixture of [C(2)mim][OAc] with the nonsolvent dimethyl sulfoxide (DMSO) at different temperatures. The dissolution process was slowed by decreasing the temperature and increasing cellulose loading, and was further retarded by addition of DMSO, enabling in-depth examination of the intermediate stages of dissolution. Results show that the cellulose I lattice expands and distorts prior to full dissolution in [C(2)mim][OAc] and that upon precipitation the former structure leads to a less ordered intermediate structure, whereas fully dissolved cellulose leads to a mixture of cellulose II and amorphous cellulose. Enzymatic hydrolysis was more rapid for the intermediate structure (crystallinity = 0.34) than for cellulose II (crystallinity = 0.54).

  8. Kinetic modeling of rapid enzymatic hydrolysis of crystalline cellulose after pretreatment by NMMO.

    PubMed

    Khodaverdi, Mahdi; Jeihanipour, Azam; Karimi, Keikhosro; Taherzadeh, Mohammad J

    2012-03-01

    Pretreatment of cellulose with an industrial cellulosic solvent, N-methylmorpholine-N-oxide, showed promising results in increasing the rate of subsequent enzymatic hydrolysis. Cotton linter was used as high crystalline cellulose. After the pretreatment, the cellulose was almost completely hydrolyzed in less than 12 h, using low enzyme loading (15 FPU/g cellulose). The pretreatment significantly decreased the total crystallinity of cellulose from 7.1 to 3.3, and drastically increased the enzyme adsorption capacity of cellulose by approximately 42 times. A semi-mechanistic model was used to describe the relationship between the cellulose concentration and the enzyme loading. In this model, two reactions for heterogeneous reaction of cellulose to glucose and cellobiose, and a homogenous reaction for cellobiose conversion to glucose was incorporated. The Langmuir model was applied to model the adsorption of cellulase onto the treated cellulose. The competitive inhibition was also considered for the effects of sugar inhibition on the rate of enzymatic hydrolysis. The kinetic parameters of the model were estimated by experimental results and evaluated.

  9. Cellulose-builder: a toolkit for building crystalline structures of cellulose.

    PubMed

    Gomes, Thiago C F; Skaf, Munir S

    2012-05-30

    Cellulose-builder is a user-friendly program that builds crystalline structures of cellulose of different sizes and geometries. The program generates Cartesian coordinates for all atoms of the specified structure in the Protein Data Bank format, suitable for using as starting configurations in molecular dynamics simulations and other calculations. Crystalline structures of cellulose polymorphs Iα, Iβ, II, and III(I) of practically any size are readily constructed which includes parallelepipeds, plant cell wall cellulose elementary fibrils of any length, and monolayers. Periodic boundary conditions along the crystallographic directions are easily imposed. The program also generates atom connectivity file in PSF format, required by well-known simulation packages such as NAMD, CHARMM, and others. Cellulose-builder is based on the Bash programming language and should run on practically any Unix-like platform, demands very modest hardware, and is freely available for download from ftp://ftp.iqm.unicamp.br/pub/cellulose-builder.

  10. Cellulose polymorphy, crystallite size, and the Segal crystallinity index

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The X-ray diffraction-based Segal Crystallinity Index (CI) was calculated for simulated different sizes of crystallites for cellulose I' and II. The Mercury software was used, and different crystallite sizes were based on different input peak widths at half of the maximum peak intensity (pwhm). The ...

  11. Identification and Characterization of a Large Protein Essential for Degradation of the Crystalline Region of Cellulose by Cytophaga hutchinsonii.

    PubMed

    Wang, Sen; Zhao, Dong; Bai, Xinfeng; Zhang, Weican; Lu, Xuemei

    2017-01-01

    Cytophaga hutchinsonii is a Gram-negative bacterium that can efficiently degrade crystalline cellulose by a unique mechanism different from the free cellulase or cellulosome strategy. In this study, chu_3220, encoding the hypothetical protein CHU_3220 (205 kDa), was identified by insertional mutation and gene deletion as the first gene essential for degradation of the crystalline region but not the amorphous region of cellulose by C. hutchinsonii A chu_3220 deletion mutant was defective in the degradation of crystalline cellulose and increased the degree of crystallinity of Avicel PH101 but could still degrade amorphous cellulose completely. CHU_3220 was found to be located on the outer surface of the outer membrane and could bind to cellulose. It contains 15 PbH1 domains and a C-terminal domain (CHU_C) that was proved to be critical for the localization of CHU_3220 on the cell surface and the function of CHU_3220 in crystalline cellulose degradation. Moreover, the degradation of crystalline cellulose was intact-cell dependent and inhibited by NaN3 Further study showed that chu_3220 was induced by cellulose and that the endoglucanase activity on the cell surface was significantly reduced without chu_3220 Real-time PCR revealed that the transcription of most genes encoding endoglucanases located on the cell surface was decreased in the chu_3220 deletion mutant, indicating that chu_3220 might also play a role in the regulation of the expression of some endoglucanases.

  12. Isolation and Characterization of Two Cellulose Morphology Mutants of Gluconacetobacter hansenii ATCC23769 Producing Cellulose with Lower Crystallinity

    PubMed Central

    Deng, Ying; Nagachar, Nivedita; Fang, Lin; Luan, Xin; Catchmark, Jeffrey M.; Tien, Ming; Kao, Teh-hui

    2015-01-01

    Gluconacetobacter hansenii, a Gram-negative bacterium, produces and secrets highly crystalline cellulose into growth medium, and has long been used as a model system for studying cellulose synthesis in higher plants. Cellulose synthesis involves the formation of β-1,4 glucan chains via the polymerization of glucose units by a multi-enzyme cellulose synthase complex (CSC). These glucan chains assemble into ordered structures including crystalline microfibrils. AcsA is the catalytic subunit of the cellulose synthase enzymes in the CSC, and AcsC is required for the secretion of cellulose. However, little is known about other proteins required for the assembly of crystalline cellulose. To address this question, we visually examined cellulose pellicles formed in growth media of 763 individual colonies of G. hansenii generated via Tn5 transposon insertion mutagenesis, and identified 85 that produced cellulose with altered morphologies. X-ray diffraction analysis of these 85 mutants identified two that produced cellulose with significantly lower crystallinity than wild type. The gene disrupted in one of these two mutants encoded a lysine decarboxylase and that in the other encoded an alanine racemase. Solid-state NMR analysis revealed that cellulose produced by these two mutants contained increased amounts of non-crystalline cellulose and monosaccharides associated with non-cellulosic polysaccharides as compared to the wild type. Monosaccharide analysis detected higher percentages of galactose and mannose in cellulose produced by both mutants. Field emission scanning electron microscopy showed that cellulose produced by the mutants was unevenly distributed, with some regions appearing to contain deposition of non-cellulosic polysaccharides; however, the width of the ribbon was comparable to that of normal cellulose. As both lysine decarboxylase and alanine racemase are required for the integrity of peptidoglycan, we propose a model for the role of peptidoglycan in the

  13. Isolation and characterization of two cellulose morphology mutants of Gluconacetobacter hansenii ATCC23769 producing cellulose with lower crystallinity

    DOE PAGES

    Deng, Ying; Nagachar, Nivedita; Fang, Lin; ...

    2015-03-19

    Gluconacetobacter hansenii, a Gram-negative bacterium, produces and secrets highly crystalline cellulose into growth medium, and has long been used as a model system for studying cellulose synthesis in higher plants. Cellulose synthesis involves the formation of β-1,4 glucan chains via the polymerization of glucose units by a multi-enzyme cellulose synthase complex (CSC). These glucan chains assemble into ordered structures including crystalline microfibrils. AcsA is the catalytic subunit of the cellulose synthase enzymes in the CSC, and AcsC is required for the secretion of cellulose. However, little is known about other proteins required for the assembly of crystalline cellulose. To addressmore » this question, we visually examined cellulose pellicles formed in growth media of 763 individual colonies of G. hansenii generated via Tn5 transposon insertion mutagenesis, and identified 85 that produced cellulose with altered morphologies. X-ray diffraction analysis of these 85 mutants identified two that produced cellulose with significantly lower crystallinity than wild type. The gene disrupted in one of these two mutants encoded a lysine decarboxylase and that in the other encoded an alanine racemase. Solid-state NMR analysis revealed that cellulose produced by these two mutants contained increased amounts of non-crystalline cellulose and monosaccharides associated with non-cellulosic polysaccharides as compared to the wild type. Monosaccharide analysis detected higher percentages of galactose and mannose in cellulose produced by both mutants. Field emission scanning electron microscopy showed that cellulose produced by the mutants was unevenly distributed, with some regions appearing to contain deposition of non-cellulosic polysaccharides; however, the width of the ribbon was comparable to that of normal cellulose. As both lysine decarboxylase and alanine racemase are required for the integrity of peptidoglycan, we propose a model for the role of peptidoglycan

  14. Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis

    DOE PAGES

    Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.; ...

    2016-07-19

    Here, cellulose is the primary biopolymer responsible for maintaining the structural and mechanical integrity of cell walls and, during the fast pyrolysis of biomass, may be restricting cell wall expansion and inhibiting phase transitions that would otherwise facilitate efficient escape of pyrolysis products. Here, we test whether modifications in two physical properties of cellulose, its crystalline allomorph and degree of crystallinity, alter its performance during fast pyrolysis. We show that both crystal allomorph and relative crystallinity of cellulose impact the slate of primary products produced by fast pyrolysis. For both cellulose-I and cellulose-II, changes in crystallinity dramatically impact the fastmore » pyrolysis product portfolio. In both cases, only the most highly crystalline samples produced vapors dominated by levoglucosan. Cellulose-III, on the other hand, produces largely the same slate of products regardless of its relative crystallinity and produced as much or more levoglucosan at all crystallinity levels compared to cellulose-I or II. In addition to changes in products, the different cellulose allomorphs affected the viscoelastic properties of cellulose during rapid heating. Real-time hot-stage pyrolysis was used to visualize the transition of the solid material through a molten phase and particle shrinkage. SEM analysis of the chars revealed additional differences in viscoelastic properties and molten phase behavior impacted by cellulose crystallinity and allomorph. Regardless of relative crystallinity, the cellulose-III samples displayed the most obvious evidence of having transitioned through a molten phase.« less

  15. Influence of crystal allomorph and crystallinity on the products and behavior of cellulose during fast pyrolysis

    SciTech Connect

    Mukarakate, Calvin; Mittal, Ashutosh; Ciesielski, Peter N.; Budhi, Sridhar; Thompson, Logan; Iisa, Kristiina; Nimlos, Mark R.; Donohoe, Bryon S.

    2016-07-19

    Here, cellulose is the primary biopolymer responsible for maintaining the structural and mechanical integrity of cell walls and, during the fast pyrolysis of biomass, may be restricting cell wall expansion and inhibiting phase transitions that would otherwise facilitate efficient escape of pyrolysis products. Here, we test whether modifications in two physical properties of cellulose, its crystalline allomorph and degree of crystallinity, alter its performance during fast pyrolysis. We show that both crystal allomorph and relative crystallinity of cellulose impact the slate of primary products produced by fast pyrolysis. For both cellulose-I and cellulose-II, changes in crystallinity dramatically impact the fast pyrolysis product portfolio. In both cases, only the most highly crystalline samples produced vapors dominated by levoglucosan. Cellulose-III, on the other hand, produces largely the same slate of products regardless of its relative crystallinity and produced as much or more levoglucosan at all crystallinity levels compared to cellulose-I or II. In addition to changes in products, the different cellulose allomorphs affected the viscoelastic properties of cellulose during rapid heating. Real-time hot-stage pyrolysis was used to visualize the transition of the solid material through a molten phase and particle shrinkage. SEM analysis of the chars revealed additional differences in viscoelastic properties and molten phase behavior impacted by cellulose crystallinity and allomorph. Regardless of relative crystallinity, the cellulose-III samples displayed the most obvious evidence of having transitioned through a molten phase.

  16. Exploring crystalline-structural variations of cellulose during alkaline pretreatment for enhanced enzymatic hydrolysis.

    PubMed

    Ling, Zhe; Chen, Sheng; Zhang, Xun; Xu, Feng

    2017-01-01

    The study aimed to explore the crystallinity and crystalline structure of alkaline pretreated cellulose. The enzymatic hydrolysis followed by pretreatment was conducted for measuring the efficiency of sugar conversion. For cellulose Iβ dominated samples, alkaline pretreatment (<8wt%) caused increased cellulose crystallinity and depolymerized hemicelluloses, that were superimposed to affect the enzymatic conversion to glucose. Varying crystallite sizes and lattice spacings indicated the separation of cellulose crystals during mercerization (8-12wt% NaOH). Completion of mercerization was proved under higher alkaline concentration (14-18wt% NaOH), leading to distortion of crystalline cellulose to some extent. Cellulose II crystallinity showed a stimulative impact on enzymatic hydrolysis due to the weakened hydrophobic interactions within cellulose chains. The current study may provide innovative explanations for enhanced enzymatic digestibility of alkaline pretreated lignocellulosic materials.

  17. New application of crystalline cellulose in rubber composites

    NASA Astrophysics Data System (ADS)

    Bai, Wen

    Rubber without reinforcement has limited applications. The strength of reinforced rubber composites can be ten times stronger than that of unreinforced rubbers. Therefore, rubber composites are widely used in various applications ranging from automobile tires to seals, valves, and gaskets because of their excellent mechanical elastic properties. Silica and carbon black are the two most commonly used reinforcing materials in rubber tires. They are derived from non-renewable materials and are expensive. Silica also contributes to a large amount of ash when used tires are disposed of by incineration. There is a need for a new reinforcing filler that is inexpensive, renewable and easily disposable. Cellulose is the most abundant natural polymer. Native cellulose includes crystalline regions and amorphous regions. Crystalline cellulose can be obtained by removing the amorphous regions with the acid hydrolysis of cellulose because the amorphous cellulose can be hydrolyzed faster than crystalline cellulose. We recently discovered that the partial replacement of silica with microcrystalline cellulose (MCC) provided numerous benefits: (1) low energy consumption for compounding, (2) good processability, (3) strong tensile properties, (4) good heat resistance, and (5) potential for good fuel efficiency in the application of rubber tires. Strong bonding between fillers and a rubber matrix is essential for imparting rubber composites with the desired properties for many specific applications. The bonding between hydrophilic MCC and the hydrophobic rubber matrix is weak and can be improved by addition of a coupling agent or surface modifications of MCC. In this study, MCC was surface-modified with acryloyl chloride or alkenyl ketene dimer (AnKD) to form acrylated MCC (A-MCC) and AnKD-modified MCC (AnKD-MCC). The surface modifications of MCC did not change the integrity and mechanical properties of MCC, but provided functional groups that were able to form covalent linkages with

  18. Vibrational sum frequency generation (SFG) spectroscopic study of crystalline cellulose in biomass

    NASA Astrophysics Data System (ADS)

    Kim, Seong H.; Lee, Christopher M.; Kafle, Kabindra; Park, Yong Bum; Xi, Xiaoning

    2013-09-01

    The noncentrosymmetry requirement of sum frequency generation (SFG) spectroscopy allows selective detection of crystalline cellulose in plant cell walls and lignocellulose biomass without spectral interferences from hemicelluloses and lignin. In addition, the phase synchronization requirement of the SFG process allows noninvasive investigation of spatial arrangement of crystalline cellulose microfibrils in the sample. This paper reviews how these principles are applied to reveal structural information of crystalline cellulose in plant cell walls and biomass.

  19. Coarse-grained model for the interconversion between different crystalline cellulose allomorphs

    SciTech Connect

    Langan, Paul

    2012-01-01

    We present the results of Langevin dynamics simulations on a coarse grained model for crystalline cellulose. In particular, we analyze two different cellulose crystalline forms: cellulose I (the natural form of cellulose) and cellulose IIII (obtained after cellulose I is treated with anhydrous liquid ammonia). Cellulose IIII has been the focus of wide interest in the field of cellulosic biofuels as it can be efficiently hydrolyzed to glucose (its enzymatic degradation rates are up to 5 fold higher than those of cellulose I ). In turn, glucose can eventually be fermented into fuels. The coarse-grained model presented in this study is based on a simplified geometry and on an effective potential mimicking the changes in both intracrystalline hydrogen bonds and stacking interactions during the transition from cellulose I to cellulose IIII. The model accurately reproduces both structural and thermomechanical properties of cellulose I and IIII. The work presented herein describes the structural transition from cellulose I to cellulose IIII as driven by the change in the equilibrium state of two degrees of freedom in the cellulose chains. The structural transition from cellulose I to cellulose IIII is essentially reduced to a search for optimal spatial arrangement of the cellulose chains.

  20. Solvent-Driven Preferential Association of Lignin with Regions of Crystalline Cellulose in Molecular Dynamics Simulation

    SciTech Connect

    Lindner, Benjamin; Petridis, Loukas; Schulz, Roland; Smith, Jeremy C

    2013-01-01

    The precipitation of lignin onto cellulose after pretreatment of lignocellulosic biomass is an obstacle to economically viable cellulosic ethanol production. Here, 750 ns nonequilibrium molecular dynamics simulations are reported of a system of lignin and cellulose in aqueous solution. Lignin is found to strongly associate with itself and the cellulose. However, noncrystalline regions of cellulose are observed to have a lower tendency to associate with lignin than crystalline regions, and this is found to arise from stronger hydration of the noncrystalline chains. The results suggest that the recalcitrance of crystalline cellulose to hydrolysis arises not only from the inaccessibility of inner fibers but also due to the promotion of lignin adhesion.

  1. Understanding changes in cellulose crystalline structure of lignocellulosic biomass during ionic liquid pretreatment by XRD.

    PubMed

    Zhang, Jiafu; Wang, Yixun; Zhang, Liye; Zhang, Ruihong; Liu, Guangqing; Cheng, Gang

    2014-01-01

    X-ray diffraction (XRD) was used to understand the interactions of cellulose in lignocellulosic biomass with ionic liquids (ILs). The experiment was designed in such a way that the process of swelling and solubilization of crystalline cellulose in plant cell walls was followed by XRD. Three different feedstocks, switchgrass, corn stover and rice husk, were pretreated using 1-butyl-3-methylimidazolium acetate ([C4mim][OAc]) at temperatures of 50-130°C for 6h. At a 5 wt.% biomass loading, increasing pretreatment temperature led to a drop in biomass crystallinity index (CrI), which was due to swelling of crystalline cellulose. After most of the crystalline cellulose was swollen with IL molecules, a low-order structure was found in the pretreated samples. Upon further increasing temperature, cellulose II structure started to form in the pretreated biomass samples as a result of solubilization of cellulose in [C4mim][OAc] and subsequent regeneration.

  2. A chemoenzymatic approach to protein immobilization onto crystalline cellulose nanoscaffolds.

    PubMed

    Uth, Christina; Zielonka, Stefan; Hörner, Sebastian; Rasche, Nicolas; Plog, Andreas; Orelma, Hannes; Avrutina, Olga; Zhang, Kai; Kolmar, Harald

    2014-11-10

    The immobilization of bioactive molecules onto nanocellulose leads to constructs that combine the properties of the grafted compounds with the biocompatibility and low cytotoxicity of cellulose carriers and the advantages given by their nanometer dimensions. However, the methods commonly used for protein grafting suffer from lack of selectivity, long reaction times, nonphysiological pH ranges and solvents, and the necessity to develop a tailor-made reaction strategy for each individual case. To overcome these restrictions, a generic two-step procedure was developed that takes advantage of the highly efficient oxime ligation combined with enzyme-mediated protein coupling onto the surface of peptide-modified crystalline nanocellulose. The described method is based on efficient and orthogonal transformations, requires no organic solvents, and takes place under physiological conditions. Being site-directed and regiospecific, it could be applied to a vast number of functional proteins.

  3. Periplasmic Cytophaga hutchinsonii Endoglucanases Are Required for Use of Crystalline Cellulose as the Sole Source of Carbon and Energy

    PubMed Central

    Zhu, Yongtao; Han, Lanlan; Hefferon, Kathleen L.; Silvaggi, Nicholas R.; Wilson, David B.

    2016-01-01

    ABSTRACT The soil bacterium Cytophaga hutchinsonii actively digests crystalline cellulose by a poorly understood mechanism. Genome analyses identified nine genes predicted to encode endoglucanases with roles in this process. No predicted cellobiohydrolases, which are usually involved in the utilization of crystalline cellulose, were identified. Chromosomal deletions were performed in eight of the endoglucanase-encoding genes: cel5A, cel5B, cel5C, cel9A, cel9B, cel9C, cel9E, and cel9F. Each mutant retained the ability to digest crystalline cellulose, although the deletion of cel9C caused a modest decrease in cellulose utilization. Strains with multiple deletions were constructed to identify the critical cellulases. Cells of a mutant lacking both cel5B and cel9C were completely deficient in growth on cellulose. Cell fractionation and biochemical analyses indicate that Cel5B and Cel9C are periplasmic nonprocessive endoglucanases. The requirement of periplasmic endoglucanases for cellulose utilization suggests that cellodextrins are transported across the outer membrane during this process. Bioinformatic analyses predict that Cel5A, Cel9A, Cel9B, Cel9D, and Cel9E are secreted across the outer membrane by the type IX secretion system, which has been linked to cellulose utilization. These secreted endoglucanases may perform the initial digestion within amorphous regions on the cellulose fibers, releasing oligomers that are transported into the periplasm for further digestion by Cel5B and Cel9C. The results suggest that both cell surface and periplasmic endoglucanases are required for the growth of C. hutchinsonii on cellulose and that novel cell surface proteins may solubilize and transport cellodextrins across the outer membrane. IMPORTANCE The bacterium Cytophaga hutchinsonii digests crystalline cellulose by an unknown mechanism. It lacks processive cellobiohydrolases that are often involved in cellulose digestion. Critical cellulolytic enzymes were identified by

  4. Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance.

    PubMed

    Park, Sunkyu; Baker, John O; Himmel, Michael E; Parilla, Philip A; Johnson, David K

    2010-05-24

    Although measurements of crystallinity index (CI) have a long history, it has been found that CI varies significantly depending on the choice of measurement method. In this study, four different techniques incorporating X-ray diffraction and solid-state 13C nuclear magnetic resonance (NMR) were compared using eight different cellulose preparations. We found that the simplest method, which is also the most widely used, and which involves measurement of just two heights in the X-ray diffractogram, produced significantly higher crystallinity values than did the other methods. Data in the literature for the cellulose preparation used (Avicel PH-101) support this observation. We believe that the alternative X-ray diffraction (XRD) and NMR methods presented here, which consider the contributions from amorphous and crystalline cellulose to the entire XRD and NMR spectra, provide a more accurate measure of the crystallinity of cellulose. Although celluloses having a high amorphous content are usually more easily digested by enzymes, it is unclear, based on studies published in the literature, whether CI actually provides a clear indication of the digestibility of a cellulose sample. Cellulose accessibility should be affected by crystallinity, but is also likely to be affected by several other parameters, such as lignin/hemicellulose contents and distribution, porosity, and particle size. Given the methodological dependency of cellulose CI values and the complex nature of cellulase interactions with amorphous and crystalline celluloses, we caution against trying to correlate relatively small changes in CI with changes in cellulose digestibility. In addition, the prediction of cellulase performance based on low levels of cellulose conversion may not include sufficient digestion of the crystalline component to be meaningful.

  5. Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance

    PubMed Central

    2010-01-01

    Although measurements of crystallinity index (CI) have a long history, it has been found that CI varies significantly depending on the choice of measurement method. In this study, four different techniques incorporating X-ray diffraction and solid-state 13C nuclear magnetic resonance (NMR) were compared using eight different cellulose preparations. We found that the simplest method, which is also the most widely used, and which involves measurement of just two heights in the X-ray diffractogram, produced significantly higher crystallinity values than did the other methods. Data in the literature for the cellulose preparation used (Avicel PH-101) support this observation. We believe that the alternative X-ray diffraction (XRD) and NMR methods presented here, which consider the contributions from amorphous and crystalline cellulose to the entire XRD and NMR spectra, provide a more accurate measure of the crystallinity of cellulose. Although celluloses having a high amorphous content are usually more easily digested by enzymes, it is unclear, based on studies published in the literature, whether CI actually provides a clear indication of the digestibility of a cellulose sample. Cellulose accessibility should be affected by crystallinity, but is also likely to be affected by several other parameters, such as lignin/hemicellulose contents and distribution, porosity, and particle size. Given the methodological dependency of cellulose CI values and the complex nature of cellulase interactions with amorphous and crystalline celluloses, we caution against trying to correlate relatively small changes in CI with changes in cellulose digestibility. In addition, the prediction of cellulase performance based on low levels of cellulose conversion may not include sufficient digestion of the crystalline component to be meaningful. PMID:20497524

  6. Thermal response in crystalline Ibeta cellulose: a molecular dynamics study.

    PubMed

    Bergenstråhle, Malin; Berglund, Lars A; Mazeau, Karim

    2007-08-02

    The influence of temperature on structure and properties of the cellulose Ibeta crystal was studied by molecular dynamics simulations with the GROMOS 45a4 force-field. At 300 K, the modeled crystal agreed reasonably with several sets of experimental data, including crystal density, corresponding packing and crystal unit cell dimensions, chain conformation parameters, hydrogen bonds, Young's modulus, and thermal expansion coefficient at room temperature. At high-temperature (500 K), the cellulose chains remained in sheets, despite differences in the fine details compared to the room-temperature structure. The density decreased while the a and b cell parameters expanded by 7.4% and 6%, respectively, and the c parameter (chain axis) slightly contracted by 0.5%. Cell angles alpha and beta divided into two populations. The hydroxymethyl groups mainly adopted the gt orientation, and the hydrogen-bonding pattern thereby changed. One intrachain hydrogen bond, O2'H2'...O6, disappeared and consequently the Young's modulus decreased by 25%. A transition pathway between the low- and high-temperature structures has been proposed, with an initial step being an increased intersheet separation, which allowed every second cellulose chain to rotate around its helix axis by about 30 degrees . Second, all hydroxymethyl groups changed their orientations, from tg to gg (rotated chains) and from tg to gt (non-rotated chains). When temperature was further increased, the rotated chains returned to their original orientation and their hydroxymethyl groups again changed their conformation, from gg to gt. A transition temperature of about 450 K was suggested; however, the transition seems to be more gradual than sudden. The simulated data on temperature-induced changes in crystal unit cell dimensions and the hydrogen-bonding pattern also compared well with experimental results.

  7. Effect of cooking temperature on the crystallinity of acid hydrolysed-oil palm cellulose

    NASA Astrophysics Data System (ADS)

    Kuthi, Fatin Afifah Binti Ahmad; Badri, Khairiah Haji

    2014-09-01

    In this research, we studied the effect of acid hydrolysis temperature on the crystallinity of cellulose produced from empty fruit bunch (EFB). The hydrolysis temperature was studied from 120 to 140 °C at a fixed time and sulfuric acid, H2SO4 concentration which were 1 h and 1% (v/v) respectively. X-ray diffractometry (XRD) was carried out to measure the crystallinity of cellulose produced at varying hydrolysis temperatures. During hydrolysis, the amorphous region of α-cellulose was removed and the crystalline region was obtained. Percentage of crystallinity (CrI) for acid hydrolysed cellulose at 120, 130 and 140 °C were 54.21, 50.59 and 50.55 % respectively. Morphological studies using scanning electron microscope (SEM) showed that acid hydrolysis defibrilised to microfibrils in α-cellulose. The extraction process to produce α-cellulose has also been successfully carried out as the impurities at the outer surface, lignin and hemicellulose were removed. These findings were supported by the disappearance of peaks at 1732, 1512 and 1243 cm-1 on Fourier Transform infrared (FTIR) spectrum of α-cellulose. Similar peaks were identified in both the commercial microcrystalline cellulose (C-MCC) and acid hydrolysed cellulose (H-EFB), indicating the effectiveness of heat-catalysed acid hydrolysis.

  8. Characterization of the crystalline structure of cellulose using static and dynamic FT-IR spectroscopy.

    PubMed

    Akerholm, Margaretha; Hinterstoisser, Barbara; Salmén, Lennart

    2004-02-25

    The cellulose structure is a factor of major importance for the strength properties of wood pulp fibers. The ability to characterize small differences in the crystalline structures of cellulose from fibers of different origins is thus highly important. In this work, dynamic FT-IR spectroscopy has been further explored as a method sensitive to cellulose structure variations. Using a model system of two different celluloses, the relation between spectral information and the relative cellulose Ialpha content was investigated. This relation was then used to determine the relative cellulose Ialpha content in different pulps. The estimated cellulose I allomorph compositions were found to be reasonable for both unbleached and bleached chemical pulps. In addition, it was found that the dynamic FT-IR spectroscopy technique had the potential to indicate possible correlation field splitting peaks of cellulose Ibeta.

  9. A TSM sensor investigation of low crystallinity cellulose films.

    PubMed

    Reason, M; Teesdale-Spittle, P; Latham, R; Dawson, G; Porteous, P; Smith, G

    2001-07-03

    A thickness shear mode (TSM) quartz sensor has been used to characterize the substantivity, viscoelasticity, and mucoadhesive properties of low crystallinity cellulose (LCC) films. LCC is a novel pharmaceutical excipient that has been attributed with mucoadhesive properties. Thin films of LCC were deposited onto TSM sensors by a spin coating technique. The films were treated by passing water or 1.0% w/v mucin solution (pH 3.7 or 7.0) over the surface. Changes in the mass and viscosity of the film were observed by monitoring changes in the impedance spectra of the coated TSM sensors. Scanning electron micrographs (SEMs) of each film were used to assist the interpretation of the TSM sensor data. This study showed that LCC forms highly tenacious and viscoelastic films able to withstand prolonged (approximately 1 h) exposure to both water and mucin solution. Furthermore, these results indicate that the films may have mucoadhesive properties as LCC was found to bind significant (P<0.05) amounts of mucin in comparison with control measurements. Mucin binding to the LCC sensor was greater at pH 3.7 (P<0.05) than at pH 7.0, suggesting that the LCC formulation is mucoadhesive under these conditions.

  10. The effect of acid hydrolysis pretreatment on crystallinity and solubility of kenaf cellulose membrane

    SciTech Connect

    Saidi, Anis Syuhada Mohd; Zakaria, Sarani; Chia, Chin Hua; Jaafar, Sharifah Nabihah Syed; Padzil, Farah Nadia Mohammad

    2015-09-25

    Cellulose was extracted from kenaf core pulp (KCP) by series of bleaching steps in the sequence (DEED) where D and E are referred as acid and alkali treatment. The bleached kenaf pulp (BKCP) is then pretreated with acid hydrolysis at room temperature for 1 and 3 h respectively. The pretreated cellulose is dissolved in lithium hydroxide/urea (LiOH/urea) and cellulose solution produced was immersed in distilled water bath. BKCP without treatment was also conducted for comparison purpose. The effects of acid hydrolysis pretreatment on solubility and crystallinity are investigated. Higher solubility of cellulose solution is achieved for treated samples. Cellulose II formation and crystallinity index of the cellulose membrane were determined by X-ray diffraction (XRD)

  11. The effect of acid hydrolysis pretreatment on crystallinity and solubility of kenaf cellulose membrane

    NASA Astrophysics Data System (ADS)

    Saidi, Anis Syuhada Mohd; Zakaria, Sarani; Chia, Chin Hua; Jaafar, Sharifah Nabihah Syed; Padzil, Farah Nadia Mohammad

    2015-09-01

    Cellulose was extracted from kenaf core pulp (KCP) by series of bleaching steps in the sequence (DEED) where D and E are referred as acid and alkali treatment. The bleached kenaf pulp (BKCP) is then pretreated with acid hydrolysis at room temperature for 1 and 3 h respectively. The pretreated cellulose is dissolved in lithium hydroxide/urea (LiOH/urea) and cellulose solution produced was immersed in distilled water bath. BKCP without treatment was also conducted for comparison purpose. The effects of acid hydrolysis pretreatment on solubility and crystallinity are investigated. Higher solubility of cellulose solution is achieved for treated samples. Cellulose II formation and crystallinity index of the cellulose membrane were determined by X-ray diffraction (XRD).

  12. Can Delignification Decrease Cellulose Digestibility in Acid Pretreated Corn Stover?

    SciTech Connect

    Ishizawa, C. I.; Jeoh, T.; Adney, W. S.; Himmel, M. E.; Johnson, D. K.; Davis, M. F.

    2009-01-01

    It has previously been shown that the improved digestibility of dilute acid pretreated corn stover is at least partially due to the removal of xylan and the consequent increase in accessibility of the cellulose to cellobiohydrolase enzymes. We now report on the impact that lignin removal has on the accessibility and digestibility of dilute acid pretreated corn stover. Samples of corn stover were subjected to dilute sulfuric acid pretreatment with and without simultaneous (partial) lignin removal. In addition, some samples were completely delignified after the pretreatment step using acidified sodium chlorite. The accessibility and digestibility of the samples were tested using a fluorescence-labeled cellobiohydrolase (Trichoderma reesei Cel7A) purified from a commercial cellulase preparation. Partial delignification of corn stover during dilute acid pretreatment was shown to improve cellulose digestibility by T. reesei Cel7A; however, decreasing the lignin content below 5% (g g{sup -1}) by treatment with acidified sodium chlorite resulted in a dramatic reduction in cellulose digestibility. Importantly, this effect was found to be enhanced in samples with lower xylan contents suggesting that the near complete removal of xylan and lignin may cause aggregation of the cellulose microfibrils resulting in decreased cellulase accessibility.

  13. Cellulose Degradation Kinetics of Two Novel Bacterial Isolates That Preferentially Hydrolyze Crystalline Domains

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conversion of cellulosic biomass to bioenergy is extremely attractive in the recent climate of renewable energy research. Although a large number of organisms and fungi that have been isolated and characterized demonstrate an ability to hydrolyze both amorphous and crystalline domains of cellulose, ...

  14. Isolation and characterization of two cellulose morphology mutants of Gluconacetobacter hansenii ATCC23769 producing cellulose with lower crystallinity

    SciTech Connect

    Deng, Ying; Nagachar, Nivedita; Fang, Lin; Luan, Xin; Catchmark, Jeffrey M.; Tien, Ming; Kao, Teh -hui; Lai, Hsin -Chih

    2015-03-19

    Gluconacetobacter hansenii, a Gram-negative bacterium, produces and secrets highly crystalline cellulose into growth medium, and has long been used as a model system for studying cellulose synthesis in higher plants. Cellulose synthesis involves the formation of β-1,4 glucan chains via the polymerization of glucose units by a multi-enzyme cellulose synthase complex (CSC). These glucan chains assemble into ordered structures including crystalline microfibrils. AcsA is the catalytic subunit of the cellulose synthase enzymes in the CSC, and AcsC is required for the secretion of cellulose. However, little is known about other proteins required for the assembly of crystalline cellulose. To address this question, we visually examined cellulose pellicles formed in growth media of 763 individual colonies of G. hansenii generated via Tn5 transposon insertion mutagenesis, and identified 85 that produced cellulose with altered morphologies. X-ray diffraction analysis of these 85 mutants identified two that produced cellulose with significantly lower crystallinity than wild type. The gene disrupted in one of these two mutants encoded a lysine decarboxylase and that in the other encoded an alanine racemase. Solid-state NMR analysis revealed that cellulose produced by these two mutants contained increased amounts of non-crystalline cellulose and monosaccharides associated with non-cellulosic polysaccharides as compared to the wild type. Monosaccharide analysis detected higher percentages of galactose and mannose in cellulose produced by both mutants. Field emission scanning electron microscopy showed that cellulose produced by the mutants was unevenly distributed, with some regions appearing to contain deposition of non-cellulosic polysaccharides; however, the width of the ribbon was comparable to that of normal cellulose. As both lysine decarboxylase and alanine racemase are required for the integrity of peptidoglycan, we propose a model for the role of

  15. Effect of different alkaline solutions on crystalline structure of cellulose at different temperatures.

    PubMed

    Keshk, Sherif M A S

    2015-01-22

    Effect of alkaline solutions such as 10% NaOH, NaOH/urea and NaOH/ethylene glycol solutions on crystalline structure of different cellulosic fibers (cotton linter and filter paper) was investigated at room temperature and -4°C. The highest dissolution of cotton linter and filter paper was observed in NaOH/ethylene glycol at both temperatures. X-ray patterns of treated cotton linter with different alkaline solutions at low temperature showed only two diffractions at 2θ=12.5° and 21.0°, which belonged to the crystalline structure of cellulose II. CP/MAS (13)C NMR spectra showed the doublet peaks at 89.2 ppm and 88.3 ppm representing C4 resonance for cellulose I at room temperature, Whereas, at low temperature the doublet peaks were observed at 89.2 ppm and 87.8 ppm representing C4 resonance for cellulose II. Degree of polymerization of cellulose plays an important role in cellulose dissolution in different alkaline solutions and temperatures, where, a low temperature gives high dissolutions percentage with change in crystalline structure from cellulose I to cellulose II forms.

  16. Directed Biosynthesis of Oriented Crystalline Cellulose for Advanced Composite Fibers

    DTIC Science & Technology

    2012-05-03

    Cellulose for Advanced Composite Fibers 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Hugh...properties will allow the synthesis of composites possessing improved strength and functionality will be investigated. The bacterial cellulose fibers will

  17. Nanoscale cellulose films with different crystallinities and mesostructures--their surface properties and interaction with water.

    PubMed

    Aulin, Christian; Ahola, Susanna; Josefsson, Peter; Nishino, Takashi; Hirose, Yasuo; Osterberg, Monika; Wågberg, Lars

    2009-07-07

    A systematic study of the degree of molecular ordering and swelling of different nanocellulose model films has been conducted. Crystalline cellulose II surfaces were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water or by using the Langmuir-Schaefer (LS) technique. Amorphous cellulose films were also prepared by spin-coating of a precursor cellulose solution onto oxidized silicon wafers. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals and low-charged microfibrillated cellulose (LC-MFC). In addition, a dispersion of high-charged MFC was used for the buildup of polyelectrolyte multilayers with polyetheyleneimine on silica with the aid of the layer-by-layer (LbL) technique. These preparation methods produced smooth thin films on the nanometer scale suitable for X-ray diffraction and swelling measurements. The surface morphology and thickness of the cellulose films were characterized in detail by atomic force microscopy (AFM) and ellipsometry measurements, respectively. To determine the surface energy of the cellulose surfaces, that is, their ability to engage in different interactions with different materials, they were characterized through contact angle measurements against water, glycerol, and methylene iodide. Small incidence angle X-ray diffraction revealed that the nanocrystal and MFC films exhibited a cellulose I crystal structure and that the films prepared from N-methylmorpholine-N-oxide (NMMO), LiCl/DMAc solutions, using the LS technique, possessed a cellulose II structure. The degree of crystalline ordering was highest in the nanocrystal films (approximately 87%), whereas the MFC, NMMO, and LS films exhibited a degree of crystallinity of about 60%. The N,N-dimethylacetamide (DMAc)/LiCl film possessed very low crystalline ordering (<15%). It was also established that the films had different

  18. Cellulose nanocrystal from pomelo (C. Grandis osbeck) albedo: Chemical, morphology and crystallinity evaluation

    SciTech Connect

    Zain, Nor Fazelin Mat; Yusop, Salma Mohamad; Ahmad, Ishak

    2013-11-27

    Citrus peel is one of the under-utilized waste materials that have potential in producing a valuable fibre, which are cellulose and cellulose nanocrystal. Cellulose was first isolated from pomelo (C. Grandis Osbeck) albedo by combination of alkali treatment and bleaching process, followed by acid hydrolysis (65% H{sub 2}SO{sub 4}, 45 °C, 45min) to produce cellulose nanocrystal. The crystalline, structural, morphological and chemical properties of both materials were studied. Result reveals the crystallinity index obtained from X-ray diffraction for cellulose nanocrystal was found higher than extracted cellulose with the value of 60.27% and 57.47%, respectively. Fourier transform infrared showed that the chemical treatments removed most of the hemicellulose and lignin from the pomelo albedo fibre. This has been confirmed further by SEM and TEM for their morphological studies. These results showed that cellulose and cellulose nanocrystal were successfully obtained from pomelo albedo and might be potentially used in producing functional fibres for food application.

  19. Cellulose nanocrystal from pomelo (C. Grandis osbeck) albedo: Chemical, morphology and crystallinity evaluation

    NASA Astrophysics Data System (ADS)

    Zain, Nor Fazelin Mat; Yusop, Salma Mohamad; Ahmad, Ishak

    2013-11-01

    Citrus peel is one of the under-utilized waste materials that have potential in producing a valuable fibre, which are cellulose and cellulose nanocrystal. Cellulose was first isolated from pomelo (C. Grandis Osbeck) albedo by combination of alkali treatment and bleaching process, followed by acid hydrolysis (65% H2SO4, 45 °C, 45min) to produce cellulose nanocrystal. The crystalline, structural, morphological and chemical properties of both materials were studied. Result reveals the crystallinity index obtained from X-ray diffraction for cellulose nanocrystal was found higher than extracted cellulose with the value of 60.27% and 57.47%, respectively. Fourier transform infrared showed that the chemical treatments removed most of the hemicellulose and lignin from the pomelo albedo fibre. This has been confirmed further by SEM and TEM for their morphological studies. These results showed that cellulose and cellulose nanocrystal were successfully obtained from pomelo albedo and might be potentially used in producing functional fibres for food application.

  20. A cellular automaton model of crystalline cellulose hydrolysis by cellulases

    PubMed Central

    2011-01-01

    Background Cellulose from plant biomass is an abundant, renewable material which could be a major feedstock for low emissions transport fuels such as cellulosic ethanol. Cellulase enzymes that break down cellulose into fermentable sugars are composed of different types - cellobiohydrolases I and II, endoglucanase and β-glucosidase - with separate functions. They form a complex interacting network between themselves, soluble hydrolysis product molecules, solution and solid phase substrates and inhibitors. There have been many models proposed for enzymatic saccharification however none have yet employed a cellular automaton approach, which allows important phenomena, such as enzyme crowding on the surface of solid substrates, denaturation and substrate inhibition, to be considered in the model. Results The Cellulase 4D model was developed de novo taking into account the size and composition of the substrate and surface-acting enzymes were ascribed behaviors based on their movements, catalytic activities and rates, affinity for, and potential for crowding of, the cellulose surface, substrates and inhibitors, and denaturation rates. A basic case modeled on literature-derived parameters obtained from Trichoderma reesei cellulases resulted in cellulose hydrolysis curves that closely matched curves obtained from published experimental data. Scenarios were tested in the model, which included variation of enzyme loadings, adsorption strengths of surface acting enzymes and reaction periods, and the effect on saccharide production over time was assessed. The model simulations indicated an optimal enzyme loading of between 0.5 and 2 of the base case concentrations where a balance was obtained between enzyme crowding on the cellulose crystal, and that the affinities of enzymes for the cellulose surface had a large effect on cellulose hydrolysis. In addition, improvements to the cellobiohydrolase I activity period substantially improved overall glucose production. Conclusions

  1. Degradation of high loads of crystalline cellulose and of unpretreated plant biomass by the thermophilic bacterium Caldicellulosiruptor bescii.

    PubMed

    Basen, Mirko; Rhaesa, Amanda M; Kataeva, Irina; Prybol, Cameron J; Scott, Israel M; Poole, Farris L; Adams, Michael W W

    2014-01-01

    The thermophilic bacterium Caldicellulosiruptor bescii grows at 78 °C on high concentrations (200 g L(-1)) of both crystalline cellulose and unpretreated switchgrass, while low concentrations (<20 g L(-1)) of acid-pretreated switchgrass inhibit growth. Degradation of crystalline cellulose, but not that of unpretreated switchgrass, was limited by nitrogen and vitamin (folate) availability. Under optimal conditions, C. bescii solubilized approximately 60% of the crystalline cellulose and 30% of the unpretreated switchgrass using initial substrate concentrations of 50 g L(-1). Further fermentation of crystalline cellulose and of switchgrass was inhibited by organic acid end-products and by a specific inhibitor of C. bescii growth that did not affect other thermophilic bacteria, respectively. Soluble mono- and oligosaccharides, organic acids, carbon dioxide, and microbial biomass, quantitatively accounted for the crystalline cellulose and plant biomass carbon utilized. C. bescii therefore degrades industrially-relevant concentrations of lignocellulosic biomass that have not undergone pretreatment thereby demonstrating its potential utility in biomass conversion.

  2. Micro- and Nanostructures from Liquid Crystalline Cellulose Materials

    DTIC Science & Technology

    2011-03-03

    for the helical winding. In order to investigate the origin of the intrinsic curvature found in the cellulosic fibers, morphological and structural...Featured Research” by  SoftMatterWorld  Newsletter , 22, 2010.   The  final part of  the  report  concerns original  results  that are not published and are

  3. An Improved X-ray Diffraction Method For Cellulose Crystallinity Measurement

    SciTech Connect

    Ju, Xiaohui; Bowden, Mark E.; Brown, Elvie E.; Zhang, Xiao

    2015-06-01

    We show in this work a modified X-ray diffraction method to determine cellulose crystallinity index (CrI). Nanocrystalline cellulose (NCC) dervided from bleached wood pulp was used as a model substrate. Rietveld refinement was applied with consideration of March-Dollase preferred orientation at the (001) plane. In contrast to most previous methods, three distinct amorphous peaks identified from new model samples which are used to calculate CrI. A 2 theta range from 10° to 75° was found to be more suitable to determine CrI and crystallite structural parameters such as d-spacing and crystallite size. This method enables a more reliable measurement of CrI of cellulose and may be applicable to other types of cellulose polymorphs.

  4. An improved X-ray diffraction method for cellulose crystallinity measurement.

    PubMed

    Ju, Xiaohui; Bowden, Mark; Brown, Elvie E; Zhang, Xiao

    2015-06-05

    We show in this work a modified X-ray diffraction method to determine cellulose crystallinity index (CrI). Nanocrystalline cellulose (NCC) derived from bleached wood pulp was used as a model substrate. Rietveld refinement was applied with consideration of March-Dollase preferred orientation at the (001) plane. In contrast to most previous methods, three distinct amorphous peaks identified from new model samples which used to calculate CrI. A 2 theta range from 10° to 75° was found to be more suitable to determine CrI and crystallite structural parameters such as d-spacing and crystallite size. This method enables a more reliable measurement of CrI of cellulose and may be applicable to other types of cellulose polymorphs.

  5. Effect of Intrinsic Twist on Length of Crystalline and Disordered Regions in Cellulose Microfibrils

    NASA Astrophysics Data System (ADS)

    Nili, Abdolmadjid; Shklyaev, Oleg; Zhao, Zhen; Zhong, Linghao; Crespi, Vincent

    2013-03-01

    Cellulose is the most abundant biological material in the world. It provides mechanical reinforcement for plant cell wall, and could potentially serve as renewable energy source for biofuel. Native cellulose forms a non-centrosymmetric chiral crystal due to lack of roto-inversion symmetry of constituent glucose chains. Chirality of cellulose crystal could result in an overall twist. Competition between unwinding torsional/extensional and twisting energy terms leads to twist induced frustration along fibril's axis. The accumulated frustration could be the origin of periodic disordered regions observed in cellulose microfibrils. These regions could play significant role in properties of cellulose bundles and ribbons as well as biological implications on plant cell walls. We propose a mechanical model based on Frenkel-Kontorova mechanism to investigate effects of radius dependent twist on crystalline size in cellulose microfibrils. Parameters of the model are adjusted according to all-atom molecular simulations. This work is supported by the US Department of Energy, Office of Basic Energy Sciences as part of The Center for LignoCellulose Structure and Formation, an Energy Frontier Research Center

  6. Non-hydrolytic Disruption of Crystalline Structure of Cellulose by Cellulose Binding Domain and Linker Sequence of Cellobiohydrolase I from Penicillium janthinellum.

    PubMed

    Gao, Pei-Ji; Chen, Guan-Jun; Wang, Tian-Hong; Zhang, Ying-Shu; Liu, Jie

    2001-01-01

    The cooperation between cellobiohydrolase (CBHI) and endoglucanase (EG) is necessary for biodegradation of native cellulose, but its mechanism is still poorly understood. The present paper report at the first time that an isolated component, the cellulose binding domain with its linker sequence of cellobiohydrolase I from Penicillium janthinellum (CBD(CBHI)), plays an important role in the synergism between CBHI and EGI during cellulose biodegradation. A recombinantplasmid (pUC18C), containing the gene fragment encoding CBD(CBHI) from P.janthinellum was derived from pUC18-181. In pUC 18C, the catalytic domain region of cbhI gene was deleted by in vitro DNA manipulations and then E.coli JM 109 was transformed for the production of LacZ-CBD fusion protein. The active LacZ-CBD fusion protein was digested by papain and then purified by re-exclusion chromatography. The purified peptide sequence of CBD(CBHI) had the ability of binding crystalline cellulose. The detailed morphological and structural changes of cotton fibers after binding CBD(CBHI) were investigated by using scanning electron microscopy, calorimetric activity and X-ray diffraction. The results demonstrated that the CBD(CBHI) not only has a high binding capacity to cellulose, but also causes non-hydrolytic disruption of crystalline cellulose, which leads to the release of short fibers. IR spectroscopy and X-ray diffraction show that destabilization is caused by the non-hydrolytic disruption of cellulose and the disruption of hydrogen bonds in crystalline cellulose. The efficiency of crystalline cellulose degradation was enhanced by synergistic action of CBD(CBHI) with EGI. These results suggest that the cellulose-binding domain with its linker plays an important role in crystalline cellulose degradation.

  7. Carbon Nanotubes as Reinforcement of Cellulose Liquid Crystalline Responsive Networks.

    PubMed

    Echeverria, Coro; Aguirre, Luis E; Merino, Esther G; Almeida, Pedro L; Godinho, Maria H

    2015-09-30

    The incorporation of small amount of highly anisotropic nanoparticles into liquid crystalline hydroxypropylcellulose (LC-HPC) matrix improves its response when is exposed to humidity gradients due to an anisotropic increment of order in the structure. Dispersed nanoparticles give rise to faster order/disorder transitions when exposed to moisture as it is qualitatively observed and quantified by stress-time measurements. The presence of carbon nanotubes derives in a improvement of the mechanical properties of LC-HPC thin films.

  8. Impact of regeneration process on the crystalline structure and enzymatic hydrolysis of cellulose obtained from ionic liquid.

    PubMed

    Cao, Xuefei; Peng, Xinwen; Sun, Shaoni; Zhong, Linxin; Wang, Sha; Lu, Fachuang; Sun, Runcang

    2014-10-13

    The present study investigated the impact of regeneration process on the crystalline structure and enzymatic hydrolysis behaviors of microcrystalline cellulose (MCC) regenerated from ionic liquid 1-butyl-3-methylimidazolium chloride. The crystalline structures of these regenerated samples were analyzed by X-ray diffraction. Results suggested that almost amorphous cellulose was obtained by regenerating MCC in acetone (DRC-a), while partial cellulose II structure could be found in these regenerated samples from water and ethanol. Additionally, the enzymatic hydrolysis behaviors of MCC and its regenerated samples were comparatively studied. Results showed that above 90% of cellulose could be converted into glucose within 4h for DRC-a and regenerated cellulose without drying (WRC-w) as compared to that of MCC (9.7%). Therefore, the regeneration process could significantly influence the crystallinity and digestibility of cellulose.

  9. Quantification of crystalline cellulose in lignocellulosic biomass using sum frequency generation (SFG) vibration spectroscopy and comparison with other analytical methods.

    PubMed

    Barnette, Anna L; Lee, Christopher; Bradley, Laura C; Schreiner, Edward P; Park, Yong Bum; Shin, Heenae; Cosgrove, Daniel J; Park, Sunkyu; Kim, Seong H

    2012-07-01

    The non-centrosymmetry requirement of sum frequency generation (SFG) vibration spectroscopy allows the detection and quantification of crystalline cellulose in lignocellulose biomass without spectral interferences from hemicelluloses and lignin. This paper shows a correlation between the amount of crystalline cellulose in biomass and the SFG signal intensity. Model biomass samples were prepared by mixing commercially available cellulose, xylan, and lignin to defined concentrations. The SFG signal intensity was found sensitive to a wide range of crystallinity, but varied non-linearly with the mass fraction of cellulose in the samples. This might be due to the matrix effects such as light scattering and absorption by xylan and lignin, as well as the non-linear density dependence of the SFG process itself. Comparison with other techniques such as XRD, FT-Raman, FT-IR and NMR demonstrate that SFG can be a complementary and sensitive tool to assess crystalline cellulose in biomass.

  10. Improvement of ethanol production from crystalline cellulose via optimizing cellulase ratios in cellulolytic Saccharomyces cerevisiae.

    PubMed

    Liu, Zhuo; Inokuma, Kentaro; Ho, Shih-Hsin; den Haan, Riaan; van Zyl, Willem H; Hasunuma, Tomohisa; Kondo, Akihiko

    2017-01-23

    Crystalline cellulose is one of the major contributors to the recalcitrance of lignocellulose to degradation, necessitating high dosages of cellulase to digest, thereby impeding the economic feasibility of cellulosic biofuels. Several recombinant cellulolytic yeast strains have been developed to reduce the cost of enzyme addition, but few of these strains are able to efficiently degrade crystalline cellulose due to their low cellulolytic activities. Here, by combining the cellulase ratio optimization with a novel screening strategy, we successfully improved the cellulolytic activity of a Saccharomyces cerevisiae strain displaying four different synergistic cellulases on the cell surface. The optimized strain exhibited an ethanol yield from Avicel of 57% of the theoretical maximum, and a 60% increase of ethanol titer from rice straw. To our knowledge, this work is the first optimization of the degradation of crystalline cellulose by tuning the cellulase ratio in a cellulase cell-surface display system. This work provides key insights in engineering the cellulase cocktail in a consolidated bioprocessing yeast strain. Biotechnol. Bioeng. 2017;9999: 1-7. © 2017 Wiley Periodicals, Inc.

  11. Comparative Community Proteomics Demonstrates the Unexpected Importance of Actinobacterial Glycoside Hydrolase Family 12 Protein for Crystalline Cellulose Hydrolysis

    SciTech Connect

    Hiras, Jennifer; Wu, Yu-Wei; Deng, Kai; Nicora, Carrie D.; Aldrich, Joshua T.; Frey, Dario; Kolinko, Sebastian; Robinson, Errol W.; Jacobs, Jon M.; Adams, Paul D.; Northen, Trent R.; Simmons, Blake A.; Singer, Steven W.

    2016-08-23

    ABSTRACT

    Glycoside hydrolases (GHs) are key enzymes in the depolymerization of plant-derived cellulose, a process central to the global carbon cycle and the conversion of plant biomass to fuels and chemicals. A limited number of GH families hydrolyze crystalline cellulose, often by a processive mechanism along the cellulose chain. During cultivation of thermophilic cellulolytic microbial communities, substantial differences were observed in the crystalline cellulose saccharification activities of supernatants recovered from divergent lineages. Comparative community proteomics identified a set of cellulases from a population closely related to actinobacteriumThermobispora bisporathat were highly abundant in the most active consortium. Among the cellulases fromT. bispora, the abundance of a GH family 12 (GH12) protein correlated most closely with the changes in crystalline cellulose hydrolysis activity. This result was surprising since GH12 proteins have been predominantly characterized as enzymes active on soluble polysaccharide substrates. Heterologous expression and biochemical characterization of the suite ofT. bisporahydrolytic cellulases confirmed that the GH12 protein possessed the highest activity on multiple crystalline cellulose substrates and demonstrated that it hydrolyzes cellulose chains by a predominantly random mechanism. This work suggests that the role of GH12 proteins in crystalline cellulose hydrolysis by cellulolytic microbes should be reconsidered.

    IMPORTANCECellulose is the most abundant organic polymer on earth, and its enzymatic hydrolysis is a key reaction in the global carbon cycle and the conversion of plant biomass to biofuels. The glycoside hydrolases that depolymerize crystalline cellulose have been primarily characterized from isolates. In this study, we demonstrate that adapting microbial consortia from compost to grow on crystalline cellulose

  12. Complete genome sequence of Streptomyces reticuli, an efficient degrader of crystalline cellulose.

    PubMed

    Wibberg, Daniel; Al-Dilaimi, Arwa; Busche, Tobias; Wedderhoff, Ina; Schrempf, Hildgund; Kalinowski, Jörn; Ortiz de Orué Lucana, Darío

    2016-03-20

    We report the complete, GC-rich genome sequence of the melanin producer Streptomyces reticuli Tü 45 (S. reticuli) that targets and degrades highly crystalline cellulose by the concerted action of a range of biochemically characterized proteins. It consists of a linear 8.3 Mb chromosome, a linear 0.8 Mb megaplasmid, a linear 94 kb plasmid and a circular 76 kb plasmid. Noteworthy, the megaplasmid is the second largest known Streptomyces plasmid. Preliminary analysis reveals, among others, 43 predicted gene clusters for the synthesis of secondary metabolites and 456 predicted genes for binding and degradation of cellulose, other polysaccharides and carbohydrate-containing compounds.

  13. Comparative Community Proteomics Demonstrates the Unexpected Importance of Actinobacterial Glycoside Hydrolase Family 12 Protein for Crystalline Cellulose Hydrolysis

    PubMed Central

    Hiras, Jennifer; Wu, Yu-Wei; Deng, Kai; Nicora, Carrie D.; Aldrich, Joshua T.; Frey, Dario; Kolinko, Sebastian; Robinson, Errol W.; Jacobs, Jon M.; Adams, Paul D.; Northen, Trent R.; Simmons, Blake A.

    2016-01-01

    ABSTRACT Glycoside hydrolases (GHs) are key enzymes in the depolymerization of plant-derived cellulose, a process central to the global carbon cycle and the conversion of plant biomass to fuels and chemicals. A limited number of GH families hydrolyze crystalline cellulose, often by a processive mechanism along the cellulose chain. During cultivation of thermophilic cellulolytic microbial communities, substantial differences were observed in the crystalline cellulose saccharification activities of supernatants recovered from divergent lineages. Comparative community proteomics identified a set of cellulases from a population closely related to actinobacterium Thermobispora bispora that were highly abundant in the most active consortium. Among the cellulases from T. bispora, the abundance of a GH family 12 (GH12) protein correlated most closely with the changes in crystalline cellulose hydrolysis activity. This result was surprising since GH12 proteins have been predominantly characterized as enzymes active on soluble polysaccharide substrates. Heterologous expression and biochemical characterization of the suite of T. bispora hydrolytic cellulases confirmed that the GH12 protein possessed the highest activity on multiple crystalline cellulose substrates and demonstrated that it hydrolyzes cellulose chains by a predominantly random mechanism. This work suggests that the role of GH12 proteins in crystalline cellulose hydrolysis by cellulolytic microbes should be reconsidered. PMID:27555310

  14. Negative Poisson ratio of crystalline cellulose in kraft cooked Norway spruce.

    PubMed

    Peura, Marko; Grotkopp, Ingo; Lemke, Henrik; Vikkula, Anne; Laine, Janne; Müller, Martin; Serimaa, Ritva

    2006-05-01

    The tensile properties of kraft cooked Norway spruce were studied by tensile testing with in situ X-ray diffraction (XRD). Samples were of earlywood, cooked for varying times. The total lignin content of the samples was between 21.7% and 9.3%. Tensile tests with XRD were performed on wet samples, without XRD on dry samples. The tensile strength, the modulus of elasticity (MOE), and the elongation at fracture/yield were determined. X-ray diffraction was used to determine the microfibril angle (MFA) and the deformation of crystalline cellulose by monitoring the reflections 200 and 004. The (X-ray) Poisson ratio of crystalline cellulose was calculated, both before and after the yield point. The tensile strength and the MOE of the wet samples were significantly lower than in the dry samples. The tensile properties of dry samples were similar to dry earlywood samples of untreated Norway spruce. The MFA only showed notable changes due to strain when it was initially large, when a diminishing effect was observed. The Poisson ratio of crystalline cellulose was negative. The average values ranged between -0.26 and -1.17 before the yield point and between -0.86 and -1.05 after the yield point.

  15. Crystallinity and thermal resistance of microcrystalline cellulose prepared from manau rattan (Calamusmanan)

    NASA Astrophysics Data System (ADS)

    Rizkiansyah, Raden Reza; Mardiyati, Steven, Suratman, R.

    2016-04-01

    The objective of this study was to prepare microcrystalline cellulose from Manau rattan (Calamusmanan) and to investigate the influence of concentration of sulfuric acid and hydrolysis time on crystallinity and thermal resistance of the microcrystalline cellulose (MCC). In this research, MCC was extracted through two stages, which is alkalization and acid hydrolysis. Alkalization was prepared by soaking manau rattan powder into sodium hydroxide (NaOH) 17.5wt% at 100°C for 8 hours. Acid hydrolysis was prepared by using sulfuric acid with concentration 0.1 M; 0.3 M; and 0.5 M for 4, 6, 8 and 10 hours. Crystallinity of MCC was measured by XRD, and thermal resistance was characterized by TGA. MCC was successfully extracted from manau rattan. The highest crystallinity of MCC obtained was 72.42% which prepared by acid hydrolysis with concentration 0.5 M for 10 hours. MCC prepared by acid hydrolysis with concentration 0.5 M for 10 hours not only resulted the highest crystallinity but also the best thermal resistance.

  16. Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy.

    PubMed

    Oh, Sang Youn; Yoo, Dong Il; Shin, Younsook; Kim, Hwan Chul; Kim, Hak Yong; Chung, Yong Sik; Park, Won Ho; Youk, Ji Ho

    2005-10-31

    Crystalline structures of cellulose (named as Cell 1), NaOH-treated cellulose (Cell 2), and subsequent CO2-treated cellulose (Cell 2-C) were analyzed by wide-angle X-ray diffraction and FTIR spectroscopy. Transformation from cellulose I to cellulose II was observed by X-ray diffraction for Cell 2 treated with 15-20 wt% NaOH. Subsequent treatment with CO2 also transformed the Cell 2-C treated with 5-10 wt% NaOH. Many of the FTIR bands including 2901, 1431, 1282, 1236, 1202, 1165, 1032, and 897 cm(-1) were shifted to higher wave number (by 2-13 cm(-1)). However, the bands at 3352, 1373, and 983 cm(-1) were shifted to lower wave number (by 3-95 cm(-1)). In contrast to the bands at 1337, 1114, and 1058 cm(-1), the absorbances measured at 1263, 993, 897, and 668 cm(-1) were increased. The FTIR spectra of hydrogen-bonded OH stretching vibrations at around 3352 cm(-1) were resolved into three bands for cellulose I and four bands for cellulose II, assuming that all the vibration modes follow Gaussian distribution. The bands of 1 (3518 cm(-1)), 2 (3349 cm(-1)), and 3 (3195 cm(-1)) were related to the sum of valence vibration of an H-bonded OH group and an intramolecular hydrogen bond of 2-OH ...O-6, intramolecular hydrogen bond of 3-OH...O-5 and the intermolecular hydrogen bond of 6-O...HO-3', respectively. Compared with the bands of cellulose I, a new band of 4 (3115 cm(-1)) related to intermolecular hydrogen bond of 2-OH...O-2' and/or intermolecular hydrogen bond of 6-OH...O-2' in cellulose II appeared. The crystallinity index (CI) was obtained by X-ray diffraction [CI(XD)] and FTIR spectroscopy [CI(IR)]. Including absorbance ratios such as A1431,1419/A897,894 and A1263/A1202,1200, the CI(IR) was evaluated by the absorbance ratios using all the characteristic absorbances of cellulose. The CI(XD) was calculated by the method of Jayme and Knolle. In addition, X-ray diffraction curves, with and without amorphous halo correction, were resolved into portions of cellulose I and

  17. Kinetic analysis of enzymatic hydrolysis of crystalline cellulose by cellobiohydrolase using an amperometric biosensor.

    PubMed

    Tatsumi, Hirosuke; Katano, Hajime; Ikeda, Tokuji

    2006-10-15

    An amperometric biosensor for the detection of cellobiose has been introduced to study the kinetics of enzymatic hydrolysis of crystalline cellulose by cellobiohydrolase. By use of a sensor in which pyrroloquinoline quinone-dependent glucose dehydrogenase was immobilized on the surface of electrode, direct and continuous observation of the hydrolysis can be achieved even in a thick cellulose suspension. The steady-state rate of the hydrolysis increased with increasing concentrations of the enzyme to approach a saturation value and was proportional to the amount of the substrate. The experimental results can be explained well by the rate equations derived from a three-step mechanism consisting of the adsorption of the free enzyme onto the surface of the substrate, the reaction of the adsorbed enzyme with the substrate, and the liberation of the product. The catalytic constant of the adsorbed enzyme was determined to be 0.044+/-0.011s(-1).

  18. Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

    DOE PAGES

    Zhang, Libing; Lu, Zhou; Velarde, Luis; ...

    2015-03-03

    Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signaturesmore » in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.« less

  19. Vibrational Spectral Signatures of Crystalline Cellulose Using High Resolution Broadband Sum Frequency Generation Vibrational Spectroscopy (HR-BB-SFG-VS)

    SciTech Connect

    Zhang, Libing; Lu, Zhou; Velarde Ruiz Esparza, Luis A.; Fu, Li; Pu, Yunqiao; Ding, Shi-You; Ragauskas, Art J.; Wang, Hongfei; Yang, Bin

    2015-03-03

    Here we reported the first sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) study on both the C-H and O-H region spectra of crystalline cellulose. HR-BB-SFG-VS has about 10 times better resolution than the conventional scanning SFG-VS and is known to be able to measure the intrinsic spectral lineshape and to resolve much more spectral details. With HR-BB-SFG-VS, we found that in cellulose from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the OH regions were unique for different allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C-H regions varied in all samples examined. Even though the origin of the different behaviors of the crystalline cellulose in the O-H and C-H vibrational frequency regions is yet to be correlated to the structure of cellulose, these results provided new spectroscopic methods and opportunities to classify and understand the basic crystalline structure, as well as variations, in polymorphism of the crystalline cellulose structure.

  20. Vibrational spectral signatures of crystalline cellulose using high resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS)

    SciTech Connect

    Zhang, Libing; Lu, Zhou; Velarde, Luis; Fu, Li; Pu, Yunqiao; Ding, Shi-You; Ragauskas, Arthur; Wang, Hong-Fei; Yang, Bin

    2015-03-03

    Both the C–H and O–H region spectra of crystalline cellulose were studied using the sub-wavenumber high-resolution broadband sum frequency generation vibrational spectroscopy (HR-BB-SFG-VS) for the first time. The resolution of HR-BB-SFG-VS is about 10-times better than conventional scanning SFG-VS and has the capability of measuring the intrinsic spectral lineshape and revealing many more spectral details. With HR-BB-SFG-VS, we found that in cellulose samples from different sources, including Avicel and cellulose crystals isolated from algae Valonia (Iα) and tunicates (Iβ), the spectral signatures in the O–H region were unique for the two allomorphs, i.e. Iα and Iβ, while the spectral signatures in the C–H regions varied in all samples examined. Even though the origin of the different spectral signatures of the crystalline cellulose in the O–H and C–H vibrational frequency regions are yet to be correlated to the structure of cellulose, these results lead to new spectroscopic methods and opportunities to classify and to understand the basic crystalline structures, as well as variations in polymorphism of the crystalline cellulose.

  1. Multi-pollutant treatment of crystalline cellulosic effluent: Function of dissolved oxygen on process control.

    PubMed

    Shanthi Sravan, J; Naresh Kumar, A; Venkata Mohan, S

    2016-10-01

    Treatment of crystalline cellulose based wastewater was carried out in periodic discontinuous batch reactor (PDBR). Specific influence of dissolved oxygen on treatment of crystalline cellulosic (CC) wastewater was evaluated in three different microenvironments such as aerobic, anoxic and anaerobic. PDBR-aerobic biosystem documented relatively higher substrate degradation [2.63kgCOD/m(3)-day (92%)] in comparison to PDBR-anoxic [2.12kgCOD/m(3)-day (71%)] and PDBR-anaerobic [1.81kgCOD/m(3)-day (63%)], which is in accordance with the observed DO levels. Similarly, multipollutants viz., phosphates and nitrates removal was observed to be higher in aerobic followed by anoxic and anaerobic operations. Higher nitrate removal in aerobic operation might be attributed to the efficient denitrification carried out by the biocatalyst, which utilizes both nitrates and oxygen as oxidizing agents. Multiscan spectral profiles depicted reduction in color intensity in all three microenvironments that correlated with the substrate degradation observed. Despite the high organic load, PDBR functioned well without exhibiting process inhibition.

  2. Segal crystallinity index revisited by the simulation of X-ray diffraction patterns of cotton cellulose Iβ and cellulose II.

    PubMed

    Nam, Sunghyun; French, Alfred D; Condon, Brian D; Concha, Monica

    2016-01-01

    The Segal method estimates the amorphous fraction of cellulose Iβ materials simply based on intensity at 18° 2θ in an X-ray diffraction pattern and was extended to cellulose II using 16° 2θ intensity. To address the dependency of Segal amorphous intensity on crystal size, cellulose polymorph, and the degree of polymorphic conversion, we simulated the diffraction patterns of cotton celluloses (Iβ and II) and compared the simulated amorphous fractions with the Segal values. The diffraction patterns of control and mercerized cottons, respectively, were simulated with perfect crystals of cellulose Iβ (1.54° FWHM) and cellulose II (2.30° FWHM) as well as 10% and 35% amorphous celluloses. Their Segal amorphous fractions were 15% and 31%, respectively. The higher Segal amorphous fraction for control cotton was attributed to the peak overlap. Although the amorphous fraction was set in the simulation, the peak overlap induced by the increase of FWHM further enhanced the Segal amorphous intensity of cellulose Iβ. For cellulose II, the effect of peak overlap was smaller; however the lower reflection of the amorphous cellulose scattering in its Segal amorphous location resulted in smaller Segal amorphous fractions. Despite this underestimation, the relatively good agreement of the Segal method with the simulation for mercerized cotton was attributed to the incomplete conversion to cellulose II. The (1-10) and (110) peaks of cellulose Iβ remained near the Segal amorphous location of cellulose II for blends of control and mercerized cotton fibers.

  3. Crystalline structure and morphological properties of porous cellulose/clay composites: The effect of water and ethanol as coagulants.

    PubMed

    Ahmadzadeh, Safoura; Desobry, Stephane; Keramat, Javad; Nasirpour, Ali

    2016-05-05

    In this study, cellulose foams incorporated with surface-modified montmorillonite (SM-MMT) were prepared following NaOH dissolution and regeneration into water and ethanol. According to the SEM images, the type of coagulating agent significantly affected the morphological properties of composite foams. The crystalline parameters were evaluated using wide-angle X-ray diffraction (WAXD), which showed an increase in crystal size as the effect of SM-MMT; however, the crystal size decreased for the samples treated with ethanol. The distribution of hydrogen bond types was also investigated using Fourier transform infrared (FTIR). Resolving the hydrogen-bonded OH stretching band at around 3340 into five bands indicated that presence of SM-MMT caused the shift of OH-stretching vibration band to lower wave number due to new hydrogen bonds between cellulose and SM-MMT. In general, the results indicated a change in the contents of the intra- and inter-molecular hydrogen bonds when the coagulant was changed or SM-MMT was incorporated.

  4. Segal crystallinity index revisited by the simulation of x-ray diffraction patterns of cotton cellulose IB and cellulose II

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The Segal method estimates the amorphous fraction of cellulose IB materials simply based on intensity at 18o 20 in an X-ray diffraction pattern and was extended to cellulose II using 16o 2O intensity. To address the dependency of Segal amorphous intensity on crystal size, cellulose polymorph, and th...

  5. Preparation of nanocellulose from micro-crystalline cellulose: The effect on the performance and properties of agar-based composite films.

    PubMed

    Shankar, Shiv; Rhim, Jong-Whan

    2016-01-01

    A facile approach has been performed to prepare nanocellulose (NC) from micro-crystalline cellulose (MCC) and test their effect on the performance properties of agar-based composite films. The NC was characterized by STEM, XRD, FTIR, and TGA. The NC was well dispersed in distilled water after sonication and their size was in the range of 100-500nm. The XRD results revealed the crystallinity of NC. The crystallinity index of NC (0.71) was decreased compared to the MCC (0.81). The effect of NC or MCC content (1, 3, 5 and 10wt% based on agar) on the mechanical, water vapor permeability (WVP), and thermal properties of the composites were studied. The NC obtained from MCC can be used as a reinforcing agent for the preparation of biodegradable composites films for their potential use in the development of biodegradable food packaging materials.

  6. In Situ Generation of Cellulose Nanocrystals in Polycaprolactone Nanofibers: Effects on Crystallinity, Mechanical Strength, Biocompatibility, and Biomimetic Mineralization.

    PubMed

    Joshi, Mahesh Kumar; Tiwari, Arjun Prasad; Pant, Hem Raj; Shrestha, Bishnu Kumar; Kim, Han Joo; Park, Chan Hee; Kim, Cheol Sang

    2015-09-09

    Post-electrospinning treatment is a facile process to improve the properties of electrospun nanofibers for various applications. This technique is commonly used when direct electrospinning is not a suitable option to fabricate a nonwoven membrane of the desired polymer in a preferred morphology. In this study, a representative natural-synthetic hybrid of cellulose acetate (CA) and polycaprolactone (PCL) in different ratios was fabricated using an electrospinning process, and CA in the hybrid fiber was transformed into cellulose (CL) by post-electrospinning treatment via alkaline saponification. Scanning electron microscopy was employed to study the effects of polymer composition and subsequent saponification on the morphology of the nanofibers. Increasing the PCL content in the PCL/CA blend solution caused a gradual decrease in viscosity, resulting in smoother and more uniform fibers. The saponification of fibers lead to pronounced changes in the physicochemical properties. The crystallinity of the PCL in the composite fiber was varied according to the composition of the component polymers. The water contact angle was considerably decreased (from 124° to less than 20°), and the mechanical properties were greatly enhanced (Young's Modulus was improved by ≈20-30 fold, tensile strength by 3-4 fold, and tensile stress by ≈2-4 fold) compared to those of PCL and PCL/CA membranes. Regeneration of cellulose chains in the nanofibers increased the number of hydroxyl groups, which increased the hydrogen bonding, thereby improving the mechanical properties and wettability of the composite nanofibers. The improved wettability and presence of surface functional groups enhanced the ability to nucleate bioactive calcium phosphate crystals throughout the matrix when exposed to a simulated body fluid solution. Experimental results of cell viability assay, confocal microscopy, and scanning electron microscopy imaging showed that the fabricated nanofibrous membranes have

  7. Enzymatic diversity of the Clostridium thermocellum cellulosome is crucial for the degradation of crystalline cellulose and plant biomass

    PubMed Central

    Hirano, Katsuaki; Kurosaki, Masahiro; Nihei, Satoshi; Hasegawa, Hiroki; Shinoda, Suguru; Haruki, Mitsuru; Hirano, Nobutaka

    2016-01-01

    The cellulosome is a supramolecular multienzyme complex comprised of a wide variety of polysaccharide-degrading enzymes and scaffold proteins. The cellulosomal enzymes that bind to the scaffold proteins synergistically degrade crystalline cellulose. Here, we report in vitro reconstitution of the Clostridium thermocellum cellulosome from 40 cellulosomal components and the full-length scaffoldin protein that binds to nine enzyme molecules. These components were each synthesized using a wheat germ cell-free protein synthesis system and purified. Cellulosome complexes were reconstituted from 3, 12, 30, and 40 components based on their contents in the native cellulosome. The activity of the enzyme-saturated complex indicated that greater enzymatic variety generated more synergy for the degradation of crystalline cellulose and delignified rice straw. Surprisingly, a less complete enzyme complex displaying fewer than nine enzyme molecules was more efficient for the degradation of delignified rice straw than the enzyme-saturated complex, despite the fact that the enzyme-saturated complex exhibited maximum synergy for the degradation of crystalline cellulose. These results suggest that greater enzymatic diversity of the cellulosome is crucial for the degradation of crystalline cellulose and plant biomass, and that efficient degradation of different substrates by the cellulosome requires not only a different enzymatic composition, but also different cellulosome structures. PMID:27759119

  8. The crystallinity of cellulose controls the physical distribution of sorbed water and the capacity to present water for chemical degradation of a solid drug.

    PubMed

    Höckerfelt, Mina Heidarian; Alderborn, Göran

    2014-12-30

    The purpose of the research was to investigate the effect of moisture content of cellulose on the degradation of a drug in binary mixtures with cellulose. Physical mixtures of acetylsalicylic acid and two forms of cellulose, either microcrystalline cellulose or low crystalline cellulose, in the proportion 1:1 were stored at 50°C at a series of relative humidities (0-90%) for up to 175 days. The degradation rate constant of the drug increased with increased cellulose moisture content in a bi-regional fashion, with a low and a high degradation rate region. The shift from region 1 to 2 occurred at higher moisture content for the low crystalline cellulose. The relationships between rate constant and the temperature of maximum endothermic value overlapped for the two celluloses. It is proposed that the amount of water available for degradation of a solid drug is controlled by the water presenting capacity of cellulose which is dependent of the mechanism of sorption of water in cellulose. The water sorption of water can for cellulose satisfactorily be described by a two-site residence model with cellulose crystallinity as the structural correlate to the distribution between the two residence sites.

  9. Multifunctional cellulolytic auxiliary activity protein HcAA10-2 from Hahella chejuensis enhances enzymatic hydrolysis of crystalline cellulose.

    PubMed

    Ghatge, Sunil S; Telke, Amar A; Waghmode, Tatoba R; Lee, Yuno; Lee, Keun-Woo; Oh, Doo-Byoung; Shin, Hyun-Dong; Kim, Seon-Won

    2015-04-01

    The modular auxiliary activity (AA) family of proteins is believed to cause amorphogenesis in addition to oxidative cleavage of crystalline cellulose although the supporting evidence is limited. HcAA10-2 is a modular AA10 family protein (58 kDa) composed of a AA10 module and a family two carbohydrate binding module (CBM2), joined by a long stretch of 222 amino acids of unknown function. The protein was expressed in Escherichia coli and purified to homogeneity. Scanning electron microscopy and X-ray diffraction analysis of Avicel treated with HcAA10-2 provided evidence for the disruption of the cellulose microfibrils ("amorphogenesis") and reduction of the crystallinity index, resulting in a twofold increase of cellulase adsorption on the polysaccharide surface. HcAA10-2 exhibited weak endoglucanase-like activity toward soluble cellulose and cello-oligosaccharides with an optimum at pH 6.5 and 45 °C. HcAA10-2 catalyzed oxidative cleavage of crystalline cellulose released native and oxidized cello-oligosaccharides in the presence of copper and an electron donor such as ascorbic acid. Multiple sequence alignment indicated that His1, His109, and Phe197 in the AA10 module formed the conserved copper-binding site. The reducing sugar released from Avicel by the endoglucanase Cel5 and Celluclast accompanying HcAA10-2 was increased by four- and sixfold, respectively. Moreover, HcAA10-2 and Celluclast acted synergistically on pretreated wheat straw biomass resulting in a threefold increase in reducing sugar than Celluclast alone. Taken together, these results suggest that HcAA10-2 is a novel multifunctional modular AA10 protein possessing amorphogenesis, weak endoglucanase, and oxidative cleavage activities useful for efficient degradation of crystalline cellulose.

  10. Effect of silicone oil heat treatment on the chemical composition, cellulose crystalline structure and contact angle of Chinese parasol wood.

    PubMed

    Okon, Kufre Edet; Lin, Fengcai; Chen, Yandan; Huang, Biao

    2017-05-15

    The effect of silicone oil heat treatment (SOTH) on the chemical composition, cellulose crystalline structure, thermal degradation and contact angle of Chinese parasol wood were examined in this study. Samples were heated at 150°C, 180°C and 210°C for 2h and 8h, after SOHT chemical composition, fourier transformed infrared (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) of the treated samples were evaluated. Results showed that the chemical components of the wood were affected after SOHT particularly when treated at 210°C for 8h. Changes in the chemical components was due to the degradation of biopolymer components of the wood during SOHT. The crystallinity index of cellulose and contact angle of the SOHT samples was increased. The findings demonstrate the potential of SOHT for modification of wood. Thus an economical and eco-friendly approach to thermally modified wood was achieved in this study.

  11. Cellulose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cellulose properties and structure are reviewed, with a primary focus on crystal structure and polymorphy. This focus highlights the conversion from cellulose I to cellulose II, which converts the molecules to being all parallel to each other in the crystal to being antiparallel. This has been co...

  12. Transition of cellulose crystalline structure and surface morphology of biomass as a function of ionic liquid pretreatment and its relation to enzymatic hydrolysis.

    PubMed

    Cheng, Gang; Varanasi, Patanjali; Li, Chenlin; Liu, Hanbin; Melnichenko, Yuri B; Simmons, Blake A; Kent, Michael S; Singh, Seema

    2011-04-11

    Cellulose is inherently resistant to breakdown, and the native crystalline structure (cellulose I) of cellulose is considered to be one of the major factors limiting its potential in terms of cost-competitive lignocellulosic biofuel production. Here we report the impact of ionic liquid pretreatment on the cellulose crystalline structure in different feedstocks, including microcrystalline cellulose (Avicel), switchgrass (Panicum virgatum), pine ( Pinus radiata ), and eucalyptus ( Eucalyptus globulus ), and its influence on cellulose hydrolysis kinetics of the resultant biomass. These feedstocks were pretreated using 1-ethyl-3-methyl imidazolium acetate ([C2mim][OAc]) at 120 and 160 °C for 1, 3, 6, and 12 h. The influence of the pretreatment conditions on the cellulose crystalline structure was analyzed by X-ray diffraction (XRD). On a larger length scale, the impact of ionic liquid pretreatment on the surface roughness of the biomass was determined by small-angle neutron scattering (SANS). Pretreatment resulted in a loss of native cellulose crystalline structure. However, the transformation processes were distinctly different for Avicel and for the biomass samples. For Avicel, a transformation to cellulose II occurred for all processing conditions. For the biomass samples, the data suggest that pretreatment for most conditions resulted in an expanded cellulose I lattice. For switchgrass, first evidence of cellulose II only occurred after 12 h of pretreatment at 120 °C. For eucalyptus, first evidence of cellulose II required more intense pretreatment (3 h at 160 °C). For pine, no clear evidence of cellulose II content was detected for the most intense pretreatment conditions of this study (12 h at 160 °C). Interestingly, the rate of enzymatic hydrolysis of Avicel was slightly lower for pretreatment at 160 °C compared with pretreatment at 120 °C. For the biomass samples, the hydrolysis rate was much greater for pretreatment at 160 °C compared with pretreatment

  13. Supermolecular structure of cellulose: stepwise decrease in LODP and particle size of cellulose hydrolyzed after chemical treatment. [Leveling-off degree of polymerization

    SciTech Connect

    Yachi, T.; Hayashi, J.; Takai, M.; Shimizu, Y.

    1983-01-01

    It was observed by electron microscopy that rayons hydrolyzed with 2.4 N HCl at 100/sup 0/C for 2 h, followed by ultrasonic treatment were split into homogeneous particles having a size of about 200 A(2000A). In the previous work with rayons, crystallite length, long period, and chain length calculated from their LODP were all about 200 A(2000A), regardless of the type of rayon. The agreement between particle size and length suggested strongly that a rayon microfibril has a periodic structure along its axis at intervals of about A(2000A). Celluloses II, III, and IV and cellulose regenerated from its esters were derived both from native cellulose and rayons in the fibrous state. After hydrolysis, all the modifications derived from native cellulose showed an LODP of about 80 and rod-like fragments which showed a maximum at 400 A(2000A) in the frequency distribution of their lengths. All of the modifications, except mercerized native cellulose, showed a meridional small-angle reflection corresponding to 400 A(2000A). All the modifications from rayons showed an LODP of about 40. The esters derived from native cellulose were recrystallized by heat treatment and then saponified into cellulose II. After hydrolysis, they showed an LODP of about 40 (200 A(2000A) in chain length), a meridional reflection showing a long period of about 200 A(2000A), and a particle-like fragment having a size of about 200 A(2000A). For native cellulose, after chemical and physical treatments, the LODP, the long period, and the fragment length all decreased stepwise and by the same amounts. The steps were an integral multiple of 200 A(2000A), which is the value of the crystallite length obtained for the native and all other celluloses. The results suggest that native cellulose has a periodic structure at intervals of 200 A(2000A) in length. 40 references, 14 figures, 5 tables.

  14. Single-molecule imaging analysis of elementary reaction steps of Trichoderma reesei cellobiohydrolase I (Cel7A) hydrolyzing crystalline cellulose Iα and IIII.

    PubMed

    Shibafuji, Yusuke; Nakamura, Akihiko; Uchihashi, Takayuki; Sugimoto, Naohisa; Fukuda, Shingo; Watanabe, Hiroki; Samejima, Masahiro; Ando, Toshio; Noji, Hiroyuki; Koivula, Anu; Igarashi, Kiyohiko; Iino, Ryota

    2014-05-16

    Trichoderma reesei cellobiohydrolase I (TrCel7A) is a molecular motor that directly hydrolyzes crystalline celluloses into water-soluble cellobioses. It has recently drawn attention as a tool that could be used to convert cellulosic materials into biofuel. However, detailed mechanisms of action, including elementary reaction steps such as binding, processive hydrolysis, and dissociation, have not been thoroughly explored because of the inherent challenges associated with monitoring reactions occurring at the solid/liquid interface. The crystalline cellulose Iα and IIII were previously reported as substrates with different crystalline forms and different susceptibilities to hydrolysis by TrCel7A. In this study, we observed that different susceptibilities of cellulose Iα and IIII are highly dependent on enzyme concentration, and at nanomolar enzyme concentration, TrCel7A shows similar rates of hydrolysis against cellulose Iα and IIII. Using single-molecule fluorescence microscopy and high speed atomic force microscopy, we also determined kinetic constants of the elementary reaction steps for TrCel7A against cellulose Iα and IIII. These measurements were performed at picomolar enzyme concentration in which density of TrCel7A on crystalline cellulose was very low. Under this condition, TrCel7A displayed similar binding and dissociation rate constants for cellulose Iα and IIII and similar fractions of productive binding on cellulose Iα and IIII. Furthermore, once productively bound, TrCel7A processively hydrolyzes and moves along cellulose Iα and IIII with similar translational rates. With structural models of cellulose Iα and IIII, we propose that different susceptibilities at high TrCel7A concentration arise from surface properties of substrate, including ratio of hydrophobic surface and number of available lanes.

  15. Concurrent microscopic observations and activity measurements of cellulose hydrolyzing and methanogenic populations during the batch anaerobic digestion of crystalline cellulose.

    PubMed

    Song, Hyohak; Clarke, William P; Blackall, Linda L

    2005-08-05

    This study compares process data with microscopic observations from an anaerobic digestion of organic particles. As the first part of the study, this article presents detailed observations of microbial biofilm architecture and structure in a 1.25-L batch digester where all particles are of an equal age. Microcrystalline cellulose was used as the sole carbon and energy source. The digestions were inoculated with either leachate from a 220-L anaerobic municipal solid waste digester or strained rumen contents from a fistulated cow. The hydrolysis rate, when normalized by the amount of cellulose remaining in the reactor, was found to reach a constant value 1 day after inoculation with rumen fluid, and 3 days after inoculating with digester leachate. A constant value of a mass specific hydrolysis rate is argued to represent full colonization of the cellulose surface and first-order kinetics only apply after this point. Additionally, the first-order hydrolysis rate constant, once surfaces were saturated with biofilm, was found to be two times higher with a rumen inoculum, compared to a digester leachate inoculum. Images generated by fluorescence in situ hybridization (FISH) probing and confocal laser scanning microscopy show that the microbial communities involved in the anaerobic biodegradation process exist entirely within the biofilm. For the reactor conditions used in these experiments, the predominant methanogens exist in ball-shaped colonies within the biofilm.

  16. Effect of compression combined with steam treatment on the porosity, chemical compositon and cellulose crystalline structure of wood cell walls.

    PubMed

    Yin, Jiangping; Yuan, Tongqi; Lu, Yun; Song, Kunlin; Li, Hanyin; Zhao, Guangjie; Yin, Yafang

    2017-01-02

    The changes of porosity, chemical composition and cellulose crystalline structure of Spruce (Picea abies Karst.) wood cell walls due to compression combined with steam treatment (CS-treatment) were investigated by nitrogen adsorption, confocal Raman microscopy (CRM) and X-ray diffraction (XRD), respectively. A number of slit-shaped mesopores with a diameter of 3.7nm was formed for the CS-treated wood, and more mesopores were found in the steam-treated wood. CRM results revealed cellulose structure was affected by treatment and β-aryl-ether links associated to guaiacyl units of lignin was depolymerized followed by re-condensation reactions. The crystallinity index (CrI) and crystallite thickness (D200) of cellulose for CS-treated wood were largely increased due to crystallization in the semicrystalline region. Higher degree of increase in both CrI and D200 was observed in both the earlywood and latewood of steam-treated wood, ascribing to the greater amount of mesopores in steam-treated wood than CS-treated wood.

  17. Single-molecule Imaging Analysis of Binding, Processive Movement, and Dissociation of Cellobiohydrolase Trichoderma reesei Cel6A and Its Domains on Crystalline Cellulose.

    PubMed

    Nakamura, Akihiko; Tasaki, Tomoyuki; Ishiwata, Daiki; Yamamoto, Mayuko; Okuni, Yasuko; Visootsat, Akasit; Maximilien, Morice; Noji, Hiroyuki; Uchiyama, Taku; Samejima, Masahiro; Igarashi, Kiyohiko; Iino, Ryota

    2016-10-21

    Trichoderma reesei Cel6A (TrCel6A) is a cellobiohydrolase that hydrolyzes crystalline cellulose into cellobiose. Here we directly observed the reaction cycle (binding, surface movement, and dissociation) of single-molecule intact TrCel6A, isolated catalytic domain (CD), cellulose-binding module (CBM), and CBM and linker (CBM-linker) on crystalline cellulose Iα The CBM-linker showed a binding rate constant almost half that of intact TrCel6A, whereas those of the CD and CBM were only one-tenth of intact TrCel6A. These results indicate that the glycosylated linker region largely contributes to initial binding on crystalline cellulose. After binding, all samples showed slow and fast dissociations, likely caused by the two different bound states due to the heterogeneity of cellulose surface. The CBM showed much higher specificity to the high affinity site than to the low affinity site, whereas the CD did not, suggesting that the CBM leads the CD to the hydrophobic surface of crystalline cellulose. On the cellulose surface, intact molecules showed slow processive movements (8.8 ± 5.5 nm/s) and fast diffusional movements (30-40 nm/s), whereas the CBM-Linker, CD, and a catalytically inactive full-length mutant showed only fast diffusional movements. These results suggest that both direct binding and surface diffusion contribute to searching of the hydrolysable point of cellulose chains. The duration time constant for the processive movement was 7.7 s, and processivity was estimated as 68 ± 42. Our results reveal the role of each domain in the elementary steps of the reaction cycle and provide the first direct evidence of the processive movement of TrCel6A on crystalline cellulose.

  18. Deamidation alters the structure and decreases the stability of human lens betaA3-crystallin.

    PubMed

    Takata, Takumi; Oxford, Julie T; Brandon, Theodore R; Lampi, Kirsten J

    2007-07-31

    According to the World Health Organization, cataracts account for half of the blindness in the world, with the majority occurring in developing countries. A cataract is a clouding of the lens of the eye due to light scattering of precipitated lens proteins or aberrant cellular debris. The major proteins in the lens are crystallins, and they are extensively deamidated during aging and cataracts. Deamidation has been detected at the domain and monomer interfaces of several crystallins during aging. The purpose of this study was to determine the effects of two potential deamidation sites at the predicted interface of the betaA3-crystallin dimer on its structure and stability. The glutamine residues at the reported in vivo deamidation sites of Q180 in the C-terminal domain and at the homologous site Q85 in the N-terminal domain were substituted with glutamic acid residues by site-directed mutagenesis. Far-UV and near-UV circular dichroism spectroscopy indicated that there were subtle differences in the secondary structure and more notable differences in the tertiary structure of the mutant proteins compared to that of the wild type betaA3-crystallin. The Q85E/Q180E mutant also was more susceptible to enzymatic digestion, suggesting increased solvent accessibility. These structural changes in the deamidated mutants led to decreased stability during unfolding in urea and increased precipitation during heat denaturation. When simulating deamidation at both residues, there was a further decrease in stability and loss of cooperativity. However, multiangle-light scattering and quasi-elastic light scattering experiments showed that dimer formation was not disrupted, nor did higher-order oligomers form. These results suggest that introducing charges at the predicted domain interface in the betaA3 homodimer may contribute to the insolubilization of lens crystallins or favor other, more stable, crystallin subunit interactions.

  19. Whey protein aerogel as blended with cellulose crystalline particles or loaded with fish oil.

    PubMed

    Ahmadi, Maede; Madadlou, Ashkan; Saboury, Ali Akbar

    2016-04-01

    Whey protein hydrogels blended with nanocrystalline and microcrystalline cellulose particles (NCC and MCC, respectively) were prepared, followed by freeze-drying, to produce aerogels. NCC blending increased the Young's modulus, and elastic character, of the protein aerogel. Aerogels were microporous and mesoporous materials, as characterized by the pores sizing 1.2 nm and 12.2 nm, respectively. Blending with NCC decreased the count of both microporous and mesoporous-classified pores at the sub-100 nm pore size range investigated. In contrast, MCC blending augmented the specific surface area and pores volume of the aerogel. It also increased moisture sorption affinity of aerogel. The feasibility of conveying hydrophobic nutraceuticals by aerogels was evaluated through loading fish oil into the non-blended aerogel. Oil loading altered its microstructure, corresponding to a peak displacement in Fourier-transform infra-red spectra, which was ascribed to increased hydrophobic interactions. Surface coating of aerogel with zein decreased the oxidation susceptibility of the loaded oil during subsequent storage.

  20. Influence of the crystalline structure of cellulose on the production of ethanol from lignocellulose biomass

    NASA Astrophysics Data System (ADS)

    Smuga-Kogut, Małgorzata; Zgórska, Kazimiera; Szymanowska-Powałowska, Daria

    2016-01-01

    In recent years, much attention has been devoted to the possibility of using lignocellulosic biomass for energy. Bioethanol is a promising substitute for conventional fossil fuels and can be produced from straw and wood biomass. Therefore, the aim of this paper was to investigate the effect of 1-ethyl-3-methylimidazolium pretreatment on the structure of cellulose and the acquisition of reducing sugars and bioethanol from cellulosic materials. Material used in the study was rye straw and microcrystalline cellulose subjected to ionic liquid 1-ethyl-3-methylimidazolium pretreatment. The morphology of cellulose fibres in rye straw and microcrystalline cellulose was imaged prior to and after ionic liquid pretreatment. Solutions of ionic liquid-treated and untreated cellulosic materials were subjected to enzymatic hydrolysis in order to obtain reducing sugars, which constituted a substrate for alcoholic fermentation. An influence of the ionic liquid on the cellulose structure, accumulation of reducing sugars in the process of hydrolysis of this material, and an increase in ethanol amount after fermentation was observed. The ionic liquid did not affect cellulolytic enzymes negatively and did not inhibit yeast activity. The amount of reducing sugars and ethyl alcohol was higher in samples purified with 1-ethyl-3-methy-limidazolium acetate. A change in the supramolecular structure of cellulose induced by the ionic liquid was also observed.

  1. Effects of ionic conduction on hydrothermal hydrolysis of corn starch and crystalline cellulose induced by microwave irradiation.

    PubMed

    Tsubaki, Shuntaro; Oono, Kiriyo; Onda, Ayumu; Yanagisawa, Kazumichi; Mitani, Tomohiko; Azuma, Jun-ichi

    2016-02-10

    This study investigated the effects of ionic conduction of electrolytes under microwave field to facilitate hydrothermal hydrolysis of corn starch and crystalline cellulose (Avicel), typical model biomass substrates. Addition of 0.1M NaCl was effective to improve reducing sugar yield by 1.61-fold at unit energy (kJ) level. Although Avicel cellulose was highly recalcitrant to hydrothermal hydrolysis, addition of 0.1M MgCl2 improved reducing sugar yield by 6.94-fold at unit energy (kJ). Dielectric measurement of the mixture of corn starch/water/electrolyte revealed that ionic conduction of electrolytes were strongly involved in facilitating hydrothermal hydrolysis of polysaccharides.

  2. The effect of microcrystalline cellulose crystallinity on the hydrophilic property of tablets and the hydrolysis of acetylsalicylic acid as active pharmaceutical ingredient inside tablets.

    PubMed

    Awa, Kimie; Shinzawa, Hideyuki; Ozaki, Yukihiro

    2015-08-01

    The crystal structures of active pharmaceutical ingredients and excipients should be strictly controlled because they influence pharmaceutical properties of products which cause the change in the quality or the bioavailability of the products. In this study, we investigated the effects of microcrystalline cellulose (MCC) crystallinity on the hydrophilic properties of tablets and the hydrolysis of active pharmaceutical ingredient, acetylsalicylic acid (ASA), inside tablets by using tablets containing 20% MCC as an excipient. Different levels of grinding were applied to MCC prior to tablet formulation, to intentionally cause structural variation in the MCC. The water penetration and moisture absorbability of the tablets increased with decreasing the crystallinity of MCC through higher level of grinding. More importantly, the hydrolysis of ASA inside tablets was also accelerated. These results indicate that the crystallinity of MCC has crucial effects on the pharmaceutical properties of tablets even when the tablets contain a relatively small amount of MCC. Therefore, controlling the crystal structure of excipients is important for controlling product qualities.

  3. The effect of crystallinity of cellulose on the rate of reducing sugars production by heterogeneous enzymatic hydrolysis.

    PubMed

    Al-Zuhair, Sulaiman

    2008-07-01

    A kinetic model is devised, from the reaction mechanism steps, to predict the rate of reducing sugar production by hydrolysis of two types of cellulose, namely, amorphous carboxymethylcellulose (CMC) and highly crystalline wood shavings, using Aspergillus niger cellulase. Experimental results in a stirred batch reactor at 40 degrees C show that the production of reducing sugar reduced at much shorter times for wood shavings in comparison to CMC at the same initial substrate concentration. The experimental results are used to determine the kinetic parameters of the model equations. The significance of crystallinity was determined using inert fraction coefficient, which is assumed to be constant and equals 0.05 and 0.98 for CMC and wood shavings, respectively. It is shown there is a good agreement between the experimental results and proposed kinetic model predictions. The effect of the inert fraction coefficient on the production of reducing sugar by the enzymatic hydrolysis of cellulose is also determined. It is found that the cellulase used extracted from A. niger is much more sensitive towards the substrate structure in comparison to that extracted from Trichoderma reesei.

  4. Real-time observation of the swelling and hydrolysis of a single crystalline cellulose fiber catalyzed by cellulase 7B from Trichoderma reesei.

    PubMed

    Wang, Jingpeng; Quirk, Amanda; Lipkowski, Jacek; Dutcher, John R; Hill, Christopher; Mark, Adam; Clarke, Anthony J

    2012-06-26

    The biodegradation of cellulose involves the enzymatic action of cellulases (endoglucanases), cellobiohydrolases (exoglucanases), and β-glucosidases that act synergistically. The rate and efficiency of enzymatic hydrolysis of crystalline cellulose in vitro decline markedly with time, limiting the large-scale, cost-effective production of cellulosic biofuels. Several factors have been suggested to contribute to this phenomenon, but there is considerable disagreement regarding the relative importance of each. These earlier investigations were hampered by the inability to observe the disruption of crystalline cellulose and its subsequent hydrolysis directly. Here, we show the application of high-resolution atomic force microscopy to observe the swelling of a single crystalline cellulose fiber and its-hydrolysis in real time directly as catalyzed by a single cellulase, the industrially important cellulase 7B from Trichoderma reesei. Volume changes, the root-mean-square roughness, and rates of hydrolysis of the surfaces of single fibers were determined directly from the images acquired over time. Hydrolysis dominated the early stage of the experiment, and swelling dominated the later stage. The high-resolution images revealed that the combined action of initial hydrolysis followed by swelling exposed individual microfibrils and bundles of microfibrils, resulting in the loosening of the fiber structure and the exposure of microfibrils at the fiber surface. Both the hydrolysis and swelling were catalyzed by the native cellulase; under the same conditions, its isolated carbohydrate-binding module did not cause changes to crystalline cellulose. We anticipate that the application of our AFM-based analysis on other cellulolytic enzymes, alone and in combination, will provide significant insight into the process of cellulose biodegradation and greatly facilitate its application for the efficient and economical production of cellulosic ethanol.

  5. Estimation of cellulose crystallinity of lignocelluloses using near-IR FT-Raman spectroscopy and comparison of the Raman and Segal-WAXS methods.

    PubMed

    Agarwal, Umesh P; Reiner, Richard R; Ralph, Sally A

    2013-01-09

    Of the recently developed univariate and multivariate near-IR FT-Raman methods for estimating cellulose crystallinity, the former method was applied to a variety of lignocelluloses: softwoods, hardwoods, wood pulps, and agricultural residues/fibers. The effect of autofluorescence on the crystallinity estimation was minimized by solvent extraction or chemical treatment or both. Additionally, when the roles of lignin and hemicellulose in the Raman crystallinity assessment were investigated, it was found that syringyl lignin containing lignocelluloses generated somewhat higher crystallinity, whereas the presence of hemicellulose reduced the crystallinity. Overall, when autofluorescence was minimized and corrections made for hemicellulose and syringyl lignin contributions, the univariate Raman method performed well and estimated cellulose crystallinity accurately. Moreover, when the Raman and Segal-WAXS methods were compared, we observed that in the absence of significant fluorescence, the Raman method was influenced mostly by hemicellulose and syringyl lignin, whereas the Segal-WAXS was affected by various types of lignin and hemicellulose. It was concluded that the near-IR FT-Raman method with corrections for influences of syringyl lignin and hemicellulose can be used to correctly estimate cellulose crystallinity.

  6. Studying the effects of laccase treatment in a softwood dissolving pulp: cellulose reactivity and crystallinity.

    PubMed

    Quintana, Elisabet; Valls, Cristina; Barneto, Agustín G; Vidal, Teresa; Ariza, José; Roncero, M Blanca

    2015-03-30

    An enzymatic biobleaching sequence (LVAQPO) using a laccase from Trametes villosa in combination with violuric acid (VA) and then followed by a pressurized hydrogen peroxide treatment (PO) was developed and found to give high bleaching properties and meet dissolving pulp requirements: high brightness, low content of hemicellulose, satisfactory pulp reactivity, no significant cellulose degradation manifested by α-cellulose and HPLC, and brightness stability against moist heat ageing. The incorporation of a laccase-mediator system (LMS) to bleach sulphite pulps can be a good alternative to traditional bleaching processes since thermogravimetric analysis (TGA) showed that the laccase treatment prevented the adverse effect of hydrogen peroxide on fibre surface as observed during a conventional hydrogen peroxide bleaching treatment (PO). Although VA exhibited the best results in terms of bleaching properties, the performance of natural mediators, such as p-coumaric acid and syringaldehyde, was discussed in relation to changes in cellulose surface detected by TGA.

  7. Effect of cellulose nanocrystals (CNCs) on crystallinity, mechanical and rheological properties of polypropylene/CNCs nanocomposites

    NASA Astrophysics Data System (ADS)

    Bagheriasl, D.; Carreau, P. J.; Dubois, C.; Riedl, B.

    2015-05-01

    Rheological and mechanical properties of polypropylene (PP)/CNCs nanocomposites were compared with those of nanocomposites containing poly(ethylene-co-vinyl alcohol) as a compatibilizer. The nanocomposites were prepared by a Brabender internal mixer at CNC contents of 5 wt%. The compression molded nanocomposite dog-bones and disks were characterized regarding their tensile and dynamic rheological behavior, respectively. The complex viscosity of the nanocomposites samples containing the compatibilizer were increased, slightly, compared to the non-compatibilized nanocomposite samples. Moreover, an overshoot in the transient start-up viscosity of the compatibilized nanocomposite was observed. The Young modulus of the nanocomposite samples containing the compatibilizer were increased up to ca. 37% compared to the neat PP. The elongation at break was decreased in all PP/CNC nanocomposite samples, but less for the nanocomposite samples containing the compatibilizer. The crystalline content of the PP in the nanocomposites and also the crystallization temperature were increased after compatibilization. These results could be ascribed to the efficiency of the poly(ethylene-co-vinyl alcohol) as a compatibilizer that favors a better dispersion and wetting of the hydrophilic CNCs within the hydrophobic PP.

  8. CelI, a Noncellulosomal Family 9 Enzyme from Clostridium thermocellum, Is a Processive Endoglucanase That Degrades Crystalline Cellulose

    PubMed Central

    Gilad, Rachel; Rabinovich, Larisa; Yaron, Sima; Bayer, Edward A.; Lamed, Raphael; Gilbert, Harry J.; Shoham, Yuval

    2003-01-01

    The family 9 cellulase gene celI of Clostridium thermocellum, was previously cloned, expressed, and characterized (G. P. Hazlewood, K. Davidson, J. I. Laurie, N. S. Huskisson, and H. J. Gilbert, J. Gen. Microbiol. 139:307-316, 1993). We have recloned and sequenced the entire celI gene and found that the published sequence contained a 53-bp deletion that generated a frameshift mutation, resulting in a truncated and modified C-terminal segment of the protein. The enzymatic properties of the wild-type protein were characterized and found to conform to those of other family 9 glycoside hydrolases with a so-called theme B architecture, where the catalytic module is fused to a family 3c carbohydrate-binding module (CBM3c); CelI also contains a C-terminal CBM3b. The intact recombinant CelI exhibited high levels of activity on all cellulosic substrates tested, with pH and temperature optima of 5.5 and 70°C, respectively, using carboxymethylcellulose as a substrate. Native CelI was capable of solubilizing filter paper, and the distribution of reducing sugar between the soluble and insoluble fractions suggests that the enzyme acts as a processive cellulase. A truncated form of the enzyme, lacking the C terminal CBM3b, failed to bind to crystalline cellulose and displayed reduced activity toward insoluble substrates. A truncated form of the enzyme, in which both the cellulose-binding CBM3b and the fused CBM3c were removed, failed to exhibit significant levels of activity on any of the substrates examined. This study underscores the general nature of this type of enzymatic theme, whereby the fused CBM3c plays a critical accessory role for the family 9 catalytic domain and changes its character to facilitate processive cleavage of recalcitrant cellulose substrates. PMID:12511483

  9. SIMULATION STUDIES OF THE WETTING OF CRYSTALLINE FACES OF COTTON CELLULOSE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Models of the surfaces of nano-sized cellulose crystals were constructed and a model droplet of water was placed on each. Then, the model atoms were given motion that corresponds to room temperature (a molecular dynamics simulation), and the spreading of the water over the surfaces was studied. Besi...

  10. Treatment of cotton with an alkaline Bacillus spp cellulase: activity towards crystalline cellulose.

    PubMed

    Caparrós, Cristina; López, Carmen; Torrell, Marc; Lant, Neil; Smets, Johan; Cavaco-Paulo, Artur

    2012-02-01

    We analysed the influence of several enzymatic treatment processes using an alkaline cellulase enzyme from Bacillus spp. on the sorption properties of cotton fabrics. Although cellulases are commonly applied in detergent formulations due to their anti-redeposition and depilling benefits, determining the mechanism of action of alkaline cellulases on cotton fibres requires a deeper understanding of the morphology and structure of cotton fibres in terms of fibre cleaning. The accessibility of cellulose fibres was studied by evaluating the iodine sorption value and by fluorescent-labelled enzyme microscopy; the surface morphology of fabrics was analysed by scanning microscopy. The action of enzyme hydrolysis over short time periods can produce fibrillation on cotton fibre surface without any release of cellulosic material. The results indicate that several short consecutive treatments were more effective in increasing the fibre accessibility than one long treatment. In addition, no detectable hydrolytic activity, in terms of reducing sugar production, was found.

  11. Characterization of cellulose I/II hybrid fibers isolated from energycane bagasse during the delignification process: Morphology, crystallinity and percentage estimation.

    PubMed

    Yue, Yiying; Han, Jingquan; Han, Guangping; Zhang, Quanguo; French, Alfred D; Wu, Qinglin

    2015-11-20

    Cellulose I, cellulose II and cellulose I/II hybrid fibers were prepared from energycane bagasse using NaOH and NaClO2 treatments. The definitive defibrillation effect with an average width of 12±5μm was observed for the fibers treated with 20wt% NaOH for 10h and NaClO2 for 2h. The ribbon shaped cellulose I fibers were converted to a swollen state with a rougher surface by 20wt% NaOH treatment for 10h. The percentage of cellulose I decreased from 100% to 5%, and the corresponding CI values increased from 58.2% to 68.8% during the conversion from cellulose I to II. After further NaClO2 treatment, the CI values were decreased because of partial destruction of hydrogen bond network. XRD, NMR and FTIR results present the same trend in the degree of crystallization for all the samples.

  12. Weak-acid sites catalyze the hydrolysis of crystalline cellulose to glucose in water: importance of post-synthetic functionalization of the carbon surface.

    PubMed

    To, Anh The; Chung, Po-Wen; Katz, Alexander

    2015-09-14

    The direct hydrolysis of crystalline cellulose to glucose in water without prior pretreatment enables the transformation of biomass into fuels and chemicals. To understand which features of a solid catalyst are most important for this transformation, the nanoporous carbon material MSC-30 was post-synthetically functionalized by oxidation. The most active catalyst depolymerized crystalline cellulose without prior pretreatment in water, providing glucose in an unprecedented 70 % yield. In comparison, virtually no reaction was observed with MSC-30, even when the reaction was conducted in aqueous solution at pH 2. As no direct correlations between the activity of this solid-solid reaction and internal-site characteristics, such as the β-glu adsorption capacity and the rate of catalytic hydrolysis of adsorbed β-glu strands, were observed, contacts of the external surface with the cellulose crystal are thought to be key for the overall efficiency.

  13. Inverse Temperature-Dependent Pathway of Cellulose Decrystallization in Trifluoroacetic Acid

    SciTech Connect

    Zhao, Haibo; Holladay, John E.; Kwak, Ja Hun; Zhang, Z. Conrad

    2007-05-17

    Abstract An unusual inverse temperature-dependent pathway was observed during cellulose decrystallization in trifluoroacetic acid (TFA). Decreasing the TFA treatment temperature accelerated the cellulose decrystallization process. It took only 100 minutes to completely decrystallize cellulose at 0 °C in TFA, a result not achieved in 48 hours at 25°C in the same medium. There was neither cellulose esterification nor a change of cellulose macrofibril morphology by TFA treatment at 0 °C. Our IR data suggest that TFA molecules are present as cyclic dimers when they penetrate into crystalline cellulose regions, transforming crystalline cellulose to amorphous cellulose. The TFA cyclic dimer does not form strong hydrogen bonds with cellulose since the IR vibration frequency of the carbonyl group of the dimer molecule remained unchanged after the dimer diffused into the cellulose matrix. On the other hand, the rate of TFA penetration into the cellulose matrix was greatly retarded at higher temperatures where monomeric TFA esterification took place on the external surface of crystalline cellulose. At elevated temperatures esterification of TFA monomers with cellulose, as well as water released from the esterification reaction, inhibit the diffusion rate of TFA into the cellulose crystalline region and decreases the TFA swelling capability. Based on experimental observations, our study indicates that cellulose decrystallization does not require that solvent molecules form strong hydrogen bonds with cellulose.

  14. The effect of the cellulose-binding domain from Clostridium cellulovorans on the supramolecular structure of cellulose fibers.

    PubMed

    Ciolacu, Diana; Kovac, Janez; Kokol, Vanja

    2010-03-30

    The cellulose-binding domain (CBD) is the second important and the most wide-spread element of cellulase structure involved in cellulose transformation with a great structural diversity and a range of adsorption behavior toward different types of cellulosic materials. The effect of the CBD from Clostridium cellulovorans on the supramolecular structure of three different sources of cellulose (cotton cellulose, spruce dissolving pulp, and cellulose linters) was studied. Fourier-transform infrared spectroscopy (FTIR) was used to record amides I and II absorption bands of cotton cellulose treated with CBD. Structural changes as weakening and splitting of the hydrogen bonds within the cellulose chains after CBD adsorption were observed. The decrease of relative crystallinity index of the treated celluloses was confirmed by FTIR spectroscopy and X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to confirm the binding of the CBD on the cellulose surface and the changing of the cellulose morphology.

  15. Cellulose microfibril crystallinity is reduced by mutating C-terminal transmembrane region residues CESA1{sup A903V} and CESA3{sup T942I} of cellulose synthase

    SciTech Connect

    Harris, Darby; Corbin, Kendall; Wang, Tuo; Gutierrez, Ryan; Bertolo, Ana; Petti, Caroalberto; Smilgies, Detlef-M; Estevez, Jose Manuel; Bonetta, Dario; Urbanowicz, Breeanna; Ehrhardt, David; Somerville, Chris; Rose, Jocelyn; Hong, Mei; DeBolt, Seth

    2012-01-08

    The mechanisms underlying the biosynthesis of cellulose in plants are complex and still poorly understood. A central question concerns the mechanism of microfibril structure and how this is linked to the catalytic polymerization action of cellulose synthase (CESA). Furthermore, it remains unclear whether modification of cellulose microfibril structure can be achieved genetically, which could be transformative in a bio-based economy. To explore these processes in planta, we developed a chemical genetic toolbox of pharmacological inhibitors and corresponding resistance-conferring point mutations in the C-terminal transmembrane domain region of CESA1{sup A903V} and CESA3{sup T942I} in Arabidopsis thaliana. Using {sup 13}C solid-state nuclear magnetic resonance spectroscopy and X-ray diffraction, we show that the cellulose microfibrils displayed reduced width and an additional cellulose C4 peak indicative of a degree of crystallinity that is intermediate between the surface and interior glucans of wild type, suggesting a difference in glucan chain association during microfibril formation. Consistent with measurements of lower microfibril crystallinity, cellulose extracts from mutated CESA1{sup A903V} and CESA3{sup T942I} displayed greater saccharification efficiency than wild type. Using live-cell imaging to track fluorescently labeled CESA, we found that these mutants show increased CESA velocities in the plasma membrane, an indication of increased polymerization rate. Collectively, these data suggest that CESA1{sup A903V} and CESA3{sup T942I} have modified microfibril structure in terms of crystallinity and suggest that in plants, as in bacteria, crystallization biophysically limits polymerization.

  16. The N-Terminal GH10 Domain of a Multimodular Protein from Caldicellulosiruptor bescii Is a Versatile Xylanase/β-Glucanase That Can Degrade Crystalline Cellulose

    PubMed Central

    Xue, Xianli; Wang, Rong; Tu, Tao; Shi, Pengjun; Ma, Rui; Luo, Huiying

    2015-01-01

    The genome of the thermophilic bacterium Caldicellulosiruptor bescii encodes three multimodular enzymes with identical C-terminal domain organizations containing two consecutive CBM3b modules and one glycoside hydrolase (GH) family 48 (GH48) catalytic module. However, the three proteins differ much in their N termini. Among these proteins, CelA (or C. bescii Cel9A [CbCel9A]/Cel48A) with a GH9/CBM3c binary partner in the N terminus has been shown to use a novel strategy to degrade crystalline cellulose, which leads to its outstanding cellulose-cleaving activity. Here we show that C. bescii Xyn10C (CbXyn10C), the N-terminal GH10 domain from CbXyn10C/Cel48B, can also degrade crystalline cellulose, in addition to heterogeneous xylans and barley β-glucan. The data from substrate competition assays, mutational studies, molecular modeling, and docking point analyses point to the existence of only one catalytic center in the bifunctional xylanase/β-glucanase. The specific activities of the recombinant CbXyn10C on Avicel and filter paper were comparable to those of GH9/CBM3c of the robust CelA expressed in Escherichia coli. Appending one or two cellulose-binding CBM3bs enhanced the activities of CbXyn10C in degrading crystalline celluloses, which were again comparable to those of the GH9/CBM3c-CBM3b-CBM3b truncation mutant of CelA. Since CbXyn10C/Cel48B and CelA have similar domain organizations and high sequence homology, the endocellulase activity observed in CbXyn10C leads us to speculate that CbXyn10C/Cel48B may use the same strategy that CelA uses to hydrolyze crystalline cellulose, thus helping the excellent crystalline cellulose degrader C. bescii acquire energy from the environment. In addition, we also demonstrate that CbXyn10C may be an interesting candidate enzyme for biotechnology due to its versatility in hydrolyzing multiple substrates with different glycosidic linkages. PMID:25819971

  17. Biofilm formation, phenotypic production of cellulose and gene expression in Salmonella enterica decrease under anaerobic conditions.

    PubMed

    Lamas, A; Miranda, J M; Vázquez, B; Cepeda, A; Franco, C M

    2016-12-05

    Salmonella enterica subsp. enterica is one of the main food-borne pathogens. This microorganism combines an aerobic life outside the host with an anaerobic life within the host. One of the main concerns related to S. enterica is biofilm formation and cellulose production. In this study, biofilm formation, morphotype, cellulose production and transcription of biofilm and quorum sensing-related genes of 11 S. enterica strains were tested under three different conditions: aerobiosis, microaerobiosis, and anaerobiosis. The results showed an influence of oxygen levels on biofilm production. Biofilm formation was significantly higher (P<0.05) in aerobiosis than in microaerobiosis and anaerobiosis. Cellulose production and RDAR (red, dry, and rough) were expressed only in aerobiosis. In microaerobiosis, the strains expressed the SAW (smooth and white) morphotype, while in anaerobiosis the colonies appeared small and red. The expression of genes involved in cellulose synthesis (csgD and adrA) and quorum sensing (sdiA and luxS) was reduced in microaerobiosis and anaerobiosis in all S. enterica strains tested. This gene expression levels were less reduced in S. Typhimurium and S. Enteritidis compared to the tested serotypes. There was a relationship between the expression of biofilm and quorum sensing-related genes. Thus, the results from this study indicate that biofilm formation and cellulose production are highly influenced by atmospheric conditions. This must be taken into account as contamination with these bacteria can occur during food processing under vacuum or modified atmospheres.

  18. Paradigmatic status of an endo- and exoglucanase and its effect on crystalline cellulose degradation

    PubMed Central

    2012-01-01

    Background Microorganisms employ a multiplicity of enzymes to efficiently degrade the composite structure of plant cell wall cellulosic polysaccharides. These remarkable enzyme systems include glycoside hydrolases (cellulases, hemicellulases), polysaccharide lyases, and the carbohydrate esterases. To accomplish this challenging task, several strategies are commonly observed either separately or in combination. These include free enzyme systems, multifunctional enzymes, and multi-enzyme self-assembled designer cellulosome complexes. Results In order to compare these different paradigms, we employed a synthetic biology approach to convert two different cellulases from the free enzymatic system of the well-studied bacterium, Thermobifida fusca, into bifunctional enzymes with different modular architectures. We then examined their performance compared to those of the combined parental free-enzyme and equivalent designer-cellulosome systems. The results showed that the cellulolytic activity displayed by the different architectures of the bifunctional enzymes was somewhat inferior to that of the wild-type free enzyme system. Conclusions The activity exhibited by the designer cellulosome system was equal or superior to that of the free system, presumably reflecting the combined proximity of the enzymes and high flexibility of the designer cellulosome components, thus enabling efficient enzymatic activity of the catalytic modules. PMID:23095278

  19. The anisotropy1 D604N Mutation in the Arabidopsis Cellulose Synthase1 Catalytic Domain Reduces Cell Wall Crystallinity and the Velocity of Cellulose Synthase Complexes1[W][OA

    PubMed Central

    Fujita, Miki; Himmelspach, Regina; Ward, Juliet; Whittington, Angela; Hasenbein, Nortrud; Liu, Christine; Truong, Thy T.; Galway, Moira E.; Mansfield, Shawn D.; Hocart, Charles H.; Wasteneys, Geoffrey O.

    2013-01-01

    Multiple cellulose synthase (CesA) subunits assemble into plasma membrane complexes responsible for cellulose production. In the Arabidopsis (Arabidopsis thaliana) model system, we identified a novel D604N missense mutation, designated anisotropy1 (any1), in the essential primary cell wall CesA1. Most previously identified CesA1 mutants show severe constitutive or conditional phenotypes such as embryo lethality or arrest of cellulose production but any1 plants are viable and produce seeds, thus permitting the study of CesA1 function. The dwarf mutants have reduced anisotropic growth of roots, aerial organs, and trichomes. Interestingly, cellulose microfibrils were disordered only in the epidermal cells of the any1 inflorescence stem, whereas they were transverse to the growth axis in other tissues of the stem and in all elongated cell types of roots and dark-grown hypocotyls. Overall cellulose content was not altered but both cell wall crystallinity and the velocity of cellulose synthase complexes were reduced in any1. We crossed any1 with the temperature-sensitive radial swelling1-1 (rsw1-1) CesA1 mutant and observed partial complementation of the any1 phenotype in the transheterozygotes at rsw1-1’s permissive temperature (21°C) and full complementation by any1 of the conditional rsw1-1 root swelling phenotype at the restrictive temperature (29°C). In rsw1-1 homozygotes at restrictive temperature, a striking dissociation of cellulose synthase complexes from the plasma membrane was accompanied by greatly diminished motility of intracellular cellulose synthase-containing compartments. Neither phenomenon was observed in the any1 rsw1-1 transheterozygotes, suggesting that the proteins encoded by the any1 allele replace those encoded by rsw1-1 at restrictive temperature. PMID:23532584

  20. Assessment of solvents for cellulose dissolution.

    PubMed

    Ghasemi, Mohammad; Tsianou, Marina; Alexandridis, Paschalis

    2017-03-01

    A necessary step in the processing of biomass is the pretreatment and dissolution of cellulose. A good solvent for cellulose involves high diffusivity, aggressiveness in decrystallization, and capability of disassociating the cellulose chains. However, it is not clear which of these factors and under what conditions should be improved in order to obtain a more effective solvent. To this end, a newly-developed phenomenological model has been applied to assess the controlling mechanism of cellulose dissolution. Among the findings, the cellulose fibers remain crystalline almost to the end of the dissolution process for decrystallization-controlled kinetics. In such solvents, decreasing the fiber crystallinity, e.g., via pretreatment, would result in a considerable increase in the dissolution rate. Such insights improve the understanding of cellulose dissolution and facilitate the selection of more efficient solvents and processing conditions for biomass. Specific examples of solvents are provided where dissolution is limited due to decrystallization or disentanglement.

  1. Polymer composites reinforced by locking-in a liquid-crystalline assembly of cellulose nanocrystallites.

    PubMed

    Tatsumi, Mio; Teramoto, Yoshikuni; Nishio, Yoshiyuki

    2012-05-14

    An attempt was made to synthesize novel composites comprising poly(2-hydroxyethyl methacrylate) (PHEMA) and cellulose nanocrystallites (CNC) (acid-treated cotton microfibrils) from suspensions of CNC in an aqueous 2-hydroxyethyl methacrylate (HEMA) monomer solution. The starting suspensions (∼5 wt % CNC) separated into an isotropic upper phase and an anisotropic bottom one in the course of quiescent standing. By way of polymerization of HEMA in different phase situations of the suspensions, we obtained films of three polymer composites, PHEMA-CNC(iso), PHEMA-CNC(aniso), and PHEMA-CNC(mix), coming from the isotropic phase, anisotropic phase, and embryonic nonseparating mixture, respectively. All the composites were transparent and, more or less, birefringent under a polarized optical microscope. A fingerprint texture typical of cholesteric liquid crystals of longer pitch spread widely in PHEMA-CNC(aniso) but rather locally appeared in PHEMA-CNC(iso). Any of the CNC incorporations into the PHEMA matrix improved the original thermal and mechanical properties of this amorphous polymer material. In dynamic mechanical measurements, the locking-in of the respective CNC assemblies gave rise to an increase in the glass-state modulus E' of PHEMA as well as a marked suppression of the E'-falling at temperatures higher than T(g) (≈ 110 °C) of the vinyl polymer. It was also observed for the composites that their modulus E' rerose in a range of about 150-190 °C, which was attributable to a secondary cross-linking formation between PHEMA chains mediated by the acidic CNC filler. The mechanical reinforcement effect of the CNC dispersions was ensured in a tensile test, whereby PHEMA-CNC(aniso) was found to surpass the other two composites in stiffness and strength.

  2. The cellulose-binding domain of the major cellobiohydrolase of Trichoderma reesei exhibits true reversibility and a high exchange rate on crystalline cellulose.

    PubMed Central

    Linder, M; Teeri, T T

    1996-01-01

    Cellulose-binding domains (CBDs) bind specifically to cellulose, and form distinct domains of most cellulose degrading enzymes. The CBD-mediated binding of the enzyme has a fundamental role in the hydrolysis of the solid cellulose substrate. In this work we have investigated the reversibility and kinetics of the binding of the CBD from Trichoderma reesei cellobiohydrolase I on microcrystalline cellulose. The CBD was produced in Escherichia coli, purified, and radioactively labeled by reductive alkylation with 3H. Sensitive detection of the labeled CBD allowed more detailed analysis of its behavior than has been possible before, and important novel features were resolved. Binding of the CBD was found to be temperature sensitive, with an increased affinity at lower temperatures. The interaction of the CBD with cellulose was shown to be fully reversible and the CBD could be eluted from cellulose by simple dilution. The rate of exchange measured for the CBD-cellulose interaction compares well with the hydrolysis rate of cellobiohydrolase I, which is consistent with its proposed mode of action as a processive exoglucanase. PMID:8901566

  3. Characterization of cellulose structure of Populus plants modified in candidate cellulose biosynthesis genes

    DOE PAGES

    Bali, Garima; Khunsupat, Ratayakorn; Akinosho, Hannah; ...

    2016-09-10

    Here, the recalcitrant nature of lignocellulosic biomass is a combined effect of several factors such as high crystallinity and high degree of polymerization of cellulose, lignin content and structure, and the available surface area for enzymatic degradation (i.e., accessibility). Genetic improvement of feedstock cell wall properties is a path to reducing recalcitrance of lignocellulosic biomass and improving conversion to various biofuels. An advanced understanding of the cellulose biosynthesis pathway is essential to precisely modify cellulose properties of plant cell walls. Here we report on the impact of modified expression of candidate cellulose biosynthesis pathway genes on the ultra-structure of cellulose,more » a key carbohydrate polymer of Populus cell wall using advanced nuclear magnetic resonance approaches. Noteworthy changes were observed in the cell wall characteristics of downregulated KORRIGAN 1 (KOR) and KOR 2 transgenic plants in comparison to the wild-type control. It was observed that all of the transgenic lines showed variation in cellulose ultrastructure, increase in cellulose crystallinity and decrease in the cellulose degree of polymerization. Additionally, the properties of cellulose allomorph abundance and accessibility were found to be variable. Application of such cellulose characterization techniques beyond the traditional measurement of cellulose abundance to comprehensive studies of cellulose properties in larger transgenic and naturally variable populations is expected to provide deeper insights into the complex nature of lignocellulosic material, which can significantly contribute to the development of precisely tailored plants for enhanced biofuels production.« less

  4. Characterization of cellulose structure of Populus plants modified in candidate cellulose biosynthesis genes

    SciTech Connect

    Bali, Garima; Khunsupat, Ratayakorn; Akinosho, Hannah; Payyavula, Raja S.; Samuel, Reichel; Tuskan, Gerald A.; Kalluri, Udaya C.; Ragauskas, Arthur J.

    2016-09-10

    Here, the recalcitrant nature of lignocellulosic biomass is a combined effect of several factors such as high crystallinity and high degree of polymerization of cellulose, lignin content and structure, and the available surface area for enzymatic degradation (i.e., accessibility). Genetic improvement of feedstock cell wall properties is a path to reducing recalcitrance of lignocellulosic biomass and improving conversion to various biofuels. An advanced understanding of the cellulose biosynthesis pathway is essential to precisely modify cellulose properties of plant cell walls. Here we report on the impact of modified expression of candidate cellulose biosynthesis pathway genes on the ultra-structure of cellulose, a key carbohydrate polymer of Populus cell wall using advanced nuclear magnetic resonance approaches. Noteworthy changes were observed in the cell wall characteristics of downregulated KORRIGAN 1 (KOR) and KOR 2 transgenic plants in comparison to the wild-type control. It was observed that all of the transgenic lines showed variation in cellulose ultrastructure, increase in cellulose crystallinity and decrease in the cellulose degree of polymerization. Additionally, the properties of cellulose allomorph abundance and accessibility were found to be variable. Application of such cellulose characterization techniques beyond the traditional measurement of cellulose abundance to comprehensive studies of cellulose properties in larger transgenic and naturally variable populations is expected to provide deeper insights into the complex nature of lignocellulosic material, which can significantly contribute to the development of precisely tailored plants for enhanced biofuels production.

  5. Brittle Culm1, a COBRA-like protein, functions in cellulose assembly through binding cellulose microfibrils.

    PubMed

    Liu, Lifeng; Shang-Guan, Keke; Zhang, Baocai; Liu, Xiangling; Yan, Meixian; Zhang, Lanjun; Shi, Yanyun; Zhang, Mu; Qian, Qian; Li, Jiayang; Zhou, Yihua

    2013-01-01

    Cellulose represents the most abundant biopolymer in nature and has great economic importance. Cellulose chains pack laterally into crystalline forms, stacking into a complicated crystallographic structure. However, the mechanism of cellulose crystallization is poorly understood. Here, via functional characterization, we report that Brittle Culm1 (BC1), a COBRA-like protein in rice, modifies cellulose crystallinity. BC1 was demonstrated to be a glycosylphosphatidylinositol (GPI) anchored protein and can be released into cell walls by removal of the GPI anchor. BC1 possesses a carbohydrate-binding module (CBM) at its N-terminus. In vitro binding assays showed that this CBM interacts specifically with crystalline cellulose, and several aromatic residues in this domain are essential for binding. It was further demonstrated that cell wall-localized BC1 via the CBM and GPI anchor is one functional form of BC1. X-ray diffraction (XRD) assays revealed that mutations in BC1 and knockdown of BC1 expression decrease the crystallite width of cellulose; overexpression of BC1 and the CBM-mutated BC1s caused varied crystallinity with results that were consistent with the in vitro binding assay. Moreover, interaction between the CBM and cellulose microfibrils was largely repressed when the cell wall residues were pre-stained with two cellulose dyes. Treating wild-type and bc1 seedlings with the dyes resulted in insensitive root growth responses in bc1 plants. Combined with the evidence that BC1 and three secondary wall cellulose synthases (CESAs) function in different steps of cellulose production as revealed by genetic analysis, we conclude that BC1 modulates cellulose assembly by interacting with cellulose and affecting microfibril crystallinity.

  6. Sensing the structural differences in cellulose from apple and bacterial cell wall materials by Raman and FT-IR spectroscopy.

    PubMed

    Szymańska-Chargot, Monika; Cybulska, Justyna; Zdunek, Artur

    2011-01-01

    Raman and Fourier Transform Infrared (FT-IR) spectroscopy was used for assessment of structural differences of celluloses of various origins. Investigated celluloses were: bacterial celluloses cultured in presence of pectin and/or xyloglucan, as well as commercial celluloses and cellulose extracted from apple parenchyma. FT-IR spectra were used to estimate of the I(β) content, whereas Raman spectra were used to evaluate the degree of crystallinity of the cellulose. The crystallinity index (X(C)(RAMAN)%) varied from -25% for apple cellulose to 53% for microcrystalline commercial cellulose. Considering bacterial cellulose, addition of xyloglucan has an impact on the percentage content of cellulose I(β). However, addition of only xyloglucan or only pectins to pure bacterial cellulose both resulted in a slight decrease of crystallinity. However, culturing bacterial cellulose in the presence of mixtures of xyloglucan and pectins results in an increase of crystallinity. The results confirmed that the higher degree of crystallinity, the broader the peak around 913 cm(-1). Among all bacterial celluloses the bacterial cellulose cultured in presence of xyloglucan and pectin (BCPX) has the most similar structure to those observed in natural primary cell walls.

  7. vapor phase lubrication of SiO2 surfaces via adsorption of short chain linear alcohols & a sum frequency generation vibration spectroscopy study of crystalline cellulose in biomass

    NASA Astrophysics Data System (ADS)

    Barnette, Anna Lorraine

    , and NMR, require the separation of cellulose from its surrounding components in biomass. The chemical processes used for this separation can alter the structure of cellulose. XRD cannot completely differentiate between the sub-types of cellulose I (alpha or beta). This study investigates the use of SFG in analyzing crystalline cellulose within biomass samples, which included hemicellulose and lignin, and the different cellulose polymorphs. This study also demonstrates that SFG is able to selectively detect crystalline cellulose within biomass samples as well as quantify the amount of crystalline cellulose present using proper calibration curves. Unlike what is observed in FTIR, Raman, and NMR, only crystalline cellulose generates a true SFG spectrum so separation from the other components in biomass is not required. Also, SFG is able to differentiate between the different polymorphs showing more distinct differences in spectra when compared to FTIR and Raman. These include distinct differences between the sub-types of cellulose I. SFG is a very promising complementary spectroscopic technique for studying crystalline cellulose.

  8. Dynamic rheology behavior of electron beam-irradiated cellulose pulp/NMMO solution

    NASA Astrophysics Data System (ADS)

    Zhou, Ruimin; Deng, Bangjun; Hao, Xufeng; Zhou, Fei; Wu, Xinfeng; Chen, Yongkang

    2008-08-01

    The rheological behavior of irradiated cellulose pulp solution by electron beam was investigated. Storage modulus G', loss modulus G″, the dependence of complex viscosity η* and frequency ω of cellulose solutions were measured by DSR-200 Rheometer (Rheometrics co., USA). The molecular weight of irradiated cellulose was measured via the intrinsic viscosity measurement using an Ubbelohde capillary viscometer. The crystalline structure was studied by FTIR Spectroscopy. The results congruously showed that the molecular weight of pulp cellulose decrease and the molecular weight distribution of cellulose become narrow with increase in the irradiation dose. Moreover, the crystalline structure of the cellulose was destroyed, the force of the snarl between the cellulose molecules weakens and the accessibility of pulp spinning is improved. The study supplies some useful data for spinnability of irradiated cellulose and technical data to the filature industry.

  9. Binding and movement of individual Cel7A cellobiohydrolases on crystalline cellulose surfaces revealed by single-molecule fluorescence imaging.

    PubMed

    Jung, Jaemyeong; Sethi, Anurag; Gaiotto, Tiziano; Han, Jason J; Jeoh, Tina; Gnanakaran, Sandrasegaram; Goodwin, Peter M

    2013-08-16

    The efficient catalytic conversion of biomass to bioenergy would meet a large portion of energy requirements in the near future. A crucial step in this process is the enzyme-catalyzed hydrolysis of cellulose to glucose that is then converted into fuel such as ethanol by fermentation. Here we use single-molecule fluorescence imaging to directly monitor the movement of individual Cel7A cellobiohydrolases from Trichoderma reesei (TrCel7A) on the surface of insoluble cellulose fibrils to elucidate molecular level details of cellulase activity. The motion of multiple, individual TrCel7A cellobiohydrolases was simultaneously recorded with ∼15-nm spatial resolution. Time-resolved localization microscopy provides insights on the activity of TrCel7A on cellulose and informs on nonproductive binding and diffusion. We measured single-molecule residency time distributions of TrCel7A bound to cellulose both in the presence of and absence of cellobiose the major product and a potent inhibitor of Cel7A activity. Combining these results with a kinetic model of TrCel7A binding provides microscopic insight into interactions between TrCel7A and the cellulose substrate.

  10. Deficient sucrose synthase activity in developing wood does not specifically affect cellulose biosynthesis, but causes an overall decrease in cell wall polymers.

    PubMed

    Gerber, Lorenz; Zhang, Bo; Roach, Melissa; Rende, Umut; Gorzsás, András; Kumar, Manoj; Burgert, Ingo; Niittylä, Totte; Sundberg, Björn

    2014-09-01

    The biosynthesis of wood in aspen (Populus) depends on the metabolism of sucrose, which is the main transported form of carbon from source tissues. The largest fraction of the wood biomass is cellulose, which is synthesized from UDP-glucose. Sucrose synthase (SUS) has been proposed previously to interact directly with cellulose synthase complexes and specifically supply UDP-glucose for cellulose biosynthesis. To investigate the role of SUS in wood biosynthesis, we characterized transgenic lines of hybrid aspen with strongly reduced SUS activity in developing wood. No dramatic growth phenotypes in glasshouse-grown trees were observed, but chemical fingerprinting with pyrolysis-GC/MS, together with micromechanical analysis, showed notable changes in chemistry and ultrastructure of the wood in the transgenic lines. Wet chemical analysis showed that the dry weight percentage composition of wood polymers was not changed significantly. However, a decrease in wood density was observed and, consequently, the content of lignin, hemicellulose and cellulose was decreased per wood volume. The decrease in density was explained by a looser structure of fibre cell walls as shown by increased wall shrinkage on drying. The results show that SUS is not essential for cellulose biosynthesis, but plays a role in defining the total carbon incorporation to wood cell walls.

  11. Preparing cationic cotton linter cellulose with high substitution degree by ultrasonic treatment.

    PubMed

    Zhang, Fulong; Pang, Zhiqiang; Dong, Cuihua; Liu, Zong

    2015-11-05

    As an important cellulose derivative, cationic cellulose has becoming an attractive material. However, it remains challenging to produce cationic cellulose with high substitute degree. In this paper, we successfully increased the substitute degree of cationic cellulose by introducing ultrasonic treatment, which efficiently breaks hydrogen bonds of the chemical structure of cationic cellulose. Properties of cationic cellulose were studied by scanning electron spectroscope (SEM), contact angle, X-ray diffraction (XRD) and thermogravimetric analysis (TGA). Experimental results show that the cationic cellulose has rougher surface and lower crystallinity degree as compared to the original sample. TGA analysis verifies that the thermostability of CLC decreases after the cationic modification. The residual of the cationic cellulose (25 wt%) after pyrolysis increases significantly as compared to that of the original cellulose (15 wt%).

  12. Molecular and Biochemical Analyses of CbCel9A/Cel48A, a Highly Secreted Multi-Modular Cellulase by Caldicellulosiruptor bescii during Growth on Crystalline Cellulose

    PubMed Central

    Yi, Zhuolin; Su, Xiaoyun; Revindran, Vanessa; Mackie, Roderick I.; Cann, Isaac

    2013-01-01

    During growth on crystalline cellulose, the thermophilic bacterium Caldicellulosiruptor bescii secretes several cellulose-degrading enzymes. Among these enzymes is CelA (CbCel9A/Cel48A), which is reported as the most highly secreted cellulolytic enzyme in this bacterium. CbCel9A/Cel48A is a large multi-modular polypeptide, composed of an N-terminal catalytic glycoside hydrolase family 9 (GH9) module and a C-terminal GH48 catalytic module that are separated by a family 3c carbohydrate-binding module (CBM3c) and two identical CBM3bs. The wild-type CbCel9A/Cel48A and its truncational mutants were expressed in Bacillus megaterium and Escherichia coli, respectively. The wild-type polypeptide released twice the amount of glucose equivalents from Avicel than its truncational mutant that lacks the GH48 catalytic module. The truncational mutant harboring the GH9 module and the CBM3c was more thermostable than the wild-type protein, likely due to its compact structure. The main hydrolytic activity was present in the GH9 catalytic module, while the truncational mutant containing the GH48 module and the three CBMs was ineffective in degradation of either crystalline or amorphous cellulose. Interestingly, the GH9 and/or GH48 catalytic modules containing the CBM3bs form low-density particles during hydrolysis of crystalline cellulose. Moreover, TM3 (GH9/CBM3c) and TM2 (GH48 with three CBM3 modules) synergistically hydrolyze crystalline cellulose. Deletion of the CBM3bs or mutations that compromised their binding activity suggested that these CBMs are important during hydrolysis of crystalline cellulose. In agreement with this observation, seven of nine genes in a C. bescii gene cluster predicted to encode cellulose-degrading enzymes harbor CBM3bs. Based on our results, we hypothesize that C. bescii uses the GH48 module and the CBM3bs in CbCel9A/Cel48A to destabilize certain regions of crystalline cellulose for attack by the highly active GH9 module and other endoglucanases

  13. Biomass enzymatic saccharification is determined by the non-KOH-extractable wall polymer features that predominately affect cellulose crystallinity in corn.

    PubMed

    Jia, Jun; Yu, Bin; Wu, Leiming; Wang, Hongwu; Wu, Zhiliang; Li, Ming; Huang, Pengyan; Feng, Shengqiu; Chen, Peng; Zheng, Yonglian; Peng, Liangcai

    2014-01-01

    Corn is a major food crop with enormous biomass residues for biofuel production. Due to cell wall recalcitrance, it becomes essential to identify the key factors of lignocellulose on biomass saccharification. In this study, we examined total 40 corn accessions that displayed a diverse cell wall composition. Correlation analysis showed that cellulose and lignin levels negatively affected biomass digestibility after NaOH pretreatments at p<0.05 & 0.01, but hemicelluloses did not show any significant impact on hexoses yields. Comparative analysis of five standard pairs of corn samples indicated that cellulose and lignin should not be the major factors on biomass saccharification after pretreatments with NaOH and H2SO4 at three concentrations. Notably, despite that the non-KOH-extractable residues covered 12%-23% hemicelluloses and lignin of total biomass, their wall polymer features exhibited the predominant effects on biomass enzymatic hydrolysis including Ara substitution degree of xylan (reverse Xyl/Ara) and S/G ratio of lignin. Furthermore, the non-KOH-extractable polymer features could significantly affect lignocellulose crystallinity at p<0.05, leading to a high biomass digestibility. Hence, this study could suggest an optimal approach for genetic modification of plant cell walls in bioenergy corn.

  14. Hydrolysis of dilute acid-pretreated cellulose under mild hydrothermal conditions.

    PubMed

    Chimentão, R J; Lorente, E; Gispert-Guirado, F; Medina, F; López, F

    2014-10-13

    The hydrolysis of dilute acid-pretreated cellulose was investigated in a conventional oven and under microwave heating. Two acids--sulfuric and oxalic--were studied. For both hydrothermal conditions (oven and microwave) the resultant total organic carbon (TOC) values obtained by the hydrolysis of the cellulose pretreated with sulfuric acid were higher than those obtained by the hydrolysis of the cellulose pretreated with oxalic acid. However, the dicarboxylic acid exhibited higher hydrolytic efficiency towards glucose. The hydrolysis of cellulose was greatly promoted by microwave heating. The Rietveld method was applied to fit the X-ray patterns of the resultant cellulose after hydrolysis. Oxalic acid preferentially removed the amorphous region of the cellulose and left the crystalline region untouched. On the other hand, sulfuric acid treatment decreased the ordering of the cellulose by partially disrupting its crystalline structure.

  15. Ethyl cellulose nanoparticles as a platform to decrease ulcerogenic potential of piroxicam: formulation and in vitro/in vivo evaluation

    PubMed Central

    El-Habashy, Salma E; Allam, Ahmed N; El-Kamel, Amal H

    2016-01-01

    Nanoparticles (NPs) have long gained significant interest for their use in various drug formulations in order to increase bioavailability, prolong drug release, and decrease side effects of highly toxic drugs. The objective of this investigation was to evaluate the potential of ethyl cellulose-based NPs (EC-NPs) to modulate the release and reduce ulcerogenicity of piroxicam (PX) after oral administration. PX-loaded EC-NPs were prepared by solvent evaporation technique using different stabilizers at three concentration levels. Morphological examination of selected formulas confirmed the formation of spherical NPs with slightly porous surface. Formulation containing poloxamer-stabilized EC-NPs (P188/0.2), having a particle size of 240.26±29.24 nm, polydispersity index of 0.562±0.030, entrapment efficiency of 85.29%±1.57%, and modulated release of PX (88% after 12 hours), was selected as the optimum formulation. Differential scanning calorimetry demonstrated the presence of PX in an amorphous form in the NPs. Fourier-transform infrared spectroscopy revealed the possible formation of hydrogen bond and the absence of chemical interaction. In vivo study, evaluation of pharmacokinetic parameters, evaluation of gastric irritation potential, and histological examination were conducted after administration of the selected formulation. Time to reach maximum plasma concentration, tmax, of poloxamer-stabilized EC-NPs was significantly higher than that of Feldene® 20 mg capsules (P≤0.001). Encapsulation of the acidic, gastric offender PX into NPs managed to significantly suppress gastric ulceration potential in rats (P≤0.05) as compared to that of PX suspension. A reduction of 66% in mean ulcer index was observed. In conclusion, poloxamer-stabilized EC-NPs (P188/0.2) had a significant potential of offsetting deleterious side effects common in PX use. PMID:27307735

  16. Grafting of bacterial polyhydroxybutyrate (PHB) onto cellulose via in situ reactive extrusion with dicumyl peroxide.

    PubMed

    Wei, Liqing; McDonald, Armando G; Stark, Nicole M

    2015-03-09

    Polyhydroxybutyrate (PHB) was grafted onto cellulose fiber by dicumyl peroxide (DCP) radical initiation via in situ reactive extrusion. The yield of the grafted (cellulose-g-PHB) copolymer was recorded and grafting efficiency was found to be dependent on the reaction time and DCP concentration. The grafting mechanism was investigated by electron spin resonance (ESR) analysis and showed the presence of radicals produced by DCP radical initiation. The grafted copolymer structure was determined by nuclear magnetic resonance (NMR) spectroscopy. Scanning electronic microscopy (SEM) showed that the cellulose-g-PHB copolymer formed a continuous phase between the surfaces of cellulose and PHB as compared to cellulose-PHB blends. The relative crystallinity of cellulose and PHB were quantified from Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) results, while the absolute degree of crystallinity was evaluated by differential scanning calorimetry (DSC). The reduction of crystallinity indicated the grafting reaction occurred not just in the amorphous region but also slightly in crystalline regions of both cellulose and PHB. The smaller crystal sizes suggested the brittleness of PHB was decreased. Thermogravimetric analysis (TGA) showed that the grafted copolymer was stabilized relative to PHB. By varying the reaction parameters the compositions (%PHB and %cellulose) of resultant cellulose-g-PHB copolymer are expected to be manipulated to obtain tunable properties.

  17. Anaerobic degradation of microcrystalline cellulose: kinetics and micro-scale structure evolution.

    PubMed

    Yu, Lei; Chen, Zi-Xiang; Tong, Xin; Li, Kuan; Li, Wen-Wei

    2012-01-01

    The degradation kinetics and micro-scale structure change of microcrystalline cellulose during anaerobic biodegradation were investigated. A modified Logistic model was established to properly describe the kinetics, which showed good fitness and wide applicability for cellulose degradation. A maximum degradation rate of 0.14 g L(-1) h(-1) was achieved after cultivating for 51.5 h. This result was in good agreement with the scanning electron microscope and X-ray diffraction analysis. Channels of 400-500 nm size started to occur on the crystalline surface of cellulose at around the inflexion time. Accordingly, the crystallinity significantly decreased at this point, indicating a degradation of the crystalline structure zones by anaerobic bacteria. This study offers direct morphological evidence and quantitative analysis of the biodegradation process of cellulose, and is beneficial to a better understanding of the cellulose degradation mechanism.

  18. Assessing the potential to decrease the Gulf of Mexico hypoxic zone with Midwest US perennial cellulosic feedstock production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The goal of this research is to determine the changes in streamflow, dissolved inorganic nitrogen (DIN) leaching and export to the Gulf of Mexico associated with a range of large-scale dedicated perennial cellulosic bioenergy production scenarios within in the Mississippi-Atchafalaya River Basin (MA...

  19. Expression of the Acidothermus cellulolyticus E1 endoglucanase in Caldicellulosiruptor bescii enhances its ability to deconstruct crystalline cellulose

    DOE PAGES

    Chung, Daehwan; Young, Jenna; Cha, Minseok; ...

    2015-08-13

    The Caldicellulosiruptor bescii genome encodes a potent set of carbohydrate-active enzymes (CAZymes), found primarily as multi-domain enzymes that exhibit high cellulolytic and hemicellulolytic activity on and allow utilization of a broad range of substrates, including plant biomass without conventional pretreatment. CelA, the most abundant cellulase in the C. bescii secretome, uniquely combines a GH9 endoglucanase and a GH48 exoglucanase in one protein. The most effective commercial enzyme cocktails used in vitro to pretreat biomass are derived from fungal cellulases (cellobiohydrolases, endoglucanases and a β-d-glucosidases) that act synergistically to release sugars for microbial conversion. The C. bescii genome contains six GH5more » domains in five different open reading frames. Four exist in multi-domain proteins and two as single catalytic domains. E1 is a GH5 endoglucanase reported to have high specific activity and simple architecture and is active at the growth temperature of C. bescii. E1 is an endo-1,4-β-glucanase linked to a family 2 carbohydrate-binding module shown to bind primarily to cellulosic substrates. As a result, we tested if the addition of this protein to the C. bescii secretome would improve its cellulolytic activity.« less

  20. Label-free Quantitative Proteomics for the Extremely Thermophilic Bacterium Caldicellulosiruptor obsidiansis Reveal Distinct Abundance Patterns upon Growth on Cellobiose, Crystalline Cellulose, and Switchgrass

    SciTech Connect

    Giannone, Richard J; Lochner, Adriane; Keller, Martin; Antranikian, Garabed; Graham, David E; Hettich, Robert {Bob} L

    2011-01-01

    Mass spectrometric analysis of Caldicellulosiruptor obsidiansis cultures grown on four different carbon sources identified 65% of the cells predicted proteins in cell lysates and supernatants. Biological and technical replication together with sophisticated statistical analysis were used to reliably quantify protein abundances and their changes as a function of carbon source. Extracellular, multifunctional glycosidases were significantly more abundant on cellobiose than on the crystalline cellulose substrates Avicel and filter paper, indicating either disaccharide induction or constitutive protein expression. Highly abundant flagellar, chemotaxis, and pilus proteins were detected during growth on insoluble substrates, suggesting motility or specific substrate attachment. The highly abundant extracellular binding protein COB47-0549 together with the COB47-1616 ATPase might comprise the primary ABC-transport system for cellooligosaccharides, while COB47-0096 and COB47-0097 could facilitate monosaccharide uptake. Oligosaccharide degradation can occur either via extracellular hydrolysis by a GH1 {beta}-glycosidase or by intracellular phosphorolysis using two GH94 enzymes. When C. obsidiansis was grown on switchgrass, the abundance of hemicellulases (including GH3, GH5, GH51, and GH67 enzymes) and certain sugar transporters increased significantly. Cultivation on biomass also caused a concerted increase in cytosolic enzymes for xylose and arabinose fermentation.

  1. Inhibitory Effect of Crocin(s) on Lens α-Crystallin Glycation and Aggregation, Results in the Decrease of the Risk of Diabetic Cataract.

    PubMed

    Bahmani, Fereshteh; Bathaie, Seyedeh Zahra; Aldavood, Seyed Javid; Ghahghaei, Arezou

    2016-01-26

    The current study investigates the inhibitory effect of crocin(s), also known as saffron apocarotenoids, on protein glycation and aggregation in diabetic rats, and α-crystallin glycation. Thus, crocin(s) were administered by intraperitoneal injection to normal and streptozotocin-induced diabetic rats. The cataract progression was recorded regularly every two weeks and was classified into four stages. After eight weeks, the animals were sacrificed and the parameters involved in the cataract formation were measured in the animal lenses. Some parameters were also determined in the serum and blood of the rats. In addition, the effect of crocin(s) on the structure and chaperone activity of α-crystallin in the presence of glucose was studied by different methods. Crocin(s) lowered serum glucose levels of diabetic rats and effectively maintained plasma total antioxidants, glutathione levels and catalase activity in the lens of the animals. In the in vitro study, crocin(s) inhibited α-crystallin glycation and aggregation. Advanced glycation end products fluorescence, hydrophobicity and protein cross-links were also decreased in the presence of crocin(s). In addition, the decreased chaperone activity of α-crystallin in the presence of glucose changed and became close to the native value by the addition of crocin(s) in the medium. Crocin(s) thus showed a powerful inhibitory effect on α-crystallin glycation and preserved the structure-function of this protein. Crocin(s) also showed the beneficial effects on prevention of diabetic cataract.

  2. Cellulose binding domain proteins

    SciTech Connect

    Shoseyov, Oded; Shpiegl, Itai; Goldstein, Marc; Doi, Roy

    1998-01-01

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production thereof. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques.

  3. Cellulose binding domain proteins

    DOEpatents

    Shoseyov, O.; Shpiegl, I.; Goldstein, M.; Doi, R.

    1998-11-17

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques. 16 figs.

  4. Quantitative determination of cellulose accessibility to cellulase based on adsorption of a nonhydrolytic fusion protein containing CBM and GFP with its applications.

    PubMed

    Hong, Jiong; Ye, Xinhao; Zhang, Y-H Percival

    2007-12-04

    Heterogeneous cellulose accessibility is an important substrate characteristic, but all methods for determining cellulose accessibility to the large-size cellulase molecule have some limitations. Characterization of cellulose accessibility to cellulase (CAC) is vital for better understanding of the enzymatic cellulose hydrolysis mechanism (Zhang and Lynd, Biotechnol. Bioeng. 2004, 88, 797-824; 2006, 94, 888-898). Quantitative determination of cellulose accessibility to cellulase (m2/g of cellulose) was established based on the Langmuir adsorption of the fusion protein containing a cellulose-binding module (CBM) and a green fluorescent protein (GFP). One molecule of the recombinant fusion protein occupied 21.2 cellobiose lattices on the 110 face of bacterial cellulose nanofibers. The CAC values of several cellulosic materials -- regenerated amorphous cellulose (RAC), bacterial microcrystalline cellulose (BMCC), Whatman No. 1 filter paper, fibrous cellulose powder (CF1), and microcrystalline cellulose (Avicel) -- were 41.9, 33.5, 9.76, 4.53, and 2.38 m2/g, respectively. The CAC value of amorphous cellulose made from Avicel was 17.6-fold larger than that of crystalline cellulose - Avicel. Avicel enzymatic hydrolysis proceeded with a transition from substrate excess to substrate limited. The declining hydrolysis rates over conversion are mainly attributed to a combination of substrate consumption and a decrease in substrate reactivity. Declining heterogeneous cellulose reactivity is significantly attributed to a loss of CAC where the easily hydrolyzed cellulose fraction is digested first.

  5. Effect of dolomite, magnesium oxide (MgO) and chalk (CaCO3) on in vitro fermentation of amorphous and crystalline cellulose and meadow hay using inoculum from sheep.

    PubMed

    Váradyová, Zora; Baran, Miroslav; Zawadzki, Wojciech; Siroka, Peter

    2003-01-01

    Some minerals can influence some biochemical parameters of rumen fermentation. The objective of this experiment was to determine the effect of different amounts (0.1, 0.25 and 0.5 g) of dolomite and to compare the effect of dolomite, magnesium oxide (MgO) and chalk (CaCO3) upon the end products of rumen fermentation in vitro. Amorphous and crystalline cellulose as well as meadow hay were used as substrates and incubated with buffered rumen fluid in sealed fermentation bottles. In dependence on the amount of dolomite and the kind of substrate an inhibitory effect of dolomite on methane production was evident. Significant differences of methane production were found between the controls, crystalline cellulose and meadow hay with 0.5 g of dolomite. An increase of total gas production was observed for cellulose with both 0.25 and 0.5 g of dolomite and also for meadow hay with 0.5 g of dolomite. It can be concluded that there was a remarkable effect of dolomite on methane production and also a slight effect of magnesium oxide and chalk as compared to the effect of dolomite on the fermentation parameters of incubated substrates.

  6. Cellobiose dehydrogenase in cellulose degradation

    SciTech Connect

    Eriksson, L.; Igarashi, Kiyohiko; Samejima, Masahiro

    1996-10-01

    Cellobiose dehydrogenase is produced by a variety of fungi. Although it was already discovered during the 70`s, it`s role in cellulose and lignin degradation is yet ambiguous. The enzyme contains both heme and FAD as prosthetic groups, and seems to have a domain specifically designed to bind the enzyme to cellulose. It`s affinity to amorphous cellulose is higher than to crystalline cellulose. We will report on the binding behavior of the enzyme, its usefulness in elucidation of cellulose structures and also, possibilities for applications such as its use in measuring individual and synergistic mechanisms for cellulose degradation by endo- and exo-glucanases.

  7. Physical properties of agave cellulose graft polymethyl methacrylate

    SciTech Connect

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan

    2013-11-27

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm{sup −1} which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  8. Physical properties of agave cellulose graft polymethyl methacrylate

    NASA Astrophysics Data System (ADS)

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan

    2013-11-01

    The grafting polymerization of methyl methacrylate and Agave cellulose was prepared and their structural analysis and morphology were investigated. The grafting reaction was carried out in an aqueous medium using ceric ammonium nitrate as an initiator. The structural analysis of the graft copolymers was carried out by Fourier transform infrared and X-ray diffraction. The graft copolymers were also characterized by field emission scanning electron microscopy (FESEM). An additional peak at 1732 cm-1 which was attributed to the C=O of ester stretching vibration of poly(methyl methacrylate), appeared in the spectrum of grafted Agave cellulose. A slight decrease of crystallinity index upon grafting was found from 0.74 to 0.68 for cellulose and grafted Agave cellulose, respectively. Another evidence of grafting showed in the FESEM observation, where the surface of the grafted cellulose was found to be roughed than the raw one.

  9. X-ray Studies of Regenerated Cellulose Fibers Wet Spun from Cotton Linter Pulp in NaOH/Thiourea Aqueous Solutions

    SciTech Connect

    Chen,X.; Burger, C.; Fang, D.; Ruan, D.; Zhang, L.; Hsiao, B.; Chu, B.

    2006-01-01

    Regenerated cellulose fibers were fabricated by dissolution of cotton linter pulp in NaOH (9.5 wt%) and thiourea (4.5 wt%) aqueous solution followed by wet-spinning and multi-roller drawing. The multi-roller drawing process involved three stages: coagulation (I), coagulation (II) and post-treatment (III). The crystalline structure and morphology of regenerated cellulose fiber was investigated by synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. Results indicated that only the cellulose II crystal structure was found in regenerated cellulose fibers, proving that the cellulose crystals were completely transformed from cellulose I to II structure during spinning from NaOH/thiourea aqueous solution. The crystallinity, orientation and crystal size at each stage were determined from the WAXD analysis. Drawing of cellulose fibers in the coagulation (II) bath (H{sub 2}SO{sub 4}/H{sub 2}O) was found to generate higher orientation and crystallinity than drawing in the post-treatment (III). Although the post-treatment process also increased crystal orientation, it led to a decrease in crystallinity with notable reduction in the anisotropic fraction. Compared with commercial rayon fibers fabricated by the viscose process, the regenerated cellulose fibers exhibited higher crystallinity but lower crystal orientation. SAXS results revealed a clear scattering maximum along the meridian direction in all regenerated cellulose fibers, indicating the formation of lamellar structure during spinning.

  10. Increased understanding of cellulose crystallinity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    According to the International Union of Crystallography, “material is a crystal if it has essentially a sharp diffraction pattern. The word essentially means that most of the intensity of the diffraction is concentrated in relatively sharp Bragg peaks, besides the always present diffuse scattering.”...

  11. [Preparation and evaluation of press-coated aminophylline tablet using crystalline cellulose and polyethylene glycol in the outer shell for timed-release dosage forms].

    PubMed

    Watanabe, Yoshiteru; Mukai, Baku; Kawamura, Ken-ichi; Ishikawa, Tatsuya; Namiki, Michihiro; Utoguchi, Naoki; Fujii, Makiko

    2002-02-01

    In an attempt to achieve chronopharmacotherapy for asthma, press-coated tablets (250 mg), which contained aminophylline in the core tablet in the form of low-substituted hydroxypropylcellulose (L-HPC) and coated with crystalline cellulose (PH-102) and polyethylene glycol (PEG) at various molecular weights and mixing ratios in the amounts of PH-102 and PEG as the outer shell (press-coating material), were prepared (chronopharmaceutics). Their applicability as timed-release (delayed-release) tablets with a lag time of disintegration and a subsequent rapid drug release phase was investigated. Various types of press-coated tablets were prepared using a tableting machine, and their aminophylline dissolution profiles were evaluated by the JP paddle method. Tablets with the timed-release characteristics could be prepared, and the lag time of disintegration was prolonged as the molecular weight and the amount of PEG, for example PEG 500,000, in the outer shell were increased. The lag time of disintegration could be controlled by the above-mentioned method, however, the pH of the medium had no effect on disintegration of the tablet and dissolution behavior of theophylline. The press-coated tablet (core tablet:aminophylline 50 mg, L-HPC and PEG 6000; outer shell:PH-102:PEG = 8:2 200 mg) with the timed-release characteristics was administered orally to rabbits for an in vivo test. Theophylline was first detected in plasma more than 2 h after administration; thus, this tablet showed a timed-release characteristics in the gastrointestinal tract. The time (tmax) required to reach the maximum plasma theophylline concentration (Cmax) observed after administration of the press-coated tablet was significantly (p < 0.05) delayed compared with that observed after administration of aminophylline solution in the control experiment. However, there was no difference in Cmax and area under the plasma theophylline concentration-time curve (AUC0-->24) between the press-coated tablet and

  12. Effects of autohydrolysis of Eucalyptus urograndis and Eucalyptus grandis on influence of chemical components and crystallinity index.

    PubMed

    da Silva Morais, Alaine Patrícia; Sansígolo, Cláudio Angeli; de Oliveira Neto, Mario

    2016-08-01

    Samples of Eucalyptus urograndis and Eucalyptus grandis sawdust were autohydrolyzed in aqueous conditions to reach temperatures in the range 110-190°C and reaction times of 0-150min in a minireactor. In each minireactor were used a liquor:wood ratio (10:1 L:kg dry wood), in order to assess the effects of the autohydrolysis severity and the crystalline properties of cellulose. The content of extractives, lignin, holocellulose, cellulose, hemicelluloses and crystallinity index obtained from the solid fraction after autohydrolysis of sawdust were determined. This study demonstrated that the hemicelluloses were extensively removed at 170 and 190°C, whereas cellulose was partly degraded to Eucalyptus urograndis and Eucalyptus grandis sawdust. The lignin content decreased, while the extractives content increased. It was defined that during autohydrolysis, had a slight decreased on crystalline structure of cellulose of Eucalyptus urogandis and Eucalyptus grandis.

  13. Characterization of cellulose nanofibrillation by micro grinding

    NASA Astrophysics Data System (ADS)

    Nair, Sandeep S.; Zhu, J. Y.; Deng, Yulin; Ragauskas, Arthur J.

    2014-04-01

    A fundamental understanding of the morphological development of cellulose fibers during fibrillation using micro grinder is very essential to develop effective strategies for process improvement and to reduce energy consumption. We demonstrated some simple measures for characterizing cellulose fibers fibrillated at different fibrillation times through the grinder. The morphology and degree of fibrillation of the samples at different stages of fibrillation were characterized. The fibrillation and mechanical properties reached a maximum in 2 h, and did not show any significant change with further grinding. The lateral dimensions of the smallest nanofibrils were between 15 and 40 nm. A slight reduction in the crystallinity and degree of polymerization did not lead to decrease in mechanical properties of cellulose films. The lower tensile properties at the initial stages of fibrillation are mainly due to the presence of limited refined and heterogeneously treated fibers.

  14. Thickness effect of kenaf cellulose membrane on its morphological, physical and tensile properties

    NASA Astrophysics Data System (ADS)

    Hashim, Sharifah Nurul Ain Syed; Zakaria, Sarani; Jaafar, Sharifah Nabihah Syed; Chia, Chin Hua

    2016-11-01

    Dissolution of kenaf core cellulose was undergone in NaOH/Urea solvent and the cellulose solution was casted with three different thicknesses (0.04 mm, 0.06 mm and 0.07 mm) followed by coagulation in 5 % of H2SO4 to form regenerated cellulose membrane. The XRD results showed that the crystallinity index (CrI) of kenaf core cellulose membrane decreased after been regenerated into cellulose II. The surface morphology showed that the pores of the membrane became smaller as the thickness of cellulose membrane increased. The transparency tests demonstrated the thinner samples (0.04 mm) gave higher light transmittance than the thickest samples (0.07 mm). The kenaf core membrane with 0.07 mm thickness possessed highest tensile strength and breaking elongation at σ = 33.48 and ɛ = 8.03 relatively and also exhibited the largest pore size.

  15. The Arabidopsis COBRA protein facilitates cellulose crystallization at the plasma membrane.

    PubMed

    Sorek, Nadav; Sorek, Hagit; Kijac, Aleksandra; Szemenyei, Heidi J; Bauer, Stefan; Hématy, Kian; Wemmer, David E; Somerville, Chris R

    2014-12-12

    Mutations in the Arabidopsis COBRA gene lead to defects in cellulose synthesis but the function of COBRA is unknown. Here we present evidence that COBRA localizes to discrete particles in the plasma membrane and is sensitive to inhibitors of cellulose synthesis, suggesting that COBRA and the cellulose synthase complex reside in close proximity on the plasma membrane. Live-cell imaging of cellulose synthesis indicated that, once initiated, cellulose synthesis appeared to proceed normally in the cobra mutant. Using isothermal calorimetry, COBRA was found to bind individual β1-4-linked glucan chains with a KD of 3.2 μm. Competition assays suggests that COBRA binds individual β1-4-linked glucan chains with higher affinity than crystalline cellulose. Solid-state nuclear magnetic resonance studies of the cell wall of the cobra mutant also indicated that, in addition to decreases in cellulose amount, the properties of the cellulose fibrils and other cell wall polymers differed from wild type by being less crystalline and having an increased number of reducing ends. We interpret the available evidence as suggesting that COBRA facilitates cellulose crystallization from the emerging β1-4-glucan chains by acting as a "polysaccharide chaperone."

  16. Method of saccharifying cellulose

    DOEpatents

    Johnson, E.A.; Demain, A.L.; Madia, A.

    1983-05-13

    A method is disclosed of saccharifying cellulose by incubation with the cellulase of Clostridium thermocellum in a broth containing an efficacious amount of thiol reducing agent. Other incubation parameters which may be advantageously controlled to stimulate saccharification include the concentration of alkaline earth salts, pH, temperature, and duration. By the method of the invention, even native crystalline cellulose such as that found in cotton may be completely saccharified.

  17. Method of saccharifying cellulose

    DOEpatents

    Johnson, Eric A.; Demain, Arnold L.; Madia, Ashwin

    1985-09-10

    A method of saccharifying cellulose by incubation with the cellulase of Clostridium thermocellum in a broth containing an efficacious amount of a reducing agent. Other incubation parameters which may be advantageously controlled to stimulate saccharification include the concentration of alkaline earth salts, pH, temperature, and duration. By the method of the invention, even native crystalline cellulose such as that found in cotton may be completely saccharified.

  18. Films based on oxidized starch and cellulose from barley.

    PubMed

    El Halal, Shanise Lisie Mello; Colussi, Rosana; Deon, Vinícius Gonçalves; Pinto, Vânia Zanella; Villanova, Franciene Almeida; Carreño, Neftali Lenin Villarreal; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

    2015-11-20

    Starch and cellulose fibers were isolated from grains and the husk from barley, respectively. Biodegradable films of native starch or oxidized starches and glycerol with different concentrations of cellulose fibers (0%, 10% and 20%) were prepared. The films were characterized by morphological, mechanical, barrier, and thermal properties. Cellulose fibers isolated from the barley husk were obtained with 75% purity and high crystallinity. The morphology of the films of the oxidized starches, regardless of the fiber addition, was more homogeneous as compared to the film of the native starch. The addition of cellulose fibers in the films increased the tensile strength and decreased elongation. The water vapor permeability of the film of oxidized starch with 20% of cellulose fibers was lower than the without fibers. However the films with cellulose fibers had the highest decomposition with the initial temperature and thermal stability. The oxidized starch and cellulose fibers from barley have a good potential for use in packaging. The addition of cellulose fibers in starch films can contribute to the development of films more resistant that can be applied in food systems to maintain its integrity.

  19. Cellulose Microfibril Formation by Surface-Tethered Cellulose Synthase Enzymes.

    PubMed

    Basu, Snehasish; Omadjela, Okako; Gaddes, David; Tadigadapa, Srinivas; Zimmer, Jochen; Catchmark, Jeffrey M

    2016-02-23

    Cellulose microfibrils are pseudocrystalline arrays of cellulose chains that are synthesized by cellulose synthases. The enzymes are organized into large membrane-embedded complexes in which each enzyme likely synthesizes and secretes a β-(1→4) glucan. The relationship between the organization of the enzymes in these complexes and cellulose crystallization has not been explored. To better understand this relationship, we used atomic force microscopy to visualize cellulose microfibril formation from nickel-film-immobilized bacterial cellulose synthase enzymes (BcsA-Bs), which in standard solution only form amorphous cellulose from monomeric BcsA-B complexes. Fourier transform infrared spectroscopy and X-ray diffraction techniques show that surface-tethered BcsA-Bs synthesize highly crystalline cellulose II in the presence of UDP-Glc, the allosteric activator cyclic-di-GMP, as well as magnesium. The cellulose II cross section/diameter and the crystal size and crystallinity depend on the surface density of tethered enzymes as well as the overall concentration of substrates. Our results provide the correlation between cellulose microfibril formation and the spatial organization of cellulose synthases.

  20. Changes in submicrometer structure of enzymatically hydrolyzed microcrystalline cellulose.

    PubMed

    Penttilä, Paavo A; Várnai, Anikó; Leppänen, Kirsi; Peura, Marko; Kallonen, Aki; Jääskeläinen, Pentti; Lucenius, Jessica; Ruokolainen, Janne; Siika-Aho, Matti; Viikari, Liisa; Serimaa, Ritva

    2010-04-12

    To understand the limitations occurring during enzymatic hydrolysis of cellulosic materials in renewable energy production, we used wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), X-ray microtomography, and transmission electron microscopy (TEM) to characterize submicrometer changes in the structure of microcrystalline cellulose (Avicel) digested with the Trichoderma reesei enzyme system. The microtomography measurements showed a clear decrease in particle size in scale of tens of micrometers. In all the TEM pictures, similar elongated and partly ramified structures were observed, independent of the hydrolysis time. The SAXS results of rewetted samples suggested a slight change in the structure in scale of 10-20 nm, whereas the WAXS results confirmed that the degree of crystallinity and the crystal sizes remained unchanged. This indicates that the enzymes act on the surface of cellulose bundles and are unable to penetrate into the nanopores of wet cellulose.

  1. Comparative study of crude and purified cellulose from wheat straw.

    PubMed

    Sun, Xiao-Feng; Sun, Run-Cang; Su, Yinquan; Sun, Jing-Xia

    2004-02-25

    A sequential totally chlorine-free procedure for isolation of cellulose from wheat straw was proposed in this study. The dewaxed straw was pretreated with 0.5 M NaOH in 60% methanol at 60 degrees C for 2.5 h under ultrasonic irradiation for 0-35 min and sequentially posttreated with 2% H(2)O(2)-0.2% TAED at pH 11.8 for 12 h at 48 degrees C, which together solubilized 85.3-86.1% of the original hemicelluloses and 91.7-93.2% of the original lignin, respectively. The yield of crude cellulose ranged between 46.2 and 49.2% on a dry weight basis related to wheat straw, which contained 11.2-12.2% residual hemicelluloses and 2.5-2.9% remaining lignin. Further treatment of the corresponding crude cellulosic preparations with 80% acetic acid-70% nitric acid under the condition given yielded 36.8-37.7% of the purified cellulose, which contained minor amounts of bound hemicelluloses (2.5-2.8%) and was relatively free of associated lignin (0.1-0.2%). The isolated crude and purified cellulose samples were comparatively studied by FT-IR and CP/MAS (13)C NMR spectroscopy, and the relative crystallinity was also estimated. The final stage treatment with 80% acetic acid-70% nitric acid decreased the hemicelluloses and lignin associated in the crude cellulose but led to 3.1-5.4% degradation of the original cellulose; in addition, the purity of the obtained cellulose was high. However, it was found that the final stage treatment is not severe enough to cause decrystallization of cellulose. The thermal stability of the purified cellulose is higher than that of the corresponding crude cellulose.

  2. Cellulose binding domain fusion proteins

    SciTech Connect

    Shoseyov, Oded; Shpiegl, Itai; Goldstein, Marc A.; Doi, Roy H.

    1998-01-01

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production thereof. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques.

  3. Cellulose binding domain fusion proteins

    DOEpatents

    Shoseyov, O.; Yosef, K.; Shpiegl, I.; Goldstein, M.A.; Doi, R.H.

    1998-02-17

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques. 16 figs.

  4. Utilization of carbohydrates by Thermomonospora sp. Grown on glucose, cellobiose, and cellulose

    SciTech Connect

    Moreira, A.R.; Phillips, J.A.; Humphrey, A.E.

    1981-01-01

    Thermomonospora was grown on glucose, cellobiose, and cellulose in order to study its growth characteristics with different carbohydrate substrates and to assess the validity of some of the assumptions made in a previously proposed model for the cellulose fermentation with this microorganism. The N and protein contents of the cells are essentially constant during the fermentation and independent of the C source when glucose or cellobiose are utilized. Under O starvation conditions it was shown that unidentifiable organic compound(s) accumulate(s) in the culture broth. Culture fluorescence was an excellent variable for monitoring and control of the fermentation process. This microorganism showed a preference for crystalline cellulose (Avicel) as substrate although it grows readily on a more amorphous cellulose (Solka Floc). The production of extracellular protein is growth related. Data were obtained confirming the decrease in the number of active adsorption sites as the cause for the decrease in the cellulose digestion rate.

  5. Synthesization, characterization and adsorption properties of sulfonic cellulose.

    PubMed

    Shi, Wenjian; Zhou, Yan; Zhang, Yuanzhang; Li, Liang; Yang, Qinlin

    2012-01-01

    The synthesization and characterization of a new environmental functional material-sulfonic cellulose - were studied in this paper. The preparation conditions were optimized through an orthogonal experiment. The modified cellulose was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The adsorption rules of cationic organic pollutants and heavy metal ions by this new material were discussed. Regeneration and recycling performances of the sulfonic cellulose were also investigated. At the temperature of 323 K, sulfonic cellulose was prepared by grafting 2-acrylamido-2-methylpropane sulfonic acid (AMPS) onto alkali-treated cellulose for 4 h with the employing of ceric ammonium nitrate as initiator. The mass ratio of AMPS to cellulose was 3:1 and the concentration of ceric ammonium nitrate was 63.8 mmol/L. The sulfur content of sulfonic cellulose was 7.32 wt%. The peaks of 1,303 and 1,159 cm⁻¹ in IR suggested the existence of the sulfonic group in sulfonic cellulose. The XRD and SEM results showed that the crystallinity decreased while the specific surface area increased after modification. Batch adsorption results showed that sulfonic cellulose had a favorable adsorption capacity for model contaminants at pH 6.0-7.0. The adsorption process was endothermic and reached equilibrium in 180 min. The adsorption rules of cationic organic pollutants and heavy metal ions indicated that sulfonic cellulose had high adsorption capacity for the cationic dyes with a coplanar macromolecule structure and organic compounds carrying the amino group. Under room temperature, 1.0 mol/L HCl can be used as a desorption solution and the equilibrium adsorption capacity had little decrease (less than 7%) after six adsorption-desorption cycles.

  6. All-cellulose nanocomposite film made from bagasse cellulose nanofibers for food packaging application.

    PubMed

    Ghaderi, Moein; Mousavi, Mohammad; Yousefi, Hossein; Labbafi, Mohsen

    2014-04-15

    All-cellulose nanocomposite (ACNC) film was produced from sugarcane bagasse nanofibers using N,N-dimethylacetamide/lithium chloride solvent. The average diameter of bagasse fibers (14 μm) was downsized to 39 nm after disk grinding process. X-ray diffraction showed that apparent crystallinity and crystallite size decreased relatively to an increased duration of dissolution time. Thermogravimetric analysis confirmed that thermal stability of the ACNC was slightly less than that of the pure cellulose nanofiber sheet. Tensile strength of the fiber sheet, nanofiber sheet and ACNC prepared with 10 min dissolution time were 8, 101 and 140 MPa, respectively. Water vapor permeability (WVP) of the ACNC film increased relatively to an increased duration of dissolution time. ACNC can be considered as a multi-performance material with potential for application in cellulose-based food packaging owing to its promising properties (tough, bio-based, biodegradable and acceptable levels of WVP).

  7. Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment

    SciTech Connect

    Sun, Qining; Foston, Marcus; Meng, Xianzhi; Sawada, Daisuke; Pingali, Sai Venkatesh; O’Neill, Hugh M.; Li, Hongjia; Wyman, Charles E.; Langan, Paul; Ragauskas, Art J.; Kumar, Rajeev

    2014-10-14

    Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have large implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of

  8. Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment

    DOE PAGES

    Sun, Qining; Foston, Marcus; Meng, Xianzhi; ...

    2014-10-14

    Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have largemore » implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of

  9. Influence of major structural features of cellulose on rate of enzymatic hydrolysis

    SciTech Connect

    Fan, L.T.; Lee, Y.H.; Beardmore, D.R.

    1981-02-01

    An attempt was made to determine the effect of two structural features of cellulose on its enzymatic hydrolysis: its crystallinity and its specific surface area. Solka Floc SW40 was pretreated in various ways prior to hydrolysis: ball milling, gamma radiation, pyrolysis, treatment by sodium hydroxide, treatment by CMCS, and treatment by sulfuric acid. Microcrystalline cellulose (Sigmacell 50) was also employed in the test. The culture filtrate of Trichoderma reesei QM9414 was the source of the enzyme. It was observed that, independent of the methods of treatment, the rate of hydrolysis would tend to increase with an increase in specific surface area and with a decrease in crystallinity index.

  10. COBRA-LIKE2, a Member of the Glycosylphosphatidylinositol-Anchored COBRA-LIKE Family, Plays a Role in Cellulose Deposition in Arabidopsis Seed Coat Mucilage Secretory Cells1,2[OPEN

    PubMed Central

    Ben-Tov, Daniela; Abraham, Yael; Stav, Shira; Thompson, Kevin; Loraine, Ann; Elbaum, Rivka; de Souza, Amancio; Pauly, Markus; Kieber, Joseph J.; Harpaz-Saad, Smadar

    2015-01-01

    Differentiation of the maternally derived seed coat epidermal cells into mucilage secretory cells is a common adaptation in angiosperms. Recent studies identified cellulose as an important component of seed mucilage in various species. Cellulose is deposited as a set of rays that radiate from the seed upon mucilage extrusion, serving to anchor the pectic component of seed mucilage to the seed surface. Using transcriptome data encompassing the course of seed development, we identified COBRA-LIKE2 (COBL2), a member of the glycosylphosphatidylinositol-anchored COBRA-LIKE gene family in Arabidopsis (Arabidopsis thaliana), as coexpressed with other genes involved in cellulose deposition in mucilage secretory cells. Disruption of the COBL2 gene results in substantial reduction in the rays of cellulose present in seed mucilage, along with an increased solubility of the pectic component of the mucilage. Light birefringence demonstrates a substantial decrease in crystalline cellulose deposition into the cellulosic rays of the cobl2 mutants. Moreover, crystalline cellulose deposition into the radial cell walls and the columella appears substantially compromised, as demonstrated by scanning electron microscopy and in situ quantification of light birefringence. Overall, the cobl2 mutants display about 40% reduction in whole-seed crystalline cellulose content compared with the wild type. These data establish that COBL2 plays a role in the deposition of crystalline cellulose into various secondary cell wall structures during seed coat epidermal cell differentiation. PMID:25583925

  11. Cellulose based hybrid hydroxylated adducts for polyurethane foams

    NASA Astrophysics Data System (ADS)

    De Pisapia, Laura; Verdolotti, Letizia; Di Mauro, Eduardo; Di Maio, Ernesto; Lavorgna, Marino; Iannace, Salvatore

    2012-07-01

    Hybrid flexible polyurethane foams (HPU) were synthesized by using a hybrid hydroxilated adduct (HHA) based on renewable resources. In particular the HHA was obtained by dispersing cellulose wastes in colloidal silica at room temperature, pressure and humidity. The colloidal silica was selected for its ability of modifying the cellulose structure, by inducing a certain "destructurization" of the crystalline phase, in order to allow cellulose to react with di-isocyanate for the final synthesis of the polyurethane foam. In fact, cellulose-polysilicate complexes are engaged in the reaction with the isocyanate groups. This study provides evidence of the effects of the colloidal silica on the cellulose structure, namely, a reduction of the microfiber cellulose diameter and the formation of hydrogen bonds between the polysilicate functional groups and the hydroxyl groups of the cellulose, as assessed by IR spectroscopy and solid state NMR. The HHA was added to a conventional polyol in different percentages (between 5 and 20%) to synthesize HPU in presence of catalysts, silicone surfactant and diphenylmethane diisocyanate (MDI). The mixture was expanded in a mold and cured for two hours at room temperature. Thermal analysis, optical microscopy and mechanical tests were performed on the foams. The results highlighted an improvement of thermal stability and a decrease of the cell size with respect neat polyurethane foam. Mechanical tests showed an improvement of the elastic modulus and of the damping properties with increasing HHA amount.

  12. Surface Plasmon Resonance Studies of Hydroxypropyl Xylan Self-Assembly on Cellulose

    NASA Astrophysics Data System (ADS)

    Drazenovich, Daniel A.; Kaya, Abdulaziz; Esker, Alan R.; Glasser, Wolfgang G.

    2006-03-01

    Wood is a multiphase material consisting of cellulose crystals embedded within a non-crystalline hetereopolysaccharide (hemicellulose) and lignin rich phase. The hierarchial arrangement of these three chief components in wood produces excellent properties like resistance to fracture and toughness. Through the study of self-assembly of hemicellulose onto a model cellulose surface, further insight into the interactions between hemicelluloses and cellulose can be gained. In our study, we used xylans with different degrees of substitution of hydroxypropyl groups. Surface plasmon resonance measurements (SPR) probe the self-assembly behavior of hydroxypropyl xylans (HPX) onto a cellulose coated gold surface. In addition, tensiometry provides the critical aggregation concentration (CAC) of different HPX samples. CAC results can be correlated to adsorption observed by SPR. Increasing the degree of hydroxypropyl substitution decreases the CAC and increases adsorption onto cellulose surfaces.

  13. Influence of homogenization treatment on physicochemical properties and enzymatic hydrolysis rate of pure cellulose fibers.

    PubMed

    Jacquet, N; Vanderghem, C; Danthine, S; Blecker, C; Paquot, M

    2013-02-01

    The aim of this study is to compare the effect of different homogenization treatments on the physicochemical properties and the hydrolysis rate of a pure bleached cellulose. Results obtained show that homogenization treatments improve the enzymatic hydrolysis rate of the cellulose fibers by 25 to 100 %, depending of the homogenization treatment applied. Characterization of the samples showed also that homogenization had an impact on some physicochemical properties of the cellulose. For moderate treatment intensities (pressure below 500 b and degree of homogenization below 25), an increase of water retention values (WRV) that correlated to the increase of the hydrolysis rate was highlighted. Result also showed that the overall crystallinity of the cellulose properties appeared not to be impacted by the homogenization treatment. For higher treatment intensities, homogenized cellulose samples developed a stable tridimentional network that contributes to decrease cellulase mobility and slowdown the hydrolysis process.

  14. Influence of steam explosion on physicochemical properties and hydrolysis rate of pure cellulose fibers.

    PubMed

    Jacquet, N; Vanderghem, C; Danthine, S; Quiévy, N; Blecker, C; Devaux, J; Paquot, M

    2012-10-01

    The aim of this study is to compare the effect of different steam explosion treatments on the physicochemical properties and the hydrolysis rate of a pure bleached cellulose. The results showed that moderate steam explosion treatments (severity factor below 5.2) did not appear to improve the enzymatic hydrolysis rate of the cellulose fibers. However, characterization of the samples showed a modification of the physicochemical properties of the cellulose, resulting in an increase of the water retention values (WRV) coupled to an increase of the overall crystallinity. For higher treatment intensities, an important thermal degradation of the cellulose was highlighted. This thermal degradation caused an important modification of the cellulose composition which leads to a decrease of the hydrolysis rate.

  15. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis.

    PubMed

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M; Park, Sunkyu; Kim, Seong H

    2015-10-14

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples--Avicel, bleached softwood, and bacterial cellulose--to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.

  16. Hazy Transparent Cellulose Nanopaper

    PubMed Central

    Hsieh, Ming-Chun; Koga, Hirotaka; Suganuma, Katsuaki; Nogi, Masaya

    2017-01-01

    The aim of this study is to clarify light scattering mechanism of hazy transparent cellulose nanopaper. Clear optical transparent nanopaper consists of 3–15 nm wide cellulose nanofibers, which are obtained by the full nanofibrillation of pulp fibers. At the clear transparent nanopaper with 40 μm thickness, their total transmittance are 89.3–91.5% and haze values are 4.9–11.7%. When the pulp fibers are subjected to weak nanofibrillation, hazy transparent nanopapers are obtained. The hazy transparent nanopaper consists of cellulose nanofibers and some microsized cellulose fibers. At the hazy transparent nanopaper with 40 μm thickness, their total transmittance were constant at 88.6–92.1% but their haze value were 27.3–86.7%. Cellulose nanofibers are solid cylinders, whereas the pulp fibers are hollow cylinders. The hollow shape is retained in the microsized cellulose fibers, but they are compressed flat inside the nanopaper. This compressed cavity causes light scattering by the refractive index difference between air and cellulose. As a result, the nanopaper shows a hazy transparent appearance and exhibits a high thermal durability (295–305 °C), and low thermal expansion (8.5–10.6 ppm/K) because of their high density (1.29–1.55 g/cm3) and crystallinity (73–80%). PMID:28128326

  17. Hazy Transparent Cellulose Nanopaper

    NASA Astrophysics Data System (ADS)

    Hsieh, Ming-Chun; Koga, Hirotaka; Suganuma, Katsuaki; Nogi, Masaya

    2017-01-01

    The aim of this study is to clarify light scattering mechanism of hazy transparent cellulose nanopaper. Clear optical transparent nanopaper consists of 3–15 nm wide cellulose nanofibers, which are obtained by the full nanofibrillation of pulp fibers. At the clear transparent nanopaper with 40 μm thickness, their total transmittance are 89.3–91.5% and haze values are 4.9–11.7%. When the pulp fibers are subjected to weak nanofibrillation, hazy transparent nanopapers are obtained. The hazy transparent nanopaper consists of cellulose nanofibers and some microsized cellulose fibers. At the hazy transparent nanopaper with 40 μm thickness, their total transmittance were constant at 88.6–92.1% but their haze value were 27.3–86.7%. Cellulose nanofibers are solid cylinders, whereas the pulp fibers are hollow cylinders. The hollow shape is retained in the microsized cellulose fibers, but they are compressed flat inside the nanopaper. This compressed cavity causes light scattering by the refractive index difference between air and cellulose. As a result, the nanopaper shows a hazy transparent appearance and exhibits a high thermal durability (295–305 °C), and low thermal expansion (8.5–10.6 ppm/K) because of their high density (1.29–1.55 g/cm3) and crystallinity (73–80%).

  18. Cellulose-silica aerogels.

    PubMed

    Demilecamps, Arnaud; Beauger, Christian; Hildenbrand, Claudia; Rigacci, Arnaud; Budtova, Tatiana

    2015-05-20

    Aerogels based on interpenetrated cellulose-silica networks were prepared and characterised. Wet coagulated cellulose was impregnated with silica phase, polyethoxydisiloxane, using two methods: (i) molecular diffusion and (ii) forced flow induced by pressure difference. The latter allowed an enormous decrease in the impregnation times, by almost three orders of magnitude, for a sample with the same geometry. In both cases, nanostructured silica gel was in situ formed inside cellulose matrix. Nitrogen adsorption analysis revealed an almost threefold increase in pores specific surface area, from cellulose aerogel alone to organic-inorganic composite. Morphology, thermal conductivity and mechanical properties under uniaxial compression were investigated. Thermal conductivity of composite aerogels was lower than that of cellulose aerogel due to the formation of superinsulating mesoporous silica inside cellulose pores. Furthermore, composite aerogels were stiffer than each of reference aerogels.

  19. Effect of Water Content in N-Methylmorpholine N-Oxide/Cellulose Solutions on Thermodynamics, Structure, and Hydrogen Bonding.

    PubMed

    Rabideau, Brooks D; Ismail, Ahmed E

    2015-12-03

    Native crystalline cellulose is notoriously difficult to dissolve due to its dense hydrogen bond network between chains and weaker hydrophobic forces between cellulose sheets. N-Methylmorpholine N-oxide (NMMO), the solvent behind the Lyocell process, is one of the most successful commercial solvents for the nonderivatized dissolution of cellulose. In this process, water plays a very important role. Its presence at low concentrations allows NMMO to dissolve substantial amounts of cellulose, while at much higher concentrations it precipitates the crystalline fibers. Using all-atom molecular dynamics, we study the thermodynamic and structural properties of ternary solutions of cellulose, NMMO, and water. Using the two-phase thermodynamic method to calculate solvent entropy, we estimate the free energy of dissolution of cellulose as a function of the water concentration and find a transition of spontaneity that is in excellent agreement with experiment. In pure water, we find that cellulose dissolution is nonspontaneous, a result that is due entirely to strong decreases in water entropy. Although the combined effect of enthalpy on dissolution in water is negligible, we observe a net loss of hydrogen bonds, resulting in a change in hydrogen bond energy that opposes dissolution. At lower water concentrations, cellulose dissolution is spontaneous and largely driven by decreases in enthalpy, with solvent entropy playing only a very minor role. When searching for the root causes of this enthalpy decrease, a complex picture emerges in which not one but many different factors contribute to NMMO's good solvent behavior. The reduction in enthalpy is led by the formation of strong hydrogen bonds between cellulose and NMMO's N-oxide, intensified through van der Waals interactions between NMMO's nonpolar body and the nonpolar surfaces of cellulose and unhindered by water at low concentrations due to the formation of efficient hydrogen bonds between water and cellulose.

  20. Cellulose hydrolysis ability of a Clostridium thermocellum cellulosome containing small-size scaffolding protein CipA.

    PubMed

    Deng, Lan; Mori, Yutaka; Sermsathanaswadi, Junjarus; Apiwatanapiwat, Waraporn; Kosugi, Akihiko

    2015-10-20

    Mutant Clostridium thermocellum YM72 that produces small-size scaffolding protein CipA (ssCipA) was isolated from wild-type YM4. Sequencing of ssCipA revealed that two domains, cohesin 6 and cohesin 7, were not present. Cellulosome prepared from YM72 exhibited a significant reduction of hydrolysis ability on crystalline celluloses such as Sigmacell type-20 and cellulose from Halocynthia. To investigate this influence in vitro, artificial cellulosomes were assembled as recombinant CipA (rCipA) and ssCipA (rssCipA) using native free-cellulosomal subunits. The cellulosome assembled using rssCipA showed a 1.8-fold decrease in the hydrolysis of crystalline cellulose compared with that of rCipA. However, no significant differences in the hydrolysis of carboxymethylcellulose and acid-swollen cellulose were observed. One protein band was missing from the complex that was assembled using rssCipA (confirmed by native-PAGE). The missing protein was identified as CelJ, which is a major cellulosomal subunit. This suggests that insufficient cooperation of CelJ into the cellulosome results in the significant reduction of hydrolysis toward crystalline cellulose. These results indicate that cohesin 6 and 7 may be responsible for the cooperation of CelJ through cohesin and dockerin interactions, and adequate cooperation of CelJ into the cellulosome is important for significant hydrolysis of crystalline cellulose.

  1. Composite polymer electrolytes based on MG49 and carboxymethyl cellulose from kenaf

    NASA Astrophysics Data System (ADS)

    Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan

    2013-11-01

    The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF3SO3 were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2-10 wt%) via solution-casting method. The conductivity was increased with carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10-7 Scm-1 upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.

  2. Composite polymer electrolytes based on MG49 and carboxymethyl cellulose from kenaf

    SciTech Connect

    Jafirin, Serawati; Ahmad, Ishak; Ahmad, Azizan

    2013-11-27

    The development of 49% poly(methyl methacrylate)-grafted natural rubber (MG49) and carboxymethyl cellulose as a composite polymer electrolyte film incorporating LiCF{sub 3}SO{sub 3} were explored. Carboxymethyl cellulose was synthesized from kenaf bast fibres via carboxymethylation process by alkali catalyzed reaction of cellulose with sodium chloroacetate. Reflection fourier transform infrared (ATR-FTIR) spectroscopy showed the presence of carboxyl peak after modification of cellulose with sodium chloroacetate. X-ray diffraction (XRD) analysis revealed that the crystallinity of cellulose was decrease after synthesis. High performance composite polymer electrolytes were prepared with various composition of carboxymethyl cellulose (2–10 wt%) via solution-casting method. The conductivity was increased with carboxymethyl cellulose loading. The highest conductivity value achieved was 3.3 × 10{sup −7} Scm{sup −1} upon addition of 6% wt carboxymethyl cellulose. 6% wt carboxymethyl cellulose composition showed the highest tensile strength value of 7.9 MPa and 273 MPa of modulus value which demonstrated high mechanical performance with accepatable level of ionic conductivity.

  3. Interrelation between the crystallinity of polysaccharides and water absorption

    NASA Astrophysics Data System (ADS)

    Prusov, A. N.; Prusova, S. M.; Radugin, M. V.; Zakharov, A. G.

    2014-05-01

    The maximum sorption of water and its vapors is calculated using experimental data from calorimetric and effusion studies of flax, wood, and cotton cellulose. X-day diffraction is used to determine the crystallinity of cellulose samples. The equations relating crystallinity ( X) with maximum sorption and the enthalpy of interaction between cellulose and water are presented. Experimental results and the literature data on water sorption by chitin, chitosan and other polysaccharides show that our equations for calculating crystallinity are correct.

  4. Utilization of carbohydrates by thermomonospora sp. grown on glucose, cellobiose, and cellulose

    SciTech Connect

    Moreira, A.R.; Phillips, J.A.; Humphrey, A.E.

    1981-06-01

    Thermomonospora sp. was grown on glucose, cellobiose, and cellulose in order to study its growth characteristics with different carbohydrate substrates. It was observed that the nitrogen and protein contents of the cells are essentially constant during the fermentation and independent of the carbon source when glucose or cellobiose are utilized. Under oxygen starvation conditions it was shown that unidentifiable organic compound(s) accumulate(s) in the culture broth. Culture fluorescence was shown to be an excellent variable for monitoring and control of the fermentation process. This microorganism showed a preference for crystalline cellulose (Avicel) as substrate although it grows readily on a more amorphous cellulose (Solka Floc). The production of extracellular protein is shown to be growth related. Data were obtained confirming the decrease in the number of active adsorption sites as the cause for the decrease in the cellulose digestion rate. 17 refs.

  5. Tensile and characterization properties of regenerated cellulose empty fruit bunch biocomposite films using ionic liquid

    NASA Astrophysics Data System (ADS)

    Husseinsyah, Salmah; Zailuddin, Nur Liyana Izyan; Li, Chew Li; Mostapha @ Zakaria, Marliza

    2016-07-01

    The regenerated cellulose (RC) empty fruit bunch (EFB) biocomposite films were prepared using ionic liquid. The tensile strength and modulus of elasticity of regenerated cellulose biocomposite films achieved maximum value at 2 wt% of EFB contents while at 3 and 4 wt% of EFB the tensile strength and modulus of elasticity tend to decreased. The elongation at break tends to decreased at 2 wt% of EFB content but increased at 3 and 4 wt% of EFB contents. The crystallinity index reaches maximum at 2 wt% EFB content, followed by declination with further addition of EFB content. The morphology study illustrated that regenerated cellulose biocomposite films at 2 wt% of EFB contents exhibit a smooth surface that suggested the reinforcement was surrounded by the regenerated cellulose matrix, while at 4 wt% EFB content shows a rough morphology.

  6. New Insights into Hydrogen Bonding and Stacking Interactions in Cellulose

    SciTech Connect

    Langan, Paul

    2011-01-01

    In this quantum chemical study, we explore hydrogen bonding (H-bonding) and stacking interactions in different crystalline cellulose allomorphs, namely cellulose I and cellulose IIII. We consider a model system representing a cellulose crystalline core, made from six cellobiose units arranged in three layers with two chains per layer. We calculate the contributions of intrasheet and intersheet interactions to the structure and stability in both cellulose I and cellulose IIII crystalline cores. Reference structures for this study were generated from molecular dynamics simulations of water-solvated cellulose I and IIII fibrils. A systematic analysis of various conformations describing different mutual orientations of cellobiose units is performed using the hybrid density functional theory (DFT) with the M06-2X with 6-31+G (d, p) basis sets. We dissect the nature of the forces that stabilize the cellulose I and cellulose IIII crystalline cores and quantify the relative strength of H-bonding and stacking interactions. Our calculations demonstrate that individual H-bonding interactions are stronger in cellulose I than in cellulose IIII. We also observe a significant contribution from cooperative stacking interactions to the stabilization of cellulose I . In addition, the theory of atoms-in-molecules (AIM) has been employed to characterize and quantify these intermolecular interactions. AIM analyses highlight the role of nonconventional CH O H-bonding in the cellulose assemblies. Finally, we calculate molecular electrostatic potential maps for the cellulose allomorphs that capture the differences in chemical reactivity of the systems considered in our study.

  7. Expression of the Acidothermus cellulolyticus E1 endoglucanase in Caldicellulosiruptor bescii enhances its ability to deconstruct crystalline cellulose

    SciTech Connect

    Chung, Daehwan; Young, Jenna; Cha, Minseok; Brunecky, Roman; Bomble, Yannick J.; Himmel, Michael E.; Westpheling, Janet

    2015-08-13

    The Caldicellulosiruptor bescii genome encodes a potent set of carbohydrate-active enzymes (CAZymes), found primarily as multi-domain enzymes that exhibit high cellulolytic and hemicellulolytic activity on and allow utilization of a broad range of substrates, including plant biomass without conventional pretreatment. CelA, the most abundant cellulase in the C. bescii secretome, uniquely combines a GH9 endoglucanase and a GH48 exoglucanase in one protein. The most effective commercial enzyme cocktails used in vitro to pretreat biomass are derived from fungal cellulases (cellobiohydrolases, endoglucanases and a β-d-glucosidases) that act synergistically to release sugars for microbial conversion. The C. bescii genome contains six GH5 domains in five different open reading frames. Four exist in multi-domain proteins and two as single catalytic domains. E1 is a GH5 endoglucanase reported to have high specific activity and simple architecture and is active at the growth temperature of C. bescii. E1 is an endo-1,4-β-glucanase linked to a family 2 carbohydrate-binding module shown to bind primarily to cellulosic substrates. As a result, we tested if the addition of this protein to the C. bescii secretome would improve its cellulolytic activity.

  8. Engineering the N-Terminal End of CelA Results in Improved Performance and Growth of Caldicellulosiruptor bescii on Crystalline Cellulose

    SciTech Connect

    Kim, Sun-Ki; Chung, Daehwan; Himmel, Michael E.; Bomble, Yannick J.; Westpheling, Janet

    2016-12-26

    CelA is the most abundant enzyme secreted by Caldicellulosiruptor bescii and has been shown to outperform mixtures of commercially available exo- and endoglucanases in vitro. CelA contains both a glycoside hydrolase family 9 endoglucanase and a glycoside hydrolase family 48 exoglucanase known to be synergistic in their activity, connected by three cellulose-binding domains via linker peptides. Here, repeated aspartate residues were introduced into the N-terminal ends of CelA GH9 and GH48 domains to improve secretion efficiency and/or catalytic efficiency of CelA. Among several constructs, the highest activity on carboxymethylcellulose (CMC), 0.81 +/- 0.03 mg/mL was observed for the C. bescii strain containing CelA with 5-aspartate tag at the N-terminal end of GH9 domain -- an 82% increase over wild type CelA. In addition, Expression of CelA with N-terminal repeated aspartate residues in C. bescii results in a dramatic increase in its ability to grow on Avicel.

  9. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

    DOE PAGES

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; ...

    2015-10-14

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

  10. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

    SciTech Connect

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

    2015-10-14

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.

  11. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

    PubMed Central

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

    2015-01-01

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component. PMID:26463274

  12. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

    NASA Astrophysics Data System (ADS)

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

    2015-10-01

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. It was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.

  13. Effects of hemicellulose removal on cellulose fiber structure and recycling characteristics of eucalyptus pulp.

    PubMed

    Wan, JinQuan; Wang, Yan; Xiao, Qing

    2010-06-01

    Eucalyptus pulp fibers with large differences in cellulose and hemicellulose proportions but similar lignin contents were produced by partial removal of the hemicellulose and studied using Cross-Polarization Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS (13)C NMR) in combination with spectral fitting, Atomic Force Microscopy (AFM), X-ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR). There were remarkable differences in both cellulose fibril structure, pore structure and cellulose supermolecular structure between the samples. CP/MAS (13)C NMR combined with spectral fitting demonstrated an increase in average fibril aggregate size (17.9-22.2 nm) with decreasing hemicellulose content. AFM observations revealed that when the hemicellulose content decreased from 27.62% to 19.80%, the average diameters of pores decreased by 12.53%, but increased by 13.55% when the hemicellulose content decreased from 19.80% to 9.09%. XRD and FTIR analysis indicated that cellulose crystallinity increased with decreasing hemicellulose content. The low and high hemicellulose-containing pulps had very different recycling characteristics, which may be explained by the changes observed at cellulose fiber structure level. Fibrils appear to aggregate and form a more compact structure when the hemicellulose is removed, which was caused by a coalescence of the cellulose microfibrils. The removal of hemicellulose had disadvantageous influence on the accessibility of fibers and enhanced fiber flattening during drying, leading to increased sheet density and increased hornification.

  14. Cellulose biogenesis in Dictyostelium discoideum

    SciTech Connect

    Blanton, R.L.

    1993-12-31

    Organisms that synthesize cellulose can be found amongst the bacteria, protistans, fungi, and animals, but it is in plants that the importance of cellulose in function (as the major structural constituent of plant cell walls) and economic use (as wood and fiber) can be best appreciated. The structure of cellulose and its biosynthesis have been the subjects of intense investigation. One of the most important insights gained from these studies is that the synthesis of cellulose by living organisms involves much more than simply the polymerization of glucose into a (1{r_arrow}4)-{beta}-linked polymer. The number of glucoses in a polymer (the degree of polymerization), the crystalline form assumed by the glucan chains when they crystallize to form a microfibril, and the dimensions and orientation of the microfibrils are all subject to cellular control. Instead of cellulose biosynthesis, a more appropriate term might be cellulose biogenesis, to emphasize the involvement of cellular structures and mechanisms in controlling polymerization and directing crystallization and deposition. Dictyostelium discoideum is uniquely suitable for the study of cellulose biogenesis because of its amenability to experimental study and manipulation and the extent of our knowledge of its basic cellular mechanisms (as will be evident from the rest of this volume). In this chapter, I will summarize what is known about cellulose biogenesis in D. discoideum, emphasizing its potential to illuminate our understanding both of D. discoideum development and plant cellulose biogenesis.

  15. Characterization of cellulose from banana pseudo-stem by heterogeneous liquefaction.

    PubMed

    Li, Wei; Zhang, Yucang; Li, Jihui; Zhou, Yijun; Li, Ruisong; Zhou, Wei

    2015-11-05

    A cellulose extraction from banana pseudo-stem through the combination of bleach and liquefaction processes was described: holocellulose was isolated by the sodium chlorite method, and then the cellulose was obtained by removing the hemicellulose through chemical liquefaction. The chemical composition, morphology, thermal properties and degree of crystallinity of the celluloses were characterized to discuss their suitability for new bio-based composite materials. It was shown that hemicellulose can be selectively liquefied to get cellulose. The hemicellulose content in cellulose is decreased from 45.69% to 8.38%. Surface morphological studies revealed that there is a reduction in fiber diameter and fiber bundles are divided into individual fibrils, which lead to an increase of the surface area and results in an increased adhesion at the fiber-matrix interface in composites. Thermal analysis results show that the cellulose exhibit enhanced thermal stability over holocellulose. XRD results indicate that the crystallinity is increased from 52.22% to 81.26% by liquefaction.

  16. Stimuli-responsive cellulose modified by epoxy-functionalized polymer nanoparticles with photochromic and solvatochromic properties.

    PubMed

    Abdollahi, Amin; Rad, Jaber Keyvan; Mahdavian, Ali Reza

    2016-10-05

    Photoresponsive papers are among the fast and simple tools for detection of polarity by solvatochromic and photochromic behaviors upon UV irradiation. Here, a new, green and facile modification strategy was employed to prepare novel stimuli-responsive cellulose materials containing spiropyran by mixing microcrystalline cellulose (MCC), as a model compound, with epoxy-functionalized photochromic latex. FTIR analysis, thermal and thermo-mechanical properties were used to confirm the microstructral properties. Crystallographic analysis revealed a decrease in crystallinity of cellulose matrix and approved the incorporation of photochromic copolymer. Then stimuli-responsive papers were prepared by using pulp paper as the cellulosic matrix and their smart characteristics were studied under UV irradiation while dried or immersed into some polar and non-polar solvents. Different color changes were observed and investigated by solid-state UV-vis spectroscopy. These significant results were attributed to the efficient chemical modification and confirmed by SEM, EDX and nitrogen mapping analyses.

  17. Dynamic-mechanical and thermomechanical properties of cellulose nanofiber/polyester resin composites.

    PubMed

    Lavoratti, Alessandra; Scienza, Lisete Cristine; Zattera, Ademir José

    2016-01-20

    Composites of unsaturated polyester resin (UPR) and cellulose nanofibers (CNFs) obtained from dry cellulose waste of softwood (Pinus sp.) and hardwood (Eucalyptus sp.) were developed. The fiber properties and the influence of the CNFs in the dynamic-mechanical and thermomechanical properties of the composites were evaluated. CNFs with a diameter of 70-90 nm were obtained. Eucalyptus sp. has higher α-cellulose content than Pinus sp. fibers. The crystallinity of the cellulose pulps decreased after grinding. However, high values were still obtained. The chemical composition of the fibers was not significantly altered by the grinding process. Eucalyptus sp. CNF composites had water absorption close to the neat resin at 1 wt% filler. The dynamic-mechanical properties of Eucalyptus sp. CNFs were slightly increased and the thermal stability was improved.

  18. Cellulose extraction from Zoysia japonica pretreated by alumina-doped MgO in AMIMCl.

    PubMed

    Liu, Le; Ju, Meiting; Li, Weizun; Jiang, Yang

    2014-11-26

    In this study, alumina-doped MgO was produced as a solid alkali for lignocellulose pretreatment. Pretreatment with alumina-doped MgO disrupted the lignocellulose structure and significantly reduced the lignin content of the Z. japonica. After pretreatment, Z. japonica showed significant solubility in 1-allyl-3-methylimidazolium chloride (AMIMCl). The similar high solubility of pretreated Z. japonica samples by original alumina-doped MgO and used alumina-doped MgO also proved that alumina-doped MgO had strong stability, which can be recycled and used repeatedly. The regenerated cellulose was similar to microcrystalline cellulose according to FTIR and NMR analyses. Compared to microcrystalline cellulose, only the crystallinity of the regenerated cellulose decreased.

  19. Radiation effects on microcrystalline cellulose in 1-butyl-3-methylimidazolium chloride ionic liquid.

    PubMed

    Hao, Yan; Peng, Jing; Ao, Yinyong; Li, Jiuqiang; Zhai, Maolin

    2012-11-06

    The radiation processing of cellulose in ionic liquids (ILs) demands a comprehensive knowledge of radiation effects on cellulose in ILs. Herein, gamma radiation-induced degradation kinetics of microcrystalline cellulose (MCC) in 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) was studied by viscometry. The intrinsic viscosity of MCC in [Bmim]Cl decreased slightly with increasing dose; while chemical structure and crystalline state of cellulose has no obvious change up to 300 kGy. The radiation degradation rate constant (k) of MCC in [Bmim]Cl was 2.60×10(-7)/kGy, lower than that of solid cellulose, but higher than that in N-methylmorpholine-N-oxide (NMMO) solvent. Furthermore, k value decreased to 1.12×10(-7)/kGy in dimethyl sulfoxide (DMSO)/[Bmim]Cl system due to the free radicals scavenging of DMSO. The radicals generated during irradiation play main role in the radiation degradation of MCC in [Bmim]Cl. This work provides a new way to control the average molecular weight of cellulose by radiation-induced degradation of cellulose in ILs.

  20. Nucleic acids encoding a cellulose binding domain

    DOEpatents

    Shoseyov, Oded; Shpiegl, Itai; Goldstein, Marc A.; Doi, Roy H.

    1996-01-01

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production thereof. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques.

  1. Nucleic acids encoding a cellulose binding domain

    DOEpatents

    Shoseyov, O.; Shpiegl, I.; Goldstein, M.A.; Doi, R.H.

    1996-03-05

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques. 15 figs.

  2. Idealized powder diffraction patterns for cellulose polymorphs

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cellulose samples are routinely analyzed by X-ray diffraction to determine their crystal type (polymorph) and crystallinity. However, the connection is seldom made between those efforts and the crystal structures of cellulose that have been determined with synchrotron X-radiation and neutron diffrac...

  3. Discovery of Cellulose Surface Layer Conformation by Nonlinear Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Libing; Fu, Li; Wang, Hong-Fei; Yang, Bin

    2017-03-01

    Significant questions remain in respect to cellulose’s structure and polymorphs, particularly the cellulose surface layers and the bulk crystalline core as well as the conformational differences. Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with conventional SFG-VS (non-TIR) enables selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose, revealing their differences for the first time. From the SFG spectra in the C-H and O-H regions, we found that the surface layers of Avicel are essentially amorphous while the surface layers of Iβ cellulose are crystalline but with different structural and spectroscopic signatures compared with its crystalline core. The differences between hydrogen bonding networks of cellulose surface and crystalline core were also shown by the SFG signal. The discovery here represents yet another instance of the importance of spectroscopic observations in transformative advances to understand the structure of the cellulosic biomass.

  4. Discovery of Cellulose Surface Layer Conformation by Nonlinear Vibrational Spectroscopy

    PubMed Central

    Zhang, Libing; Fu, Li; Wang, Hong-fei; Yang, Bin

    2017-01-01

    Significant questions remain in respect to cellulose’s structure and polymorphs, particularly the cellulose surface layers and the bulk crystalline core as well as the conformational differences. Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with conventional SFG-VS (non-TIR) enables selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose, revealing their differences for the first time. From the SFG spectra in the C-H and O-H regions, we found that the surface layers of Avicel are essentially amorphous while the surface layers of Iβ cellulose are crystalline but with different structural and spectroscopic signatures compared with its crystalline core. The differences between hydrogen bonding networks of cellulose surface and crystalline core were also shown by the SFG signal. The discovery here represents yet another instance of the importance of spectroscopic observations in transformative advances to understand the structure of the cellulosic biomass. PMID:28290542

  5. The influence of supramolecular structure of cellulose allomorphs on the interactions with cellulose-binding domain, CBD3b from Paenibacillus barcinonensis.

    PubMed

    Ciolacu, Diana; Chiriac, Alina Iulia; Pastor, F I Javier; Kokol, Vanja

    2014-04-01

    The interaction of recombinant cellulose-binding domains (CBDs) of endoglucanase Cel9B from Paenibacillus barcinonensis with different cotton cellulose allomorphs (I, II and III) has been investigated, in order to bring new insights regarding the CBD adsorption and desorption processes. The highest CBD adsorption capacity was recorded for cellulose I, confirming the affinity of proteins to the most crystalline substrate. The weakening and splitting of the hydrogen bonds within cellulose structure after CBD adsorption, as well as a decrease of the crystallinity degree were identified by ATR-FTIR spectroscopy and XRD. The CBD's adsorption kinetic was shown to be rendered by properties as, specific surface area and porosity, being confirmed by dynamic vapor sorption measurements. An important influence of temperature (25, 37 and 50°C) and/or pH medium (4, 5.5, 7 and 10) on the CBD desorption capacity was confirmed, being related to the hydrophobic interactions formed between the CBD and the cellulose allomorphs.

  6. The properties of catalytically-inactivated Trichoderma reesei cellobiohydrolase I: Role of the cellulose binding domain

    SciTech Connect

    Woodward, J.; Donner, T.R.; Affholter, K.A.

    1993-12-31

    Cellobiohydrolase I (CBH I) was purified from a crude cellulase by preparative isoelectric focusing. Treatment of CBH I with 1-ethyl-3-3(3-dimethylaminopropyl)-carbodiimide (EDC) resulted in its catalytic inactivation but did not abolish its ability to be absorbed to microcrystalline cellulose (Avicel). CBH I thus modified possessed a pI of between 8.5 and 9.3 and decreased tryptophan fluorescence compared to native CBH I. A comparison of the effect of native and modified CBH I on the morphology of crystalline cotton cellulose fibers was made using scanning electron microscopy.

  7. Adsorption of cellulase on cellulose: effect of physicochemical properties of cellulose on adsorption and rate of hydrolysis

    SciTech Connect

    Lee, S.B.; Shin, H.S.; Ryu, D.D.Y.

    1982-11-01

    In the cellulase-cellulose reaction system, the adsorption of cellulase on the solid cellulose substrate was found to be one of the important parameters that govern the enzymatic hydrolysis rate of cellulose. The adsorption of cellulase usually parallels the rate of hydrolysis of cellulose. The affinity for cellulase varies depending on the structural properties of cellulose. Adsorption parameters such as the half-saturation constant, the maximum adsorption constant, and the distribution coefficient for both the cellulase and cellulose have been experimentally determined for several substrates. These adsorption parameters vary with the source of cellulose and the pretreatment methods and are correlated with the crystallinity and the specific surface area of cellulose substrates. The changing pattern of adsorption profile of cellulase during the hydrolysis reaction has also been elucidated. For practical utilization of cellulosic materials, the cellulose structural properties and their effects on cellulase adsorption, and the rate of hydrolysis must be taken into consideration. (Refs. 24).

  8. Characterization of the cellulose-binding domain of the Clostridium cellulovorans cellulose-binding protein A.

    PubMed Central

    Goldstein, M A; Takagi, M; Hashida, S; Shoseyov, O; Doi, R H; Segel, I H

    1993-01-01

    Cellulose-binding protein A (CbpA), a component of the cellulase complex of Clostridium cellulovorans, contains a unique sequence which has been demonstrated to be a cellulose-binding domain (CBD). The DNA coding for this putative CBD was subcloned into pET-8c, an Escherichia coli expression vector. The protein produced under the direction of the recombinant plasmid, pET-CBD, had a high affinity for crystalline cellulose. Affinity-purified CBD protein was used in equilibrium binding experiments to characterize the interaction of the protein with various polysaccharides. It was found that the binding capacity of highly crystalline cellulose samples (e.g., cotton) was greater than that of samples of low crystallinity (e.g., fibrous cellulose). At saturating CBD concentration, about 6.4 mumol of protein was bound by 1 g of cotton. Under the same conditions, fibrous cellulose bound only 0.2 mumol of CBD per g. The measured dissociation constant was in the 1 microM range for all cellulose samples. The results suggest that the CBD binds specifically to crystalline cellulose. Chitin, which has a crystal structure similar to that of cellulose, also was bound by the CBD. The presence of high levels of cellobiose or carboxymethyl cellulose in the assay mixture had no effect on the binding of CBD protein to crystalline cellulose. This result suggests that the CBD recognition site is larger than a simple cellobiose unit or more complex than a repeating cellobiose moiety. This CBD is of particular interest because it is the first CBD from a completely sequenced nonenzymatic protein shown to be an independently functional domain. Images PMID:8376323

  9. Incorporation of poly(glycidylmethacrylate) grafted bacterial cellulose nano-whiskers in poly(lactic acid) nanocomposites: improved barrier and mechanical properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Poly(glycidyl methacrylate) (PGMA) was grafted onto bacterial cellulose nanowhiskers (BCNW) by means of a redox-initiated free radical copolymerization reaction. The incorporation of PGMA chains decreased the thermal stability and crystallinity of BCNW. The neat and the PGMA-grafted BCNW were subseq...

  10. [Supramolecular reorganizations in cellulose during hydration].

    PubMed

    Grunin, Iu B; Grunin, L Iu; Talantsev, V I; Nikol'skaia, E A; Masas, D S

    2015-01-01

    The analysis of modern ideas about the structural organization of the cellulose microfibrils is carried out. The mechanism of the formation of additional capillary-porous system of cellulose under moistening is offered. It is established that when the moisture content of cellulose reaches 8-10%, the filling of its micropores occurs with a simultaneous increase in their cross sizes, a specific surface and reduction in the degree of crystallinity of specimens. Within the proposed model of microfibril construction the parameters of supramolecular structure and capillary-porous system of cotton cellulose are determined.

  11. Cellulose nanocrystals/cellulose core-in-shell nanocomposite assemblies.

    PubMed

    Magalhães, Washington Luiz Esteves; Cao, Xiaodong; Lucia, Lucian A

    2009-11-17

    We report herein for the first time how a co-electrospinning technique can be used to overcome the issue of orienting cellulose nanocrystals within a neat cellulose matrix. A home-built co-electrospinning apparatus was fabricated that was comprised of a high-voltage power supply, two concentric capillary needles, and one screw-type pump syringe. Eucalyptus-derived cellulose was dissolved in N-methylmorpholine oxide (NMMO) at 120 degrees C and diluted with dimethyl sulfoxide (DMSO) which was used in the external concentric capillary needle as the shell solution. A cellulose nanocrystal suspension obtained by the sulfuric acid hydrolysis of bleached sisal and cotton fibers was used as the core liquid in the internal concentric capillary needle. Three flow rate ratios between the shell and core, four flow rates for the shell dope solution, and four high voltages were tested. The resultant co-electrospun composite fibers were collected onto a grounded metal screen immersed in cold water. Micrometer and submicrometer cellulose fiber assemblies were obtained which were reinforced with cellulose nanocrystals and characterized by FESEM, FTIR, TGA, and XRD. Surprisingly, it was determined that the physical properties for the cellulose controls are superior to the composites; in addition, the crystallinity of the controls was slightly greater.

  12. UV-radiation induced disruption of dry-cavities in human γD-crystallin results in decreased stability and faster unfolding.

    PubMed

    Xia, Zhen; Yang, Zaixing; Huynh, Tien; King, Jonathan A; Zhou, Ruhong

    2013-01-01

    Age-onset cataracts are believed to be expedited by the accumulation of UV-damaged human γD-crystallins in the eye lens. Here we show with molecular dynamics simulations that the stability of γD-crystallin is greatly reduced by the conversion of tryptophan to kynurenine due to UV-radiation, consistent with previous experimental evidences. Furthermore, our atomic-detailed results reveal that kynurenine attracts more waters and other polar sidechains due to its additional amino and carbonyl groups on the damaged tryptophan sidechain, thus breaching the integrity of nearby dry center regions formed by the two Greek key motifs in each domain. The damaged tryptophan residues cause large fluctuations in the Tyr-Trp-Tyr sandwich-like hydrophobic clusters, which in turn break crucial hydrogen-bonds bridging two β-strands in the Greek key motifs at the "tyrosine corner". Our findings may provide new insights for understanding of the molecular mechanism of the initial stages of UV-induced cataractogenesis.

  13. A new locus affects cell motility, cellulose binding, and degradation by Cytophaga hutchinsonii.

    PubMed

    Ji, Xiaofei; Xu, Yuanxi; Zhang, Cong; Chen, Ning; Lu, Xuemei

    2012-10-01

    Cytophaga hutchinsonii is a Gram-negative gliding bacterium, which can rapidly degrade crystalline cellulose via a novel strategy without any recognizable processive cellulases. Its mechanism of cellulose binding and degradation is still a mystery. In this study, the mutagenesis of C. hutchinsonii with the mariner-based transposon HimarEm3 and gene complementation with the oriC-based plasmid carrying the antibiotic resistance gene cfxA or tetQ were reported for the first time to provide valuable tools for mutagenesis and genetic manipulation of the bacterium. Mutant A-4 with a transposon mutation in gene CHU_0134, which encodes a putative thiol-disulfide isomerase exhibits defects in cell motility and cellulose degradation. The cellulose binding ability of A-4 was only half of that of the wild-type strain, while the endo-cellulase activity of the cell-free supernatants and on the intact cell surface of A-4 decreased by 40%. Sodium dodecyl sulfate polyacrylamide gel electrophoresis of proteins binding to cellulose in the outer membrane showed that most of them were significantly decreased or disappeared in A-4 including some Gld proteins and hypothetical proteins, indicating that these proteins might play an important role in cell motility and cellulose binding and degradation by the bacterium.

  14. Effect of Water Vapor Adsorption on Electrical Properties of Carbon Nanotube/Nanocrystalline Cellulose Composites.

    PubMed

    Safari, Salman; van de Ven, Theo G M

    2016-04-13

    It has been long known that the electrical properties of cellulose are greatly influenced by adsorption of water vapor. Incorporating conductive nanofillers in a cellulose matrix is an example of an approach to tailor their characteristics for use in electronics and sensing devices. In this work, we introduce two new nanocomposites comprising carbon nanotubes (CNTs) and conventional or electrosterically stabilized nanocrystalline celluloses matrices. While conventional nanocrystalline cellulose (NCC) consists of a rigid crystalline backbone, electrosterically stabilized cellulose (ENCC) is composed of a rigid crystalline backbone with carboxylated polymers protruding from both ends. By tuning CNT loading, we can tailor a CNT/NCC composite with minimal electrical sensitivity to the ambient relative humidity, despite the fact that the composite has a high moisture uptake. The expected decrease in CNT conductivity upon water vapor adsorption, due to electron donation, is counterbalanced by an increase in the conductivity of NCC due to proton hopping at an optimum CNT loading (1-2%). Contrary to the CNT/NCC composite, a CNT/ENCC composite at 1% CNT loading shows insulating behavior for relative humidities up to 75%, after which the composite becomes conductive. This interesting behavior can be ascribed to the low moisture uptake of ENCC at low and moderate relative humidities due to the limited number of hydroxyl groups and hydrogen bond formation between carboxyl groups on ENCC, which endow ENCC with limited water molecule adsorption sites.

  15. Structure and transformation of tactoids in cellulose nanocrystal suspensions

    PubMed Central

    Wang, Pei-Xi; Hamad, Wadood Y.; MacLachlan, Mark J.

    2016-01-01

    Cellulose nanocrystals obtained from natural sources are of great interest for many applications. In water, cellulose nanocrystals form a liquid crystalline phase whose hierarchical structure is retained in solid films after drying. Although tactoids, one of the most primitive components of liquid crystals, are thought to have a significant role in the evolution of this phase, they have evaded structural study of their internal organization. Here we report the capture of cellulose nanocrystal tactoids in a polymer matrix. This method allows us to visualize, for the first time, the arrangement of cellulose nanocrystals within individual tactoids by electron microscopy. Furthermore, we can follow the structural evolution of the liquid crystalline phase from tactoids to iridescent-layered films. Our insights into the early nucleation events of cellulose nanocrystals give important information about the growth of cholesteric liquid crystalline phases, especially for cellulose nanocrystals, and are crucial for preparing photonics-quality films. PMID:27143197

  16. Thermophilic Bacillus coagulans requires less cellulases for simultaneous saccharification and fermentation of cellulose to products than mesophilic microbial biocatalysts.

    PubMed

    Ou, Mark S; Mohammed, Nazimuddin; Ingram, L O; Shanmugam, K T

    2009-05-01

    Ethanol production from lignocellulosic biomass depends on simultaneous saccharification of cellulose to glucose by fungal cellulases and fermentation of glucose to ethanol by microbial biocatalysts (SSF). The cost of cellulase enzymes represents a significant challenge for the commercial conversion of lignocellulosic biomass into renewable chemicals such as ethanol and monomers for plastics. The cellulase concentration for optimum SSF of crystalline cellulose with fungal enzymes and a moderate thermophile, Bacillus coagulans, was determined to be about 7.5 FPU g(-1) cellulose. This is about three times lower than the amount of cellulase required for SSF with Saccharomyces cerevisiae, Zymomonas mobilis, or Lactococcus lactis subsp. lactis whose growth and fermentation temperature optimum is significantly lower than that of the fungal cellulase activity. In addition, B. coagulans also converted about 80% of the theoretical yield of products from 40 g/L of crystalline cellulose in about 48 h of SSF with 10 FPU g(-1) cellulose while yeast, during the same period, only produced about 50% of the highest yield produced at end of 7 days of SSF. These results show that a match in the temperature optima for cellulase activity and fermentation is essential for decreasing the cost of cellulase in cellulosic ethanol production.

  17. Ultrasonic enhance acid hydrolysis selectivity of cellulose with HCl-FeCl3 as catalyst.

    PubMed

    Li, Jinbao; Zhang, Xiangrong; Zhang, Meiyun; Xiu, Huijuan; He, Hang

    2015-03-06

    The effect of ultrasonic pretreatment coupled with HCl-FeCl3 catalyst was evaluated to hydrolyze cellulose amorphous regions. The ultrasonic pretreatment leads to cavitation that affects the morphology and microstructure of fibers, enhancing the accessibility of chemical reagent to the loosened amorphous regions of cellulose. In this work, Fourier transform infrared spectroscopy (FTIR) was used to identify characteristic absorption bands of the constituents and the crystallinity was evaluated by the X-ray diffraction (XRD) technique. The results indicated that appropriate ultrasonic pretreatment assisted with FeCl3 can enhance the acid hydrolysis of amorphous regions of cellulose, thus improving the crystallinity of the remaining hydrocellulose. It was observed that sonication samples that were pretreated for 300 W and 20 min followed by acid hydrolysis had maximum of 78.9% crystallinity. The crystallinity was 9.2% higher than samples that were not subjected to ultrasound. In addition, the average fines length decreased from 49 μm to 37 μm.

  18. The segal crystallinity index as it relates to crystallite size

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cotton fibers are composed of crystals of cellulose that yield a diffraction pattern, although fibers from varying sources and histories are said to have different degrees of crystallinity. There are many methods to assess this crystallinity. One of the most popular is the Segal Crystallinity Index ...

  19. Responsive behavior of regenerated cellulose in hydrolysis under microwave radiation.

    PubMed

    Ni, Jinping; Na, Haining; She, Zhen; Wang, Jinggang; Xue, Wenwen; Zhu, Jin

    2014-09-01

    This work studied the responsive behavior of regenerated cellulose (RC) in hydrolysis under microwave radiation. Four types of RC with different crystallinity (Cr) and degree of polymerization (DP) are produced to evaluate the reactivity of RC by step-by-step hydrolysis. Results show Cr is the key factor to affect the reactivity of RCs. With hydrolysis of amorphous region and the formation of recrystallization, the Cr of RC reaches a high value and thus weakens the reactivity. As a result, the increment of cellulose conversion and sugar yield gradually reduces. Decrease of the DP of RC is helpful to increase the speed at the onset of hydrolysis and produce high sugar yield. But, there is no direct influence with the reactivity of RC to prolong the time of pretreatment. This research provides an accurate understanding to guide the RC preparation for sugar formation with relative high efficiency under mild reaction conditions.

  20. Electron beam irradiation of cellulose

    NASA Astrophysics Data System (ADS)

    Driscoll, Mark; Stipanovic, Arthur; Winter, William; Cheng, Kun; Manning, Mellony; Spiese, Jessica; Galloway, Richard A.; Cleland, Marshall R.

    2009-07-01

    Using a 90 kW, 3 MeV Dynamitron™, the molecular weight of microcrystalline cellulose (MCC) was reduced from 82,000 to 5000 Da with a dose of 100 kGy. The relative crystallinity of the MCC was reduced from 87% to 45% with a dose of 1000 kGy. The available surface area, an indication on how well cellulose will react with chemical agents, was increased from 274 m 2/g for the control sample (0 kGy) to 318 m 2/g at a dose 1000 kGy.

  1. Isolation and characterization of cellulose nanowhiskers from oil palm biomass microcrystalline cellulose.

    PubMed

    Haafiz, M K Mohamad; Hassan, Azman; Zakaria, Zainoha; Inuwa, I M

    2014-03-15

    The objective of this study is to compare the effect of two different isolation techniques on the physico-chemical and thermal properties of cellulose nanowhiskers (CNW) from oil palm biomass obtained microcrystalline cellulose (MCC). Fourier transform infrared analysis showed that there are no significant changes in the peak positions, suggesting that the treatments did not affect the chemical structure of the cellulose fragment. Scanning electron microscopy showed that the aggregated structure of MCC is broken down after treatment. Transmission electron microscopy revealed that the produced CNW displayed a nanoscale structure. X-ray diffraction analysis indicated that chemical swelling improves the crystallinity of MCC while maintaining the cellulose I structure. Acid hydrolysis however reduced the crystallinity of MCC and displayed the coexistence of cellulose I and II allomorphs. The produced CNW is shown to have a good thermal stability and hence is suitable for a range of applications such as green biodegradable nanocomposites reinforced with CNW.

  2. Lung biodurability and free radical production of cellulose nanomaterials

    PubMed Central

    Stefaniak, Aleksandr B.; Seehra, Mohindar S.; Fix, Natalie R.; Leonard, Stephen S.

    2015-01-01

    The potential applications of cellulose nanomaterials in advanced composites and biomedicine makes it imperative to understand their pulmonary exposure to human health. Here, we report the results on the biodurability of three cellulose nanocrystal (CNC), two cellulose nanofibril (CNF) and a benchmark cellulose microcrystal (CMC) when exposed to artificial lung airway lining fluid (SUF, pH 7.3) for up to 7 days and alveolar macrophage phagolysosomal fluid (PSF, pH 4.5) for up to 9 months. X-ray diffraction analysis was used to monitor biodurability and thermogravimetry, surface area, hydrodynamic diameter, zeta potential and free radical generation capacity of the samples were determined (in vitro cell-free and RAW 264.7 cell line models). The CMC showed no measurable changes in crystallinity (xCR) or crystallite size D in either SUF or PSF. For one CNC, a slight decrease in xCR and D in SUF was observed. In acidic PSF, a slight increase in xCR with exposure time was observed, possibly due to dissolution of the amorphous component. In a cell-free reaction with H2O2, radicals were observed; the CNCs and a CNF generated significantly more ●OH radicals than the CMC (p<0.05). The ●OH radical production correlates with particle decomposition temperature and is explained by the higher surface area to volume ratio of the CNCs. Based on their biodurability, mechanical clearance would be the primary mechanism for lung clearance of cellulose materials. The production of ●OH radicals indicates the need for additional studies to characterize the potential inhalation hazards of cellulose. PMID:25265049

  3. Time-resolved X-ray diffraction microprobe studies of the conversion of cellulose I to ethylenediamine-cellulose I

    SciTech Connect

    Nishiyama, Yoshiharu; Wada, Masahisa; Hanson, B. Leif; Langan, Paul

    2010-08-03

    Structural changes during the treatment of films of highly crystalline microfibers of Cladophora cellulose with ethylenediamine (EDA) have been studied by time-resolved X-ray microprobe diffraction methods. As EDA penetrates the sample and converts cellulose I to EDA-cellulose I, the measured profile widths of reflections reveal changes in the shapes and average dimensions of cellulose I and EDA-cellulose I crystals. The (200) direction of cellulose I is most resistant to EDA penetration, with EDA penetrating most effectively at the hydrophilic edges of the hydrogen bonded sheets of cellulose chains. Most of the cellulose chains in the initial crystals of cellulose I are incorporated into crystals of EDA-cellulose I. The size of the emerging EDA-cellulose I crystals is limited to about half of their size in cellulose I, most likely due to strains introduced by the penetration of EDA molecules. There is no evidence of any gradual structural transition from cellulose I to EDA-cellulose I involving a continuously changing intermediate phase. Rather, the results point to a rapid transition to EDA-cellulose I in regions of the microfibrils that have been penetrated by EDA.

  4. Co-electrospun poly(ɛ-caprolactone)/cellulose nanofibers-fabrication and characterization.

    PubMed

    Ahmed, Farooq; Saleemi, Sidra; Khatri, Zeeshan; Abro, Muhammad Ishaque; Kim, Ick-Soo

    2015-01-22

    We report fabrication of poly (ɛ-caprolactone) (PCL)/cellulose (CEL) nanofiber blends via co-electrospinning for the possible use as biofilters and biosensor strips. Five different ratios of PCL to CEL were fabricated to investigate the wicking behavior. The cellulose acetate (CA) was taken as precursor to make cellulose nanofibers. Double nozzles were employed for jetting constituent polymers toward collector drum independently and resultant nanofibers webs were deacetylated in aqueous alkaline solution to convert CA into CEL as confirmed by FTIR spectra. FTIR further revealed that there is no effect of deacetylation on PCL nanofiber. The morphology of each blend webs under SEM showed uniform and bead-free nanofibers. Wicking behavior for five different ratios of PCL/CEL suggested that increasing CEL ratio in the blend enhanced the wicking front height; however, X-ray diffraction patterns of PCL/CEL showed a slight decrease in crystallinity.

  5. Processing of cellulose for the advancement of biofuels

    NASA Astrophysics Data System (ADS)

    Watson, Brian James

    2011-12-01

    The enzymatic degradation of cellulose polymers is currently a rate-limiting step in the bioconversion of biomass to biofuels. Cellulose polymers self assemble to form crystalline structures stabilized by a complex network of intermolecular interactions such as hydrogen bonding. The network of interactions in crystalline cellulose (cellulose nanostructure) poses an energy barrier that limits enzymatic degradation as apparent from the activity of Cel5H. To improve the degradability of cellulose the intermolecular interactions must be disrupted. The interactions of the cellulose nanostructure prevent solubilization by water and most other common solvents, but some organic solvents aid degradation of cellulose suggesting they influence cellulose nanostructure. The objective of this work is to understand the influence of solvents on cellulose nanostructure with the goal of improving the degradability of cellulose nanostructure using solvents. To understand solvent interaction with cellulose, phosphoric acid was used to first solubilize cellulose (PAS cellulose) followed by adding an organic liquid or water to wash the phosphate from the system. The Flory Huggins theory was used to predict wash liquids that could favorably interact with cellulose. A favorable wash liquid was predicted to prevent the reformation of crystalline domains to yield a disrupted cellulose nanostructure, which should be more degradable. Low molecular weight alcohols and glycols were calculated to be favorable wash liquids. Washing PAS cellulose with the predicted favorable liquids yielded semi-transparent gel-like materials compared to the opaque white precipitate formed when water or unfavorable solvents were used in the wash. Fractal analysis of small angle neutron scattering (SANS) of these apparent gels indicated cellulose polymers likely have the properties of clustered rods. This partial disruption increased degradability relative to the water washed PAS cellulose. The apparent rod

  6. The thermochemical characteristics of cellulose and its mixtures with water

    NASA Astrophysics Data System (ADS)

    Ur'yash, V. F.; Larina, V. N.; Kokurina, N. Yu.; Novoselova, N. V.

    2010-06-01

    The heat capacity of cotton microcrystalline cellulose was measured on an adiabatic vacuum calorimeter over the temperature range 80-330 K, and the differential thermal analysis data on the substance were obtained from 80 to 550 K. The enthalpy of cellulose interaction with water was measured at 303 K using a differential microcalorimeter. The standard enthalpies of combustion and formation of microcrystalline cellulose and wood celluloses with different crystallinity indices were determined. The concentration of saturated water solution in microcrystalline cellulose at 273 K was determined calorimetrically from the enthalpy of fusion of the excess water phase.

  7. Multi-scale cellulose based new bio-aerogel composites with thermal super-insulating and tunable mechanical properties.

    PubMed

    Seantier, Bastien; Bendahou, Dounia; Bendahou, Abdelkader; Grohens, Yves; Kaddami, Hamid

    2016-03-15

    Bio-composite aerogels based on bleached cellulose fibers (BCF) and cellulose nanoparticles having various morphological and physico-chemical characteristics are prepared by a freeze-drying technique and characterized. The various composite aerogels obtained were compared to a BCF aerogel used as the reference. Severe changes in the material morphology were observed by SEM and AFM due to a variation of the cellulose nanoparticle properties such as the aspect ratio, the crystalline index and the surface charge density. BCF fibers form a 3D network and they are surrounded by the cellulose nanoparticle thin films inducing a significant reduction of the size of the pores in comparison with a neat BCF based aerogel. BET analyses confirm the appearance of a new organization structure with pores of nanometric sizes. As a consequence, a decrease of the thermal conductivities is observed from 28mWm(-1)K(-1) (BCF aerogel) to 23mWm(-1)K(-1) (bio-composite aerogel), which is below the air conductivity (25mWm(-1)K(-1)). This improvement of the insulation properties for composite materials is more pronounced for aerogels based on cellulose nanoparticles having a low crystalline index and high surface charge (NFC-2h). The significant improvement of their insulation properties allows the bio-composite aerogels to enter the super-insulating materials family. The characteristics of cellulose nanoparticles also influence the mechanical properties of the bio-composite aerogels. A significant improvement of the mechanical properties under compression is obtained by self-organization, yielding a multi-scale architecture of the cellulose nanoparticles in the bio-composite aerogels. In this case, the mechanical property is more dependent on the morphology of the composite aerogel rather than the intrinsic characteristics of the cellulose nanoparticles.

  8. Structural changes of Salix miyabeana cellulose fibres during dilute-acid steam explosion: impact of reaction temperature and retention time.

    PubMed

    Diop, Chérif Ibrahima Khalil; Lavoie, Jean-Michel; Huneault, Michel A

    2015-03-30

    Dilute-acid steam explosion of Salix miyabeana has been carried out to understand the effect of processing conditions, expressed through a severity factors (SFT), on the changes in cellulose fibre structures in a perspective of using these in polymer composites. This thermo-chemico-mechanical extraction leads to the isolation of cellulose fibres as observed by SEM images. Fibre length as well as length to diameter aspect ratios decreased with the severity of the treatment. Likewise, fibre whiteness diminished with an increasing severity factor, which could be a tangible effect of physical degradation. Variations in crystallinity seemed to be dependent upon the reaction temperature, generally decreasing with regards to retention time. Above a severity threshold, a structural disorganization was observed. Overall, dilute-acid steam explosion was shown to be a valuable cellulose extraction process that can provide a variety of fibre structures.

  9. Transcriptomic analysis of Clostridium thermocellum ATCC 27405 cellulose fermentation

    SciTech Connect

    McKeown, Catherine K; Brown, Steven D

    2011-01-01

    The ability of Clostridium thermocellum ATCC 27405 wild-type strain to hydrolyze cellulose and ferment the degradation products directly to ethanol and other metabolic byproducts makes it an attractive candidate for consolidated bioprocessing of cellulosic biomass to biofuels. In this study, whole-genome microarrays were used to investigate the expression of C. thermocellum mRNA during growth on crystalline cellulose in controlled replicate batch fermentations. A time-series analysis of gene expression revealed changes in transcript levels of {approx}40% of genes ({approx}1300 out of 3198 ORFs encoded in the genome) during transition from early-exponential to late-stationary phase. K-means clustering of genes with statistically significant changes in transcript levels identified six distinct clusters of temporal expression. Broadly, genes involved in energy production, translation, glycolysis and amino acid, nucleotide and coenzyme metabolism displayed a decreasing trend in gene expression as cells entered stationary phase. In comparison, genes involved in cell structure and motility, chemotaxis, signal transduction and transcription showed an increasing trend in gene expression. Hierarchical clustering of cellulosome-related genes highlighted temporal changes in composition of this multi-enzyme complex during batch growth on crystalline cellulose, with increased expression of several genes encoding hydrolytic enzymes involved in degradation of non-cellulosic substrates in stationary phase. Overall, the results suggest that under low substrate availability, growth slows due to decreased metabolic potential and C. thermocellum alters its gene expression to (i) modulate the composition of cellulosomes that are released into the environment with an increased proportion of enzymes than can efficiently degrade plant polysaccharides other than cellulose, (ii) enhance signal transduction and chemotaxis mechanisms perhaps to sense the oligosaccharide hydrolysis products

  10. Looking at hydrogen bonds in cellulose.

    PubMed

    Nishiyama, Yoshiharu; Langan, Paul; Wada, Masahisa; Forsyth, V Trevor

    2010-11-01

    A series of cellulose crystal allomorphs has been studied using high-resolution X-ray and neutron fibre diffraction to locate the positions of H atoms involved in hydrogen bonding. One type of position was always clearly observed in the Fourier difference map (F(d)-F(h)), while the positions of other H atoms appeared to be less well established. Despite the high crystallinity of the chosen samples, neutron diffraction data favoured some hydrogen-bonding disorder in native cellulose. The presence of disorder and a comparison of hydrogen-bond geometries in different allomorphs suggests that although hydrogen bonding may not be the most important factor in the stabilization of cellulose I, it is essential for stabilizing cellulose III, which is the activated form, and preventing it from collapsing back to the more stable cellulose I.

  11. Structural changes in microcrystalline cellulose in subcritical water treatment.

    PubMed

    Tolonen, Lasse K; Zuckerstätter, Gerhard; Penttilä, Paavo A; Milacher, Walter; Habicht, Wilhelm; Serimaa, Ritva; Kruse, Andrea; Sixta, Herbert

    2011-07-11

    Subcritical water is a high potential green chemical for the hydrolysis of cellulose. In this study microcrystalline cellulose was treated in subcritical water to study structural changes of the cellulose residues. The alterations in particle size and appearance were studied by scanning electron microscopy (SEM) and those in the degree of polymerization (DP) and molar mass distributions by gel permeation chromatography (GPC). Further, changes in crystallinity and crystallite dimensions were quantified by wide-angle X-ray scattering and (13)C solid-state NMR. The results showed that the crystallinity remained practically unchanged throughout the treatment, whereas the size of the remaining cellulose crystallites increased. Microcrystalline cellulose underwent significant depolymerization in subcritical water. However, depolymerization leveled off at a relatively high degree of polymerization. The molar mass distributions of the residues showed a bimodal form. We infer that cellulose gets dissolved in subcritical water only after extensive depolymerization.

  12. The biological degradation of cellulose.

    PubMed

    Béguin, P; Aubert, J P

    1994-01-01

    Cellulolytic microorganisms play an important role in the biosphere by recycling cellulose, the most abundant carbohydrate produced by plants. Cellulose is a simple polymer, but it forms insoluble, crystalline microfibrils, which are highly resistant to enzymatic hydrolysis. All organisms known to degrade cellulose efficiently produce a battery of enzymes with different specificities, which act together in synergism. The study of cellulolytic enzymes at the molecular level has revealed some of the features that contribute to their activity. In spite of a considerable diversity, sequence comparisons show that the catalytic cores of cellulases belong to a restricted number of families. Within each family, available data suggest that the various enzymes share a common folding pattern, the same catalytic residues, and the same reaction mechanism, i.e. either single substitution with inversion of configuration or double substitution resulting in retention of the beta-configuration at the anomeric carbon. An increasing number of three-dimensional structures is becoming available for cellulases and xylanases belonging to different families, which will provide paradigms for molecular modeling of related enzymes. In addition to catalytic domains, many cellulolytic enzymes contain domains not involved in catalysis, but participating in substrate binding, multi-enzyme complex formation, or possibly attachment to the cell surface. Presumably, these domains assist in the degradation of crystalline cellulose by preventing the enzymes from being washed off from the surface of the substrate, by focusing hydrolysis on restricted areas in which the substrate is synergistically destabilized by multiple cutting events, and by facilitating recovery of the soluble degradation products by the cellulolytic organism. In most cellulolytic organisms, cellulase synthesis is repressed in the presence of easily metabolized, soluble carbon sources and induced in the presence of cellulose

  13. Nanomechanics of cellulose crystals and cellulose-based polymer composites

    NASA Astrophysics Data System (ADS)

    Pakzad, Anahita

    Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: - Dispersion quality and macro-mechanical properties - Nanomechanical properties at the surface and tensile properties - CNC diameter and interphase thickness. Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on

  14. Methods of detection using a cellulose binding domain fusion product

    DOEpatents

    Shoseyov, Oded; Shpiegl, Itai; Goldstein, Marc A.; Doi, Roy H.

    1999-01-01

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production thereof. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques.

  15. Methods of use of cellulose binding domain proteins

    SciTech Connect

    Shoseyov, Oded; Shpiegl, Itai; Goldstein, Marc A.; Doi, Roy H.

    1997-01-01

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production thereof. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques.

  16. Methods of use of cellulose binding domain proteins

    SciTech Connect

    Shoseyov, O.; Shpiegl, I.; Goldstein, M.A.; Doi, R.H.

    1997-09-23

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques. 16 figs.

  17. Methods of detection using a cellulose binding domain fusion product

    DOEpatents

    Shoseyov, O.; Shpiegl, I.; Goldstein, M.A.; Doi, R.H.

    1999-01-05

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques. 34 figs.

  18. [Study on spectroscopic characterization and property of PES/ micro-nano cellulose composite membrane material].

    PubMed

    Tang, Huan-Wei; Zhang, Li-Ping; Li, Shuai; Zhao, Guang-Jie; Qin, Zhu; Sun, Su-Qin

    2010-03-01

    In the present paper, the functional groups of PES/micro-nano cellulose composite membrane materials were characterized by Fourier transform infrared spectroscopy (FTIR). Also, changes in crystallinity in composite membrane materials were analyzed using X-ray diffraction (XRD). The effects of micro-nano cellulose content on hydrophilic property of composite membrane material were studied by measuring hydrophilic angle. The images of support layer structure of pure PES membrane material and composite membrane material were showed with scanning electron microscope (SEM). These results indicated that in the infrared spectrogram, the composite membrane material had characteristic peaks of both PES and micro-nano cellulose without appearance of other new characteristics peaks. It revealed that there were no new functional groups in the composite membrane material, and the level of molecular compatibility was achieved, which was based on the existence of inter-molecular hydrogen bond association between PES and micro-nano cellulose. Due to the existence of micro-nano cellulose, the crystallinity of composite membrane material was increased from 37.7% to 47.9%. The more the increase in micro-nano cellulose mass fraction, the better the van de Waal force and hydrogen bond force between composite membrane material and water were enhanced. The hydrophilic angle of composite membrane material was decreased from 55.8 degrees to 45.8 degrees and the surface energy was raised from 113.7 to 123.5 mN x m(-2). Consequently, the hydrophilic property of composite membrane material was improved. The number of pores in the support layer of composite membrane material was lager than that of pure PES membrane. Apparently, pores were more uniformly distributed.

  19. Effects of dilution rate and pH on the ruminal cellulolytic bacterium Fibrobacter succinogenes S85 in cellulose-fed continuous culture.

    PubMed

    Weimer, P J

    1993-01-01

    The ruminal cellulolytic bacterium Fibrobacter succinogenes S85 was grown in cellulose-fed continuous culture at 22 different combinations of dilution rate (D, 0.014-0.076 h-1) and extracellular pH (6.11-6.84). Effects of pH and D on the fermentation were determined by subjecting data on cellulose consumption, cell yield, product yield (succinate, acetate, formate), and soluble sugar concentration to response surface analysis. The extent of cellulose conversion decreased with increasing D. First-order rate constants at rapid growth rates were estimated as 0.07-0.11 h-1, and decreased with decreasing pH. Apparent decreases in the rate constant with increasing D was not due to inadequate mixing or preferential utilization of the more amorphous regions of the cellulose. Significant quantities of soluble sugars (0.04-0.18 g/l, primarily glucose) were detected in all cultures, suggesting that glucose uptake was rather inefficient. Cell yields (0.11-0.24 g cells/g cellulose consumed) increased with increasing D. Pirt plots of the predicted yield data were used to determine that maintenance coefficient (0.04-0.06 g cellulose/g cells.h) and true growth yield (0.23-0.25 g cells/g cellulose consumed) varied slightly with pH. Yields of succinate, the major fermentation endproduct, were as high as 1.15 mol/mol anhydroglucose fermented, and were slightly affected by dilution rate but were not affected by pH. Comparison of the fermentation data with that of other ruminal cellulolytic bacteria indicates that F. succinogenes S85 is capable of rapid hydrolysis of crystalline cellulose and efficient growth, despite a lower mu max on microcrystalline cellulose.

  20. Gravity effects on cellulose assembly

    NASA Technical Reports Server (NTRS)

    Brown, R. M. Jr; Kudlicka, K.; Cousins, S. K.; Nagy, R.; Brown RM, J. r. (Principal Investigator)

    1992-01-01

    The effect of microgravity on cellulose synthesis using the model system of Acetobacter xylinum was the subject of recent investigations using The National Aeronautics and Space Administration's Reduced Gravity Laboratory, a modified KC-135 aircraft designed to produce 20 sec of microgravity during the top of a parabolic dive. Approximately 40 parabolas were executed per mission, and a period of 2 x g was integral to the pullout phase of each parabola. Cellulose biosynthesis was initiated on agar surfaces, liquid growth medium, and buffered glucose during parabolic flight and terminated with 2.0% sodium azide or 50.0% ethanol. While careful ground and in-flight controls indicated normal, compact ribbons of microbial cellulose, data from five different flights consistently showed that during progression into the parabola regime, the cellulose ribbons became splayed. This observation suggests that some element of the parabola (the 20 sec microgravity phase, the 20 sec 2 x g phase, or a combination of both) was responsible for this effect. Presumably the cellulose I alpha crystalline polymorph normally is produced under strain, and the microgravity/hypergravity combination may relieve this stress to produce splayed ribbons. An in-flight video microscopy analysis of bacterial motions during a parabolic series demonstrated that the bacteria continue to synthesize cellulose during all phases of the parabolic series. Thus, the splaying may be a reflection of a more subtle alteration such as reduction of intermicrofibrillar hydrogen bonding. Long-term microgravity exposures during spaceflight will be necessary to fully understand the cellulose alterations from the short-term microgravity experiments.

  1. Cavitation milling of natural cellulose to nanofibrils.

    PubMed

    Pinjari, Dipak Vitthal; Pandit, Aniruddha B

    2010-06-01

    Cavitation holds the promise of a new and exciting approach to fabricate both top down and bottom up nanostructures. Cavitation bubbles are created when a liquid boils under less than atmospheric pressure. The collapse process occurs supersonically and generates a host of physical and chemical effects. We have made an attempt to fabricate natural cellulose material using hydrodynamic as well as acoustic cavitation. The cellulose material having initial size of 63 micron was used for the experiments. 1% (w/v) slurry of cellulose sample was circulated through the hydrodynamic cavitation device or devices (orifice) for 6h. The average velocity of the fluid through the device was 10.81m/s while average pressure applied was 7.8 kg/cm(2). Cavitation number was found to be 2.61. The average particle size obtained after treatment was 1.36 micron. This hydrodynamically processed sample was sonicated for 1h 50 min. The average size of ultrasonically processed particles was found to be 301 nm. Further, the cellulose particles were characterized with X-ray diffraction (XRD) and differential scanning calorimetry (DSC) to see the effect of cavitation on crystallinity (X(c)) as well as on melting temperature (T(m)). Cellulose structures consist of amorphous as well as crystalline regions. The initial raw sample was 86.56% crystalline but due to the effect of cavitation, the crystallinity reduced to 37.76%. Also the melting temperature (T(m)) was found to be reduced from 101.78 degrees C of the original to 60.13 degrees C of the processed sample. SEM images for the cellulose (processed and unprocessed) shows the status and fiber-fiber alignment and its orientation with each other. Finally cavitation has proved to be very efficient tool for reduction in size from millimeter to nano scale for highly crystalline materials.

  2. Characterization of cellulose II nanoparticles regenerated from ionic liquid, 1-butyl-3-methylimidazolium chloride

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Regenerated cellulose nanoparticles (RCNs) including both elongated fiber and spherical structures were prepared from microcrystalline cellulose (MCC)and cotton using 1-butyl-3-methylimidazolium chloride followed by high-pressure homogenization. The crystalline structure of RCNs was cellulose II in ...

  3. Cyanoresin, cyanoresin/cellulose triacetate blends for thin film, dielectric capacitors

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping S. (Inventor); Lewis, Carol R. (Inventor); Cygan, Peter J. (Inventor); Jow, T. Richard (Inventor)

    1996-01-01

    Non brittle dielectric films are formed by blending a cyanoresin such as cyanoethyl, hydroxyethyl cellulose (CRE) with a compatible, more crystalline resin such as cellulose triacetate. The electrical breakdown strength of the blend is increased by orienting the films by uniaxial or biaxial stretching. Blends of high molecular weight CRE with high molecular weight cyanoethyl cellulose (CRC) provide films with high dielectric constants.

  4. Cyanoresin, cyanoresin/cellulose triacetate blends for thin film, dielectric capacitors

    NASA Technical Reports Server (NTRS)

    Yen, Shiao-Ping (Inventor); Jow, T. Richard (Inventor)

    1993-01-01

    Non-brittle dielectric films are formed by blending a cyanoresin such as cyanoethyl, hydroxyethyl cellulose (CRE) with a compatible, more crystalline resin such as cellulose triacetate. The electrical breakdown strength of the blend is increased by orienting the films by uniaxial or biaxial stretching. Blends of high molecular weight CRE with high molecular weight cyanoethyl cellulose (CRC) provide films with high dielectric constants.

  5. Engineering of a novel cellulose-adherent cellulolytic Saccharomyces cerevisiae for cellulosic biofuel production.

    PubMed

    Liu, Zhuo; Ho, Shih-Hsin; Sasaki, Kengo; den Haan, Riaan; Inokuma, Kentaro; Ogino, Chiaki; van Zyl, Willem H; Hasunuma, Tomohisa; Kondo, Akihiko

    2016-04-15

    Cellulosic biofuel is the subject of increasing attention. The main obstacle toward its economic feasibility is the recalcitrance of lignocellulose requiring large amount of enzyme to break. Several engineered yeast strains have been developed with cellulolytic activities to reduce the need for enzyme addition, but exhibiting limited effect. Here, we report the successful engineering of a cellulose-adherent Saccharomyces cerevisiae displaying four different synergistic cellulases on the cell surface. The cellulase-displaying yeast strain exhibited clear cell-to-cellulose adhesion and a "tearing" cellulose degradation pattern; the adhesion ability correlated with enhanced surface area and roughness of the target cellulose fibers, resulting in higher hydrolysis efficiency. The engineered yeast directly produced ethanol from rice straw despite a more than 40% decrease in the required enzyme dosage for high-density fermentation. Thus, improved cell-to-cellulose interactions provided a novel strategy for increasing cellulose hydrolysis, suggesting a mechanism for promoting the feasibility of cellulosic biofuel production.

  6. Effects of microcrystalline cellulose based comilled powder on the compression and dissolution of ibuprofen.

    PubMed

    Mallick, Subrata; Pradhan, Saroj K; Mohapatra, Rajaram

    2013-09-01

    Ibuprofen is a poorly soluble and poorly compressible drug and is unsuitable for "direct tableting". Microcrystalline cellulose (Avicel(®) PH 101) based ibuprofen powder formulations have been comilled in presence of Aerosil(®) (colloidal silicon dioxide) as lubricant, and the total compression behavior was evaluated using the Cooper-Eaton equation. Scanning electron microscopy (SEM) revealed about the damage of crystal geometry of the crystalline drug after comilling. Differential scanning calorimetry (DSC) indicated decrease of melting endotherm (partially) attributing to the decrease in crystalline intensity of ibuprofen upon comilling. Small changes in the infrared spectra such as shift of characteristic bands, reduction in intensity, and appearance of new bands are mainly related to the possible physical interaction and/or amorphization of the drug in the comilled mixtures. Increased compaction can be achieved after milling of the microcrystalline cellulose based blends. Milling decreased particle size and improved wettability of the drug and increased dissolution. Microcrystalline cellulose based comilled ibuprofen powder with improved compression and dissolution may be taken as a future scope of scale up for "direct tableting".

  7. Lytic polysaccharide monooxygenases disrupt the cellulose fibers structure

    PubMed Central

    Villares, Ana; Moreau, Céline; Bennati-Granier, Chloé; Garajova, Sona; Foucat, Loïc; Falourd, Xavier; Saake, Bodo; Berrin, Jean-Guy; Cathala, Bernard

    2017-01-01

    Lytic polysaccharide monooxygenases (LPMOs) are a class of powerful oxidative enzymes that breakdown recalcitrant polysaccharides such as cellulose. Here we investigate the action of LPMOs on cellulose fibers. After enzymatic treatment and dispersion, LPMO-treated fibers show intense fibrillation. Cellulose structure modifications visualized at different scales indicate that LPMO creates nicking points that trigger the disintegration of the cellulose fibrillar structure with rupture of chains and release of elementary nanofibrils. Investigation of LPMO action using solid-state NMR provides direct evidence of modification of accessible and inaccessible surfaces surrounding the crystalline core of the fibrils. The chains breakage likely induces modifications of the cellulose network and weakens fibers cohesion promoting their disruption. Besides the formation of new initiation sites for conventional cellulases, this work provides the first evidence of the direct oxidative action of LPMOs with the mechanical weakening of the cellulose ultrastructure. LPMOs can be viewed as promising biocatalysts for enzymatic modification or degradation of cellulose fibers. PMID:28071716

  8. Lytic polysaccharide monooxygenases disrupt the cellulose fibers structure.

    PubMed

    Villares, Ana; Moreau, Céline; Bennati-Granier, Chloé; Garajova, Sona; Foucat, Loïc; Falourd, Xavier; Saake, Bodo; Berrin, Jean-Guy; Cathala, Bernard

    2017-01-10

    Lytic polysaccharide monooxygenases (LPMOs) are a class of powerful oxidative enzymes that breakdown recalcitrant polysaccharides such as cellulose. Here we investigate the action of LPMOs on cellulose fibers. After enzymatic treatment and dispersion, LPMO-treated fibers show intense fibrillation. Cellulose structure modifications visualized at different scales indicate that LPMO creates nicking points that trigger the disintegration of the cellulose fibrillar structure with rupture of chains and release of elementary nanofibrils. Investigation of LPMO action using solid-state NMR provides direct evidence of modification of accessible and inaccessible surfaces surrounding the crystalline core of the fibrils. The chains breakage likely induces modifications of the cellulose network and weakens fibers cohesion promoting their disruption. Besides the formation of new initiation sites for conventional cellulases, this work provides the first evidence of the direct oxidative action of LPMOs with the mechanical weakening of the cellulose ultrastructure. LPMOs can be viewed as promising biocatalysts for enzymatic modification or degradation of cellulose fibers.

  9. Relative Crystallinity of Plant Biomass: Studies on Assembly, Adaptation and Acclimation

    PubMed Central

    Harris, Darby; DeBolt, Seth

    2008-01-01

    Plant biomechanical design is central to cell shape, morphogenesis, reproductive performance and protection against environmental and mechanical stress. The cell wall forms the central load bearing support structure for plant design, yet a mechanistic understanding of its synthesis is incomplete. A key tool for studying the structure of cellulose polymorphs has been x-ray diffraction and fourier transform infrared spectroscopy (FTIR). Relative crystallinity index (RCI) is based on the x-ray diffraction characteristics of two signature peaks and we used this technique to probe plant assembly, adaptation and acclimation. Confocal microscopy was used to visualize the dynamics of cellulose synthase in transgenic Arabidopsis plants expressing a homozygous YFP::CESA6. Assembly: RCI values for stems and roots were indistinguishable but leaves had 23.4 and 21.6% lower RCI than stems and roots respectively. Adaptation: over 3-fold variability in RCI was apparent in leaves from 35 plant species spanning Ordovician to Cretaceous periods. Within this study, RCI correlated positively with leaf geometric constraints and with mass per unit area, suggestive of allometry. Acclimation: biomass crystallinity was found to decrease under conditions of thigmomorphogenesis in Arabidopsis. Further, in etiolated pea hypocotyls, RCI values also decreased compared to plants that were grown in light, consistent with alterations in FTIR cellulose fingerprint peaks and live cell imaging experiments revealing rapid orientation of the YFP::cellulose synthase-6 array in response to light. Herein, results and technical challenges associated with the structure of the cell wall that gives rise to sample crystallinity are presented and examined with respect to adaptation, acclimation and assembly in ecosystem-level processes. PMID:18682826

  10. Cellulose fibers extracted from rice and oat husks and their application in hydrogel.

    PubMed

    Oliveira, Jean Paulo de; Bruni, Graziella Pinheiro; Lima, Karina Oliveira; Halal, Shanise Lisie Mello El; Rosa, Gabriela Silveira da; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

    2017-04-15

    The commercial cellulose fibers and cellulose fibers extracted from rice and oat husks were analyzed by chemical composition, morphology, functional groups, crystallinity and thermal properties. The cellulose fibers from rice and oat husks were used to produce hydrogels with poly (vinyl alcohol). The fibers presented different structural, crystallinity, and thermal properties, depending on the cellulose source. The hydrogel from rice cellulose fibers had a network structure with a similar agglomeration sponge, with more homogeneous pores compared to the hydrogel from oat cellulose fibers. The hydrogels prepared from the cellulose extracted from rice and oat husks showed water absorption capacity of 141.6-392.1% and high opacity. The highest water absorption capacity and maximum stress the compression were presented by rice cellulose hydrogel at 25°C. These results show that the use of agro-industrial residues is promising for the biomaterial field, especially in the preparation of hydrogels.

  11. Mechanical and structural property analysis of bacterial cellulose composites.

    PubMed

    Dayal, Manmeet Singh; Catchmark, Jeffrey M

    2016-06-25

    Bacterial cellulose (BC) exhibits unique properties including high mechanical strength and high crystallinity. Improvement in the mechanical properties of BC is sought for many applications ranging from food to structural composites to biomedical materials. In this study, different additives including carboxymethyl cellulose (CMC), pectin, gelatin, cornstarch, and corn steep liquor were included in the fermentation media to alter the BC produced. Three different concentrations (1%, 3% and 5%) were chosen for each of the additives, with no additive (0%) as the control. The produced BC was then analyzed to determine tensile and compression modulus. Amongst the tested additives, BC produced in media containing 3% (w/v) pectin had the maximum compressive modulus (142kPa), and BC produced in media containing 1% (w/v) gelatin exhibited the maximum tensile modulus (21MPa). Structural characteristics of BC and BC-additive composites were compared using X-Ray diffraction (XRD). The crystal size and crystallinity of BC was reduced when grown in the presence of CMC and gelatin while pectin only decreased the crystallite size. This suggested that CMC and gelatin may be incorporated into the BC fibril structure. The field emission scanning electron microscopy (FESEM) images showed the increased micro-fibril aggregation in BC pellicles grown in the presence of additives to the culture media.

  12. Laser cleaning of particulates from paper: Comparison between sized ground wood cellulose and pure cellulose

    NASA Astrophysics Data System (ADS)

    Arif, S.; Kautek, W.

    2013-07-01

    Visible laser cleaning of charcoal particulates from yellow acid mechanical ground wood cellulose paper was compared with that from bleached sulphite softwood cellulose paper. About one order of magnitude of fluence range is available for a cleaning dynamics between the cleaning threshold and the destruction threshold for two laser pulses. Wood cellulose paper exhibited a higher destruction threshold of the original paper than that of the contaminated specimen because of heat transfer from the hot or evaporating charcoal particulates. In contrast, the contaminated bleached cellulose paper exhibited a higher destruction threshold due to shading by the particulates. The graphite particles are not only detached thermo-mechanically, but also by evaporation or combustion. A cleaning effect was found also outside the illuminated areas due to lateral blasting. Infrared measurements revealed dehydration/dehydrogenation reactions and cross-links by ether bonds together with structural changes of the cellulose chain arrangement and the degree of crystallinity.

  13. CRYSTALLINE DESOXYRIBONUCLEASE

    PubMed Central

    Kunitz, M.

    1950-01-01

    A crystalline enzyme capable of digesting thymus nucleic acid (desoxyribonucleic acid) has been isolated from fresh beef pancreas. The enzyme called "desoxyribonuclease" is a protein of the albumin type. Its molecular weight is about 60,000 and its isoelectric point is near pH 5.0. It contains about 8 per cent tyrosine and 2 per cent tryptophane. It is readily denatured by heat. The denaturation is reversible if heated in dilute acid at pH about 3.0. The digestion of thymus nucleic acid by crystalline desoxyribonuclease is accompanied by a gradual increase in the specific absorption of ultraviolet light by the acid. The spectrophotometric measurement of the rate of increase in the light absorption can be conveniently used as a general method for estimating desoxyribonuclease activity. Details are given of the method for isolation of crystalline desoxyribonuclease and of the spectrophotometric procedure for the measurement of desoxyribonuclease activity. PMID:15406373

  14. Crystalline Membranes

    NASA Technical Reports Server (NTRS)

    Tsapatsis, Michael (Inventor); Lai, Zhiping (Inventor)

    2008-01-01

    In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.

  15. Novel method for producing amorphous cellulose only by milling.

    PubMed

    Shimura, Ryoichiro; Nishioka, Akihiro; Kano, Ichiro; Koda, Tomonori; Nishio, Taichi

    2014-02-15

    The present study investigated a novel method for producing amorphous cellulose by milling without adding water. A new type of milling machine was developed (called a shear and cooling milling machine (SCMM)), which was capable of applying mechanical shear and cooling during the milling process. The SCMM consisted of a pair of mortars attached to a servomotor and a ring cooler. Wide-angle X-ray diffraction (WAXD) analysis was used to determine the cellulose crystallinity in samples produced using the SCMM at different milling temperatures. The results of WAXD for cellulose powder milled at lower temperatures exhibited no diffraction peaks. This experimental result demonstrates that the SCMM produces amorphous cellulose easily by cooled milling without the addition of water. The milling conditions, such as the applied shear and cooling, can be used to control the crystallinity of cellulose.

  16. Modeling of Carbohydrate Binding Modules Complexed to Cellulose

    SciTech Connect

    Nimlos, M. R.; Beckham, G. T.; Bu, L.; Himmel, M. E.; Crowley, M. F.; Bomble, Y. J.

    2012-01-01

    Modeling results are presented for the interaction of two carbohydrate binding modules (CBMs) with cellulose. The family 1 CBM from Trichoderma reesei's Cel7A cellulase was modeled using molecular dynamics to confirm that this protein selectively binds to the hydrophobic (100) surface of cellulose fibrils and to determine the energetics and mechanisms for locating this surface. Modeling was also conducted of binding of the family 4 CBM from the CbhA complex from Clostridium thermocellum. There is a cleft in this protein, which may accommodate a cellulose chain that is detached from crystalline cellulose. This possibility is explored using molecular dynamics.

  17. Cellulose Insulation

    NASA Technical Reports Server (NTRS)

    1980-01-01

    Fire retardant cellulose insulation is produced by shredding old newspapers and treating them with a combination of chemicals. Insulating material is blown into walls and attics to form a fiber layer which blocks the flow of air. All-Weather Insulation's founders asked NASA/UK-TAP to help. They wanted to know what chemicals added to newspaper would produce an insulating material capable of meeting federal specifications. TAP researched the query and furnished extensive information. The information contributed to successful development of the product and helped launch a small business enterprise which is now growing rapidly.

  18. Use of cellobiohydrolase-free cellulase blends for the hydrolysis of microcrystalline cellulose and sugarcane bagasse pretreated by either ball milling or ionic liquid [Emim][Ac].

    PubMed

    Teixeira, Ricardo Sposina Sobral; da Silva, Ayla Sant'Ana; Kim, Han-Woo; Ishikawa, Kazuhiko; Endo, Takashi; Lee, Seung-Hwan; Bon, Elba P S

    2013-12-01

    This study investigated the requirement of cellobiohydrolases (CBH) for saccharification of microcrystalline cellulose and sugarcane bagasse pretreated either by ball milling (BM) or by ionic liquid (IL) [Emim][Ac]. Hydrolysis was done using CBH-free blends of Pyrococcus horikoshii endoglucanase (EG) plus Pyrococcus furiosus β-glucosidase (EGPh/BGPf) or Optimash™ BG while Acremonium Cellulase was used as control. IL-pretreated substrates were hydrolyzed more effectively by CBH-free enzymes than were the BM-pretreated substrates. IL-treatment decreased the crystallinity and increased the specific surface area (SSA), whereas BM-treatment decreased the crystallinity without increasing the SSA. The hydrolysis of IL-treated cellulose by EGPh/BGPf showed a saccharification rate of 3.92 g/Lh and a glucose yield of 81% within 9h. These results indicate the efficiency of CBH-free enzymes for the hydrolysis of IL-treated substrates.

  19. Investigation of griseofulvin and hydroxypropylmethyl cellulose acetate succinate miscibility in ball milled solid dispersions.

    PubMed

    Al-Obaidi, Hisham; Lawrence, M Jayne; Al-Saden, Noor; Ke, Peng

    2013-02-25

    Solid dispersions of varying weight ratios compositions of the nonionic drug, griseofulvin and the hydrophilic, anionic polymer, hydroxylpropylmethyl cellulose acetate succinate, have been prepared by ball milling and the resulting samples characterized using a combination of Fourier transform infra-red spectroscopy, X-ray powder diffraction and differential scanning calorimetry. The results suggest that griseofulvin forms hydrogen bonds with the hydroxylpropylmethyl cellulose acetate succinate polymer when prepared in the form of a solid dispersion but not when prepared in a physical mixture of the same composition. As anticipated, the actual measured glass transition temperature of the solid dispersions displayed a linear relationship between that predicted using the Gordon-Taylor and Fox equations assuming ideal mixing, but interestingly only at griseofulvin contents less than 50 wt%. At griseofulvin concentrations greater than this, the measured glass transition temperature of the solid dispersions was almost constant. Furthermore, the crystalline content of the solid dispersions, as determined by differential scanning calorimetry and X-ray powder diffraction followed a similar trend in that the crystalline content significantly decreased at ratios less than 50 wt% of griseofulvin. When the physical mixtures of griseofulvin and the hydroxylpropylmethyl cellulose acetate succinate polymer were analyzed using the Flory-Huggins model, a negative free energy of mixing with an interaction parameter of -0.23 were obtained. Taken together these results suggest that anionic hydrophilic hydroxylpropylmethyl cellulose acetate succinate polymer is a good solvent for crystalline nonionic griseofulvin with the solubility of griseofulvin in the solid dispersion being was estimated to be within the range 40-50 wt%. Below this solubility limit, the amorphous drug exists as amorphous glassy solution while above these values the system is supersaturated and glassy suspension and

  20. Manganese-containing cellulose nanocomposites: the restrain effect of cellulose treated with NaOH/urea aqueous solutions.

    PubMed

    Ma, Ming-Guo; Deng, Fu; Yao, Ke

    2014-10-13

    In this article, the manganese-containing cellulose nanocomposites were obtained using microcrystalline cellulose and Mn(CH3COO)2 · 4H2O in the NaOH/urea aqueous solutions by a efficient microwave-assisted method. The effects of the heating time and Mn(CH3COO)2 · 4H2O concentration on the cellulose nanocomposites were investigated. It was found that the microcrystalline cellulose pretreated with NaOH/urea aqueous solutions played an important role in the phase, shape, and thermal stability of manganese-containing cellulose nanocomposites. Well-crystalline phases of manganese oxides were not observed in the manganese-containing cellulose nanocomposites. Furthermore, well-crystalline phases of manganese oxides were not also observed by thermal treatment of the manganese-containing cellulose nanocomposites at 600 °C for 3h. These results could be attributed to the restrain effect of cellulose treated with NaOH/urea aqueous solutions. It was supposed the possible mechanism during the phase transformation of cellulose nanocomposites.

  1. Depolymerization of microcrystalline cellulose by the combination of ultrasound and Fenton reagent.

    PubMed

    Zhang, Mei-Fang; Qin, Yuan-Hang; Ma, Jia-Yu; Yang, Li; Wu, Zai-Kun; Wang, Tie-Lin; Wang, Wei-Guo; Wang, Cun-Wen

    2016-07-01

    In this study, the combined use of Fenton reagent and ultrasound to the pretreatment of microcrystalline cellulose (MCC) for subsequent enzyme hydrolysis was investigated. The morphological analysis showed that the aspect ratio of MCC was greatly reduced after pretreatment. The X-ray diffraction (XRD) and degree of polymerization (DP) analyses showed that Fenton reagent was more efficient in decreasing the crystallinity of MCC while ultrasound was more efficient in decreasing the DP of MCC. The combination of Fenton reaction and ultrasound, which produced the lowest crystallinity (84.8 ± 0.2%) and DP (124.7 ± 0.6) of MCC and the highest yield of reducing sugar (22.9 ± 0.3 g/100 g), provides a promising pretreatment process for MCC depolymerization.

  2. Clean conversion of cellulose into fermentable glucose.

    PubMed

    Sun, Yong; Zhuang, Junping; Lin, Lu; Ouyang, Pingkai

    2009-01-01

    We studied the process of conversion of microcrystalline-cellulose into fermentable glucose in the formic acid reaction system using cross polarization/magic angle spinning (13)C-nuclear magnetic resonance, X-ray diffraction and Fourier transform infrared spectroscopy. The results indicated that formic acid as an active agent was able to effectively penetrate into the interior space of the cellulose molecules, thus collapsing the rigid crystalline structure and allowing hydrolysis to occur easily in the amorphous zone as well as in the crystalline zone. The microcrystalline-cellulose was hydrolyzed using formic acid and 4% hydrochloric acid under mild conditions. The effects of hydrochloric acid concentration, the ratio of solid to liquid, temperature (55-75 degrees C) and retention time (0-9 h), and the concentration of glucose were analyzed. The hydrolysis velocities of microcrystalline-cellulose were 6.14 x 10(-3) h(-1) at 55 degrees C, 2.94 x 10(-2) h(-1) at 65 degrees C, and 6.84x10(-2) h(-1) at 75 degrees C. The degradation velocities of glucose were 0.01 h(-1) at 55 degrees C, 0.14 h(-1) at 65 degrees C, 0.34 h(-1) at 75 degrees C. The activation energy of microcrystalline-cellulose hydrolysis was 105.61 kJ/mol, and the activation energy of glucose degradation was 131.37 kJ/mol.

  3. Evaluation of cellulose and carboxymethyl cellulose/poly(vinyl alcohol) membranes.

    PubMed

    Ibrahim, Maha M; Koschella, Andreas; Kadry, Ghada; Heinze, Thomas

    2013-06-05

    Cellulose was isolated from rice straw and converted to carboxymethyl cellulose (CMC). Both polymers were crosslinked with poly(vinyl alcholo) (PVA). The physical properties of the resulting membranes were characterized by FT-IR, TGA, DSC and SEM. The cellulose and CMC were first prepared from bleached rice straw pulp. The infrared spectroscopy of the resulting polymer membranes indicated a decrease in the absorbance of the OH group at 3300-3400 cm(-1), which is due to bond formation with either the cellulose or CMC with the PVA. The thermal stability of PVA/cellulose and PVA/CMC membranes was lower than PVA membrane. The surface of the resulting polymer membranes showed smooth surface in case of the PVA/CMC membrane and rough surface in case of the PVA/cellulose membrane. Desalination test, using 0.2% NaCl, showed that pure PVA membranes had no effect while membranes containing either cellulose or CMC as filler were able to decrease the content of the NaCl from the solution by 25% and 15%, respectively. Transport properties, including water and chloroform vapor were studied. The moisture transport was reduced by the presence of both cellulose and CMC. Moreover, the membranes containing cellulose and CMC showed significantly reduced flux compared to the pure PVA. The water sorption, solubility and soaking period at different pH solutions were also studied and showed that the presence of both cellulose and CMC influences the properties.

  4. Pretreatment assisted synthesis and characterization of cellulose nanocrystals and cellulose nanofibers from absorbent cotton.

    PubMed

    Abu-Danso, Emmanuel; Srivastava, Varsha; Sillanpää, Mika; Bhatnagar, Amit

    2017-03-30

    In this work, cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) were synthesized from absorbent cotton. Two pretreatments viz. dewaxing and bleaching with mild alkali were applied to the precursor (cotton). Acid hydrolysis was conducted with H2SO4 and dissolution of cotton was achieved with a mixture of NaOH-thiourea-urea-H2O at -3°C. Synthesized cellulose samples were characterized using FTIR, XRD, SEM, BET, and zeta potential. It seems that synthesis conditions contributed to negative surface charge on cellulose samples and CNCs had the higher negative surface charge compared to CNFs. Furthermore, BET surface area, pore volume and pore diameter of CNCs were found to be higher as compared to CNFs. The dewaxed cellulose nanofibers (CNF D) had a slightly higher BET surface area (0.47m(2)/g) and bigger pore diameter (59.87Å) from attenuated contraction compared to waxed cellulose nanofibers (CNFW) (0.38m(2)/g and 44.89Å). The XRD of CNCs revealed a semi-crystalline structure and the dissolution agents influenced the crystallinity of CNFs. SEM images showed the porous nature of CNFs, the flaky nature and the nano-sized width of CNCs. Synthesized CNF D showed a better potential as an adsorbent with an average lead removal efficiency of 91.49% from aqueous solution.

  5. Properties of polylactic acid composites reinforced with oil palm biomass microcrystalline cellulose.

    PubMed

    Haafiz, M K Mohamad; Hassan, Azman; Zakaria, Zainoha; Inuwa, I M; Islam, M S; Jawaid, M

    2013-10-15

    In this work, polylactic acid (PLA) composites filled with microcrystalline cellulose (MCC) from oil palm biomass were successfully prepared through solution casting. Fourier transform infrared (FT-IR) spectroscopy indicates that there are no significant changes in the peak positions, suggesting that incorporation of MCC in PLA did not result in any significant change in chemical structure of PLA. Thermogravimetric analysis was conducted on the samples. The T50 decomposition temperature improved with addition of MCC, showing increase in thermal stability of the composites. The synthesized composites were characterized in terms of tensile properties. The Young's modulus increased by about 30%, while the tensile strength and elongation at break for composites decreased with addition of MCC. Scanning electron microscopy (SEM) of the composites fractured surface shows that the MCC remained as aggregates of crystalline cellulose. Atomic force microscopy (AFM) topographic image of the composite surfaces show clustering of MCC with uneven distribution.

  6. Pretreatment for cellulose hydrolysis by carbon dioxide explosion

    SciTech Connect

    Zheng, Y.; Lin, H.M.; Tsao, G.T.

    1998-11-01

    Cellulosic materials were treated with supercritical carbon dioxide to increase the reactivity of cellulose, thereby to enhance the rate and the extent of cellulose hydrolysis. In this pretreatment process, the cellulosic materials such as Avicel, recycled paper mix, sugarcane bagasse and the repulping waste of recycled paper are placed in a reactor under pressurized carbon dioxide at 35 C for a controlled time period. Upon an explosive release of the carbon dioxide pressure, the disruption of the cellulosic structure increases the accessible surface area of the cellulosic substrate to enzymatic hydrolysis. Results indicate that supercritical carbon dioxide is effective for pretreatment of cellulose. An increase in pressure facilitates the faster penetration of carbon dioxide molecules into the crystalline structures, thus more glucose is produced from cellulosic materials after the explosion as compared to those without the pretreatment. This explosion pretreatment enhances the rate of cellulosic material hydrolysis as well as increases glucose yield by as much as 50%. Results from the simultaneous saccharification and fermentation tests also show the increase in the available carbon source from the cellulosic materials for fermentation to produce ethanol. As an alternative method, this supercritical carbon dioxide explosion has a possibility to reduce expense compared with ammonia explosion, and since it is operated at the low temperature, it will not cause degradation of sugars such as those treated with steam explosion due to the high-temperature involved.

  7. Langmuir-Blodgett films of cellulose nanocrystals: preparation and characterization.

    PubMed

    Habibi, Youssef; Foulon, Laurence; Aguié-Béghin, Véronique; Molinari, Michaël; Douillard, Roger

    2007-12-15

    The goal of this work is the preparation of monolayers of cellulose I nanocrystals providing flat crystalline cellulose surfaces. Suspensions of cellulose nanocrystals were prepared by hydrolyzing ramie and tunicin fibers with sulfuric acid. Due to surface grafted sulfate groups, the negatively charged, rod-like cellulose nanocrystals were found to form stable layers at the air-water interface in the presence of a cationic amphiphilic molecule such as dioctadecyldimethylammonium (DODA) used in this work. These layers were formed at different cellulose-DODA weight ratios, compressed and analyzed by tensiometry, ellipsometry and Brewster angle microscopy. At low cellulose concentrations the layers are discontinuous, becoming dense and homogeneous upon reaching a critical weight ratio, which depends on the aspect ratio of the cellulose nanocrystals. After transfer onto silicon wafers, the surface composition and morphology as well as the thickness of the films were examined by X-ray photoelectron spectroscopy, ellipsometry and atomic force microscopy. The results indicate that they are monolayer films, well structured, relatively smooth and pure. These films offer a crystalline and easily reproducible model cellulose surface.

  8. Does the Cellulose-Binding Module Move on the Cellulose Surface?

    SciTech Connect

    Liu, Y. S.; Zeng, Y.; Luo, Y.; Xu, Q.; Himmel, M. E.; Smith, S. J.; Ding, S. Y.

    2009-01-01

    Exoglucanases are key enzymes required for the efficient hydrolysis of crystalline cellulose. It has been proposed that exoglucanases hydrolyze cellulose chains in a processive manner to produce primarily cellobiose. Usually, two functional modules are involved in the processive mechanism: a catalytic module and a carbohydrate-binding module (CBM). In this report, single molecule tracking techniques were used to analyze the molecular motion of CBMs labeled with quantum dots (QDs) and bound to cellulose crystals. By tracking the single QD, we observed that the family 2 CBM from Acidothermus cellulolyticus (AcCBM2) exhibited linear motion along the long axis of the cellulose fiber. This apparent movement was observed consistently when different concentrations (25 {micro}M to 25 nM) of AcCBM2 were used. Although the mechanism of AcCBM2 motion remains unknown, single-molecule spectroscopy has been demonstrated to be a promising tool for acquiring new fundamental understanding of cellulase action.

  9. Cellulose metabolism in plants.

    PubMed

    Hayashi, Takahisa; Yoshida, Kouki; Park, Yong Woo; Konishi, Teruko; Baba, Kei'ichi

    2005-01-01

    Many bacterial genomes contain a cellulose synthase operon together with a cellulase gene, indicating that cellulase is required for cellulose biosynthesis. In higher plants, there is evidence that cell growth is enhanced by the overexpression of cellulase and prevented by its suppression. Cellulase overexpression could modify cell walls not only by trimming off the paracrystalline sites of cellulose microfibrils, but also by releasing xyloglucan tethers between the microfibrils. Mutants for membrane-anchored cellulase (Korrigan) also show a typical phenotype of prevention of cellulose biosynthesis in tissues. All plant cellulases belong to family 9, which endohydrolyzes cellulose, but are not strong enough to cause the bulk degradation of cellulose microfibrils in a plant body. It is hypothesized that cellulase participates primarily in repairing or arranging cellulose microfibrils during cellulose biosynthesis in plants. A scheme for the roles of plant cellulose and cellulases is proposed.

  10. The effect of different anti-solvent and coconut shell content on properties of coconut shell regenerated cellulose biocomposite films

    NASA Astrophysics Data System (ADS)

    Hahary, Farah Norain; Husseinsyah, Salmah; Mostapha@Zakaria, Marliza

    2016-07-01

    In this study, coconut shell (CS) regenerated cellulose (RC) biocomposite films was prepared using dimethylacetamide/lithium chloride (DMAc/LiCl) solvent system. The effect of anti-solvents such as water and methanol for regeneration of cellulose and coconut shell content on properties of CS-RC biocomposite films was investigated. The used of water as anti-solvent for cellulose regeneration was found to have higher tensile properties compared to regenerated cellulose using methanol. Besides, the X-Ray diffraction (XRD) analysis also revealed that RC using water as anti-solvent have higher crystallinity index (CrI) than CS-RC biocomposite film using methanol. The tensile strength and modulus elasticity of CS-RC biocomposite films increased up to 3 wt% CS and decreased with further addition of CS. The elongation at break of CS-RC biocomposite films decreased with the increment of CS. The CrI of CS-RC bioocmposite films up to 3 wt% and decreased with at higher content of CS.

  11. Isolation and characterization of cellulose nanocrystals from parenchyma and vascular bundle of oil palm trunk (Elaeis guineensis).

    PubMed

    Lamaming, Junidah; Hashim, Rokiah; Leh, Cheu Peng; Sulaiman, Othman; Sugimoto, Tomoko; Nasir, Mohammed

    2015-12-10

    In this study cellulose nanocrystals were isolated through acid hydrolysis process from parenchyma and vascular bundle of oil palm trunk (Elaeis guineensis). The morphological properties of obtained cellulose nanocrystals were studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The microscopy images showed smoother and cleaner surface of parenchyma cellulose nanocrystals when compared to vascular bundle cellulose nanocrystals. The TEM image shows a higher length and diameter for parenchyma cellulose nanocrystals compared to vascular bundle cellulose nanocrystals. The Fourier transform infrared (FTIR) spectra showed changes in functional groups after acid hydrolysis due to removal of lignin, hemicelluloses and other impurities in both type of cellulose nanocrystals. Crystallinity index of cellulose nanocrystals was observed higher for vascular bundle as compared to parenchyma. Thermogravimetric analysis (TGA) was performed to study the thermal stability of cellulose nanocrystals and it was observed higher for parenchyma cellulose nanocrystals compared to vascular bundle.

  12. Poly(methyl methacrylate)-cellulose nitrate copolymers. I. Preparation

    SciTech Connect

    Badran, B.M.; Sherif, S.; Abu-Sedira, A.A.

    1981-03-01

    Poly(methyl methacrylate)-cellulose nitrate copolymers were prepared in the form of rods and sheets by bulk polymerization using benzoyl peroxide as initiator. Suspension polymerization did not succeed in preparing poly(methyl methacrylate)-cellulose nitrate copolymers, especially when cellulose nitrate of 11.4% nitrogen content was used. The parameters such as cellulose nitrate concentration, nitrogen content of cellulose nitrate, the amount of initiator and the reaction time, and the temperature are discussed. The prepared copolymers were irradiated for specified periods of up to 11.83 Mrad. It was found that poly(methyl methacrylate)-cellulose nitrate copolymers did not dissolve in any conventional solvent, but they swelled. Swelling decreases with increasing cellulose nitrate concentrations, nitrogen content of cellulose nitrate, and irradiation dose, indicating the crosslinked structure of the prepared copolymers.

  13. Dielectric barrier discharge plasma pretreatment on hydrolysis of microcrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Fangmin, HUANG; Zhouyang, LONG; Sa, LIU; Zhenglong, Qin

    2017-04-01

    Dielectric barrier discharge (DBD) plasma was used as a pretreatment method for downstream hydrolysis of microcrystalline cellulose (MCC). The degree of polymerization (DP) of MCC decreased after it was pretreated by DBD plasma under a carrier gas of air/argon. The effectiveness of depolymerization was found to be influenced by the crystallinity of MCC when under the pretreatment of DBD plasma. With the addition of tert-butyl alcohol in the treated MCC water suspension solution, depolymerization effectiveness of MCC was inhibited. When MCC was pretreated by DBD plasma for 30 min, the total reducing sugar concentration (TRSC) and liquefaction yield (LY) of pretreated-MCC (PMCC) increased by 82.98% and 34.18% respectively compared with those for raw MCC.

  14. Reconstitution of cellulose and lignin after [C2mim][OAc] pretreatment and its relation to enzymatic hydrolysis.

    PubMed

    Yuan, Tong-Qi; Wang, Wei; Zhang, Li-Ming; Xu, Feng; Sun, Run-Cang

    2013-03-01

    Although the effects of cellulose crystallinity and lignin content as two major structural features on enzymatic hydrolysis have been extensively studied, debates regarding their effects still exist. In this study, reconstitution of cellulose and lignin after 1-ethyl-3-methylimidazolium acetate ([C(2)mim][OAc]) pretreatment was proposed as a new method to study their effects on enzymatic digestibility. Different mechanisms of lignin content for reduction of cellulose hydrolysis were found between the proposed method and the traditional method (mixing of cellulose and lignin). The results indicated that a slight change of the crystallinity of the reconstituted materials may play a minor role in the change of enzyme efficiency. In addition, the present study suggested that the lignin content does not significantly affect the digestibility of cellulose, whereas the conversion of cellulose fibers from the cellulose I to the cellulose II crystal phase plays an important role when an ionic liquid pretreatment of biomass was conducted.

  15. Mitigation of Cellulose Recalcitrance to Enzymatic Hydrolysis by Ionic Liquid Pretreatment

    NASA Astrophysics Data System (ADS)

    Dadi, Anantharam P.; Schall, Constance A.; Varanasi, Sasidhar

    Efficient hydrolysis of cellulose-to-glucose is critically important in producing fuels and chemicals from renewable feedstocks. Cellulose hydrolysis in aqueous media suffers from slow reaction rates because cellulose is a water-insoluble crystalline biopolymer. The high-crystallinity of cellulose fibrils renders the internal surface of cellulose inaccesible to the hydrolyzing enzymes (cellulases) as well as water. Pretreatment methods, which increase the surface area accessible to water and cellulases are vital to improving the hydrolysis kinetics and conversion of cellulose to glucose. In a novel technique, the microcrystalline cellulose was first subjected to an ionic liquid (IL) treatment and then recovered as essentially amorphous or as a mixture of amorphous and partially crystalline cellulose by rapidly quenching the solution with an antisolvent. Because of their extremely low-volatility, ILs are expected to have minimal environmental impact. Two different ILs, 1-n-butyl-3-methylimidazolium chloride (BMIMCI) and 1-allyl-3-methylimidazolium chloride (AMIMC1) were investigated. Hydrolysis kinetics of the IL-treated cellulose is significantly enhanced. With appropriate selection of IL treatment conditions and enzymes, the intial hydrolysis rates for IL-treated cellulose were up to 90 times greater than those of untreated cellulose. We infer that this drastic improvement in the "overall hydrolysis rates" with IL-treated cellulose is mainly because of a significant enhancement in the kinetics of the "primary hydrolysis step" (conversion of solid cellulose to soluble oligomers), which is the rate-limiting step for untreated cellulose. Thus, with IL-treated cellulose, primary hydrolysis rates increase and become comparable with the rates of inherently faster "secondary hydrolysis" (conversion of soluble oligomers to glucose).

  16. Influence of Hydroxypropyl Methylcellulose on Metronidazole Crystallinity in Spray-Congealed Polyethylene Glycol Microparticles and Its Impact with Various Additives on Metronidazole Release.

    PubMed

    Oh, Ching Mien; Heng, Paul Wan Sia; Chan, Lai Wah

    2015-12-01

    The purpose of this study was to investigate the effect of a hydrophilic polymer, hydroxypropyl methylcellulose (HPMC), on the crystallinity and drug release of metronidazole (MNZ) in spray-congealed polyethylene glycol (PEG) microparticles and to further modify the drug release using other additives in the formulation. HPMC has been used in many pharmaceutical formulations and processes but to date, it has not been employed as an additive in spray congealing. Crystallinity of a drug is especially important to the development of pharmaceutical products as active pharmaceutical ingredients (APIs) are mostly crystalline in nature. A combination of X-ray diffractometry, differential scanning calorimetry, Raman spectroscopy and Fourier transform-infrared spectroscopy (FT-IR) spectroscopy was employed to investigate the degree of crystallinity and possible solid-state structure of MNZ in the microparticles. The microparticles with HPMC were generally spherical. Spray congealing decreased MNZ crystallinity, and the presence of HPMC reduced the drug crystallinity further. The reduction in MNZ crystallinity was dependent on the concentration of HPMC. Smaller HPMC particles also resulted in a greater percentage reduction in MNZ crystallinity. Appreciable modification to MNZ release could be obtained with HPMC. However, this was largely attributed to the role of HPMC in forming a diffusion barrier. Further modification of drug release from spray-congealed PEG-HPMC microparticles was achieved with the addition of 5% w/w dicalcium phosphate but not with magnesium stearate, methyl cellulose, polyvinylpyrrolidone, silicon dioxide and sodium oleate/citric acid. Dicalcium phosphate facilitated formation of the diffusion barrier.

  17. Magnetic and electric field alignments of cellulose chains for electro-active paper actuator

    NASA Astrophysics Data System (ADS)

    Yun, Sungryul; Chen, Yi; Lee, Sang Woo; Kim, Jaehwan; Kim, Heung Soo

    2008-03-01

    To improve the piezoelectricity of cellulose electro-active paper (EAPap), electrical field and magnetic field alignments were investigated. EAPap is made with cellulose by dissolving cotton pulp and regenerating cellulose with aligned cellulose fibers. EAPap made with cellulose has piezoelectric property due to its structural crystallinity. Noncentro-symmetric crystal structure of EAPap, which is mostly cellulose II, can exhibit piezoelectricity. However, EAPap has ordered crystal parts as well as disordered parts of cellulose. Thus, well alignment of cellulose chains in EAPap is important to improve its piezoelectricity. In this paper, uniaxial alignments of cellulose chains were investigated by applying electric field and magnetic field. As exposing different fields to EAPap samples, the changed characteristics were analyzed by X-Ray diffractometer (XRD) and Scanning electron microscopy (SEM). Finally, the piezoelectricity of EAPap samples was evaluated by comparing their piezoelectric charge constant [d 31]. As increasing applied electric field up to 40V/mm, d 31 value was gradually improved due to increased cellulose crystallinity as well as alignment of cellulose chains. Also the alignment of cellulose chains was improved with increasing the exposing time to magnetic field (5.3T) and well alignment was achieved by exposing EAPap sample on the magnetic field for 180min.

  18. Structure of the Cellulose Synthase Complex of Gluconacetobacter hansenii at 23.4 Å Resolution

    PubMed Central

    Du, Juan; Vepachedu, Venkata; Cho, Sung Hyun; Kumar, Manish; Nixon, B. Tracy

    2016-01-01

    Bacterial crystalline cellulose is used in biomedical and industrial applications, but the molecular mechanisms of synthesis are unclear. Unlike most bacteria, which make non-crystalline cellulose, Gluconacetobacter hansenii extrudes profuse amounts of crystalline cellulose. Its cellulose synthase (AcsA) exists as a complex with accessory protein AcsB, forming a 'terminal complex' (TC) that has been visualized by freeze-fracture TEM at the base of ribbons of crystalline cellulose. The catalytic AcsAB complex is embedded in the cytoplasmic membrane. The C-terminal portion of AcsC is predicted to form a translocation channel in the outer membrane, with the rest of AcsC possibly interacting with AcsD in the periplasm. It is thus believed that synthesis from an organized array of TCs coordinated with extrusion by AcsC and AcsD enable this bacterium to make crystalline cellulose. The only structural data that exist for this system are the above mentioned freeze-fracture TEM images, fluorescence microscopy images revealing that TCs align in a row, a crystal structure of AcsD bound to cellopentaose, and a crystal structure of PilZ domain of AcsA. Here we advance our understanding of the structural basis for crystalline cellulose production by bacterial cellulose synthase by determining a negative stain structure resolved to 23.4 Å for highly purified AcsAB complex that catalyzed incorporation of UDP-glucose into β-1,4-glucan chains, and responded to the presence of allosteric activator cyclic diguanylate. Although the AcsAB complex was functional in vitro, the synthesized cellulose was not visible in TEM. The negative stain structure revealed that AcsAB is very similar to that of the BcsAB synthase of Rhodobacter sphaeroides, a non-crystalline cellulose producing bacterium. The results indicate that the crystalline cellulose producing and non-crystalline cellulose producing bacteria share conserved catalytic and membrane translocation components, and support the

  19. Enzymatic Hydrolysis of Cellulosic Biomass

    SciTech Connect

    Yang, Bin; Dai, Ziyu; Ding, Shi-You; Wyman, Charles E.

    2011-08-22

    Biological conversion of cellulosic biomass to fuels and chemicals offers the high yields to products vital to economic success and the potential for very low costs. Enzymatic hydrolysis that converts lignocellulosic biomass to fermentable sugars may be the most complex step in this process due to substrate-related and enzyme-related effects and their interactions. Although enzymatic hydrolysis offers the potential for higher yields, higher selectivity, lower energy costs, and milder operating conditions than chemical processes, the mechanism of enzymatic hydrolysis and the relationship between the substrate structure and function of various glycosyl hydrolase components are not well understood. Consequently, limited success has been realized in maximizing sugar yields at very low cost. This review highlights literature on the impact of key substrate and enzyme features that influence performance to better understand fundamental strategies to advance enzymatic hydrolysis of cellulosic biomass for biological conversion to fuels and chemicals. Topics are summarized from a practical point of view including characteristics of cellulose (e.g., crystallinity, degree of polymerization, and accessible surface area) and soluble and insoluble biomass components (e.g., oligomeric xylan, lignin, etc.) released in pretreatment, and their effects on the effectiveness of enzymatic hydrolysis. We further discuss the diversity, stability, and activity of individual enzymes and their synergistic effects in deconstructing complex lignocellulosic biomass. Advanced technologies to discover and characterize novel enzymes and to improve enzyme characteristics by mutagenesis, post-translational modification, and over-expression of selected enzymes and modifications in lignocellulosic biomass are also discussed.

  20. Surface Photochemistry: 3,3′-Dialkylthia and Selenocarbocyanine Dyes Adsorbed onto Microcrystalline Cellulose

    PubMed Central

    Vieira Ferreira, Luís F.; Ferreira, Diana P.; Duarte, Paulo; Oliveira, A. S.; Torres, E.; Machado, I. Ferreira; Almeida, P.; Reis, Lucinda V.; Santos, Paulo F.

    2012-01-01

    In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission ΦF and τF, on powdered solid samples a decrease of ΦF and τF was observed. The use of an integrating sphere enabled us to obtain absolute ΦF’s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the ΦF values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples. PMID:22312274

  1. Surface photochemistry: 3,3'-dialkylthia and selenocarbocyanine dyes adsorbed onto microcrystalline cellulose.

    PubMed

    Vieira Ferreira, Luís F; Ferreira, Diana P; Duarte, Paulo; Oliveira, A S; Torres, E; Machado, I Ferreira; Almeida, P; Reis, Lucinda V; Santos, Paulo F

    2012-01-01

    In this work, thia and selenocarbocyanines with n-alkyl chains of different length, namely with methyl, ethyl, propyl, hexyl and decyl substituents, were studied in homogeneous and heterogeneous media for comparison purposes. For both carbocyanine dyes adsorbed onto microcrystalline cellulose, a remarkable increase in the fluorescence quantum yields and lifetimes were detected, when compared with solution. Contrary to the solution behaviour, where the increase in the n-alkyl chains length increases to a certain extent the fluorescence emission Φ(F) and τ(F), on powdered solid samples a decrease of Φ(F) and τ(F) was observed. The use of an integrating sphere enabled us to obtain absolute Φ(F)'s for all the powdered samples. The main difference for liquid homogeneous samples is that the increase of the alkyl chain strongly decreases the Φ(F) values, both for thiacarbocyanines and selenocarbocyanines. A lifetime distribution analysis for the fluorescence of these dyes adsorbed onto microcrystalline cellulose, evidenced location on the ordered and crystalline part of the substrate, as well as on the more disordered region where the lifetime is smaller. The increase of the n-alkyl chains length decreases the photoisomer emission for the dyes adsorbed onto microcrystalline cellulose, as detected for high fluences of the laser excitation, for most samples.

  2. Investigation and characterization of oxidized cellulose and cellulose nanofiber films

    NASA Astrophysics Data System (ADS)

    Yang, Han

    Over the last two decades, a large amount of research has focused on natural cellulose fibers, since they are "green" and renewable raw materials. Recently, nanomaterials science has attracted wide attention due to the large surface area and unique properties of nanoparticles. Cellulose certainly is becoming an important material in nanomaterials science, with the increasing demand of environmentally friendly materials. In this work, a novel method of preparing cellulose nanofibers (CNF) is being presented. This method contains up to three oxidation steps: periodate, chlorite and TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) oxidation. The first two oxidation steps are investigated in the first part of this work. Cellulose pulp was oxidized to various extents by a two step-oxidation with sodium periodate, followed by sodium chlorite. The oxidized products can be separated into three different fractions. The mass ratio and charge content of each fraction were determined. The morphology, size distribution and crystallinity index of each fraction were measured by AFM, DLS and XRD, respectively. In the second part of this work, CNF were prepared and modified under various conditions, including (1) the introduction of various amounts of aldehyde groups onto CNF by periodate oxidation; (2) the carboxyl groups in sodium form on CNF were converted to acid form by treated with an acid type ion-exchange resin; (3) CNF were cross-linked in two different ways by employing adipic dihydrazide (ADH) as cross-linker and water-soluble 1-ethyl-3-[3-(dimethylaminopropyl)] carbodiimide (EDC) as carboxyl-activating agent. Films were fabricated with these modified CNF suspensions by vacuum filtration. The optical, mechanical and thermo-stability properties of these films were investigated by UV-visible spectrometry, tensile test and thermogravimetric analysis (TGA). Water vapor transmission rates (WVTR) and water contact angle (WCA) of these films were also studied.

  3. Cellulose biosynthesis and function in bacteria.

    PubMed Central

    Ross, P; Mayer, R; Benziman, M

    1991-01-01

    The current model of cellulose biogenesis in plants, as well as bacteria, holds that the membranous cellulose synthase complex polymerizes glucose moieties from UDP-Glc into beta-1,4-glucan chains which give rise to rigid crystalline fibrils upon extrusion at the outer surface of the cell. The distinct arrangement and degree of association of the polymerizing enzyme units presumably govern extracellular chain assembly in addition to the pattern and width of cellulose fibril deposition. Most evident for Acetobacter xylinum, polymerization and assembly appear to be tightly coupled. To date, only bacteria have been effectively studied at the biochemical and genetic levels. In A. xylinum, the cellulose synthase, composed of at least two structurally similar but functionally distinct subunits, is subject to a multicomponent regulatory system. Regulation is based on the novel nucleotide cyclic diguanylic acid, a positive allosteric effector, and the regulatory enzymes maintaining its intracellular turnover: diguanylate cyclase and Ca2(+)-sensitive bis-(3',5')-cyclic diguanylic acid (c-di-GMP) phosphodiesterase. Four genes have been isolated from A. xylinum which constitute the operon for cellulose synthesis. The second gene encodes the catalytic subunit of cellulose synthase; the functions of the other three gene products are still unknown. Exclusively an extracellular product, bacterial cellulose appears to fulfill diverse biological roles within the natural habitat, conferring mechanical, chemical, and physiological protection in A. xylinum and Sarcina ventriculi or facilitating cell adhesion during symbiotic or infectious interactions in Rhizobium and Agrobacterium species. A. xylinum is proving to be most amenable for industrial purposes, allowing the unique features of bacterial cellulose to be exploited for novel product applications. Images PMID:2030672

  4. Alginate/bacterial cellulose nanocomposite beads prepared using Gluconacetobacter xylinus and their application in lipase immobilization.

    PubMed

    Kim, Ji Hyun; Park, Saerom; Kim, Hyungsup; Kim, Hyung Joo; Yang, Yung-Hun; Kim, Yong Hwan; Jung, Sang-Kyu; Kan, Eunsung; Lee, Sang Hyun

    2017-02-10

    Alginate/bacterial cellulose nanocomposite beads, with well-controlled size and regular spherical shapes, were prepared in a simple manner by entrapping Gluconacetobacter xylinus in barium alginate hydrogel beads, followed by cultivation of the entrapped cells in culture media with a low sodium ion concentration. The entire surface of the alginate hydrogel beads containing the cells was covered with cellulose fibers (∼30nm) after 36h of cultivation. The cellulose crystallinity index of the alginate/bacterial cellulose beads was 0.7, which was slightly lower than that of bacterial cellulose prepared by cultivating dispersed cells. The water vapor sorption capacity of the alginate/bacterial cellulose beads increased significantly from 0.07 to 38.00 (g/g dry bead) as cultivation time increased. These results clearly indicate that alginate/bacterial cellulose beads have a much higher surface area, crystallinity, and water-holding capacity than alginate beads. The immobilization of lipase on the surface of the nanocomposite beads was also investigated as a potential application of this system. The activity and specific activity of lipase immobilized on alginate/bacterial cellulose beads were 2.6- and 3.8-fold higher, respectively, than that of lipase immobilized on cellulose beads. The alginate/bacterial cellulose nanocomposite beads prepared in this study have several potential applications in the biocatalytic, biomedical, and pharmaceutical fields because of their biocompatibility, biodegradability, high crystallinity, and large surface area.

  5. Rheology of nanocrystalline cellulose aqueous suspensions.

    PubMed

    Shafiei-Sabet, Sadaf; Hamad, Wadood Y; Hatzikiriakos, Savvas G

    2012-12-11

    The rheological properties and microstructure of nanocrystalline cellulose (NCC) aqueous suspensions have been investigated at different concentrations. The suspension is isotropic up to 3 wt %, and phase separates to liquid crystalline and isotropic domains at higher concentrations where the samples exhibit a fingerprint texture and the viscosity profile shows a three-region behavior, typical of liquid crystals. The suspension behaves as a rheological gel at even higher concentrations where the viscosity profile shows a single shear thinning behavior over the whole range of shear rates investigated. The effects of ultrasound energy and temperature on the rheological properties and structure of these suspensions were studied using polarized optical microscopy and rheometry. Our results indicate that the amount of applied ultrasound energy affects the microstructure of the suspensions and the pitch of the chiral nematic domains. The viscosity profile is changed significantly at low shear rates, whereas the viscosity of biphasic suspensions at intermediate and high shear rates decreased with increasing temperature. This suggests that, between 30 and 40 °C, structural rearrangement takes place. At higher concentrations of about 10 wt %, the temperature has no significant effect on viscosity; however, a marked increase in viscosity has been observed at around 50 °C. Finally, the Cox-Merz rule was found to fail after a critical concentration, thereby implying significant structural formation. This critical concentration is much higher for sonicated compared to unsonicated suspensions.

  6. Transcriptomic and genomic analysis of cellulose fermentation by Clostridium thermocellum ATCC 27405

    SciTech Connect

    Raman, Babu; McKeown, Catherine K; Rodriguez, Jr., Miguel; Brown, Steven D; Mielenz, Jonathan R

    2011-01-01

    The ability of Clostridium thermocellum ATCC 27405 wild-type strain to hydrolyze cellulose and ferment the degradation products directly to ethanol and other metabolic byproducts makes it an attractive candidate for consolidated bioprocessing of cellulosic biomass to biofuels. In this study, whole-genome microarrays were used to investigate the expression of C. thermocellum mRNA during growth on crystalline cellulose in controlled replicate batch fermentations. A time-series analysis of gene expression revealed changes in transcript levels of {approx}40% of genes ({approx}1300 out of 3198 ORFs encoded in the genome) during transition from early-exponential to late-stationary phase. K-means clustering of genes with statistically significant changes in transcript levels identified six distinct clusters of temporal expression. Broadly, genes involved in energy production, translation, glycolysis and amino acid, nucleotide and coenzyme metabolism displayed a decreasing trend in gene expression as cells entered stationary phase. In comparison, genes involved in cell structure and motility, chemotaxis, signal transduction and transcription showed an increasing trend in gene expression. Hierarchical clustering of cellulosome-related genes highlighted temporal changes in composition of this multi-enzyme complex during batch growth on crystalline cellulose, with increased expression of several genes encoding hydrolytic enzymes involved in degradation of non-cellulosic substrates in stationary phase. Overall, the results suggest that under low substrate availability, growth slows due to decreased metabolic potential and C. thermocellum alters its gene expression to (i) modulate the composition of cellulosomes that are released into the environment with an increased proportion of enzymes than can efficiently degrade plant polysaccharides other than cellulose, (ii) enhance signal transduction and chemotaxis mechanisms perhaps to sense the oligosaccharide hydrolysis products

  7. Acetylation of cellulose nanowhiskers with vinyl acetate under moderate conditions.

    PubMed

    Cetin, Nihat Sami; Tingaut, Philippe; Ozmen, Nilgül; Henry, Nathan; Harper, David; Dadmun, Mark; Sèbe, Gilles

    2009-10-08

    A novel and straightforward method for the surface acetylation of cellulose nanowhiskers by transesterification of vinyl acetate is proposed. The reaction of vinyl acetate with the hydroxyl groups of cellulose nanowhiskers obtained from cotton linters was examined with potassium carbonate as catalyst. Results indicate that during the first stage of the reaction, only the surface of the nanowhiskers was modified, while their dimensions and crystallinity remained unchanged. With increasing reaction time, diffusion mechanisms controlled the rate, leading to nanowhiskers with higher levels of acetylation, smaller dimensions, and lower crystallinity. In THF, a solvent of low polarity, the suspensions from modified nanowhiskers showed improved stability with increased acetylation.

  8. Characterization of Bacterial Cellulose by Gluconacetobacter hansenii CGMCC 3917.

    PubMed

    Feng, Xianchao; Ullah, Niamat; Wang, Xuejiao; Sun, Xuchun; Li, Chenyi; Bai, Yun; Chen, Lin; Li, Zhixi

    2015-10-01

    In this study, comprehensive characterization and drying methods on properties of bacterial cellulose were analyzed. Bacterial cellulose was prepared by Gluconacetobacter hansenii CGMCC 3917, which was mutated by high hydrostatic pressure (HHP) treatment. Bacterial cellulose is mainly comprised of cellulose Iα with high crystallinity and purity. High-water holding and absorption capacity were examined by reticulated structure. Thermogravimetric analysis showed high thermal stability. High tensile strength and Young's modulus indicated its mechanical properties. The rheological analysis showed that bacterial cellulose had good consistency and viscosity. These results indicated that bacterial cellulose is a potential food additive and also could be used for a food packaging material. The high textural stability during freeze-thaw cycles makes bacterial cellulose an effective additive for frozen food products. In addition, the properties of bacterial cellulose can be affected by drying methods. Our results suggest that the bacterial cellulose produced from HHP-mutant strain has an effective characterization, which can be used for a wide range of applications in food industry.

  9. Microcalorimetric study of cellulose degradation by Cellulomonas uda ATCC 21399

    SciTech Connect

    Dermoun, Z.; Belaich, J.P.

    1985-07-01

    A newly designed batch calorimeter was used to investigate the degradability of some celluloses having varying degrees of crystallinity. The PTC of an aerobic culture of Cellulomonas uda ATCC 21399 obtained revealed a diauxic growth which is attributed to the presence of hemicellulose contaminating Avicel and MN300 cellulose. The microcrystalline celluloses used were not completely utilized, whereas amorphous cellulose was easily metabolized, indicating that under the growth conditions used here, the physical structure of cellulose strongly influenced its microbial degradability. An equivalent growth yield of ca. 0.44 g/g was found with all the substrates used. The heat evolved by metabolism of one g cellulose was - 5.86 kJ/g, a value similar to that obtained with glucose culture. The growth rate was the only variable parameter. The data obtained showed as expected that the hydrolysis product of cellulose was consumed in the same way as that of glucose and that the only limiting factor to the biodegradability of cellulose was the breakdown of the polymeric substrate. It is concluded that data obtained with glucose metabolism can be used to evaluate the extent of cellulose degradation.

  10. Regenerated cellulose/wool blend enhanced biomimetic hydroxyapatite mineralization.

    PubMed

    Salama, Ahmed; El-Sakhawy, Mohamed

    2016-11-01

    The current article investigates the effect of bioactive cellulose/wool blend on calcium phosphate biomimetic mineralization. Regenerated cellulose/wool blend was prepared by dissolution-regeneration of neat cellulose and natural wool in 1-butyl-3-methyl imidazolium chloride [Bmim][Cl], as a solvent for the two polymers. Crystalline hydroxyapatite nanofibers with a uniform size, shape and dimension were formed after immersing the bioactive blend in simulated body fluid. The cytotoxicity of cellulose/wool/hydroxyapatite was studied using animal fibroblast baby hamster kidney cells (BHK-21) and the result displayed good cytocompatability. This research work presents a green processing method for the development of novel cellulose/wool/hydroxyapatite hybrid materials for tissue engineering applications.

  11. Adsorption of cellulase from Trichoderma viride on cellulose

    SciTech Connect

    Ooshima, H.; Sakata, M.; Harano, Y.

    1983-12-01

    The adsorption of cellulase from Trichoderma viride (Meicelase CEP) on the surface of pure cellulose was studied. The adsorption was found to obey apparently the Langmuir isotherm. From the data concerning the effects of temperature and the crystallinity of cellulose on the Langmuir adsorption parameters, the characteristics of the adsorption of the individual cellulase components, namely CMCase (endoglucanase) and Avicelase (exoglucanase), were discussed. While beta-glucosidase also adsorbed on the surface of cellulose at 5 degrees C, it did not at 50 degrees C. (Refs. 27).

  12. Preparation and characterization of the foam-stabilizing properties of cellulose-ethyl cellulose complexes for use in foods.

    PubMed

    Murray, Brent S; Durga, Kalpana; de Groot, Peter W N; Kakoulli, Antonia; Stoyanov, Simeon D

    2011-12-28

    Surface active cellulose particles have been prepared for use as foam stabilizing agents in foods. Various sources of cellulose were broken down by combinations of milling, acid dissolution and treatment with cellulase. The most efficient and simple method was hammer and freezer milling of dry crystalline α-cellulose (Tencel). The resultant Tencel particles were made partially hydrophobic through precipitation of ethyl cellulose (EC) onto them in acetone-water dispersions. The optimum ratio of EC to cellulose and the optimum solids concentration (C(x)) at which to form the complexes were 1:1 and C(x) ≈ 1 wt %, respectively. Complexes combined at low concentrations (e.g., C(x) ≈ 0.1 wt %) with caseins or whey proteins gave significant improvements in stability of foams and bubbles to coalescence and disproportionation compared to either component alone. As such, the complexes could be a useful ingredient in improving the quality of various food foams.

  13. Cellulose nanocrystals: A layered host candidate for fabricating intercalated nanocomposites.

    PubMed

    Guo, Juan; Du, Wenbo; Wang, Siqun; Yin, Yafang; Gao, Yong

    2017-02-10

    The stacking of cellulose chains along planes and weak intersheet interactions make cellulose nanocrystals (CNCs) promising as a layered host candidate for fabricating intercalated nanocomposites. As a proof-of-concept, we demonstrate the intercalation of alkyls into CNCs through the in situ intercalative chemical reaction between terminal groups of N-octadecyl isocyanates and hydroxyl groups on the (200) planes in CNCs. Results showed that CNCs could intercalate alkyls in a high degree of substitution to form dense brushes on their (200) planes. After intercalation, a significant enlargement of interlayer spacing was observed. Moreover, alkyls were fully extended in all-trans configuration and crystallized in a co-existing organization of αH, βH and βO crystalline forms. This meant that the molecular arrangement in CNCs/alkyl intercalated nanocomposites would involve a bilayer model in which alkyls were in the ordered packing and titled to (200) plane. Furthermore, CNCs/alkyl intercalated nanocomposites possessed increased thermal properties and decreased char residue.

  14. Electrically conductive cellulose composite

    DOEpatents

    Evans, Barbara R.; O'Neill, Hugh M.; Woodward, Jonathan

    2010-05-04

    An electrically conductive cellulose composite includes a cellulose matrix and an electrically conductive carbonaceous material incorporated into the cellulose matrix. The electrical conductivity of the cellulose composite is at least 10 .mu.S/cm at 25.degree. C. The composite can be made by incorporating the electrically conductive carbonaceous material into a culture medium with a cellulose-producing organism, such as Gluconoacetobacter hansenii. The composites can be used to form electrodes, such as for use in membrane electrode assemblies for fuel cells.

  15. Kits and methods of detection using cellulose binding domain fusion proteins

    SciTech Connect

    Shoseyov, O.; Yosef, K.

    1998-04-14

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques. 16 figs.

  16. Kits and methods of detection using cellulose binding domain fusion proteins

    DOEpatents

    Shoseyov, Oded

    1998-01-01

    A cellulose binding domain (CBD) having a high affinity for crystalline cellulose and chitin is disclosed, along with methods for the molecular cloning and recombinant production thereof. Fusion products comprising the CBD and a second protein are likewise described. A wide range of applications are contemplated for both the CBD and the fusion products, including drug delivery, affinity separations, and diagnostic techniques.

  17. Combining computational chemistry and crystallography for a better understanding of the structure of cellulose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The approaches in this article seek to enhance understanding of cellulose at the molecular level, independent of the source and the particular crystalline form of cellulose. Four main areas of structure research are reviewed. Initially the molecular shape is inferred from the crystal structures of m...

  18. Exploring biosensor applications with cotton cellulose nanocrystalline protein and peptide conjugates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sensor I: Nano-crystalline preparations were produced through acid hydrolysis and mechanical breakage of the cotton fibers from a scoured and bleached cotton fabric and a scoured and bleached, mercerized fabric, which was shown to produce cellulose I (NCI) and cellulose II (NCII) crystals respective...

  19. Two poplar cellulose synthase-like D genes, PdCSLD5 and PdCSLD6, are functionally conserved with Arabidopsis CSLD3.

    PubMed

    Qi, Guang; Hu, Ruibo; Yu, Li; Chai, Guohua; Cao, Yingping; Zuo, Ran; Kong, Yingzhen; Zhou, Gongke

    2013-09-15

    Root hairs are tip-growing long tubular outgrowths of specialized epidermal cells, and are important for nutrient and water uptake and interaction with the soil microflora. Here we characterized two poplar cellulose synthase-like D (CSLD) genes, PdCSLD5 and PdCSLD6, the most probable orthologs to the Arabidopsis AtCSLD3/KOJAK gene. Both PdCSLD5 and PdCSLD6 are strongly expressed in roots, including in the root hairs. Subcellular localization experiments showed that these two proteins are located not only in the polarized plasma membrane of root hair tips, but also in Golgi apparatus of the root hair and non-hair-forming cells. Overexpression of these two poplar genes in the atcsld3 mutant was able to rescue most of the defects caused by disruption of AtCSLD3, including root hair morphological changes, altered cell wall monosaccharide composition, increased non-crystalline β-1,4-glucan and decreased crystalline cellulose contents. Taken together, our results provide evidence indicating that PdCSLD5 and PdCSLD6 are functionally conserved with AtCSLD3 and support a role for PdCSLD5 and PdCSL6 specifically in crystalline cellulose production in poplar root hair tips. The results presented here also suggest that at least part of the mechanism of root hair formation is conserved between herbaceous and woody plants.

  20. Synthesis of highly substituted carboxymethyl cellulose depending on cellulose particle size.

    PubMed

    Yeasmin, Mst Sarmina; Mondal, Md Ibrahim H

    2015-09-01

    Corn husk is an abundant agricultural waste. It has great potential for use as a cellulose source for the production of carboxymethyl cellulose (CMC). The chemical composition of corn husk, such as cellulose, hemicelluloses, lignin, fatty and waxy matter, pectic matter and aqueous extract was determined. The cellulose extracted from corn husk was carboxymethylated using sodium hydroxide (NaOH) and monochloroacetic acid (MCA), in aqueous ethanolic medium, under heterogeneous conditions. The carboxymethylation reaction was optimized as to the NaOH concentration, MCA concentration, reaction temperature, reaction time and cellulose particle size. The degree of substitution (DS) was determined with respect to the reaction conditions using chemical methods. The produced CMC was identified by FTIR and the crystallinity of the CMC was determined by XRD. The CMC product had an optimized DS of 2.41 and the optimal conditions for carboxymethylation were NaOH concentration, 7.5 mol/L; MCA concentration, 12 mol/L; reaction temperature, 55 °C; reaction time, 3.5 h and cellulose particle size, 74 μm. These optimization factors allowed to prepare highly substituted CMC with higher yield, 2.40 g/g, providing plenty of opportunities for its many applications.

  1. The Effect of Cellulose Crystal Structure and Solid-State Morphology on the Activity of Cellulases

    SciTech Connect

    Stipanovic, Arthur J

    2014-11-17

    Consistent with the US-DOE and USDA “Roadmap” objective of producing ethanol and chemicals from cellulosic feedstocks more efficiently, a three year research project entitled “The Effect of Cellulose Crystal Structure and Solid-State Morphology on the Activity of Cellulases” was initiated in early 2003 under DOE sponsorship (Project Number DE-FG02-02ER15356). A three year continuation was awarded in June 2005 for the period September 15, 2005 through September 14, 2008. The original goal of this project was to determine the effect of cellulose crystal structure, including allomorphic crystalline form (Cellulose I, II, III, IV and sub-allomorphs), relative degree of crystallinity and crystallite size, on the activity of different types of genetically engineered cellulase enzymes to provide insight into the mechanism and kinetics of cellulose digestion by “pure” enzymes rather than complex mixtures. We expected that such information would ultimately help enhance the accessibility of cellulose to enzymatic conversion processes thereby creating a more cost-effective commercial process yielding sugars for fermentation into ethanol and other chemical products. Perhaps the most significant finding of the initial project phase was that conversion of native bacterial cellulose (Cellulose I; BC-I) to the Cellulose II (BC-II) crystal form by aqueous NaOH “pretreatment” provided an increase in cellulase conversion rate approaching 2-4 fold depending on enzyme concentration and temperature, even when initial % crystallinity values were similar for both allomorphs.

  2. Assessing the impact of lyophilization process in production of implants based on the bacterial cellulose using Raman spectroscopy method

    NASA Astrophysics Data System (ADS)

    Timchenko, E. V.; Timchenko, P. E.; Pisareva, E. V.; Vlasov, M. Yu; Revin, V. V.; Klenova, N. A.; Asadova, A. A.

    2017-01-01

    In this article we present the research results of lyophilization process influence on the composition of hybrid materials based on the bacterial cellulose (BC) using Raman spectroscopy method. As an object of research was used BC, as well as hybrids based on it, comprising the various combinations of hydroxyapatite (HAP) and collagen. Our studies showed that during the lyophilization process changes the ratio of the individual components. It was found that for samples hybrid based on BC with addition of HAP occurs increase of PO4 3- peak intensity in the region 956 cm-1 with decreasing width, which indicates a change in the degree of HAP crystallinity.

  3. CRYSTALLINE SOYBEAN TRYPSIN INHIBITOR

    PubMed Central

    Kunitz, M.

    1947-01-01

    A study has been made of the general properties of crystalline soybean trypsin inhibitor. The soy inhibitor is a stable protein of the globulin type of a molecular weight of about 24,000. Its isoelectric point is at pH 4.5. It inhibits the proteolytic action approximately of an equal weight of crystalline trypsin by combining with trypsin to form a stable compound. Chymotrypsin is only slightly inhibited by soy inhibitor. The reaction between chymotrypsin and the soy inhibitor consists in the formation of a reversibly dissociable compound. The inhibitor has no effect on pepsin. The inhibiting action of the soybean inhibitor is associated with the native state of the protein molecule. Denaturation of the soy protein by heat or acid or alkali brings about a proportional decrease in its inhibiting action on trypsin. Reversal of denaturation results in a proportional gain in the inhibiting activity. Crystalline soy protein when denatured is readily digestible by pepsin, and less readily by chymotrypsin and by trypsin. Methods are given for measuring trypsin and inhibitor activity and also protein concentration with the aid of spectrophotometric density measurements at 280 mµ. PMID:19873496

  4. Nitrogen and Sulfur Requirements for Clostridium thermocellum and Caldicellulosiruptor bescii on Cellulosic Substrates in Minimal Nutrient Media

    SciTech Connect

    Kridelbaugh, Donna M; Nelson, Josh C; Engle, Nancy L; Tschaplinski, Timothy J; Graham, David E

    2013-01-01

    Growth media for cellulolytic Clostridium thermocellum and Caldicellulosiruptor bescii bacteria usually contain excess nutrients that would increase costs for consolidated bioprocessing for biofuel production and create a waste stream with nitrogen, sulfur and phosphate. C. thermocellum was grown on crystalline cellulose with varying concentrations of nitrogen and sulfur compounds, and growth rate and alcohol production response curves were determined. Both bacteria assimilated sulfate in the presence of ascorbate reductant, increasing the ratio of oxidized to reduced fermentation products. From these results, a low ionic strength, defined minimal nutrient medium with decreased nitrogen, sulfur, phosphate and vitamin supplements was developed for the fermentation of cellobiose, cellulose and acid-pretreated Populus. Carbon and electron balance calculations indicate the unidentified residual fermentation products must include highly reduced molecules. Both bacterial populations were maintained in co-cultures with substrates containing xylan or hemicellulose in defined medium with sulfate and basal vitamin supplements.

  5. Pea Xyloglucan and Cellulose

    PubMed Central

    Hayashi, Takahisa; Marsden, Margery P. F.; Delmer, Deborah P.

    1987-01-01

    Since xyloglucan is believed to bind to cellulose microfibrils in the primary cell walls of higher plants and, when isolated from the walls, can also bind to cellulose in vitro, the binding mechanism of xyloglucan to cellulose was further investigated using radioiodinated pea xyloglucan. A time course for the binding showed that the radioiodinated xyloglucan continued to be bound for at least 4 hours at 40°C. Binding was inhibited above pH 6. Binding capacity was shown to vary for celluloses of different origin and was directly related to the relative surface area of the microfibrils. The binding of xyloglucan to cellulose was very specific and was not affected by the presence of a 10-fold excess of (1→2)-β-glucan, (1→3)-β-glucan, (1→6)-β-glucan, (1→3, 1→4)-β-glucan, arabinogalactan, or pectin. When xyloglucan (0.1%) was added to a cellulose-forming culture of Acetobacter xylinum, cellulose ribbon structure was partially disrupted indicating an association of xyloglucan with cellulose at the time of synthesis. Such a result suggests that the small size of primary wall microfibrils in higher plants may well be due to the binding of xyloglucan to cellulose during synthesis which prevents fasciation of small fibrils into larger bundles. Fluorescent xyloglucan was used to stain pea cell wall ghosts prepared to contain only the native xyloglucan:cellulose network or only cellulose. Ghosts containing only cellulose showed strong fluorescence when prepared before or after elongation; as predicted, the presence of native xyloglucan in the ghosts repressed binding of added fluorescent xyloglucan. Such ghosts, prepared after elongation when the ratio of native xyloglucan:cellulose is substantially reduced, still showed only faint fluorescence, indicating that microfibrils continue to be coated with xyloglucan throughout the growth period. Images Fig. 5 Fig. 6 PMID:16665254

  6. Cellulose: A review as natural, modified and activated carbon adsorbent.

    PubMed

    Suhas; Gupta, V K; Carrott, P J M; Singh, Randhir; Chaudhary, Monika; Kushwaha, Sarita

    2016-09-01

    Cellulose is a biodegradable, renewable, non-meltable polymer which is insoluble in most solvents due to hydrogen bonding and crystallinity. Natural cellulose shows lower adsorption capacity as compared to modified cellulose and its capacity can be enhanced by modification usually by chemicals. This review focuses on the utilization of cellulose as an adsorbent in natural/modified form or as a precursor for activated carbon (AC) for adsorbing substances from water. The literature revealed that cellulose can be a promising precursor for production of activated carbon with appreciable surface area (∼1300m(2)g(-1)) and total pore volume (∼0.6cm(3)g(-1)) and the surface area and pore volume varies with the cellulose content. Finally, the purpose of review is to report a few controversies and unresolved questions concerning the preparation/properties of ACs from cellulose and to make aware to readers that there is still considerable scope for future development, characterization and utilization of ACs from cellulose.

  7. Cellulose synthesizing Complexes in Vascular Plants andProcaryotes

    SciTech Connect

    Brown, Richard M, Jr; Saxena, Inder Mohan

    2009-07-07

    Continuing the work initiated under DE-FG03-94ER20145, the following major accomplishments were achieved under DE-FG02-03ER15396 from 2003-2007: (a) we purified the acsD gene product of the Acetobacter cellulose synthase operon as well as transferred the CesA cellulose gene from Gossypium into E. coli in an attempt to crystallize this protein for x-ray diffraction structural analysis; however, crystallization attempts proved unsuccessful; (b) the Acetobacter cellulose synthase operon was successfully incorporated into Synechococcus, a cyanobacterium2; (c) this operon in Synechococcus was functionally expressed; (d) we successfully immunolabeled Vigna cellulose and callose synthase components and mapped their distribution before and after wounding; (e) we developed a novel method to produce replicas of cellulose synthases in tobacco BY-2 cells, and we demonstrated the cytoplasmic domain of the rosette TC; (f) from the moss Physcomitrella, we isolated two full-length cDNA sequences of cellulose synthase (PpCesA1 and PpCesA2) and attempted to obtain full genomic DNA sequences; (g) we examined the detailed molecular structure of a new form of non-crystalline cellulose known as nematic ordered cellulose (=NOC)3.

  8. Synthesis of carboxymethyl cellulose from waste of cotton ginning industry.

    PubMed

    Haleem, Noor; Arshad, Muhammad; Shahid, Muhammad; Tahir, Muhammad Ashraf

    2014-11-26

    The aim of present work was to isolate cellulose from cotton gin waste (CGW) and synthesis of carboxymethyl cellulose (CMC) from it. Scoured and bleached CGW was used to investigate the effects of temperature, reaction time, acid-base concentration on the physiology of the resultant cellulose polymer. The isolated cellulose from CGW was converted to CMC by etherification using sodium monochloroacetic acid and different sodium hydroxide (NaOH) concentrations (5-40 g/100mL) were tested to get high quality product. The optimum condition for carboxymethylation was found to be 20 g/100mL NaOH which provided the highest viscosity and degree of substitution (DS=0.874). Isolated cellulose and CMC were characterized using Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). FT-IR analysis revealed that the produced cellulose was of very good quality. Furthermore, X-ray diffraction (XRD) analysis spotlighted crystalline nature of cellulose. SEM images showed rough structure of cellulose while that of the CMC had a smooth surface. This optimized method will be tested at pilot scale in collaboration with local industry.

  9. Acid hydrolysis of cellulosic fibres: Comparison of bleached kraft pulp, dissolving pulps and cotton textile cellulose.

    PubMed

    Palme, Anna; Theliander, Hans; Brelid, Harald

    2016-01-20

    The behaviour of different cellulosic fibres during acid hydrolysis has been investigated and the levelling-off degree of polymerisation (LODP) has been determined. The study included a bleached kraft pulp (both never-dried and once-dried) and two dissolving pulps (once-dried). Additionally, cotton cellulose from new cotton sheets and sheets discarded after long-time use was studied. Experimental results from the investigation, together with results found in literature, imply that ultrastructural differences between different fibres affect their susceptibility towards acid hydrolysis. Drying of a bleached kraft pulp was found to enhance the rate of acid hydrolysis and also result in a decrease in LODP. This implies that the susceptibility of cellulosic fibres towards acid hydrolysis is affected by drying-induced stresses in the cellulose chains. In cotton cellulose, it was found that use and laundering gave a substantial loss in the degree of polymerisation (DP), but that the LODP was only marginally affected.

  10. Nanocellulose prepared by acid hydrolysis of isolated cellulose from sugarcane bagasse

    NASA Astrophysics Data System (ADS)

    Wulandari, W. T.; Rochliadi, A.; Arcana, I. M.

    2016-02-01

    Cellulose in nanometer range or called by nano-cellulose has attracted much attention from researchers because of its unique properties. Nanocellulose can be obtained by acid hydrolysis of cellulose. The cellulose used in this study was isolated from sugarcane bagasse, and then it was hydrolyzed by 50% sulfuric acid at 40 °C for 10 minutes. Nanocellulose has been characterized by Transmission Electron Microscope (TEM), Particle Size Analyzer (PSA), Fourier Transform Infrared Spectroscopy (FTIR) and X-Ray Diffraction (XRD). Analysis of FTIR showed that there were not a new bond which formed during the hydrolysis process. Based on the TEM analysis, nano-cellulose has a spherical morphology with an average diameter of 111 nm and a maximum distribution of 95.9 nm determined by PSA. The XRD analysis showed that the crystallinity degree of nano-cellulose was higher than cellulose in the amount of 76.01%.

  11. Multi-scale model for the hierarchical architecture of native cellulose hydrogels.

    PubMed

    Martínez-Sanz, Marta; Mikkelsen, Deirdre; Flanagan, Bernadine; Gidley, Michael J; Gilbert, Elliot P

    2016-08-20

    The structure of protiated and deuterated cellulose hydrogels has been investigated using a multi-technique approach combining small-angle scattering with diffraction, spectroscopy and microscopy. A model for the multi-scale structure of native cellulose hydrogels is proposed which highlights the essential role of water at different structural levels characterised by: (i) the existence of cellulose microfibrils containing an impermeable crystalline core surrounded by a partially hydrated paracrystalline shell, (ii) the creation of a strong network of cellulose microfibrils held together by hydrogen bonding to form cellulose ribbons and (iii) the differential behaviour of tightly bound water held within the ribbons compared to bulk solvent. Deuterium labelling provides an effective platform on which to further investigate the role of different plant cell wall polysaccharides in cellulose composite formation through the production of selectively deuterated cellulose composite hydrogels.

  12. Interactions of Endoglucanases with Amorphous Cellulose Films Resolved by Neutron Reflectometry and Quartz Crystal Microbalance with Dissipation Monitoring

    SciTech Connect

    Cheng, Gang; Liu, Zelin; Kent, Michael S; Majewski, Jaroslaw; Michael, Jablin; Jaclyn, Murton K; Halbert, Candice E; Datta, Supratim; Chao, Wang; Brown, Page

    2012-01-01

    A study of the interaction of four endoglucanases with amorphous cellulose films by neutron reflectometry (NR) and quartz crystal microbalance with dissipation monitoring (QCM-D) is reported. The endoglucanases include a mesophilic fungal endoglucanase (Cel45A from H. insolens), a processive endoglucanase from a marine bacterium (Cel5H from S. degradans), and two from thermophilic bacteria (Cel9A from A. acidocaldarius and Cel5A from T. maritima). The use of amorphous cellulose is motivated by the promise of ionic liquid pretreatment as a second generation technology that disrupts the native crystalline structure of cellulose. The endoglucanases displayed highly diverse behavior. Cel45A and Cel5H, which possess carbohydrate-binding modules (CBMs), penetrated and digested within the bulk of the films to a far greater extent than Cel9A and Cel5A, which lack CBMs. While both Cel45A and Cel5H were active within the bulk of the films, striking differences were observed. With Cel45A, substantial film expansion and interfacial broadening were observed, whereas for Cel5H the film thickness decreased with little interfacial broadening. These results are consistent with Cel45A digesting within the interior of cellulose chains as a classic endoglucanase, and Cel5H digesting predominantly at chain ends consistent with its designation as a processive endoglucanase.

  13. Homogeneous preparation of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from sugarcane bagasse cellulose in ionic liquid.

    PubMed

    Huang, Kelin; Wang, Ben; Cao, Yan; Li, Huiquan; Wang, Jinshu; Lin, Weijiang; Mu, Chaoshi; Liao, Dankui

    2011-05-25

    Cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) were prepared homogeneously in a 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid system from sugarcane bagasse (SB). The reaction temperature, reaction time, and molar ratio of butyric (propionic) anhydride/anhydroglucose units in the cellulose affect the butyryl (B) or propionyl (P) content of CAB or CAP samples. The (13)C NMR data revealed the distribution of the substituents of CAB and CAP. The thermal stability of sugar cane bagasse cellulose was found by thermogravimetric analysis to have decreased after chemical modification. After reaction, the ionic liquid was effectively recycled and reused. This study provides a new way for high-value-added utilization of SB and realizing the objective of turning waste into wealth.

  14. Cellulose and the twofold screw axis: Modeling and experimental arguments

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Crystallography indicates that molecules in crystalline cellulose either have 2-fold screw-axis (21) symmetry or closely approximate it, leading to short distances between H4 and H1' across the glycosidic linkage. Therefore, modeling studies of cellobiose often show elevated energies for 21 structur...

  15. Stability of two-fold screw axis structures for cellulose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Diffraction crystallography indicates that most forms of crystalline cellulose have two-fold screw axis symmetry. Even if exact symmetry is absent, the degree of pseudo symmetry is very high. On the other hand, this symmetry leads to short contacts between H4 and H1' across the glycosidic linkage....

  16. Engineering of a novel cellulose-adherent cellulolytic Saccharomyces cerevisiae for cellulosic biofuel production

    PubMed Central

    Liu, Zhuo; Ho, Shih-Hsin; Sasaki, Kengo; den Haan, Riaan; Inokuma, Kentaro; Ogino, Chiaki; van Zyl, Willem H.; Hasunuma, Tomohisa; Kondo, Akihiko

    2016-01-01

    Cellulosic biofuel is the subject of increasing attention. The main obstacle toward its economic feasibility is the recalcitrance of lignocellulose requiring large amount of enzyme to break. Several engineered yeast strains have been developed with cellulolytic activities to reduce the need for enzyme addition, but exhibiting limited effect. Here, we report the successful engineering of a cellulose-adherent Saccharomyces cerevisiae displaying four different synergistic cellulases on the cell surface. The cellulase-displaying yeast strain exhibited clear cell-to-cellulose adhesion and a “tearing” cellulose degradation pattern; the adhesion ability correlated with enhanced surface area and roughness of the target cellulose fibers, resulting in higher hydrolysis efficiency. The engineered yeast directly produced ethanol from rice straw despite a more than 40% decrease in the required enzyme dosage for high-density fermentation. Thus, improved cell-to-cellulose interactions provided a novel strategy for increasing cellulose hydrolysis, suggesting a mechanism for promoting the feasibility of cellulosic biofuel production. PMID:27079382

  17. Cellulose synthase interacting protein: a new factor in cellulose synthesis.

    PubMed

    Gu, Ying; Somerville, Chris

    2010-12-01

    Cellulose is the most abundant biopolymer on earth. The great abundance of cellulose places it at the forefront as a primary source of biomass for renewable biofuels. However, the knowledge of how plant cells make cellulose remains very rudimentary. Cellulose microfibrils are synthesized at the plasma membrane by hexameric protein complexes, also known as cellulose synthase complexes. The only known components of cellulose synthase complexes are cellulose synthase (CESA) proteins until the recent identification of a novel component. CSI1, which encodes CESA interacting protein 1 (CSI1) in Arabidopsis. CSI1, as the first non-CESA proteins associated with cellulose synthase complexes, opens up many opportunities.

  18. Solid dispersion of quercetin in cellulose derivative matrices influences both solubility and stability.

    PubMed

    Li, Bin; Konecke, Stephanie; Harich, Kim; Wegiel, Lindsay; Taylor, Lynne S; Edgar, Kevin J

    2013-02-15

    Amorphous solid dispersions (ASD) of quercetin (Que) in cellulose derivative matrices, carboxymethylcellulose acetate butyrate (CMCAB), hydroxypropylmethylcellulose acetate succinate (HPMCAS), and cellulose acetate adipate propionate (CAAdP) were prepared with the goal of identifying an ASD that effectively increased Que aqueous solution concentration. Crystalline quercetin and Que/poly(vinylpyrrolidinone) (PVP) ASD were evaluated for comparison. Powder X-ray diffraction (XRPD) and differential scanning calorimetry (DSC) were used to examine the crystallinity of ASDs, physical mixtures (PM) and quercetin. ASDs were amorphous up to 50 wt% Que. Que stability against crystallization and solution concentrations from these ASDs were significantly higher than those observed for physical mixtures and crystalline Que. PVP stabilizes against both Que degradation and recrystallization; in contrast, these carboxylated cellulose derivatives inhibit recrystallization but release Que slowly. PVP ASDs afforded fast and complete drug release, while ASDs using these three cellulose derivatives provide slow, incomplete, pH-triggered drug release.

  19. Simple X-ray diffraction algorithm for direct determination of cotton crystallinity

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Traditionally, XRD had been used to study the crystalline structure of cotton celluloses. Despite considerable efforts in developing the curve-fitting protocol to evaluate the crystallinity index (CI), in its present state, XRD measurement can only provide a qualitative or semi-quantitative assessme...

  20. Cellulose micro/nanofibres from Eucalyptus kraft pulp: preparation and properties.

    PubMed

    Tonoli, G H D; Teixeira, E M; Corrêa, A C; Marconcini, J M; Caixeta, L A; Pereira-da-Silva, M A; Mattoso, L H C

    2012-06-05

    There is growing interest in cellulose nanofibres from renewable sources for several industrial applications. However, there is a lack of information about one of the most abundant cellulose pulps: bleached Eucalyptus kraft pulp. The objective of the present work was to obtain Eucalyptus cellulose micro/nanofibres by three different processes, namely: refining, sonication and acid hydrolysis of the cellulose pulp. The refining was limited by the low efficiency of isolated nanofibrils, while sonication was more effective for this purpose. However, the latter process occurred at the expense of considerable damage to the cellulose structure. The whiskers obtained by acid hydrolysis resulted in nanostructures with lower diameter and length, and high crystallinity. Increasing hydrolysis reaction time led to narrower and shorter whiskers, but increased the crystallinity index. The present work contributes to the different widespread methods used for the production of micro/nanofibres for different applications.

  1. Hydrophobic modification of cellulose isolated from Agave angustifolia fibre by graft copolymerisation using methyl methacrylate.

    PubMed

    Rosli, Noor Afizah; Ahmad, Ishak; Abdullah, Ibrahim; Anuar, Farah Hannan; Mohamed, Faizal

    2015-07-10

    Graft copolymerisation of methyl methacrylate (MMA) onto Agave angustifolia was conducted with ceric ammonium nitrate (CAN) as the redox initiator. The maximum grafting efficiency was observed at CAN and MMA concentrations of 0.91 × 10(-3) and 5.63 × 10(-2)M, respectively, at 45°C for 3h reaction time. Four characteristic peaks at 2995, 1738, 1440, and 845 cm(-1), attributed to PMMA, were found in the IR spectrum of grafted cellulose. The crystallinity index dropped from 0.74 to 0.46, while the thermal stability improved upon grafting. The water contact angle increased with grafting yield, indicating increased hydrophobicity of cellulose. SEM images showed the grafted cellulose to be enlarged and rougher. The changes in the physical nature of PMMA-grafted cellulose can be attributed to the PMMA grafting in the amorphous regions of cellulose, causing it to expand at the expense of the crystalline component.

  2. Purification and characterization of a cellulose-binding {beta}-glucosidase from cellulose-degrading cultures of phanerochaete chrysosporium

    SciTech Connect

    Lymar, E.S.; Li, B.; Renganathan, V.

    1995-08-01

    Extracellular {beta}-glucosidase from cellulose-degrading cultures of Phanerochaete chrysosporium was purified by DEAE-Sephadex chromatography, by Sephacryl S-200 chromatography, and by fast protein liquid chromatography (FPLC) using a Mono Q anion-exchange column. Sodium dodecyl sulfate-polyacrylamide gel electrophoretic (SDS-PAGE) analysis of FPLC-purified {beta}-glucosidase indicated the presence of three enzyme forms with molecular weights of 96,000, 98,000, and 114,000. On further fractionation with a microcrystalline cellulose column, the 114,000-molecular-weight {beta}-glucosidase, which had 82% of the {beta}-glucosidase activity, was bound to cellulose. The {beta}-glucosidases with molecular weights of 96,000 and 98,000 did not bind to cellulose. The cellulose-bound {beta}-glucosidase was eluted completely from the cellulose matrix with water. Cellulose-bound {beta}-glucosidase catalyzed p-nitrophenylglucoside hydrolysis, suggesting that the catalytic site is not involved in cellulose binding. When the cellulose-binding form was incubated with papain for 20 h, no decrease in the enzyme activity was observed; however, approximately 74% of the papain-treated glucosidase did not bind to microcrystalline cellulose. SDS-PAGE analysis of the nonbinding glucosidase produced by papain indicated the presence of three bands with molecular weights in the range of 95,000 to 97,000. On the basis of these results, we propose that the low-molecular-weight (96,000 and 98,000) non-cellulose-binding {beta}-glucosidase forms are most probably formed from the higher-molecular-weight (114,000) cellulose-binding {beta}-glucosidase via extracellular proteolytic hydrolysis. Also, it appears that the extracellular {beta}-glucosidase from P. chrysosporium might be organized into two domains, a cellulose-binding domain and a catalytic domain. Kinetic characterization of the cellulose-binding form is also presented. 31 refs., 6 figs., 1 tab.

  3. Surface structure, crystallographic and ice-nucleating properties of cellulose

    NASA Astrophysics Data System (ADS)

    Hiranuma, Naruki; Möhler, Ottmar; Kiselev, Alexei; Saathoff, Harald; Weidler, Peter; Shutthanandan, Shuttha; Kulkarni, Gourihar; Jantsch, Evelyn; Koop, Thomas

    2015-04-01

    Increasing evidence of the high diversity and efficient freezing ability of biological ice-nucleating particles is driving a reevaluation of their impact upon climate. Despite their potential importance, little is known about their atmospheric abundance and ice nucleation efficiency, especially non-proteinaceous ones, in comparison to non-biological materials (e.g., mineral dust). Recently, microcrystalline cellulose (MCC; non-proteinaceous plant structural polymer) has been identified as a potential biological ice-nucleating particle. However, it is still uncertain if the ice-nucleating activity is specific to the MCC structure or generally relevant to all cellulose materials, such that the results of MCC can be representatively scaled up to the total cellulose content in the atmosphere to address its role in clouds and the climate system. Here we use the helium ion microscopy (HIM) imaging and the X-ray diffraction (XRD) technique to characterize the nanoscale surface structure and crystalline properties of the two different types of cellulose (MCC and fibrous cellulose extracted from natural wood pulp) as model proxies for atmospheric cellulose particles and to assess their potential accessibility for water molecules. To complement these structural characterizations, we also present the results of immersion freezing experiments using the cold stage-based droplet freezing BINARY (Bielefeld Ice Nucleation ARaY) technique. The HIM results suggest that both cellulose types have a complex porous morphology with capillary spaces between the nanoscale fibrils over the microfiber surface. These surface structures may make cellulose accessible to water. The XRD results suggest that the structural properties of both cellulose materials are in agreement (i.e., P21 space group; a=7.96 Å, b=8.35 Å, c=10.28 Å) and comparable to the crystallographic properties of general monoclinic cellulose (i.e., Cellulose Iβ). The results obtained from the BINARY measurements suggest

  4. Regenerating cellulose from ionic liquids for an accelerated enzymatic hydrolysis

    SciTech Connect

    Zhao, Hua; Jones, Cecil L; Baker, Gary A; Xia, Shuqian; Olubajo, Olarongbe; Person, Vernecia

    2009-01-01

    The efficient conversion of lignocellulosic materials into fuel ethanol has become a research priority in producing affordable and renewable energy. The pretreatment of lignocelluloses is known to be key to the fast enzymatic hydrolysis of cellulose. Recently, certain ionic liquids (ILs)were found capable of dissolving more than 10 wt% cellulose. Preliminary investigations [Dadi, A.P., Varanasi, S., Schall, C.A., 2006. Enhancement of cellulose saccharification kinetics using an ionic liquid pretreatment step. Biotechnol. Bioeng. 95, 904 910; Liu, L., Chen, H., 2006. Enzymatic hydrolysis of cellulose materials treated with ionic liquid [BMIM]Cl. Chin. Sci. Bull. 51, 2432 2436; Dadi, A.P., Schall, C.A., Varanasi, S., 2007. Mitigation of cellulose recalcitrance to enzymatic hydrolysis by ionic liquid pretreatment. Appl. Biochem. Biotechnol. 137 140, 407 421] suggest that celluloses regenerated from IL solutions are subject to faster saccharification than untreated substrates. These encouraging results offer the possibility of using ILs as alternative and nonvolatile solvents for cellulose pretreatment. However, these studies are limited to two chloride-based ILs: (a) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), which is a corrosive, toxic and extremely hygroscopic solid (m.p. 70 C), and (b) 1-allyl-3-methylimidazolium chloride ([AMIM]Cl), which is viscous and has a reactive side-chain. Therefore, more in-depth research involving other ILs is much needed to explore this promising pretreatment route. For this reason, we studied a number of chloride- and acetate-based ILs for cellulose regeneration, including several ILs newly developed in our laboratory. This will enable us to select inexpensive, efficient and environmentally benign solvents for processing cellulosic biomass. Our data confirm that all regenerated celluloses are less crystalline (58 75% lower) and more accessible to cellulase (>2 times) than untreated substrates. As a result, regenerated Avicel

  5. Carbohydrate components and crystalline structure of organosolv hemp (Cannabis sativa L.) bast fibers pulp.

    PubMed

    Gümüşkaya, Esat; Usta, Mustafa; Balaban, Mualla

    2007-02-01

    Changes in carbohydrate components and crystalline structure of hemp bast fibers during organosolv pulping were investigated by X-ray diffractometry, FT-IR spectroscopy and high performance liquid chromatography (HPLC). The reasons for defibrillation and beating problems with organosolv hemp bast fiber pulp were investigated with reference to these properties of pulp samples. Hemp bast fibers and organosolv pulp samples had low hemicellulose contents and high cellulose contents. It was found that the disorder parameter of cellulose in hemp bast fibers was very low, when crystalline cellulose ratio was high and the crystalline structure of cellulose in hemp bast fibers was very stable. These properties affected defibrillation and beating of organosolv hemp bast fibers pulp negatively.

  6. Characterization of Cellulose regenerated from solutions of pine and eucalyptus woods in 1-allyl-3-methilimidazolium chloride.

    PubMed

    Casas, A; Alonso, M V; Oliet, M; Santos, T M; Rodriguez, F

    2013-02-15

    Cellulose is currently separated from lignocellulosic materials using non-environmentally friendly processes. The development of new methods for treating biomass and separating cellulose remains a challenge and would be very useful in the context of the biorefinery philosophy. In this work, cellulose has been regenerated from solutions of Pinus radiata and Eucalyptus globulus woods in 1-allyl-3-methylimidazolium chloride. Wood dissolution was performed in a microwave oven at 120 °C for 20 min. Cellulose was characterized and compared to the reference material, microcrystalline cellulose (MCC). Regenerated celluloses showed lower crystallinity and thermal stability than MCC, although the ash contents at 400 °C were higher than in MCC. The regenerated celluloses were obtained without lignin and almost free from hemicellulose. Furthermore, cellulose was not significantly degraded in the dissolution process of both woods. The insoluble solids showed higher content of lignin and hemicellulose than the raw materials.

  7. Simple citric acid-catalyzed surface esterification of cellulose nanocrystals.

    PubMed

    Ávila Ramírez, Jhon Alejandro; Fortunati, Elena; Kenny, José María; Torre, Luigi; Foresti, María Laura

    2017-02-10

    A simple straightforward route for the surface esterification of cellulose nanocrystals (CNC) is herein proposed. CNC obtained from microcrystalline cellulose were acetylated using as catalyst citric acid, a α-hydroxy acid present in citrus fruits and industrially produced by certain molds in sucrose or glucose-containing medium. No additional solvent was added to the system; instead, the acylant (acetic anhydride) was used in sufficient excess to allow CNC dispersion and proper suspension agitation. By tuning the catalyst load, CNC with two different degree of substitution (i.e. DS=0.18 and 0.34) were obtained. Acetylated cellulose nanocrystals were characterized in terms of chemical structure, crystallinity, morphology, thermal decomposition and dispersion in a non-polar solvent. Results illustrated for the first time the suitability of the protocol proposed for the simple surface acetylation of cellulose nanocrystals.

  8. A comparative study on properties of micro and nanopapers produced from cellulose and cellulose nanofibres.

    PubMed

    Mtibe, A; Linganiso, Linda Z; Mathew, Aji P; Oksman, K; John, Maya J; Anandjiwala, Rajesh D

    2015-03-15

    Cellulose nanocrystals (CNCs) and cellulose nanofibres (CNFs) were successfully extracted from cellulose obtained from maize stalk residues. A variety of techniques, such as Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were used for characterization and the experimental results showed that lignin and hemicellulose were removed to a greater extent by following the chemical methods. Atomic force microscopy (AFM) results confirmed that the diameters of CNCs and CNFs were ranging from 3 to 7 nm and 4 to 10nm, respectively, with their lengths in micro scale. CNCs suspension showed a flow of birefringence, however, the same was not observed in the case of suspension containing CNFs. XRD analysis confirmed that CNCs had high crystallinity index in comparison to cellulose and CNFs. Nanopapers were prepared from CNCs and CNFs by solvent evaporation method. Micropapers were also prepared from cellulose pulp by the same technique. Nanopapers made from CNFs showed less transparency as compared to nanopapers produced from CNCs whereas high transparency as compared to micropaper. Nanopapers produced from CNFs provided superior mechanical properties as compared to both micropaper and nanopapers produced from CNCs. Also, nanopapers produced from CNFs were thermally more stable as compared to nanopapers produced from CNCs but thermally less stable as compared to micropapers.

  9. Nanofabrication in cellulose acetate.

    PubMed

    Zeng, Hongjun; Lajos, Robert; Metlushko, Vitali; Elzy, Ed; An, Se Young; Sautner, Joshua

    2009-03-07

    We have demonstrated nanofabrication with commercialized cellulose acetate. Cellulose acetate is used for bulk nanofabrication and surface nanofabrication. In bulk nanofabrication, cellulose acetate reacts with an e-beam and permanent patterns are formed in it instead of being transferred to other substrates. We have studied the nano relief modulation performance of cellulose acetate before and after development. The depth of the nanopatterns is magnified after development, and is varied by exposing dosage and line width of the pattern. The thinnest 65 nm wide line is achieved in the bulk fabrication. We also demonstrate a binary phase Fresnel lens array which is directly patterned in a cellulose acetate sheet. Because of its unique mechanical and optical properties, cellulose is a good candidate for a template material for soft imprinting lithography. In the surface nanofabrication, cellulose acetate thin film spin-coated on silicon wafers is employed as a new resist for e-beam lithography. We achieved 50 nm lines with 100 nm pitches, dots 50 nm in diameter, and single lines with the smallest width of 20 nm. As a new resist of e-beam lithography, cellulose acetate has high resolution comparable with conventional resists, while having several advantages such as low cost, long stock time and less harmfulness to human health.

  10. Crystalline and Crystalline International Disposal Activities

    SciTech Connect

    Viswanathan, Hari S.; Chu, Shaoping; Reimus, Paul William; Makedonska, Nataliia; Hyman, Jeffrey De'Haven; Karra, Satish; Dittrich, Timothy M.

    2015-12-21

    This report presents the results of work conducted between September 2014 and July 2015 at Los Alamos National Laboratory in the crystalline disposal and crystalline international disposal work packages of the Used Fuel Disposition Campaign (UFDC) for DOE-NE’s Fuel Cycle Research and Development program.

  11. Microwave-assisted pretreatment of cellulose in ionic liquid for accelerated enzymatic hydrolysis.

    PubMed

    Ha, Sung Ho; Mai, Ngoc Lan; An, Gwangmin; Koo, Yoon-Mo

    2011-01-01

    For increasing cellulose accessibility to the enzymatic attack, the pretreatment is a necessary step to alter some structural characteristics of cellulosic materials. As a new pretreatment method, microwave irradiation on cellulose dissolution pretreatment with ionic liquids (ILs) was investigated in this study. Microwave irradiation not only enhanced the solubility of cellulose in ILs but also significantly decreased the degree of polymerization of regenerated cellulose after IL dissolution pretreatment, resulting in significant improvement of cellulose hydrolysis. The rate of enzymatic hydrolysis of cotton cellulose was increased by at least 12-fold after IL dissolution pretreatment at 110 °C and by 50-fold after IL dissolution pretreatment with microwave irradiation. Our results demonstrate that cellulose pretreatment with ILs and microwave irradiation is a potential alternative method for the pretreatment of cellulosic materials.

  12. Bacterial cellulose-kaolin nanocomposites for application as biomedical wound healing materials

    NASA Astrophysics Data System (ADS)

    Wanna, Dwi; Alam, Catharina; Toivola, Diana M.; Alam, Parvez

    2013-12-01

    This short communication provides preliminary experimental details on the structure-property relationships of novel biomedical kaolin-bacterial cellulose nanocomposites. Bacterial cellulose is an effective binding agent for kaolin particles forming reticulated structures at kaolin-cellulose interfaces and entanglements when the cellulose fraction is sufficiently high. The mechanical performance of these materials hence improves with an increased fraction of bacterial cellulose, though this also causes the rate of blood clotting to decrease. These composites have combined potential as both short-term (kaolin) and long-term (bacterial cellulose) wound healing materials.

  13. Enhanced cellulose degradation using cellulase-nanosphere complexes.

    PubMed

    Blanchette, Craig; Lacayo, Catherine I; Fischer, Nicholas O; Hwang, Mona; Thelen, Michael P

    2012-01-01

    Enzyme catalyzed conversion of plant biomass to sugars is an inherently inefficient process, and one of the major factors limiting economical biofuel production. This is due to the physical barrier presented by polymers in plant cell walls, including semi-crystalline cellulose, to soluble enzyme accessibility. In contrast to the enzymes currently used in industry, bacterial cellulosomes organize cellulases and other proteins in a scaffold structure, and are highly efficient in degrading cellulose. To mimic this clustered assembly of enzymes, we conjugated cellulase obtained from Trichoderma viride to polystyrene nanospheres (cellulase:NS) and tested the hydrolytic activity of this complex on cellulose substrates from purified and natural sources. Cellulase:NS and free cellulase were equally active on soluble carboxymethyl cellulose (CMC); however, the complexed enzyme displayed a higher affinity in its action on microcrystalline cellulose. Similarly, we found that the cellulase:NS complex was more efficient in degrading natural cellulose structures in the thickened walls of cultured wood cells. These results suggest that nanoparticle-bound enzymes can improve catalytic efficiency on physically intractable substrates. We discuss the potential for further enhancement of cellulose degradation by physically clustering combinations of different glycosyl hydrolase enzymes, and applications for using cellulase:NS complexes in biofuel production.

  14. Nanocrystalline cellulose extracted from pine wood and corncob.

    PubMed

    Ditzel, Fernanda I; Prestes, Eduardo; Carvalho, Benjamim M; Demiate, Ivo M; Pinheiro, Luís A

    2017-02-10

    The extraction of nanocrystalline cellulose from agro-residues is an interesting alternative to recover these materials. In the present study, nanocrystalline cellulose was extracted from pine wood and corncob. In addition, microcrystalline cellulose was used as a reference to compare results. Initially, the lignocellulosic residues were submitted to delignification pre-treatments. At the end of the process, the bleached fibre was submitted to acid hydrolysis. Additionally, microparticles were obtained from the spray-drying of the nanocrystalline cellulose suspensions. The nanocrystalline cellulose yield for the pine wood was 9.0-% of the value attained for the microcrystalline cellulose. For the corncob, the value was 23.5-%. Therefore, complementary studies are necessary to improve the yield. The spray-dried microparticles showed a crystallinity index of 67.8-% for the pine wood, 70.9-% for the corncob and 79.3-% for the microcrystalline cellulose. These microparticles have great potential for use in the production of polymer composites processed by extrusion.

  15. Preparation and Characterization of Cellulose Microcrystalline (MCC) from Fiber of Empty Fruit Bunch Palm Oil

    NASA Astrophysics Data System (ADS)

    Nasution, H.; Yurnaliza; Veronicha; Irmadani; Sitompul, S.

    2017-03-01

    Alpha cellulose which was isolated from cellulose of fiber empty fruit bunch palm oil was hidrolized with hydrochloric acid (2,5N) at 80°C to produce microcrystalline cellulose (MCC). Microcrystalline cellulose is an important additional ingredient in the pharmaceutical, food, cosmetics, and structural composites. In this study, MCC, alpha cellulose, and cellulose were characterized and thereafter were compared. Characterizations were made using some equipment such as x-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and thermogravimetry analyzer (TGA). X-ray diffraction and infrared spectroscopy were studied to determine crystallinity and molecular structure of MCC, where scanning electron microscopy images were conducted for information about morfology of MCC. Meanwhile, thermal resistance of MCC was determined using thermogravimetry analyzer (TGA). From XRD and FTIR, the obtained results showed that the crystalline part was traced on MCC, where the –OH and C-O groups tended to reduced as alpha cellulose has changed to MCC. From SEM the image showed the reduction of particle size of MCC, while the thermal resistance of MCC was found lower as compared with cellulose and alpha cellulose as well, which was attributed to the lower molecular weight of MCC.

  16. Visualization of Trichoderma reesei cellobiohydrolase I and endoglucanase I on aspen cellulose by using monoclonal antibody-colloidal gold conjugates

    SciTech Connect

    Nieves, R.A.; Grohmann, K.; Himmel, M.E. ); Ellis, R.P.; Todd, R.J.; Johnson, T.J.A. )

    1991-11-01

    Monoclonal antibodies (MAbs) specific for cellobiohydrolase I (CBH I) and endoglucanase I (EG I) were conjugated to 10- and 15-nm colloidal gold particles, respectively. The binding of CBH I and EG I was visualized by utilizing the MAb-colloidal gold probes. The visualization procedure involved immobilization of cellulose microfibrils on copper electron microscopy grids, incubation of the cellulose-coated grids with cellulase(s), binding of MAb-colloidal gold conjugates to cellulase(s), and visualization via transmission electron microscopy. CBH I was seen bound to apparent crystalline cellulose as well as apparent amorphous cellulose. EG I was seen bound extensively to apparent amorphous cellulose with minimal binding to crystalline cellulose.

  17. Cellulose produced by Gluconacetobacter xylinus strains ATCC 53524 and ATCC 23768: Pellicle formation, post-synthesis aggregation and fiber density.

    PubMed

    Lee, Christopher M; Gu, Jin; Kafle, Kabindra; Catchmark, Jeffrey; Kim, Seong H

    2015-11-20

    The pellicle formation, crystallinity, and bundling of cellulose microfibrils produced by bacterium Gluconacetobacter xylinus were studied. Cellulose pellicles were produced by two strains (ATCC 53524 and ATCC 23769) for 1 and 7 days; pellicles were analyzed with scanning electron microscopy (SEM), X-ray diffraction (XRD), vibrational sum-frequency-generation (SFG) spectroscopy, and attenuated total reflectance infrared (ATR-IR) spectroscopy. The bacterial cell population was higher at the surface exposed to air, indicating that the newly synthesized cellulose is deposited at the top of the pellicle. XRD, ATR-IR, and SFG analyses found no significant changes in the cellulose crystallinity, crystal size or polymorphic distribution with the culture time. However, SEM and SFG analyses revealed cellulose macrofibrils produced for 7 days had a higher packing density at the top of the pellicle, compared to the bottom. These findings suggest that the physical properties of cellulose microfibrils are different locally within the bacterial pellicles.

  18. Expression of a mutant form of cellulose synthase AtCesA7 causes dominant negative effect on cellulose biosynthesis.

    PubMed

    Zhong, Ruiqin; Morrison, W Herbert; Freshour, Glenn D; Hahn, Michael G; Ye, Zheng-Hua

    2003-06-01

    Cellulose synthase catalytic subunits (CesAs) have been implicated in catalyzing the biosynthesis of cellulose, the major component of plant cell walls. Interactions between CesA subunits are thought to be required for normal cellulose synthesis, which suggests that incorporation of defective CesA subunits into cellulose synthase complex could potentially cause a dominant effect on cellulose synthesis. However, all CesA mutants so far reported have been shown to be recessive in terms of cellulose synthesis. In the course of studying the molecular mechanisms regulating secondary wall formation in fibers, we have found that a mutant allele of AtCesA7 gene in the fra5 (fragile fiber 5) mutant causes a semidominant phenotype in the reduction of fiber cell wall thickness and cellulose content. The fra5 missense mutation occurred in a conserved amino acid located in the second cytoplasmic domain of AtCesA7. Overexpression of the fra5 mutant cDNA in wild-type plants not only reduced secondary wall thickness and cellulose content but also decreased primary wall thickness and cell elongation. In contrast, overexpression of the fra6 mutant form of AtCesA8 did not cause any reduction in cell wall thickness and cellulose content. These results suggest that the fra5 mutant protein may interfere with the function of endogenous wild-type CesA proteins, thus resulting in a dominant negative effect on cellulose biosynthesis.

  19. Monitoring meso-scale ordering of cellulose in intact plant cell walls using sum frequency generation spectroscopy.

    PubMed

    Park, Yong Bum; Lee, Christopher M; Koo, Bon-Wook; Park, Sunkyu; Cosgrove, Daniel J; Kim, Seong H

    2013-10-01

    Sum frequency generation (SFG) vibration spectroscopy can selectively detect crystalline cellulose without spectral interference from cell wall matrix components. Here, we show that the cellulose SFG spectrum is sensitive to cellulose microfibril alignment and packing within the cell wall. SFG intensity at 2,944 cm(-1) correlated well with crystalline cellulose contents of various regions of the Arabidopsis (Arabidopsis thaliana) inflorescence, while changes in the 3,320/2,944 cm(-1) intensity ratio suggest subtle changes in cellulose ordering as tissues mature. SFG analysis of two cellulose synthase mutants (irx1/cesa8 and irx3/cesa7) indicates a reduction in cellulose content without evidence of altered cellulose structure. In primary cell walls of Arabidopsis, cellulose exhibited a characteristic SFG peak at 2,920 and 3,320 cm(-1), whereas in secondary cell walls, it had peaks at 2,944 and 3,320 cm(-1). Starch (amylose) gave an SFG peak at 2,904 cm(-1) (CH methine) whose intensity increased with light exposure prior to harvest. Selective removal of matrix polysaccharides from primary cell walls by acid hydrolysis resulted in an SFG spectrum resembling that of secondary wall cellulose. Our results show that SFG spectroscopy is sensitive to the ordering of cellulose microfibrils in plant cell walls at the meso scale (nm to μm) that is important for cell wall architecture but cannot be probed by other spectroscopic or diffraction techniques.

  20. Conductance phenomena in microcrystalline cellulose

    NASA Astrophysics Data System (ADS)

    Nilsson, M.

    2006-02-01

    We have investigated the conduction phenomena in compacted tablets of cellulose with varying relative humidity (RH) with techniques such as Low Frequency Dielectric Spectroscopy (LFDS) and Transient Current (TC) at room temperature. Two exponential decaying regions in the transient current measurements indicate two ionic species contributing to the conduction mechanism. A high power-law exponent of 9 for the conductance with moisture content has been found. The mobility initially decreases with RH up to monolayer coverage, and further water vapor increases the mobility, indicating a blocking of available positions for the charge carrier ions. When the amount of water molecules present in the tablet increases one order of magnitude, the number of charge carriers increases 5-6 orders of magnitude, suggesting a transition from a power-law increase to a linear effective medium theory for the conduction. The charge carrier dependence on RH suggests that a percolating network of water molecules adsorbed to 6-OH units on the cellulose chain span through the sample. The conductivity mechanisms in cellulose are still not clear.

  1. Surface Plasmon Resonance Studies of Polysaccharide Self-Assembly on Cellulose

    NASA Astrophysics Data System (ADS)

    Kaya, Abdulaziz; Esker, Alan R.; Glasser, Wolfgang G.

    2006-03-01

    Wood is a multiphase material consisting of cellulose crystals embedded within a non-crystalline hetereopolysaccharide (hemicellulose) and lignin rich phase. The hierarchial arrangement of these three chief components in wood produces excellent properties like resistance to fracture and toughness. Through the study of polysaccharide self-assembly onto a model cellulose surface, further insight into the interactions between hemicelluloses and cellulose can be gained. In our study, we synthesized pullulan cinnamates with different degrees of substitution of cinnamoyl groups as a model for a hemicellulose with lignin-like moieties. Surface plasmon resonance measurements probe the self-assembly behavior of pullulan and pullulan cinnamate onto a cellulose coated gold surface. Our results suggest that pullulan does not adsorb onto the model cellulose surface, whereas pullulan cinnamate does. These preliminary results signify the important role that lignin-like substituents play on hemicellulose self-assembly onto cellulose surfaces.

  2. Effect of phosphoric acid pretreatment on enzymatic hydrolysis of microcrystalline cellulose.

    PubMed

    Zhang, Juanhua; Zhang, Beixiao; Zhang, Jingqiang; Lin, Lu; Liu, Shijie; Ouyang, Pingkai

    2010-01-01

    Microcrystalline cellulose (MCC) was pretreated with phosphoric acid at 323K for 10h. X-ray diffraction (XRD) and Atomic Force Microscope (AFM) analyses revealed that the fiber surface morphology of pretreated MCC (P-MCC) were uneven and rough with the crystalline diffraction peaks of P-MCC decreased to a distinct range. The X-ray Photoelectron Spectroscopy (XPS) analysis showed that the uneven and rough surface of P-MCC could enhance the adsorption of cellulose to the molecular surface of cellulose, which is one of the key factors affecting enzymatic hydrolysis of cellulose. A reversible first order kinetics was employed to describe the adsorption kinetics of cellulase to MCC and P-MCC, and the adsorption rate constants of MCC and P-MCC were found to be 0.016, 0.024, 0.041, and 0.095, 0.149, 0.218min(-1), respectively at 278K, 293K and 308K. The activation energies of MCC and P-MCC hydrolysis reactions were found to be 22.257 and 19.721kJ mol(-1). The major hydrolysis products of MCC and P-MCC were cellobiose and glucose. Hydrolysis of MCC for 120h resulted in yields of glucose (7.21%), cellobiose (13.16%) and total sugars (20.37%). However, after the pretreatment with phosphoric acid, the corresponding sugar yields resulted from enzymatic hydrolysis of P-MCC were increased to 24.10%, 41.42%, and 65.52%; respectively, which were 3.34, 3.15, and 3.22 times of the sugars yields from enzymatic hydrolysis of MCC.

  3. Cellulose Nanocrystals as Water in Water Emulsion Stabilizers

    NASA Astrophysics Data System (ADS)

    Peddireddy, Karthik Reddy; Capron, Isabelle; Nicolai, Taco; Benyahia, Lazhar

    Cellulose is the most abundant polymer on the earth. Thus, it is very much desirable to find as many practical applications as possible for it. Cellulose, in its original form, contains both amorphous and crystalline parts. It is possible to separate both parts by dissolving the amorphous part in concentrated sulfuric acid. The remaining crystalline cellulose part exist in the form of rod-like particles. The dimensions of the particles depend on the source. We produce the particles from the acid hydrolysis of cotton cellulose fibers. It results in cellulose nanocrystals (CNCs) with dimensions of ~150 nm x 6 nm x 6 nm. It is well known that CNCs could very efficiently stabilize oil in water (O/W) emulsions by forming very dense monolayers of CNCs at O-W interfaces. However, it is not yet known whether they could also stabilize water in water (W/W) emulsions. The W/W emulsions can be produced by any two incompatible polymers. It is challenging to find effective stabilizers for W/W emulsions due to ultralow interfacial tension and large interfacial thickness. In this talk, I will show the efficiency and effectiveness of these one-dimensional rods as W/W emulsion stabilizers.

  4. Alexa fluor-labeled fluorescent cellulose nanocrystals for bioimaging solid cellulose in spatially structured microenvironments.

    PubMed

    Grate, Jay W; Mo, Kai-For; Shin, Yongsoon; Vasdekis, Andreas; Warner, Marvin G; Kelly, Ryan T; Orr, Galya; Hu, Dehong; Dehoff, Karl J; Brockman, Fred J; Wilkins, Michael J

    2015-03-18

    Methods to covalently conjugate Alexa Fluor dyes to cellulose nanocrystals, at limiting amounts that retain the overall structure of the nanocrystals as model cellulose materials, were developed using two approaches. In the first, aldehyde groups are created on the cellulose surfaces by reaction with limiting amounts of sodium periodate, a reaction well-known for oxidizing vicinal diols to create dialdehyde structures. Reductive amination reactions were then applied to bind Alexa Fluor dyes with terminal amino-groups on the linker section. In the absence of the reductive step, dye washes out of the nanocrystal suspension, whereas with the reductive step, a colored product is obtained with the characteristic spectral bands of the conjugated dye. In the second approach, Alexa Fluor dyes were modified to contain chloro-substituted triazine ring at the end of the linker section. These modified dyes then were reacted with cellulose nanocrystals in acetonitrile at elevated temperature, again isolating material with the characteristic spectral bands of the Alexa Fluor dye. Reactions with Alexa Fluor 546 are given as detailed examples, labeling on the order of 1% of the total glucopyranose rings of the cellulose nanocrystals at dye loadings of ca. 5 μg/mg cellulose. Fluorescent cellulose nanocrystals were deposited in pore network microfluidic structures (PDMS) and proof-of-principle bioimaging experiments showed that the spatial localization of the solid cellulose deposits could be determined, and their disappearance under the action of Celluclast enzymes or microbes could be observed over time. In addition, single molecule fluorescence microscopy was demonstrated as a method to follow the disappearance of solid cellulose deposits over time, following the decrease in the number of single blinking dye molecules with time instead of fluorescent intensity.

  5. Crystallite width determines monolayer hydration across a wide spectrum of celluloses isolated from plants.

    PubMed

    Driemeier, Carlos; Bragatto, Juliano

    2013-01-10

    Relating cellulose structure to its water uptake is a classical problem with many investigations done through measurements of cellulose "crystallinity". However, there is presently a growing consensus that crystallinity measurements are appreciably uncertain, leading to ambiguous interpretations of underlying cellulose organization. In this scenario, this article revisits the relations between cellulose structure and water uptake, moving the emphasis away from degree of crystallinity and directing it toward crystallite width, which is inferred with less ambiguity from the broadening of 200 X-ray diffraction peaks. With this approach, analysis of a wide spectrum of celluloses isolated from plants (preserving cellulose I phase and having variable contents of residual hemicelluloses) reveals a simple linear relation (R(2) = 0.98) between reciprocal crystallite width and monolayer hydration (determined from vapor sorption). The primary role of crystallite width supports that most water-accessible polysaccharides are laterally associated with the crystallites, with a minor fraction in disordered domains along the fibrils. Furthermore, the secondary role left to hemicellulosic contents indicates cellulose being partly decrystallized to complement the disordered amount required to interface the crystallites. Finally, a substantial part of hydration is attributed to polysaccharides in voids left by the imperfect packing of aggregated crystallites.

  6. A uniaxially oriented nanofibrous cellulose scaffold from pellicles produced by Gluconacetobacter xylinus in dissolved oxygen culture.

    PubMed

    Nagashima, Aya; Tsuji, Tsubasa; Kondo, Tetsuo

    2016-01-01

    An aerobic, Gram-negative bacterium, Gluconacetobacter xylinus, was successfully employed to produce a stretchable cellulose nanofiber pellicle using dissolved oxygen in a conventional cultured medium. The obtained nanofibers were highly crystalline with the metastable cellulose Iα phase being apparently the dominant phase by more than 90%. The obtained pellicle could be stretched by up to 1.5 times to provide oriented crystalline nanofibrous films. Low heating of the nanofibrous film induced the transformation of the dominant cellulosecrystalline phase into the Iβ crystalline phase without a loss of crystallinity or the high Young's modulus. The film also exhibited unique and anisotropic viscoelastic and mechanical properties as well as superior thermal stability compared with conventional high-performance synthetic polymeric materials. In addition, when G. xylinus cells were transferred to the oriented surface after stretched, they started to synthesize cellulose ribbons that parallel the nanofiber orientation of the substrate. This function as a template was evidenced by direct video imaging of the motion of the bacteria. The application of a bacterial culture using dissolved oxygen in the medium offers the fabrication of novel anisotropic and nanofibrous scaffold of cellulose Iα.

  7. Fulton Cellulosic Ethanol Biorefinery

    SciTech Connect

    Sumait, Necy; Cuzens, John; Klann, Richard

    2015-07-24

    Final report on work performed by BlueFire on the deployment of acid hydrolysis technology to convert cellulosic waste materials into renewable fuels, power and chemicals in a production facility to be located in Fulton, Mississippi.

  8. Acid hydrolysis of cellulose in zinc chloride solution

    SciTech Connect

    Cao, N.J.; Xu, Q.; Chen, L.F.

    1995-12-31

    The efficient conversion of cellulosic materials to ethanol has been hindered by the low yield of sugars, the high energy consumption in pretreatment processes, and the difficulty of recycling the pre-treatment agents. Zinc chloride may provide an alternative for pre-treating biomass prior to the hydrolysis of cellulose. The formation of a zinc-cellulose complex during the pretreatment of cellulose improves the yield of glucose in both the enzymatic and acid hydrolysis of cellulose. Low-temperature acid hydrolysis of cellulose in zinc chloride solution is carried out in two stages, a liquefaction stage and a saccharification stage. Because of the formation of zinc-cellulose complex in the first stage, the required amount of acid in the second stage has been decreased significantly. In 67% zinc chloride solution, a 99.5% yield of soluble sugars has been obtained at 70{degrees}C and 0.5M acid concentration. The ratio of zinc chloride to cellulose has been reduced from 4.5 to 1.5, and the yield of soluble sugars is kept above 80%. The rate of hydrolysis is affected by the ratio of zinc chloride to cellulose, acid concentration, and temperature.

  9. Genomics of cellulosic biofuels.

    PubMed

    Rubin, Edward M

    2008-08-14

    The development of alternatives to fossil fuels as an energy source is an urgent global priority. Cellulosic biomass has the potential to contribute to meeting the demand for liquid fuel, but land-use requirements and process inefficiencies represent hurdles for large-scale deployment of biomass-to-biofuel technologies. Genomic information gathered from across the biosphere, including potential energy crops and microorganisms able to break down biomass, will be vital for improving the prospects of significant cellulosic biofuel production.

  10. Functional Studies of β-Glucosidases of Cytophaga hutchinsonii and Their Effects on Cellulose Degradation

    PubMed Central

    Bai, Xinfeng; Wang, Xifeng; Wang, Sen; Ji, Xiaofei; Guan, Zhiwei; Zhang, Weican; Lu, Xuemei

    2017-01-01

    Cytophaga hutchinsonii can rapidly digest crystalline cellulose without free cellulases or cellulosomes. Its cell-contact cellulose degradation mechanism is unknown. In this study, the four β-glucosidase (bgl) genes in C. hutchinsonii were singly and multiply deleted, and the functions of these β-glucosidases in cellobiose and cellulose degradation were investigated. We found that the constitutively expressed BglB played a key role in cellobiose utilization, while BglA which was induced by cellobiose could partially make up for the deletion of bglB. The double deletion mutant ΔbglA/bglB lost the ability to digest cellobiose and could not thrive in cellulose medium, indicating that β-glucosidases were important for cellulose degradation. When cultured in cellulose medium, a small amount of glucose accumulated in the medium in the initial stage of growth for the wild type, while almost no glucose accumulated for ΔbglA/bglB. When supplemented with a small amount of glucose, ΔbglA/bglB started to degrade cellulose and grew in cellulose medium. We inferred that glucose might be essential for initiating cellulose degradation, and with additional glucose, C. hutchinsonii could partially utilize cellulose without β-glucosidases. We also found that there were both cellulose binding cells and free cells when cultured in cellulose. Since direct contact between C. hutchinsonii cells and cellulose is necessary for cellulose degradation, we deduced that the free cells which were convenient to explore new territory in the environment might be fed by the adherent cells which could produce cello-oligosaccharide and glucose into the environment. This study enriched our knowledge of the cellulolytic pathway of C. hutchinsonii. PMID:28210251

  11. Functional Studies of β-Glucosidases of Cytophaga hutchinsonii and Their Effects on Cellulose Degradation.

    PubMed

    Bai, Xinfeng; Wang, Xifeng; Wang, Sen; Ji, Xiaofei; Guan, Zhiwei; Zhang, Weican; Lu, Xuemei

    2017-01-01

    Cytophaga hutchinsonii can rapidly digest crystalline cellulose without free cellulases or cellulosomes. Its cell-contact cellulose degradation mechanism is unknown. In this study, the four β-glucosidase (bgl) genes in C. hutchinsonii were singly and multiply deleted, and the functions of these β-glucosidases in cellobiose and cellulose degradation were investigated. We found that the constitutively expressed BglB played a key role in cellobiose utilization, while BglA which was induced by cellobiose could partially make up for the deletion of bglB. The double deletion mutant ΔbglA/bglB lost the ability to digest cellobiose and could not thrive in cellulose medium, indicating that β-glucosidases were important for cellulose degradation. When cultured in cellulose medium, a small amount of glucose accumulated in the medium in the initial stage of growth for the wild type, while almost no glucose accumulated for ΔbglA/bglB. When supplemented with a small amount of glucose, ΔbglA/bglB started to degrade cellulose and grew in cellulose medium. We inferred that glucose might be essential for initiating cellulose degradation, and with additional glucose, C. hutchinsonii could partially utilize cellulose without β-glucosidases. We also found that there were both cellulose binding cells and free cells when cultured in cellulose. Since direct contact between C. hutchinsonii cells and cellulose is necessary for cellulose degradation, we deduced that the free cells which were convenient to explore new territory in the environment might be fed by the adherent cells which could produce cello-oligosaccharide and glucose into the environment. This study enriched our knowledge of the cellulolytic pathway of C. hutchinsonii.

  12. Facile approach for the dispersion of regenerated cellulose in aqueous system in the form of nanoparticles.

    PubMed

    Adsul, Mukund; Soni, Sarvesh K; Bhargava, Suresh K; Bansal, Vipul

    2012-09-10

    This study reports a facile method to disperse cellulose in deionized water, wherein a critical condition of regenerated cellulose is discovered, where it completely disperses up to a maximum of 5 g L(-1) concentration in deionized water with the help of ultrasonication. The dispersed cellulose is characterized by TEM and DLS, the latter among which shows 200 nm hydrodynamic radii of cellulose nanoparticles dispersed in deionized water. FTIR analysis of dispersed cellulose reveals that dispersed cellulose losses its crystallinity during regeneration and dispersion step employed in this study. The dispersed cellulose reported in this study is able to form free-standing, transparent films, which were characterized by SEM, XRD, TGA, EDX, and FTIR spectroscopy and show resistance against dissolution in water. Additionally, the dispersed cellulose is able to undergo at least three times faster enzymatic hydrolysis in comparison to pristine microcrystalline cellulose under similar reaction conditions. The dispersed cellulose reported here could be a better material for reinforcement, preparation of hydrogels, and drug delivery applications under physiological environment.

  13. Characterisation of spray dried soy sauce powders made by adding crystalline carbohydrates to drying carrier.

    PubMed

    Wang, Wei; Zhou, Weibiao

    2015-02-01

    This study aimed to reduce stickiness and caking of spray dried soy sauce powders by introducing a new crystalline structure into powder particles. To perform this task, soy sauce powders were formulated by using mixtures of cellulose and maltodextrin or mixtures of waxy starch and maltodextrin as drying carriers, with a fixed carrier addition rate of 30% (w/v) in the feed solution. The microstructure, crystallinity, solubility as well as stickiness and caking strength of all the different powders were analysed and compared. Incorporating crystalline carbohydrates in the drying carrier could significantly reduce the stickiness and caking strength of the powders when the ratio of crystalline carbohydrates to maltodextrin was above 1:5 and 1:2, respectively. X-ray Diffraction (XRD) results showed that adding cellulose or waxy starch could induce the crystallinity of powders. Differential Scanning Calorimetry (DSC) results demonstrated that the native starch added to the soy sauce powders did not fully gelatinize during spray drying.

  14. Cellulose fermentation by nitrogen-fixing anaerobic bacteria

    SciTech Connect

    Canale-Parola, E.

    1992-12-13

    In anaerobic natural environments cellulose is degraded to methane, carbon dioxide and other products by the combined activities of many diverse microorganisms. We are simulating processes occurring in natural environments by constructing biologically-defined, stable, heterogeneous bacterial communities (consortia) that we use as in vitro systems for quantitative studies of cellulose degradation under conditions of combined nitrogen deprivation. These studies include the investigation of (i) metabolic interactions among members of cellulose-degrading microbial populations, and (ii) processes that regulate the activity or biosynthesis of cellulolytic enzymes. In addition, we are studying the sensory mechanisms that, in natural environments, may enable motile cellulolytic bacteria to migrate toward cellulose. This part of our work includes biochemical characterization of the cellobiose chemoreceptor of cellulolytic bacteria. Finally, an important aspect of our research is the investigation of the mechanisms by which multienzyme complexes of anaerobic bacteria catalyze the depolymerization of crystalline cellulose and of other plant cell wall polysacchaddes. The research will provide fundamental information on the physiology and ecology of cellulose-fermenting, N{sub 2}-fixing bacteria, and on the intricate processes involved in C and N cycling in anaerobic environments. Furthermore, the information will be valuable for the development of practical applications, such as the conversion of plant biomass (e.g., agricultural, forestry and municipal wastes) to automotive fuels such as ethanol.

  15. Manufacture of cellulose nanocrystals by cation exchange resin-catalyzed hydrolysis of cellulose.

    PubMed

    Tang, Li-rong; Huang, Biao; Ou, Wen; Chen, Xue-rong; Chen, Yan-dan

    2011-12-01

    Cellulose nanocrystals (CNC) were prepared from microcrystalline cellulose (MCC) by hydrolysis with cation exchange resin (NKC-9) or 64% sulfuric acid. The cation exchange resin hydrolysis parameters were optimized by using the Box-Behnken design and response surface methodology. An optimum yield (50.04%) was achieved at a ratio of resin to MCC (w/w) of 10, a temperature of 48 °C and a reaction time of 189 min. Electron microscopy (EM) showed that the diameter of CNCs was about 10-40 nm, and the length was 100-400 nm. Regular short rod-like CNCs were obtained by sulfuric acid hydrolysis, while long and thin crystals of cellulose were obtained with the cation exchange resin. X-ray diffraction (XRD) showed that, compared with MCC, the crystallinity of H2SO4-CNC and resin-CNC increased from 72.25% to 77.29% and 84.26%, respectively. The research shows that cation exchange resin-catalyzed hydrolysis of cellulose could be an excellent method for manufacturing of CNC in an environmental-friendly way.

  16. The correlation between cellulose allomorphs (I and II) and conversion after removal of hemicellulose and lignin of lignocellulose.

    PubMed

    Song, Yanliang; Zhang, Jingzhi; Zhang, Xu; Tan, Tianwei

    2015-10-01

    H2SO4, NaOH and H3PO4 were applied to decompose lignocellulose samples (giant reeds, pennisetum and cotton stalks) to investigate the correlation between cellulose allomorphs (cellulose I and II) and conversion of cellulose. The effect of removal of hemicellulose and lignin on the surface morphology, crystallinity index (CrI), cellulose allomorphs (cellulose I and II), and enzymatic hydrolysis under different pretreatments was also studied. CrI caused by H3PO4 pretreatment reached 11.19%, 24.93% and 8.15% for the three samples, respectively. Corn stalk showed highest conversion of cellulose among three samples, irrespective of the pretreatment used. This accounted for the widely use of corn stalk as the renewable crop substrate to synthesize biofuels like ethanol. CrI of cellulose I (CrI-I) negatively affects cellulose conversion but CrI of cellulose II (CrI-II) positively affects cellulose conversion. It contributes to make the strategy to transform cellulose I to cellulose II and enhancing enzymatic hydrolysis of lignocellulose.

  17. Modification of bacterial cellulose through exposure to the rotating magnetic field.

    PubMed

    Fijałkowski, Karol; Żywicka, Anna; Drozd, Radosław; Niemczyk, Agata; Junka, Adam Feliks; Peitler, Dorota; Kordas, Marian; Konopacki, Maciej; Szymczyk, Patrycja; Fray, Mirosława El; Rakoczy, Rafał

    2015-11-20

    The aim of the study was to assess the influence of rotating magnetic field (RMF) on production rate and quality parameters of bacterial cellulose synthetized by Glucanacetobacter xylinus. Bacterial cultures were exposed to RMF (frequency f=50Hz, magnetic induction B=34mT) for 72h at 28°C. The study revealed that cellulose obtained under RMF influence displayed higher water absorption, lower density and less interassociated microfibrils comparing to unexposed control. The application of RMF significantly increased the amount of obtained wet cellulose pellicles but decreased the weight and thickness of dry cellulose. Summarizing, the exposure of cellulose-synthesizing G. xylinus to RMF alters cellulose biogenesis and may offer a new biotechnological tool to control this process. As RMF-modified cellulose displays better absorbing properties comparing to non-modified cellulose, our finding, if developed, may find application in the production of dressings for highly exudative wounds.

  18. High-Strength Composite Fibers from Cellulose-Lignin Blends Regenerated from Ionic Liquid Solution.

    PubMed

    Ma, Yibo; Asaadi, Shirin; Johansson, Leena-Sisko; Ahvenainen, Patrik; Reza, Mehedi; Alekhina, Marina; Rautkari, Lauri; Michud, Anne; Hauru, Lauri; Hummel, Michael; Sixta, Herbert

    2015-12-07

    Composite fibres that contain cellulose and lignin were produced from ionic liquid solutions by dry-jet wet spinning. Eucalyptus dissolving pulp and organosolv/kraft lignin blends in different ratios were dissolved in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate to prepare a spinning dope from which composite fibres were spun successfully. The composite fibres had a high strength with slightly decreasing values for fibres with an increasing share of lignin, which is because of the reduction in crystallinity. The total orientation of composite fibres and SEM images show morphological changes caused by the presence of lignin. The hydrophobic contribution of lignin reduced the vapour adsorption in the fibre. Thermogravimetric analysis curves of the composite fibres reveal the positive effect of the lignin on the carbonisation yield. Finally, the composite fibre was found to be a potential raw material for textile manufacturing and as a precursor for carbon fibre production.

  19. Effects of processing on the properties of chitosan/cellulose nanocrystal films.

    PubMed

    Celebi, Hande; Kurt, Ayse

    2015-11-20

    Biocomposites of chitosan (CS)/cellulose nanocrystals (CN) were prepared by using solution casting method. Influences of solution preparation method and CN content on the properties of composites were investigated. Mechanical stirring/ultrasonication or microfluidization were used to disperse nanocrystals in the chitosan matrix. The prepared nanocomposites were characterized by FTIR, XRD, SEM, DSC, TGA, TMA and contact angle measurements. SEM analysis revealed that microfluidization decreased CN aggregates in matrix. Formation of hydrogen bonds between CS and CN in nanocomposites prepared by using microfluidization was confirmed by FTIR spectroscopy. This high interaction led to an increment of the crystallinity of chitosan films. Tg values within a range of 53-58°C were obtained in DSC and TMA measurements. The thermal stability of CS film showed no significant effect of CN addition, whereas contact angle measurements revealed that CN addition resulted in an increment of hydrophilicity of chitosan films.

  20. A coarse-grain force-field for xylan and its interaction with cellulose.

    PubMed

    Li, Liang; Pérré, Patrick; Frank, Xavier; Mazeau, Karim

    2015-01-01

    We have built a coarse-grain (CG) model describing xylan and its interaction with crystalline cellulose surfaces. Each xylosyl or glucosyl unit was represented by a single grain. Our calculations rely on force-field parameters adapted from the atomistic description of short xylan fragments and their adsorption on cellulose. This CG model was first validated for xylan chains both isolated and in the bulk where a good match was found with its atomistic counterpart as well as with experimental measurements. A similar agreement was also found when short xylan fragments were adsorbed on the (110) surface of crystalline cellulose. The CG model, which was extended to the (100) and (1-10) surfaces, revealed that the adsorbed xylan, which was essentially extended in the atomistic situation, could also adopt coiled structures, especially when laying on the hydrophobic cellulose surfaces.

  1. The Rietveld method as a tool to quantify the amorphous amount of microcrystalline cellulose.

    PubMed

    De Figueiredo, Laysa Pires; Ferreira, Fabio Furlan

    2014-05-01

    With the use of X-ray powder diffraction data and the Rietveld method, we verified that both microcrystalline cellulose PH-101 and PH-102 presented differences in the crystallinity degree. The results revealed these samples are semicrystalline in nature and via Rietveld refinements, it was possible, adding a known amount of an internal standard of corundum to the samples, to perform quantitative phase analyses, which allowed us to determine the amorphous amount of the studied samples: 63.7(11) wt % in microcrystalline cellulose PH-101 and 51.0(11) wt % in microcrystalline cellulose PH-102. An important contribution of this work refers to the attempt of using this simple method, permitting to evaluate the degree of crystallinity of microcrystalline cellulose.

  2. Physico-chemical properties and thermal stability of microcrystalline cellulose isolated from Alfa fibres.

    PubMed

    Trache, Djalal; Donnot, André; Khimeche, Kamel; Benelmir, Riad; Brosse, Nicolas

    2014-04-15

    In this study, microcrystalline cellulose (Alfa-MCC) was extracted from Alfa fibres using acid hydrolysis method. The molecular weight of the cellulose samples was determined by gel permeation chromatography. The crystallinities were studied by means of X-ray diffraction and solid state cross polarization magic angle spinning (13)C nuclear magnetic resonance spectroscopy, revealing that Alfa-MCC was more crystalline than the native cellulose isolated from Alfa fibres. The morphology of the celluloses was investigated using scanning electron microscopy, showing a compact structure and a rough surface. Furthermore, a good thermal stability was shown for Alfa-MCC. Based on these analyses, Alfa-MCC showed tremendous potential use as composites reinforcing agent, foods stabilizer and pharmaceutical additive.

  3. Review: Enzymatic Hydrolysis of Cellulosic Biomass

    SciTech Connect

    Yang, Bin; Dai, Ziyu; Ding, Shi-You; Wyman, Charles E.

    2011-07-16

    Biological conversion of cellulosic biomass to fuels and chemicals offers the high yields to products vital to economic success and the potential for very low costs. Enzymatic hydrolysis that converts lignocellulosic biomass to fermentable sugars may be the most complex step in this process due to substrate-related and enzyme-related effects and their interactions. Although enzymatic hydrolysis offers the potential for higher yields, higher selectivity, lower energy costs, and milder operating conditions than chemical processes, the mechanism of enzymatic hydrolysis and the relationship between the substrate structure and function of various glycosyl hydrolase components are not well understood. Consequently, limited success has been realized in maximizing sugar yields at very low cost. This review highlights literature on the impact of key substrate and enzyme features that influence performance to better understand fundamental strategies to advance enzymatic hydrolysis of cellulosic biomass for biological conversion to fuels and chemicals. Topics are summarized from a practical point of view including characteristics of cellulose (e.g., crystallinity, degree of polymerization, and accessible surface area) and soluble and insoluble biomass components (e.g., oligomeric xylan, lignin, etc.) released in pretreatment, and their effects on the effectiveness of enzymatic hydrolysis. We further discuss the diversity, stability, and activity of individual enzymes and their synergistic effects in deconstructing complex lignocellulosic biomass. Advanced technologies to discover and characterize novel enzymes and to improve enzyme characteristics by mutagenesis, post-translational modification, and over-expression of selected enzymes and modifications in lignocellulosic biomass are also discussed.

  4. All-cellulose and all-wood composites by partial dissolution of cotton fabric and wood in ionic liquid.

    PubMed

    Shibata, Mitsuhiro; Teramoto, Naozumi; Nakamura, Taro; Saitoh, Yoshinobu

    2013-11-06

    After cotton fabric (CF) and hinoki lumber (HL) were dipped in 1-butyl-3-methylimidazolium chloride (BMIMCl) at 100 °C, the BMIMCl-impregnated CF and HL were hot-pressed to give CF-BMIMCl and HL-BMIMCl composites, respectively. The BMIMCl contained in the composites was removed by Soxhlet extraction, and subsequently annealed to produce all-cellulose and all-wood composites (CF-A and HL-A). The SEM analyses revealed that cellulose fibers combined together for CF-A and the surface of HL-A became smooth, respectively. The XRD measurements indicated that the crystallinity index of cellulose component decreased by the hot press, increased by the extraction, and further increased by the annealing for both the composites. The tensile modulus of CF-A increased with increasing pressure of hot-press. Although tensile strength of HL-A was a little lower than that of original HL, tensile modulus of the former was much higher than that of the latter.

  5. Study on stimulus-responsive cellulose-based polymeric materials

    NASA Astrophysics Data System (ADS)

    Luo, Hongsheng

    Stimulus-responsive cellulose-based polymeric materials were developed by physical and chemical approaches. The thermal, structural, mechanical and morphological properties of the samples were comprehensively investigated by multiple tools. Shape memory effect (SME), programming-structure-property relationship and underling mechanisms were emphasized in this study. Some new concepts, such as heterogeneous-twin-switch, path-dependent multi-shape, rapidly switchable water-sensitive SME were established. The samples were divided into two categories. For the first category, cellulose nano-whiskers (CNWs) were incorporated into crystalline shape memory polyurethane (SMPU) and thermal plastic polyurethane (TPU). The CNW-SMPU nano-composites had heterogeneous switches. Triple- and multi-shape effects were achieved for the CNW-SMPU nano-composites by applying into appropriate thermal-aqueous-mechanical programming. Furthermore, the thermally triggered shape recovery of the composites was found to be tuneable, depending on the PCN content. Theoretical prediction along with numerical analysis was conducted, providing evidence on the possible microstructure of the CNW-SMPU nano-composites. Rapidly switchable water-sensitive SME of the CNW-TPU nano-composites was unprecedentedly studied, which originated from the reversible regulation of hydrogen bonding by water. The samples in the second category consisted of cellulose-polyurethane (PU) blends, cellulose-poly(acrylic acid) (PAA) composites and modified cellulose with supramolecular switches, featuring the requirement of homogeneous cellulose solution in the synthesis process. The reversible behaviours of the cellulose-PU blends in wet-dry cycles as well as the underlying shape memory mechanism were characterized and disclosed. The micro-patterns of the blends were found to be self-similar in fractal dimensions. Cellulose-PAA semi-interpenetrating networks exhibited mechanical adaptability in wet-dry cycles. A type of

  6. Solid-State 13C Nuclear Magnetic Resonance Characterization of Cellulose in the Cell Walls of Arabidopsis thaliana Leaves.

    PubMed Central

    Newman, R. H.; Davies, L. M.; Harris, P. J.

    1996-01-01

    Solid-state 13C nuclear magnetic resonance was used to characterize the molecular ordering of cellulose in a cell-wall preparation containing mostly primary walls obtained from the leaves of Arabidopsis thaliana. Proton and 13C spin relaxation time constants showed that the cellulose was in a crystalline rather than a paracrystalline state or amorphous state. Cellulose chains were distributed between the interiors (40%) and surfaces (60%) of crystallites, which is consistent with crystallite cross-sectional dimensions of about 3 nm. Digital resolution enhancement revealed signals indicative of triclinic and monoclinic crystalline forms of cellulose mixed in similar proportions. Of the five nuclear spin relaxation processes used, proton rotating-frame relaxation provided the clearest distinction between cellulose and other cell-wall components for purposes of editing solid-state 13C nuclear magnetic resonance spectra. PMID:12226303

  7. Probing crystal structure and mesoscale assembly of cellulose microfibrils in plant cell walls, tunicate tests, and bacterial films using vibrational sum frequency generation (SFG) spectroscopy.

    PubMed

    Lee, Christopher M; Kafle, Kabindra; Park, Yong Bum; Kim, Seong H

    2014-06-14

    This study reports that the noncentrosymmetry and phase synchronization requirements of the sum frequency generation (SFG) process can be used to distinguish the three-dimensional organization of crystalline cellulose distributed in amorphous matrices. Crystalline cellulose is produced as microfibrils with a few nanometer diameters by plants, tunicates, and bacteria. Crystalline cellulose microfibrils are embedded in wall matrix polymers and assembled into hierarchical structures that are precisely designed for specific biological and mechanical functions. The cellulose microfibril assemblies inside cell walls are extremely difficult to probe. The comparison of vibrational SFG spectra of uniaxially-aligned and disordered films of cellulose Iβ nanocrystals revealed that the spectral features cannot be fully explained with the crystallographic unit structure of cellulose. The overall SFG intensity, the alkyl peak shape, and the alkyl/hydroxyl intensity ratio are sensitive to the lateral packing and net directionality of the cellulose microfibrils within the SFG coherence length scale. It was also found that the OH SFG stretch peaks could be deconvoluted to find the polymorphic crystal structures of cellulose (Iα and Iβ). These findings were used to investigate the cellulose crystal structure and mesoscale cellulose microfibril packing in intact plant cell walls, tunicate tests, and bacterial films.

  8. Enhancement of enzymatic hydrolysis of cellulose by surfactant

    SciTech Connect

    Ooshima, H.; Sakata, M.; Harano, Y.

    1986-01-01

    Effects of surfactants on enzymatic saccharification of cellulose have been studied. Nonionic, amphoteric, and cationic surfactants enhanced the saccharification, while anionic surfactant did not. Cationic and anionic surfactants denatured cellulase in their relatively low concentrations, namely, more than 0.008 and 0.001%, respectively. Using nonionic surfactant Tween 20, which is most effective to the enhancement (e.g., the fractional conversion attained by 72 h saccharification of 5 wt % Avicel in the presence of 0.05 wt % Tween 20 is increased by 35%), actions of surfactant have been examined. As the results, it was suggested that Tween 20 plays an important role in the hydrolysis of crystalline cellulose and that Tween 20 disturbs the adsorption of endoglucanase on cellulose, i.e., varies the adsorption balance of endo- and exoglucanase, resulting in enhancing the reaction. The influence of Tween 20 to the saccharification was found to remain in simultaneous saccharification and fermentation of Avicel.

  9. Cellulose nanowhiskers extracted from TEMPO-oxidized jute fibers.

    PubMed

    Cao, Xinwang; Ding, Bin; Yu, Jianyong; Al-Deyab, Salem S

    2012-10-01

    Cellulose nanowhiskers is a kind of renewable and biocompatible nanomaterials evoke much interest because of its versatility in various applications. Here, for the first time, a novel controllable fabrication of cellulose nanowhiskers from jute fibers with a high yield (over 80%) via a 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)/NaBr/NaClO system selective oxidization combined with mechanical homogenization is reported. The versatile jute cellulose nanowhiskers with ultrathin diameters (3-10 nm) and high crystallinity (69.72%), contains C6 carboxylate groups converted from C6 primary hydroxyls, which would be particularly useful for applications in the nanocomposites as reinforcing phase, as well as in tissue engineering, pharmaceutical and optical industries as additives.

  10. Electrochemical synthesis of cellulose mesylate

    NASA Astrophysics Data System (ADS)

    Khidirov, Sh Sh; Akhmedov, M. A.; Khibiev, H. S.

    2016-04-01

    The article deal with the possibility anode modification of cellulose to form its ester - mesylate by voltametric measurement method and preparative electrosynthesis on a platinum electrode in the system cellulose - dimethyl sulfoxide - methanesulfonic

  11. Monitoring molecular dynamics of bacterial cellulose composites reinforced with graphene oxide by carboxymethyl cellulose addition.

    PubMed

    Sanchis, M J; Carsí, M; Gómez, C M; Culebras, M; Gonzales, K N; Torres, F G

    2017-02-10

    Broadband Dielectric Relaxation Spectroscopy was performed to study the molecular dynamics of dried Bacterial Cellulose/Carboxymethyl Cellulose-Graphene Oxide (BC/CMC-GO) composites as a function of the concentration of CMC in the culture media. At low temperature the dielectric spectra are dominated by a dipolar process labelled as a β-relaxation, whereas electrode polarization and the contribution of dc-conductivity dominate the spectra at high temperatures and low frequency. The CMC concentration affects the morphological structure of cellulose and subsequently alters its physical properties. X-ray diffractometry measurements show that increasing the concentration of CMC promotes a decrease of the Iα/Iβ ratio. This structural change in BC, that involves a variation in inter- and intramolecular interactions (hydrogen-bonding interactions), affects steeply their molecular dynamics. So, an increase of CMC concentration produces a significantly decrease of the β-relaxation strength and an increase of the dc-conductivity.

  12. Impact of selected solvent systems on the pore and solid structure of cellulose aerogels.

    PubMed

    Pircher, Nicole; Carbajal, Leticia; Schimper, Christian; Bacher, Markus; Rennhofer, Harald; Nedelec, Jean-Marie; Lichtenegger, Helga C; Rosenau, Thomas; Liebner, Falk

    The impact of selected cellulose solvent systems based on the principal constituents tetrabutylammonium fluoride (TBAF), 1-ethyl-3-methyl-1H-imidazolium-acetate, N-methylmorpholine-N-oxide, or calcium thiocyanate octahydrate (CTO) on the properties of cellulose II aerogels prepared from these solvent systems has been investigated as a means towards tailoring cellulose aerogel properties with respect to specific applications. Cotton linters were used as representative plant cellulose. Cellulose was coagulated from solutions with comparable cellulose content, and dried with supercritical carbon dioxide after solvent exchange. The resulting bulk aerogels were comprehensively morphologically and mechanically tested to relate structure and mechanical properties. Different solvent systems caused considerable differences in the properties of the bulk samples, such as internal surface area (nitrogen sorption), morphology, porosity (He pycnometry, thermoporosimetry), and mechanical stability (compression testing). The results of SAXS, WAXS, and solid-state (13)C NMR spectroscopy suggest that this is due to different mechanisms of cellulose self-assembling on the supramolecular and nanostructural level, respectively, as reflected by the broad ranges of cellulose crystallinity, fibril diameter, fractal dimension and skeletal density. Both solid state NMR and WAXS experiments confirmed the sole existence of the cellulose II allomorph for all aerogels, with crystallinity reaching a maximum of 46-50 % for CTO-derived aerogels. Generally, higher fibril diameter, degree of crystallinity, hence increased skeletal density were associated with good preservation of shape and dimension throughout conversion of lyogels to aerogels, and enhanced mechanical stability, but somewhat reduced specific surface area. Amorphous, yet highly rigid aerogels derived from TBAF/DMSO mixtures deviated from this trend, most likely due to their particular homogeneous and nanostructured morphology.

  13. The cellulose resource matrix.

    PubMed

    Keijsers, Edwin R P; Yılmaz, Gülden; van Dam, Jan E G

    2013-03-01

    The emerging biobased economy is causing shifts from mineral fossil oil based resources towards renewable resources. Because of market mechanisms, current and new industries utilising renewable commodities, will attempt to secure their supply of resources. Cellulose is among these commodities, where large scale competition can be expected and already is observed for the traditional industries such as the paper industry. Cellulose and lignocellulosic raw materials (like wood and non-wood fibre crops) are being utilised in many industrial sectors. Due to the initiated transition towards biobased economy, these raw materials are intensively investigated also for new applications such as 2nd generation biofuels and 'green' chemicals and materials production (Clark, 2007; Lange, 2007; Petrus & Noordermeer, 2006; Ragauskas et al., 2006; Regalbuto, 2009). As lignocellulosic raw materials are available in variable quantities and qualities, unnecessary competition can be avoided via the choice of suitable raw materials for a target application. For example, utilisation of cellulose as carbohydrate source for ethanol production (Kabir Kazi et al., 2010) avoids the discussed competition with easier digestible carbohydrates (sugars, starch) deprived from the food supply chain. Also for cellulose use as a biopolymer several different competing markets can be distinguished. It is clear that these applications and markets will be influenced by large volume shifts. The world will have to reckon with the increase of competition and feedstock shortage (land use/biodiversity) (van Dam, de Klerk-Engels, Struik, & Rabbinge, 2005). It is of interest - in the context of sustainable development of the bioeconomy - to categorize the already available and emerging lignocellulosic resources in a matrix structure. When composing such "cellulose resource matrix" attention should be given to the quality aspects as well as to the available quantities and practical possibilities of processing the

  14. A new route to improved glucose yields in cellulose hydrolysis

    SciTech Connect

    Zhao, Haibo; Holladay, John E.; Kwak, Ja Hun; Zhang, Z. Conrad

    2007-08-01

    An unusual inverse temperature-dependent pathway was discovered for cellulose decrystallization in trifluoroacetic acid (TFA). Cellulose was completely decrystallized by TFA at 0 °C in less than 2 hours, a result not achieved in 48 hours at 25°C in the same medium. The majority of TFA used in cellulose decrystallization was recycled via a vacuum process. The small remaining amount of TFA was diluted with water to make a 0.5% TFA solution and used as a catalyst in dilute acid hydrolysis. After one minute, under batch conditions at 185 °C, the glucose yield reached 63.5% without production of levulinic acid. In comparison, only 15.0% glucose yield was achieved in the hydrolysis of untreated cellulose by 0.5% H2SO4 under the same condition. Further improvement of glucose yield is possible by optimizing reaction conditions. Alternatively, the remaining TFA can be completely removed by water while keeping the regenerated cellulose in a highly amorphous state. This regenerated cellulose is much more reactive than untreated cellulose in hydrolysis reactions, but still less reactive than corn starch. The lower temperatures and shorter reaction times with this activated cellulose makes it possible to reduce operating costs and decrease byproduct yields such as HMF and levulinic acid.

  15. Ab Initio Study of Molecular Interactions in Cellulose

    SciTech Connect

    Devarajan, Ajitha; Markutsya, Serjiy; Lamm, Monica H.; Cheng, Xiaolin; Smith, Jeremy C.; Baluyut, John Y.; Kholod, Yana; Gordon, Mark S.; Windus, Theresa L.

    2013-08-12

    Biomass recalcitrance, the resistance of cellulosic biomass to degradation, is due in part to the stability of the hydrogen bond network and stacking forces between the polysaccharide chains in cellulose microfibers. The fragment molecular orbital (FMO) method at the correlated Møller–Plesset second order perturbation level of theory was used on a model of the crystalline cellulose Iα core with a total of 144 glucose units. These computations show that the intersheet chain interactions are stronger than the intrasheet chain interactions for the crystalline structure, while they are more similar to each other for a relaxed structure. An FMO chain pair interaction energy decomposition analysis for both the crystal and relaxed structures reveals an intricate interplay between electrostatic, dispersion, charge transfer, and exchange repulsion effects. The role of the primary alcohol groups in stabilizing the interchain hydrogen bond network in the inner sheet of the crystal and relaxed structures of cellulose Iα, where edge effects are absent, was analyzed. The maximum attractive intrasheet interaction is observed for the GT-TG residue pair with one intrasheet hydrogen bond, suggesting that the relative orientation of the residues is as important as the hydrogen bond network in strengthening the interaction between the residues.

  16. A facile one-pot route to cationic cellulose nanocrystals

    NASA Astrophysics Data System (ADS)

    Jasmani, Latifah; Eyley, Samuel; Wallbridge, Rachel; Thielemans, Wim

    2013-10-01

    Pyridinium-grafted-cellulose nanocrystals were prepared by a simple one-pot reaction using 4-(1-bromoethyl/bromomethyl)benzoic acid, pyridine and cellulose nanocrystals (CNCs). The grafting consists of an esterification reaction between 4-(1-bromoethyl/bromomethyl)benzoic acid and CNCs and a nucleophilic attack on the C-Br bond of 4-(1-bromoethyl/bromomethyl)benzoic acid by pyridine. This reaction simplifies existing cationization methods, which leads to a higher grafting density while retaining the CNC crystallinity.Pyridinium-grafted-cellulose nanocrystals were prepared by a simple one-pot reaction using 4-(1-bromoethyl/bromomethyl)benzoic acid, pyridine and cellulose nanocrystals (CNCs). The grafting consists of an esterification reaction between 4-(1-bromoethyl/bromomethyl)benzoic acid and CNCs and a nucleophilic attack on the C-Br bond of 4-(1-bromoethyl/bromomethyl)benzoic acid by pyridine. This reaction simplifies existing cationization methods, which leads to a higher grafting density while retaining the CNC crystallinity. Electronic supplementary information (ESI) available: Experimental description, FTIR, XPS and XRD spectra and detailed characterisation results of all compounds. See DOI: 10.1039/c3nr03456a

  17. Crystalline boron nitride aerogels

    DOEpatents

    Zettl, Alexander K.; Rousseas, Michael; Goldstein, Anna P.; Mickelson, William; Worsley, Marcus A.; Woo, Leta

    2017-04-04

    This disclosure provides methods and materials related to boron nitride aerogels. In one aspect, a material comprises an aerogel comprising boron nitride. The boron nitride has an ordered crystalline structure. The ordered crystalline structure may include atomic layers of hexagonal boron nitride lying on top of one another, with atoms contained in a first layer being superimposed on atoms contained in a second layer.

  18. Perturbation of wood cellulose synthesis causes pleiotropic effects in transgenic aspen.

    PubMed

    Joshi, Chandrashekhar P; Thammannagowda, Shivegowda; Fujino, Takeshi; Gou, Ji-Qing; Avci, Utku; Haigler, Candace H; McDonnell, Lisa M; Mansfield, Shawn D; Mengesha, Bemnet; Carpita, Nicholas C; Harris, Darby; Debolt, Seth; Peter, Gary F

    2011-03-01

    Genetic manipulation of cellulose biosynthesis in trees may provide novel insights into the growth and development of trees. To explore this possibility, the overexpression of an aspen secondary wall-associated cellulose synthase (PtdCesA8) gene was attempted in transgenic aspen (Populus tremuloides L.) and unexpectedly resulted in silencing of the transgene as well as its endogenous counterparts. The main axis of the transgenic aspen plants quickly stopped growing, and weak branches adopted a weeping growth habit. Furthermore, transgenic plants initially developed smaller leaves and a less extensive root system. Secondary xylem (wood) of transgenic aspen plants contained as little as 10% cellulose normalized to dry weight compared to 41% cellulose typically found in normal aspen wood. This massive reduction in cellulose was accompanied by proportional increases in lignin (35%) and non-cellulosic polysaccharides (55%) compared to the 22% lignin and 36% non-cellulosic polysaccharides in control plants. The transgenic stems produced typical collapsed or 'irregular' xylem vessels that had altered secondary wall morphology and contained greatly reduced amounts of crystalline cellulose. These results demonstrate the fundamental role of secondary wall cellulose within the secondary xylem in maintaining the strength and structural integrity required to establish the vertical growth habit in trees.

  19. Preparation and characterization of cellulose nanofibers from de-pectinated sugar beet pulp.

    PubMed

    Li, Meng; Wang, Li-jun; Li, Dong; Cheng, Yan-ling; Adhikari, Benu

    2014-02-15

    Cellulose nanofibers (diameter=10-70 nm) were produced using chemical treatments (alkali treatment and bleaching) and high pressure homogenization from de-pectinated sugar beet pulp (DSBP). Chemical analysis and Fourier transform infrared spectroscopy (FTIR) indicated that the chemical treatments greatly removed the hemicellulose and lignin from the DSBP and significantly increased the cellulose content. The crystallinity of the cellulose nanofibers increased from 35.67% to 69.62% after alkali treatment and bleaching. The thermal degradation temperature of DSBP cellulose nanofibers was 271.7 °C which was found to be 47.3 °C higher than that of the untreated DSBP. The DSBP cellulose nanofibers can be preferably used as reinforcement in the biocomposite material at high temperature.

  20. X-ray Coherent Diffraction Imaging of Cellulose Fibrils in Situ

    SciTech Connect

    Lal, Jyotsana; Harder, Ross J.; Makowski, Lee

    2011-01-01

    Cellulose is the most abundant renewable source of organic molecules on earth[1]. As fossil fuel reserves become depleted, the use of cellulose as a feed stock for fuels and chemicals is being aggressively explored. Cellulose is a linear polymer of glucose that packs tightly into crystalline fibrils that make up a substantial proportion of plant cell walls. Extraction of the cellulose chains from these fibrils in a chemically benign process has proven to be a substantial challenge [2]. Monitoring the deconstruction of the fibrils in response to physical and chemical treatments would expedite the development of efficient processing methods. As a step towards achieving that goal, we here describe Bragg-coherent diffraction imaging (CDI) as an approach to producing images of cellulose fibrils in situ within vascular bundles from maize.

  1. Two structurally discrete GH7-cellobiohydrolases compete for the same cellulosic substrate fiber

    PubMed Central

    2012-01-01

    Background Cellulose consisting of arrays of linear beta-1,4 linked glucans, is the most abundant carbon-containing polymer present in biomass. Recalcitrance of crystalline cellulose towards enzymatic degradation is widely reported and is the result of intra- and inter-molecular hydrogen bonds within and among the linear glucans. Cellobiohydrolases are enzymes that attack crystalline cellulose. Here we report on two forms of glycosyl hydrolase family 7 cellobiohydrolases common to all Aspergillii that attack Avicel, cotton cellulose and other forms of crystalline cellulose. Results Cellobiohydrolases Cbh1 and CelD have similar catalytic domains but only Cbh1 contains a carbohydrate-binding domain (CBD) that binds to cellulose. Structural superpositioning of Cbh1 and CelD on the Talaromyces emersonii Cel7A 3-dimensional structure, identifies the typical tunnel-like catalytic active site while Cbh1 shows an additional loop that partially obstructs the substrate-fitting channel. CelD does not have a CBD and shows a four amino acid residue deletion on the tunnel-obstructing loop providing a continuous opening in the absence of a CBD. Cbh1 and CelD are catalytically functional and while specific activity against Avicel is 7.7 and 0.5 U.mg prot-1, respectively specific activity on pNPC is virtually identical. Cbh1 is slightly more stable to thermal inactivation compared to CelD and is much less sensitive to glucose inhibition suggesting that an open tunnel configuration, or absence of a CBD, alters the way the catalytic domain interacts with the substrate. Cbh1 and CelD enzyme mixtures on crystalline cellulosic substrates show a strong combinatorial effort response for mixtures where Cbh1 is present in 2:1 or 4:1 molar excess. When CelD was overrepresented the combinatorial effort could only be partially overcome. CelD appears to bind and hydrolyze only loose cellulosic chains while Cbh1 is capable of opening new cellulosic substrate molecules away from the cellulosic

  2. The Dickeya dadantii biofilm matrix consists of cellulose nanofibres, and is an emergent property dependent upon the type III secretion system and the cellulose synthesis operon.

    PubMed

    Jahn, Courtney E; Selimi, Dija A; Barak, Jeri D; Charkowski, Amy O

    2011-10-01

    Dickeya dadantii is a plant-pathogenic bacterium that produces cellulose-containing biofilms, called pellicles, at the air-liquid interface of liquid cultures. D. dadantii pellicle formation appears to be an emergent property dependent upon at least three gene clusters, including cellulose synthesis, type III secretion system (T3SS) and flagellar genes. The D. dadantii cellulose synthesis operon is homologous to that of Gluconacetobacter xylinus, which is used for industrial cellulose production, and the cellulose nanofibres produced by D. dadantii were similar in diameter and branching pattern to those produced by G. xylinus. Salmonella enterica, an enterobacterium closely related to D. dadantii, encodes a second type of cellulose synthesis operon, and it produced biofilm strands that differed in width and branching pattern from those of D. dadantii and G. xylinus. Unlike any previously described cellulose fibre, the D. dadantii cellulose nanofibres were decorated with bead-like structures. Mutation of the cellulose synthesis operon genes resulted in loss of cellulose synthesis and production of a cellulase-resistant biofilm. Mutation of other genes required for pellicle formation, including those encoding FliA (a sigma factor that regulates flagella production), HrpL (a sigma factor that regulates the T3SS), and AdrA, a GGDEF protein, affected both biofilm and cell morphology. Mutation of the cellulose synthase bcsA or of bcsC resulted in decreased accumulation of the T3SS-secreted protein HrpN.

  3. Enantioselective separations using chiral supported liquid crystalline membranes.

    PubMed

    Han, Sangil; Rabie, Feras; Marand, Eva; Martin, Stephen M

    2012-07-01

    Porous and nonporous supported liquid crystalline membranes were produced by impregnating porous cellulose nitrate supports with cholesteric liquid crystal (LC) materials consisting of 4-cyano-4'-pentylbiphenyl (5CB) mixed with a cholesterol-based dopant (cholesteryl oleyl carbonate [COC], cholesteryl nonanoate [CN], or cholesteryl chloride [CC]). The membranes exhibit selectivity for R-phenylglycine and R-1-phenylethanol because of increased interactions between the S enantiomers and the left-handed cholesteric phase. The selectivity of both phenylglycine and 1-phenylethanol in 5CB/CN membranes decreases with effective pore diameter while the permeabilities increase, as expected. Phenylglycine, which is insoluble in the LC phase, exhibits no transport in the nonporous (completely filled) membranes; however, 1-phenylethanol, which is soluble in the LC phase, exhibits transport but negligible enantioselectivity. The enantioselectivity for 1-phenylethanol was higher (1.20 in 5CB/COC and 5CB/CN membranes) and the permeability was lower in the cholesteric phase than in the isotropic phase. Enantioselectivity was also higher in the 5CB/COC cholesteric phase than in the nematic phase of undoped 5CB (1.03). Enantioselectivity in the cholesteric phase of 5CB doped with CC (1.1), a dopant lacking hydrogen bonding groups, was lower than in the 5CB/COC phases. Finally, enantioselectivity increases with the dopant concentration up to a plateau value at approximately 17 mol%.

  4. A possible role of cellulose-binding protein A (CBPA) in the adhesion of Eubacterium cellulosolvens 5 to cellulose.

    PubMed

    Toyoda, Atsushi; Takano, Kazunori; Minato, Hajime

    2003-08-01

    The cellulose-binding protein A (CBPA) of Eubacterium cellulosolvens 5 is a modular enzyme comprised of a catalytic domain, a cellulose-binding domain and a cell wall-binding domain. Cellobiose-grown cells changed their adhesion ability to cellulose depending on the growth phase. On the other hand, carboxymethyl cellulose (CMC)-grown cells bound to cellulose regardless of their growth phase. The distribution of CBPA in the culture supernatant and cell fractions changed depending on the carbon source contained in the medium and growth phase. The cellobiose-grown cells harvested from the culture of the late stationary growth phase did not bind to cellulose, but their adhesion ability was recovered by treatment with recombinant CBPA. Moreover, cellobiose-grown cells harvested from the culture of an early exponential growth phase bound to cellulose, but their adhesion ability was inhibited by treatment with anti-CBPA antiserum. CBPA rapidly decreased the viscosity of CMC, indicating that CBPA was endoglucanase. The results obtained in this study indicate that CBPA plays an important role in the adhesion of E. cellulosolvens 5 cells to cellulose.

  5. Appetite - decreased

    MedlinePlus

    ... cancer Ovarian cancer Stomach cancer Pancreatic cancer Other causes of decreased appetite include: Chronic liver disease Chronic kidney disease Chronic obstructive pulmonary disease (COPD) Dementia Heart failure ...

  6. Cellulose gel dispersion: From pure hydrogel suspensions to encapsulated oil-in-water emulsions.

    PubMed

    Napso, Sofia; Rein, Dmitry M; Khalfin, Rafail; Kleinerman, Olga; Cohen, Yachin

    2016-01-01

    Cellulose hydrogel particles were fabricated from molecularly-dissolved cellulose/IL solutions. The characteristics of the formed hydrogels (cellulose content, particles' size and porosity) were determined as a function of cellulose concentration in the precursor solutions. There is a significant change in the hydrogel structure when the initial cellulose solution concentration increases above about 7-9%wt. These changes include increase of the cellulose content in the hydrogel, and decrease in its pore size. The finest cellulose particle dispersions can be obtained using low concentration cellulose/IL solutions (cellulose concentration in dispersion less than 2%wt.) or hydrogels (concentration less than 1%wt.) in a dispersing medium consisting of IL with no more than 20%wt. water. Stable paraffin oil-in-water emulsions are achieved by mixing oil and water with cellulose/IL solutions. The optimal conditions for obtaining the finest particles (about 20μm in diameter) are attained using cellulose solutions of concentration between 0.7 and 4%wt. at temperature of 70°C and oil/cellulose mass ratios between 1 and 1.5.

  7. Physicochemical of microcrystalline cellulose from oil palm fronds as potential methylene blue adsorbents.

    PubMed

    Hussin, M Hazwan; Pohan, Nurul Aqilah; Garba, Zaharaddeen N; Kassim, M Jain; Rahim, Afidah Abdul; Brosse, Nicolas; Yemloul, Mehdi; Fazita, M R Nurul; Haafiz, M K Mohamad

    2016-11-01

    The present study sheds light on the physical and chemical characteristics of microcrystalline cellulose (MCC) isolated from oil palm fronds (OPF) pulps. It was found that the OPF MCC was identified as cellulose II polymorph, with higher crystallinity index than OPF α-cellulose (CrIOPFMCC: 71%>CrIOPFα-cellulose: 47%). This indicates that the acid hydrolysis allows the production of cellulose that is highly crystalline. BET surface area of OPF MCC was found to be higher than OPF α-cellulose (SBETOPFMCC: 5.64m(2)g(-1)>SBETOPFα-cellulose:Qa(0) 2.04m(2)g(-1)), which corroborates their potential as an adsorbent. In batch adsorption studies, it was observed that the experimental data fit well with Langmuir adsorption isotherm in comparison to Freundlich isotherm. The monolayer adsorption capacity (Qa(0)) of OPF MCC was found to be around 51.811mgg(-1) and the experimental data fitted well to pseudo-second-order kinetic model.

  8. Calculating cellulose diffraction patterns

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although powder diffraction of cellulose is a common experiment, the patterns are not widely understood. The theory is mathematical, there are numerous different crystal forms, and the conventions are not standardized. Experience with IR spectroscopy is not directly transferable. An awful error, tha...

  9. Alcohol from cellulose

    SciTech Connect

    Hsu, T.A.; Ladisch, M.R.; Tsao, G.T.

    1980-05-01

    A process is described which completely converts cellulose to fermentable sugars as compared to 50-70% conversion obtained with other methods. The process uses chemical solvents followed by hydrolysis. The new method was tried using corn residue and bagasse. It is stated that the pretreated substances showed much improved conversions over untreated corn residue and bagasse.

  10. Water Adsorption in Wood Microfibril-Hemicellulose System: Role of the Crystalline-Amorphous Interface.

    PubMed

    Kulasinski, Karol; Guyer, Robert; Derome, Dominique; Carmeliet, Jan

    2015-09-14

    A two-phase model of a wood microfibril consisting of crystalline cellulose and amorphous hemicellulose is investigated with molecular dynamics in full range of sorption to understand the molecular origin of swelling and weakening of wood. Water is adsorbed in hemicellulose, and an excess of sorption is found at the interface, while no sorption occurs within cellulose. Water molecules adsorbed on the interface push away polymer chains, forcing the two phases to separate and causing breaking of h-bonds, particularly pronounced on the interface. Existence of two different regions in moisture response is demonstrated. At low moisture content, water is uniformly adsorbed within hemicellulose, breaking a small amount of hydrogen bonds. Microfibril does not swell, and the porosity does not change. As moisture content increases, water is adsorbed preferentially at the interface, which leads to additional swelling and porosity increase at the interface. Young's and shear moduli decrease importantly due to breaking of h-bonds and screening of the long-range interactions.

  11. Adsorption of glucose, cellobiose, and cellotetraose onto cellulose model surfaces.

    PubMed

    Hoja, Johannes; Maurer, Reinhard J; Sax, Alexander F

    2014-07-31

    Reliable simulation of molecular adsorption onto cellulose surfaces is essential for the design of new cellulose nanocomposite materials. However, the applicability of classical force field methods to such systems remains relatively unexplored. In this study, we present the adsorption of glucose, cellobiose, and cellotetraose on model surfaces of crystalline cellulose Iα and Iβ. The adsorption of the two large carbohydrates was simulated with the GLYCAM06 force field. To validate this approach, quantum theoretical calculations for the adsorption of glucose were performed: Equilibrium geometries were studied with density functional theory (DFT) and dispersion-corrected DFT, whereas the adsorption energies were calculated with two standard density functional approximations and five dispersion-containing DFT approaches. We find that GLYCAM06 gives a good account of geometries and, in most cases, accurate adsorption energies when compared to dispersion-corrected DFT energies. Adsorption onto the (100) surface of cellulose Iα is, in general, stronger than onto the (100) surface of cellulose Iβ. Contrary to intuition, the adsorption energy is not directly correlated with the number of hydrogen bonds; rather, it is dominated by dispersion interactions. Especially for bigger adsorbates, a neglect of these interactions leads to a dramatic underestimation of adsorption energies.

  12. Acetobixan, an inhibitor of cellulose synthesis identified by microbial bioprospecting.

    PubMed

    Xia, Ye; Lei, Lei; Brabham, Chad; Stork, Jozsef; Strickland, James; Ladak, Adam; Gu, Ying; Wallace, Ian; DeBolt, Seth

    2014-01-01

    In plants, cellulose biosynthesis is an essential process for anisotropic growth and therefore is an ideal target for inhibition. Based on the documented utility of small-molecule inhibitors to dissect complex cellular processes we identified a cellulose biosynthesis inhibitor (CBI), named acetobixan, by bio-prospecting among compounds secreted by endophytic microorganisms. Acetobixan was identified using a drug-gene interaction screen to sift through hundreds of endophytic microbial secretions for one that caused synergistic reduction in root expansion of the leaky AtcesA6prc1-1 mutant. We then mined this microbial secretion for compounds that were differentially abundant compared with Bacilli that failed to mimic CBI action to isolate a lead pharmacophore. Analogs of this lead compound were screened for CBI activity, and the most potent analog was named acetobixan. In living Arabidopsis cells visualized by confocal microscopy, acetobixan treatment caused CESA particles localized at the plasma membrane (PM) to rapidly re-localize to cytoplasmic vesicles. Acetobixan inhibited 14C-Glc uptake into crystalline cellulose. Moreover, cortical microtubule dynamics were not disrupted by acetobixan, suggesting specific activity towards cellulose synthesis. Previous CBI resistant mutants such as ixr1-2, ixr2-1 or aegeus were not cross resistant to acetobixan indicating that acetobixan targets a different aspect of cellulose biosynthesis.

  13. Cellulose Synthesis and Its Regulation

    PubMed Central

    Li, Shundai; Bashline, Logan; Lei, Lei; Gu, Ying

    2014-01-01

    Cellulose, the most abundant biopolymer synthesized on land, is made of linear chains of ß (1–4) linked D-glucose. As a major structural component of the cell wall, cellulose is important not only for industrial use but also for plant growth and development. Cellulose microfibrils are tethered by other cell wall polysaccharides such as hemicellulose, pectin, and lignin. In higher plants, cellulose is synthesized by plasma membrane-localized rosette cellulose synthase complexes. Despite the recent advances using a combination of molecular genetics, live cell imaging, and spectroscopic tools, many aspects of the cellulose synthesis remain a mystery. In this chapter, we highlight recent research progress towards understanding the mechanism of cellulose synthesis in Arabidopsis. PMID:24465174

  14. Green synthesis of silver nanoparticles using cellulose extracted from an aquatic weed; water hyacinth.

    PubMed

    Mochochoko, Tanki; Oluwafemi, Oluwatobi S; Jumbam, Denis N; Songca, Sandile P

    2013-10-15

    As part of the desire to save the environment through "green" chemistry practices, we herein report an environmentally benign synthesis of silver nanoparticles (Ag-NPs) using cellulose extracted from an environmentally problematic aquatic weed, water hyacinth (WH), as both reducing and capping agent in an aqueous medium. By varying the pH of the solution and reaction time, the temporal evolutions of the optical and morphological properties of the as-synthesised Ag-NPs were investigated. The as-synthesised cellulose capped silver nanoparticles (C-Ag-NPs) were characterised using Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). The maximum surface plasmon resonance (SPR) peak decreased as the pH increased indicating that an increase in the pH of the solution favoured the formation of smaller particles. In addition, instantaneous change in the colour of the solution from colourless to brown within 5 min at pH 11 showed that the rate of reduction is faster at this pH compared to those at lower pH. The TEM micrographs showed that the materials are small, highly monodispersed and spherical in shape. The average particle mean diameters were calculated to be 5.69±5.89 nm, 4.53±1.36 nm and 2.68±0.69 nm nm at pH 4, 8 and 11 respectively. The HRTEM confirmed the crystallinity of the material while the FTIR spectra confirmed the capping of the as-synthesised Ag-NPs by the cellulose. It has been shown therefore that based on this synthetic method, this aquatic plant can be used to the advantage of mankind.

  15. Cellulose production in Pseudomonas syringae pv. syringae: a compromise between epiphytic and pathogenic lifestyles.

    PubMed

    Arrebola, Eva; Carrión, Víctor J; Gutiérrez-Barranquero, José Antonio; Pérez-García, Alejandro; Rodríguez-Palenzuela, Pablo; Cazorla, Francisco M; de Vicente, Antonio

    2015-07-01

    Genome sequencing and annotation have revealed a putative cellulose biosynthetic operon in the strain Pseudomonas syringae pv. syringae UMAF0158, the causal agent of bacterial apical necrosis. Bioinformatics analyses and experimental methods were used to confirm the functionality of the cellulose biosynthetic operon. In addition, the results showed the contribution of the cellulose operon to important aspects of P. syringae pv. syringae biology, such as the formation of biofilms and adhesion to the leaf surface of mango, suggesting that this operon increases epiphytic fitness. However, based on the incidence and severity of the symptoms observed in tomato leaflets, cellulose expression reduces virulence, as cellulose-deficient mutants increased the area of necrosis, whereas the cellulose-overproducing strain decreased the area of necrosis compared with the wild type. In conclusion, the results of this study show that the epiphytic and pathogenic stages of the P. syringae pv. syringae UMAF0158 lifestyle are intimately affected by cellulose production.

  16. Chemical modification of cellulose by in situ reactive extrusion in ionic liquid.

    PubMed

    Zhang, Yue; Li, Haifeng; Li, Xinda; Gibril, Magdi E; Yu, Muhuo

    2014-01-01

    In order to prepare the spinning solution of cellulose with high concentration in environmentally friendly solvent, cellulose was chemically modified by in situ reactive extrusion with several chemicals, such as urea, phthalic anhydride (PA), maleic anhydride (MA) and butyl glycidyl ether (BGE) and with ionic liquid namely 1-N-butyl-3-methylimidazolium chloride (BMIMCl) as reaction medium. These four modifiers all in situ grafted onto cellulose and the modification effectiveness was found to decrease in the sequence, MA>PA>BGE>urea. The formation of side chain on cellulose backbone destroyed the regularity of cellulose chains and the hydrogen bond network efficiently. The concentration of modified cellulose in spinning solution can be up to 14-25%, comparing with 9% for unmodified cellulose in BMIMCl. The high solid content results in high efficiency and less energy consumption of fiber production and solvent recycle.

  17. The contribution of cellulosomal scaffoldins to cellulose hydrolysis by Clostridium thermocellum analyzed by using thermotargetrons

    PubMed Central

    2014-01-01

    Background Clostridium thermocellum is a thermophilic anaerobic bacterium that degrades cellulose by using a highly effective cellulosome, a macromolecular complex consisting of multiple cellulose degrading enzymes organized and attached to the cell surface by non-catalytic scaffoldins. However, due largely to lack of efficient methods for genetic manipulation of C. thermocellum, it is still unclear how the different scaffoldins and their functional modules contribute to cellulose hydrolysis. Results We constructed C. thermocellum mutants with the primary scaffoldin CipA (cellulosome-integrating protein A) truncated at different positions or lacking four different secondary scaffoldins by using a newly developed thermotargetron system, and we analyzed cellulose hydrolysis, cellulosome formation, and cellulose binding of the mutants. A CipA truncation that deletes six type I cohesin modules, which bind cellulolytic enzymes, decreased cellulose hydrolysis rates by 46%, and slightly longer truncations that also delete the carbohydrate binding module decreased rates by 89 to 92%, indicating strong cellulosome-substrate synergy. By contrast, a small CipA truncation that deletes only the C-terminal type II dockerin (XDocII) module detached cellulosomes from the cells, but decreased cellulose hydrolysis rates by only 9%, suggesting a relatively small contribution of cellulosome-cell synergy. Disruptants lacking any of four different secondary scaffoldins (OlpB, 7CohII, Orf2p, or SdbA) showed moderately decreased cellulose hydrolysis rates, suggesting additive contributions. Surprisingly, the CipA-ΔXDocII mutant, which lacks cell-associated polycellulosomes, adheres to cellulose almost as strongly as wild-type cells, revealing an alternate, previously unknown cellulose-binding mechanism. Conclusions Our results emphasize the important role of cellulosome-substrate synergy in cellulose degradation, demonstrate a contribution of secondary scaffoldins, and suggest a

  18. Efficient sugar release by the cellulose solvent-based lignocellulose fractionation technology and enzymatic cellulose hydrolysis.

    PubMed

    Moxley, Geoffrey; Zhu, Zhiguang; Zhang, Y-H Percival

    2008-09-10

    Efficient liberation of fermentable soluble sugars from lignocellulosic biomass waste not only decreases solid waste handling but also produces value-added biofuels and biobased products. Industrial hemp, a special economic crop, is cultivated for its high-quality fibers and high-value seed oil, but its hollow stalk cords (hurds) are a cellulosic waste. The cellulose-solvent-based lignocellulose fractionation (CSLF) technology has been developed to separate lignocellulose components under modest reaction conditions (Zhang, Y.-H. P.; Ding, S.-Y.; Mielenz, J. R.; Elander, R.; Laser, M.; Himmel, M.; McMillan, J. D.; Lynd, L. R. Biotechnol. Bioeng. 2007, 97 (2), 214- 223). Three pretreatment conditions (acid concentration, reaction temperature, and reaction time) were investigated to treat industrial hemp hurds for a maximal sugar release: a combinatorial result of a maximal retention of solid cellulose and a maximal enzymatic cellulose hydrolysis. At the best treatment condition (84.0% H3PO4 at 50 degrees C for 60 min), the glucan digestibility was 96% at hour 24 at a cellulase loading of 15 filter paper units of cellulase per gram of glucan. The scanning electron microscopic images were presented for the CSLF-pretreated biomass for the first time, suggesting that CSLF can completely destruct the plant cell-wall structure, in a good agreement with the highest enzymatic cellulose digestibility and fastest hydrolysis rate. It was found that phosphoric acid only above a critical concentration (83%) with a sufficient reaction time can efficiently disrupt recalcitrant lignocellulose structures.

  19. SANS Study of Cellulose Extracted from Switchgrass

    SciTech Connect

    Pingali, Sai Venkatesh; Urban, Volker S; Heller, William T; McGaughey, Joseph; O'Neill, Hugh Michael; Foston, Marcus B; Myles, Dean A A; Ragauskas, Arthur J; Evans, Barbara R

    2010-01-01

    AbstractLignocellulosic biomass, an abundant renewable natural resource, has the potential to play a major role in generation of renewable biofuels through its conversion to bio-ethanol. Unfortunately, it is a complex biological composite material that shows significant recalcitrance making it a cost-ineffective feedstock for bioethanol production. Small-angle neutron scattering (SANS) was employed to probe the multi-scale structure of cellulosic materials. Cellulose was extracted from milled native switchgrass and switchgrass that had undergone the dilute acid pretreatment method to disrupt the lignocellulose structure. The high-Q structural feature (Q > 0.07 -1) can be assigned to cellulose fibrils based on comparison with the switchgrass purified by solvent extraction of native and dilute acid pretreated and a commercial preparation of microcrystalline cellulose. Dilute acid pretreatment results in an increase in the smallest structural size, a decrease in the interconnectivity of the fibrils; and no change in the smooth domain boundaries at length scales larger than 1000 .

  20. Crystalline Silica Primer

    USGS Publications Warehouse

    ,

    1992-01-01

    substance and will present a nontechnical overview of the techniques used to measure crystalline silica. Because this primer is meant to be a starting point for anyone interested in learning more about crystalline silica, a list of selected readings and other resources is included. The detailed glossary, which defines many terms that are beyond the scope of this publication, is designed to help the reader move from this presentation to a more technical one, the inevitable next step.

  1. Separation characteristics of lignin from Eucalyptus camaldulensis lignin celluloses for biomedical cellulose.

    PubMed

    Peng, Wanxi; Wang, Lansheng; Zhang, Minglong; Lin, Zhi

    2014-05-01

    The separation characteristics of Eucalyptus camaldulensis biomass cell wall were investigated and analyzed by FTIR, UV and XRD. The result showed that the crystallinity of untreated sample were lower than ones of treated samples at 10° C, 20° C and 30° C. Effect of temperature was very notable so as to use the lower temperature if cellulose would be kept natural structure during lignin separation from lignincellulose. Treatment time and temperature had a notably significant effect on SLR of E. camaldulensis lignin cellulose, and the SLR increased gradually with the temperature increment, and SLR were 73.35% at 10° C, 80.14% at 20° C, 83.73% at 30° C. The maximum of SLR increased with the rising of temperature 10° C, 20° C and 30° C. Consequently, the best separation conditions of lignin were 24h and 30° C. During hemicelluloses separation, the peak of C=O disappeared, and the peak of CO-OR, O-H and C-O abated, resulting that acetyl in hemicelluloses were mainly broken by the dehydration, heat decomposition reaction and mild thermal degradation. During lignin separation, the side chain and benzene ring of lignin of E. urophynis lignin cellulose reached the largest bond breaking characteristics under the temperature of 10° C at 7h, 20° C at 7h and 30° C at 24h.

  2. SO2 -catalyzed steam explosion: the effects of different severity on digestibility, accessibility, and crystallinity of lignocellulosic biomass.

    PubMed

    Kang, Yuzhi; Bansal, Prabuddha; Realff, Matthew J; Bommarius, Andreas S

    2013-01-01

    Lignocellulosic biomass is the most promising feedstock for biofuels production. To enhance the efficiency of enzymatic hydrolysis, lignocellulosics needs to be pretreated to lower their recalcitrance. SO(2) -catalyzed steam explosion is an efficient and relatively cost-efficient pretreatment method for softwood. This work investigates the effects of steam explosion severity on the digestibility, accessibility, and crystallinity of Loblolly pine. Higher severity was found to increase the accessibility of the feedstock while also promoting nonselective degradation of carbohydrates. The adsorption behavior of Celluclast® enzymes on steam-exploded Loblolly pine (SELP) can be described by a Langmuir isotherm. Cellulose crystallinity was found to first increase and then decrease with increasing pretreatment severity. A linear relationship between initial hydrolysis rates and crystallinity index (CrI) of pretreated Loblolly pine was found; moreover, a strong correlation between X-ray diffraction intensities and initial rates was confirmed. The findings demonstrate the significance of CrI in enzymatic hydrolysis of pretreated lignocellulosic biomass.

  3. Preferential interactions between lithium chloride and glucan chains in N,N-dimethylacetamide drive cellulose dissolution.

    PubMed

    Gross, Adam S; Bell, Alexis T; Chu, Jhih-Wei

    2013-03-28

    Naturally occurring cellulose is crystalline as a consequence of the strong interactions between the glucan chains that comprise it and therefore is insoluble in most solvents. One of the few solvent systems able to dissolve cellulose is lithium chloride (LiCl) dissolved in N,N-dimethylacetamide (DMA). By an integrated application of all-atom molecular dynamics (MD) simulations, reaction path optimization, free-energy calculations, and a force-matching analysis of coarse-grained atomistic simulations, we establish that DMA-mediated preferential interactions of Li(+) cations and Cl(-) anions with glucan chains enable cellulose dissolution in LiCl/DMA. The relatively weak solvation of Li(+), Cl(-), and glucan chains by DMA results in strong effective interactions of Li(+) and Cl(-) ions with the glucans, leading to cellulose dissolution. The small size of the Li(+) cations allows them to strongly couple to multiple interaction sites on the glucan chains of cellulose, including the spatially restricted regions around the ether linkages connecting neighboring glucose residues. Li(+) cations were thus identified as the main component responsible for driving cellulose dissolution. The mechanism for explaining the solubility of cellulose in the LiCl/DMA system deduced from the analysis of atomistic-scale simulations conducted in this work is also consistent with most of the empirical observations related to cellulose dissolution in salt/amide solvent systems.

  4. TECHNICAL NOTE: Electrically aligned cellulose film for electro-active paper and its piezoelectricity

    NASA Astrophysics Data System (ADS)

    Yun, Sungryul; Jang, Sangdong; Yun, Gyu-Young; Kim, Jaehwan

    2009-11-01

    Electrically aligned regenerated cellulose films were fabricated and the effect of applied electric field was investigated for the piezoelectricity of electro-active paper (EAPap). The EAPap was fabricated by coating gold electrodes on both sides of regenerated cellulose film. The cellulose film was prepared by dissolving cotton pulp in LiCl/N,N-dimethylacetamide solution followed by a cellulose chain regeneration process. During the regeneration process an external electric field was applied in the direction of mechanical stretching. Alignment of cellulose fiber chains was investigated as a function of applied electric field. The material characteristics of the cellulose films were analyzed by using an x-ray diffractometer, a field emission scanning electron microscope and a high voltage electron microscope. The application of external electric fields was found to induce formation of nanofibers in the cellulose, resulting in an increase in the crystallinity index (CI) values. It was also found that samples with higher CI values showed higher in-plane piezoelectric constant, d31, values. The piezoelectricity of the current EAPap films was measured to be equivalent or better than that of ordinary PVDF films. Therefore, an external electric field applied to a cellulose film along with a mechanical stretching during the regeneration process can enhance the piezoelectricity.

  5. Adsorption and inactivation behavior of horseradish peroxidase on cellulosic fiber surfaces.

    PubMed

    Di Risio, Sabina; Yan, Ning

    2009-10-15

    The physical immobilization behavior of horseradish peroxidase (HRP) on cellulosic fiber surfaces was characterized using adsorption and inactivation isotherms measured by the depletion method followed by fitting of Langmuir's and Freundlich's models to the experimental data. The adsorption and inactivation behavior of simpler and relatively non-porous high and low crystalline cellulosic substrates (microcrystalline cellulose and regenerated cellulose) as well as more complex and porous cellulosic pulp fibers (bleached kraft softwood fibers) were investigated. The effect of the sorbent surface energy on HRP adsorption was demonstrated by increasing the hydrophobicity of the cellulosic fibers using an internal sizing agent. The influence of the fiber surface charge density on HRP adsorption was studied via modification of the cellulosic fibers using TEMPO (2,2,6,6-tetramethyl-1-piperidiniloxy radical)-mediated oxidation methods. Results showed that hydrophobic interactions had a much larger effect on HRP adsorption than electrostatic interactions. More hydrophobic fiber surfaces (lower polar surface energy) result in larger enzyme-fiber binding affinity constants and higher binding heterogeneity. It was also found that oxidation of the cellulosic fiber substrate reduces enzyme adsorption affinity but significantly increases the loading capacity per unit weight of the surface.

  6. Real-time detection of the morphological change in cellulose by a nanomechanical sensor.

    PubMed

    Zhao, Liming; Bulhassan, Ahmed; Yang, Guoliang; Ji, Hai-Feng; Xi, Jun

    2010-09-01

    Up to now, experimental limitations have prevented researchers from achieving the molecular-level understanding for the initial steps of the enzymatic hydrolysis of cellulose, where cellulase breaks down the crystal structure on the surface region of cellulose and exposes cellulose chains for the subsequent hydrolysis by cellulase. Because one of these non-hydrolytic enzymatic steps could be the rate-limiting step for the entire enzymatic hydrolysis of crystalline cellulose by cellulase, being able to analyze and understand these steps is instrumental in uncovering novel leads for improving the efficiency of cellulase. In this communication, we report an innovative application of the microcantilever technique for a real-time assessment of the morphological change of cellulose induced by a treatment of sodium chloride. This sensitive nanomechanical approach to define changes in surface structure of cellulose has the potential to permit a real-time assessment of the effect of the non-hydrolytic activities of cellulase on cellulose and thereby to provide a comprehensive understanding of the initial steps of the enzymatic hydrolysis of cellulose.

  7. Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

    NASA Astrophysics Data System (ADS)

    Minnick, David L.

    Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

  8. Tunicate cellulose nanocrystals: preparation, neat films and nanocomposite films with glucomannans.

    PubMed

    Zhao, Yadong; Zhang, Yujia; Lindström, Mikael E; Li, Jiebing

    2015-03-06

    Cellulose nanocrystals (CNs) were prepared from tunicate by enzymatic hydrolysis (ECN), TEMPO-mediated oxidation (TCN) and acid hydrolysis (ACN). They were cast alone or blended with glucomannan (GM) from konjac or spruce to prepare films. Different CNs were obtained with a yield of ECN>TCN>ACN with corresponding order of decreased Mw but increased crystallinity. The CNs' diameters were on the nanometre scale, with lengths of ECN>TCN>ACN. For CN-films, TCN and ACN fibrils were stretched and parallel to each other due to surface charges. For CN-GM films, both components interacted strongly with each other, resulting in changes of crystallinity, specific surface area, fibril diameter and contact angle compared with CN films. The composite films had good thermal, optical and mechanical properties; the last ones are apparently better than similar films reported in the literature. This is the first systematic study of different tunicate CN-GM nanocomposite films and the first ever for spruce GM.

  9. Lamellar, micro-phase separated blends of methyl cellulose and dendritic polyethylene glycol, POSS-PEG.

    PubMed

    Chinnam, Parameswara Rao; Mantravadi, Ramya; Jimenez, Jayvic C; Dikin, Dmitriy A; Wunder, Stephanie L

    2016-01-20

    Blends of methyl cellulose (MC) and liquid pegylated polyoctahedralsilsesquioxane (POSS-PEG) were prepared from non-gelled, aqueous solutions at room temperature (RT), which was below their gel temperatures (Tm). Lamellar, fibrillated films (pure MC) and increasingly micro-porous morphologies with increasing POSS-PEG content were formed, which had RT moduli between 1 and 5GPa. Evidence of distinct micro-phase separated MC and POSS-PEG domains was indicated by the persistence of the MC and POSS-PEG (at 77K) crystal structures in the X-ray diffraction data, and scanning transmission electron images. Mixing of MC and POSS-PEG in the interface region was indicated by suppression of crystallinity in the POSS-PEG, and increases/decreases in the glass transition temperatures (Tg) of POSS-PEG/MC in the blends compared with the pure components. These interface interactions may serve as cross-link sites between the micro-phase separated domains that permit incorporation of high amounts of POSS-PEG in the blends, prevent macro-phase separation and result in rubbery material properties (at high POSS-PEG content). Above Tg/Tm of POSS-PEG, the moduli of the blends increase with MC content as expected. However, below Tg/Tm of POSS-PEG, the moduli are greater for blends with high POSS-PEG content, suggesting that it behaves like semi-crystalline polyethylene oxide reinforced with silica (SiO1.5).

  10. Isolation of bacterial cellulose nanocrystalline from pineapple peel waste: Optimization of acid concentration in the hydrolysis method

    NASA Astrophysics Data System (ADS)

    Anwar, Budiman; Rosyid, Nurul Huda; Effendi, Devi Bentia; Nandiyanto, Asep Bayu Dani; Mudzakir, Ahmad; Hidayat, Topik

    2016-02-01

    Isolation of needle-shaped bacterial cellulose nanocrystalline with a diameter of 16-64 nm, a fiber length of 258-806 nm, and a degree of crystallinity of 64% from pineapple peel waste using an acid hydrolysis process was investigated. Experimental showed that selective concentration of acid played important roles in isolating the bacterial cellulose nanocrystalline from the cellulose source. To achieve the successful isolation of bacterial cellulose nanocrystalline, various acid concentrations were tested. To confirm the effect of acid concentration on the successful isolation process, the reaction conditions were fixed at a temperature of 50°C, a hydrolysis time of 30 minutes, and a bacterial cellulose-to-acid ratio of 1:50. Pineapple peel waste was used as a model for a cellulose source because to the best of our knowledge, there is no report on the use of this raw material for producing bacterial cellulose nanocrystalline. In fact, this material can be used as an alternative for ecofriendly and cost-free cellulose sources. Therefore, understanding in how to isolate bacterial cellulose nanocrystalline from pineapple peel waste has the potential for large-scale production of inexpensive cellulose nanocrystalline.

  11. Enhanced enzymatic hydrolysis of cellulose in microgels.

    PubMed

    Chang, Aiping; Wu, Qingshi; Xu, Wenting; Xie, Jianda; Wu, Weitai

    2015-07-04

    A cellulose-based microgel, where an individual microgel contains approximately one cellulose chain on average, is synthesized via free radical polymerization of a difunctional small-molecule N,N'-methylenebisacrylamide in cellulose solution. This microgelation leads to a low-ordered cellulose, favoring enzymatic hydrolysis of cellulose to generate glucose.

  12. A coarse-grained model for synergistic action of multiple enzymes on cellulose

    SciTech Connect

    Asztalos, Andrea; Daniels, Marcus; Sethi, Anurag; Shen, Tongye; Langan, Paul; Redondo, Antonio; Gnanakaran, Sandrasegaram

    2012-08-01

    In this study, degradation of cellulose to glucose requires the cooperative action of three classes of enzymes, collectively known as cellulases. Endoglucanases randomly bind to cellulose surfaces and generate new chain ends by hydrolyzing -1,4-D-glycosidic bonds. Exoglucanases bind to free chain ends and hydrolyze glycosidic bonds in a processive manner releasing cellobiose units. Then, -glucosidases hydrolyze soluble cellobiose to glucose. Optimal synergistic action of these enzymes is essential for efficient digestion of cellulose. Experiments show that as hydrolysis proceeds and the cellulose substrate becomes more heterogeneous, the overall degradation slows down. As catalysis occurs on the surface of crystalline cellulose, several factors affect the overall hydrolysis. Therefore, spatial models of cellulose degradation must capture effects such as enzyme crowding and surface heterogeneity, which have been shown to lead to a reduction in hydrolysis rates. As a result, we present a coarse-grained stochastic model for capturing the key events associated with the enzymatic degradation of cellulose at the mesoscopic level. This functional model accounts for the mobility and action of a single cellulase enzyme as well as the synergy of multiple endo- and exo-cellulases on a cellulose surface. The quantitative description of cellulose degradation is calculated on a spatial model by including free and bound states of both endo- and exo-cellulases with explicit reactive surface terms (e.g., hydrogen bond breaking, covalent bond cleavages) and corresponding reaction rates. The dynamical evolution of the system is simulated by including physical interactions between cellulases and cellulose. In conclusion, our coarse-grained model reproduces the qualitative behavior of endoglucanases and exoglucanases by accounting for the spatial heterogeneity of the cellulose surface as well as other spatial factors such as enzyme crowding. Importantly, it captures the endo

  13. Characterization of cellulose production by a Gluconacetobacter xylinus strain from Kombucha.

    PubMed

    Nguyen, Vu Tuan; Flanagan, Bernadine; Gidley, Michael J; Dykes, Gary A

    2008-11-01

    The aims of this work were to characterize and improve cellulose production by a Gluconoacetobacter xylinus strain isolated from Kombucha and determine the purity and some structural features of the cellulose from this strain. Cellulose yield in tea medium with both black tea and green tea and in Hestrin and Schramm (HS) medium under both static and agitated cultures was compared. In the tea medium, the highest cellulose yield was obtained with green tea (approximately 0.20 g/L) rather than black tea (approximately 0.14 g/L). Yield in HS was higher (approximately 0.28 g/L) but did not differ between static and agitated incubation. (1)H-NMR and (13)C-NMR spectroscopy indicated that the cellulose is pure (free of acetan) and has high crystallinity, respectively. Cellulose yield was improved by changing the type and level of carbon and nitrogen source in the HS medium. A high yield of approximately 2.64 g/L was obtained with mannitol at 20 g/L and corn steep liquor at 40 g/L in combination. In the tea medium, tea at a level of 3 g/L gave the highest cellulose yield and the addition of 3 g/L of tea to the HS medium increased cellulose yield to 3.34 g/L. In conclusion, the G. xylinus strain from Kombucha had different cellulose-producing characteristics than previous strains isolated from fruit. Cellulose was produced in a pure form and showed high potential applicability. Our studies extensively characterized cellulose production from a G. xylinus strain from Kombucha for the first time, indicating both similarities and differences to strains from different sources.

  14. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko, David J.

    2004-07-13

    The present invention provides phyllosilicate-polymer compositions which are useful as liquid crystalline composites. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while at the same time be transparent. Because of the ordering of the particles liquid crystalline composite, liquid crystalline composites are particularly useful as barriers to gas transport.

  15. Insights on how the activity of an endoglucanase is affected by physical properties of insoluble celluloses.

    PubMed

    Bragatto, Juliano; Segato, Fernando; Cota, Junio; Mello, Danilo B; Oliveira, Marcelo M; Buckeridge, Marcos S; Squina, Fabio M; Driemeier, Carlos

    2012-05-31

    Cellulose physical properties like crystallinity, porosity, and particle size are known to influence cellulase activity, but knowledge is still insufficient for activity prediction from such measurable substrate characteristics. With the aim of illuminating enzyme-substrate relationships, this work evaluates a purified hyperthermophilic endo-1,4-beta-glucanase (from Pyrococcus furiosus) acting on 13 celluloses characterized for crystallinity and crystal width (by X-ray diffraction), wet porosity (by thermoporometry), and particle size (by light scattering). Activities are analyzed by the Michaelis-Menten kinetic equation, which is justified by low enzyme-substrate affinity. Michaelis-Menten coefficients K(m) and k(cat) are reinterpreted in the context of heterogeneous cellulose hydrolysis. For a set of as-received and milled microcrystalline celluloses, activity is successfully described as a function of accessible substrate concentration, with accessibility proportional to K(m)(-1). Accessibility contribution from external particle areas, pore areas, and crystalline packing are discriminated to have comparable magnitudes, implying that activity prediction demands all these substrate properties to be considered. Results additionally suggest that looser crystalline packing increases the lengths of released cello-oligomers as well as the maximum endoglucanase specific activity (k(cat)).

  16. Dynamically Controlled Iridescence of Cholesteric Cellulose Nanocrystal Suspensions Using Electric Fields.

    PubMed

    Frka-Petesic, Bruno; Radavidson, Harisoa; Jean, Bruno; Heux, Laurent

    2017-03-01

    Cellulose nanocrystal suspensions in apolar solvent spontaneously form iridescent liquid-crystalline phases but the control of their macroscopic order is usually poor. The use of electric fields can provide control on the cholesteric orientation and its periodicity, allowing macroscopic sample homogeneity and dynamical tuning of their iridescent hues, and is demonstrated here.

  17. Activation of microcrystalline cellulose in a CO(2)-based switchable system.

    PubMed

    Zhang, Qinghua; Oztekin, Nermin Simge; Barrault, Joël; De Oliveira Vigier, Karine; Jérôme, François

    2013-04-01

    MCC Hammer: Microcrystalline cellulose (MCC) is dissolved and subsequently regenerated in a CO2 -based switchable solvent system, drastically reducing its crystallinity index and thereby its recalcitrance to hydrolysis. Among the investigated systems, based on cheap, widely available chemicals, is one capable of dissolving up to 15 wt % MCC within 1 h at room temperature. Break it down!

  18. Crystalline-amorphous interaction in relation to the phase diagrams of binary polymer blends containing a crystalline constituent.

    PubMed

    Rathi, Pankaj; Huang, Tsang-Min; Dayal, Pratyush; Kyu, Thein

    2008-05-22

    The present article describes an equilibrium theory for determining binary phase diagrams of various crystalline-amorphous polymer blends by taking into account the contributions from both liquid-liquid phase separation between the constituents and solid-liquid phase transition of the crystalline component. An analytical expression for determining a crystal-amorphous interaction parameter is deduced based on the solid-liquid transition, involving the solidus and liquidus lines in conjunction with the coexistence curve of an upper critical solution temperature type. Of particular importance is that the crystalline-amorphous interaction parameter can be determined directly from the melting point depression data. The present analysis is therefore different from the conventional Flory-Huggins interaction parameter, which is associated with the liquid-liquid phase separation. The validity of the present theory is tested with the experimental phase diagrams of blends of poly(ethylene oxide)/diacrylate and poly(vinyl alcohol)/cellulose.

  19. The human crystallin gene families

    PubMed Central

    2012-01-01

    Crystallins are the abundant, long-lived proteins of the eye lens. The major human crystallins belong to two different superfamilies: the small heat-shock proteins (α-crystallins) and the βγ-crystallins. During evolution, other proteins have sometimes been recruited as crystallins to modify the properties of the lens. In the developing human lens, the enzyme betaine-homocysteine methyltransferase serves such a role. Evolutionary modification has also resulted in loss of expression of some human crystallin genes or of specific splice forms. Crystallin organization is essential for lens transparency and mutations; even minor changes to surface residues can cause cataract and loss of vision. PMID:23199295

  20. Processes for treating cellulosic material

    NASA Technical Reports Server (NTRS)

    Ladisch, Michael R. (Inventor); Kohlman, Karen L. (Inventor); Westgate, Paul L. (Inventor); Weil, Joseph R. (Inventor); Yang, Yiqi (Inventor)

    1998-01-01

    Disclosed are processes for pretreating cellulosic materials in liquid water by heating the materials in liquid water at a temperature at or above their glass transition temperature but not substantially exceeding 220.degree. C., while maintaining the pH of the reaction medium in a range that avoids substantial autohydrolysis of the cellulosic materials. Such pretreatments minimize chemical changes to the cellulose while leading to physical changes which substantially increase susceptibility to hydrolysis in the presence of cellulase.

  1. Arabinan-cellulose composite in Opuntia ficus-indica prickly pear spines.

    PubMed

    Vignon, M R; Heux, L; Malainine, M-E; Mahrouz, M

    2004-01-02

    The ultrastructure of the spines decorating the cladodes of the cactus Opuntia ficus-indica was investigated by optical microscopy, scanning and transmission electron microscopy, wide angle X-ray, and solid state 13C NMR analyses. Each spine consisted of a compact parallel arrangement of slender cellulosic fibers (0.4 mm in length and 6-10 microm in diameter) with small lumens. The fibers were disencrusted by alkali and sodium chlorite bleaching, yielding a remarkable arabinan-cellulose (1:1) product. X-ray fiber diagrams of the spines before and after purification confirmed the presence of crystalline cellulose domains with molecular axis parallel to the spine axis. CP-MAS 13C T1 NMR data showed a strong interaction at a nanometric level of a fraction of the arabinan and the cellulose crystalline domains. By sequential hydrothermal extractions, followed by a trifluoroacetic acid treatment, a relatively pure cellulose was isolated while the extracted fibers became fibrillated into slender microfibrils having no more than 4-6 nm diameter. The hydrothermal extract yielded the alpha-L-arabinofuranan consisting of a chain of (1-->5)-linked L-arabinosyl residues with branching either at C-2 or C-3 or at both C-2 and C-3. Taken together, these observations suggest that the bulk of the spine fibers consists of an intimate composite of cellulose microfibrils embedded in an arabinan matrix.

  2. Hydrogen bond formation in regioselectively functionalized 3-mono-O-methyl cellulose.

    PubMed

    Kondo, Tetsuo; Koschella, Andreas; Heublein, Brigitte; Klemm, Dieter; Heinze, Thomas

    2008-10-13

    The hydrogen bond systems of cellulose and its derivatives are one of the most important factors regarding their physical- and chemical properties such as solubility, crystallinity, gel formation, and resistance to enzymatic degradation. In this paper, it was attempted to clarify the intra- and intermolecular hydrogen bond formation in regioselectively functionalized 3-mono-O-methyl cellulose (3MC). First, the 3MC was synthesized and the cast film thereof was characterized in comparison to 2,3-di-O-methyl cellulose, 6-mono-O-methyl cellulose, and 2,3,6-tri-O-methyl cellulose by means of wide angle X-ray diffraction (WAXD) and (13)C cross polarization/magic angle spinning NMR spectroscopy. Second, the hydrogen bonds in the 3MC film were analyzed by means of FTIR spectroscopy in combination with a curve fitting method. After deconvolution, the resulting two main bands (Fig. 3) indicated that instead of intramolecular hydrogen bonds between position OH-3 and O-5 another intramolecular hydrogen bond between OH-2 and OH-6 may exist. The large deconvoluted band at 3340cm(-1) referred to strong interchain hydrogen bonds involving the hydroxyl groups at C-6. The crystallinity of 54% calculated from the WAXD supports also the dependency of the usually observed crystallization in cellulose of the hydroxyl groups at C-6 to engage in interchain hydrogen bonding.

  3. Obtaining fermentable sugars by dilute acid hydrolysis of hemicellulose and fast pyrolysis of cellulose.

    PubMed

    Jiang, Liqun; Zheng, Anqing; Zhao, Zengli; He, Fang; Li, Haibin; Liu, Weiguo

    2015-04-01

    The objective of this study was to get fermentable sugars by dilute acid hydrolysis of hemicellulose and fast pyrolysis of cellulose from sugarcane bagasse. Hemicellulose could be easily hydrolyzed by dilute acid as sugars. The remained solid residue of acid hydrolysis was utilized to get levoglucosan by fast pyrolysis economically. Levoglucosan yield from crystalline cellulose could be as high as 61.47%. Dilute acid hydrolysis was also a promising pretreatment for levoglucosan production from lignocellulose. The dilute acid pretreated sugarcane bagasse resulted in higher levoglucosan yield (40.50%) in fast pyrolysis by micropyrolyzer, which was more effective than water washed (29.10%) and un-pretreated (12.84%). It was mainly ascribed to the effective removal of alkali and alkaline earth metals and the accumulation of crystalline cellulose. This strategy seems a promising route to achieve inexpensive fermentable sugars from lignocellulose for biorefinery.

  4. Multifunctional PLA-PHB/cellulose nanocrystal films: processing, structural and thermal properties.

    PubMed

    Arrieta, M P; Fortunati, E; Dominici, F; Rayón, E; López, J; Kenny, J M

    2014-07-17

    Cellulose nanocrystals (CNCs) synthesized from microcrystalline cellulose by acid hydrolysis were added into poly(lactic acid)-poly(hydroxybutyrate) (PLA-PHB) blends to improve the final properties of the multifunctional systems. CNC were also modified with a surfactant (CNCs) to increase the interfacial adhesion in the systems maintaining the thermal stability. Firstly, masterbatch pellets were obtained for each formulation to improve the dispersion of the cellulose structures in the PLA-PHB and then nanocomposite films were processed. The thermal stability as well as the morphological and structural properties of nanocomposites was investigated. While PHB increased the PLA crystallinity due to its nucleation effect, well dispersed CNC and CNCs not only increased the crystallinity but also improved the processability, the thermal stability and the interaction between both polymers especially in the case of the modified CNCs based PLA-PHB formulation. Likewise, CNCs were better dispersed in PLA-CNCs and PLA-PHB-CNCs, than CNC.

  5. Multidimensional Self-Assembled Structures of Alkylated Cellulose Oligomers Synthesized via in Vitro Enzymatic Reactions.

    PubMed

    Yataka, Yusuke; Sawada, Toshiki; Serizawa, Takeshi

    2016-10-04

    The self-assembly of biomolecules into highly ordered nano-to-macroscale structures is essential in the construction of biological tissues and organs. A variety of biomolecular assemblies composed of nucleic acids, peptides, and lipids have been used as molecular building units for self-assembled materials. However, crystalline polysaccharides have rarely been utilized in self-assembled materials. In this study, we describe multidimensional self-assembled structures of alkylated cellulose oligomers synthesized via in vitro enzymatic reactions. We found that the alkyl chain length drastically affected the assembled morphologies and allomorphs of cellulose moieties. The modulation of the intermolecular interactions of cellulose oligomers by alkyl substituents was highly effective at controlling their assembly into multidimensional structures. This study proposes a new potential of crystalline oligosaccharides for structural components of molecular assemblies with controlled morphologies and crystal structures.

  6. Ethanol production from cellulose by two lignocellulolytic soil fungi

    SciTech Connect

    Durrant, L.R.

    1996-12-31

    The present work examines the production of ethanol via direct fermentation of pure celluloses and lignocellulosic wastes by two soil fungi isolated under anaerobic conditions. The strains were cultured on a defined medium containing filter paper slurry as the carbon source under anaerobic, microaerophilic, and aerobic conditions. After complete degradation of the cellulose, lignocellulases and fermentation products were determined. Highest activities for Trichocladium canadense (strain Q10) and the basidiomycete strain (strain H2), were obtained when cultures were incubated under microaerophilic conditions and air, respectively. Laccase activity was present in the culture supernatants of both strains, but peroxidase was only produced by strain H2. Ethanol was the major nongaseous fermentation product. Highest conversion of available cellulose to ethanol was obtained with strain Q10 (90-96%), under microaerophilic conditions. Ethanol production decreased when microcrystalline cellulose and lignocellulosic substrates were used. 29 refs., 4 figs., 2 tabs.

  7. Topological nonsymmorphic crystalline superconductors

    NASA Astrophysics Data System (ADS)

    Wang, Qing-Ze; Liu, Chao-Xing

    2016-01-01

    Topological superconductors possess a nodeless superconducting gap in the bulk and gapless zero energy modes, known as "Majorana zero modes," at the boundary of a finite system. In this work, we introduce a new class of topological superconductors, which are protected by nonsymmorphic crystalline symmetry and thus dubbed "topological nonsymmorphic crystalline superconductors." We construct an explicit Bogoliubov-de Gennes type of model for this superconducting phase in the D class and show how Majorana zero modes in this model are protected by glide plane symmetry. Furthermore, we generalize the classification of topological nonsymmorphic crystalline superconductors to the classes with time reversal symmetry, including the DIII and BDI classes, in two dimensions. Our theory provides guidance to search for new topological superconducting materials with nonsymmorphic crystal structures.

  8. Topological Nonsymmorphic Crystalline Superconductors

    NASA Astrophysics Data System (ADS)

    Wang, Qing-Ze; Liu, Chao-Xing

    Topological superconductors possess a nodeless superconducting gap in the bulk and gapless zero energy modes, known as ``Majorana zero modes'', at the boundary of a finite system. In this work, we introduce a new class of topological superconductors, which are protected by nonsymmorphic crystalline symmetry and thus dubbed ``topological nonsymmorphic crystalline superconductors''. We construct an explicit Bogoliubov-de Gennes type of model for this superconducting phase in the D class and show how Majorana zero modes in this model are protected by glide symmetry. Furthermore, we generalize the classification of topological nonsymmorphic crystalline superconductors to the classes with time reversal symmetry, including the DIII and BDI classes, in two dimensions. Our theory provides a guidance to search for new topological superconducting materials with nonsymmorphic crystal structures.

  9. Crystalline molecular flasks.

    PubMed

    Inokuma, Yasuhide; Kawano, Masaki; Fujita, Makoto

    2011-05-01

    A variety of host compounds have been used as molecular-scale reaction vessels, protecting guests from their environment or restricting the space available around them, thus favouring particular reactions. Such molecular 'flasks' can endow guest molecules with reactivities that differ from those in bulk solvents. Here, we extend this concept to crystalline molecular flasks, solid-state crystalline networks with pores within which pseudo-solution-state reactions can take place. As the guest molecules can spontaneously align along the walls and channels of the hosts, structural changes in the substrates can be directly observed by in situ X-ray crystallography during reaction. Recently, this has enabled observation of the molecular structures of transient intermediates and other labile species, in the form of sequential structural snapshots of the chemical transformation. Here, we describe the principles, development and applications of crystalline molecular flasks.

  10. Acid hydrolysis of cellulose to yield glucose

    DOEpatents

    Tsao, George T.; Ladisch, Michael R.; Bose, Arindam

    1979-01-01

    A process to yield glucose from cellulose through acid hydrolysis. Cellulose is recovered from cellulosic materials, preferably by pretreating the cellulosic materials by dissolving the cellulosic materials in Cadoxen or a chelating metal caustic swelling solvent and then precipitating the cellulose therefrom. Hydrolysis is accomplished using an acid, preferably dilute sulfuric acid, and the glucose is yielded substantially without side products. Lignin may be removed either before or after hydrolysis.

  11. Polymer-mediated disruption of drug crystallinity.

    PubMed

    Rawlinson, Clare F; Williams, Adrian C; Timmins, Peter; Grimsey, Ian

    2007-05-04

    Ibuprofen (IB), a BCS Class II compound, is a highly crystalline substance with poor solubility properties. Here we report on the disruption of this crystalline structure upon intimate contact with the polymeric carrier cross-linked polyvinylpyrrolidone (PVP-CL) facilitated by low energy simple mixing. Whilst strong molecular interactions between APIs and carriers within delivery systems would be expected on melting or through solvent depositions, this is not the case with less energetic mixing. Simple mixing of the two compounds resulted in a significant decrease in the differential scanning calorimetry (DSC) melting enthalpy for IB, indicating that approximately 30% of the crystalline content was disordered. This structural change was confirmed by broadening and intensity diminution of characteristic IB X-ray powder diffractometry (PXRD) peaks. Unexpectedly, the crystalline content of the drug continued to decrease upon storage under ambient conditions. The molecular environment of the mixture was further investigated using Fourier transform infrared (FT-IR) and Fourier transform Raman (FT-Raman) spectroscopy. These data suggest that the primary interaction between these components of the physical mix is hydrogen bonding, with a secondary mechanism involving electrostatic/hydrophobic interactions through the IB benzene ring. Such interactions and subsequent loss of crystallinity could confer a dissolution rate advantage for IB.

  12. Production of nanotubes in delignified porous cellulosic materials after hydrolysis with cellulase.

    PubMed

    Koutinas, Αthanasios Α; Papafotopoulou-Patrinou, Evgenia; Gialleli, Angelika-Ioanna; Petsi, Theano; Bekatorou, Argyro; Kanellaki, Maria

    2016-08-01

    In this study, tubular cellulose (TC), a porous cellulosic material produced by delignification of sawdust, was treated with a Trichoderma reesei cellulase in order to increase the proportion of nano-tubes. The effect of enzyme concentration and treatment duration on surface characteristics was studied and the samples were analyzed with BET, SEM and XRD. Also, a composite material of gelatinized starch and TC underwent enzymatic treatment in combination with amylase (320U) and cellulase (320U) enzymes. For TC, the optimum enzyme concentration (640U) led to significant increase of TC specific surface area and pore volume along with the reduction of pore diameter. It was also shown that the enzymatic treatment did not result to a significant change of cellulose crystallinity index. The produced nano-tubular cellulose shows potential for application to drug and chemical preservative delivery systems.

  13. Synchrotron SAXS and WAXD Studies of Cellulose Nascent Crystals: Experiment and Structure Analysis

    NASA Astrophysics Data System (ADS)

    Su, Ying; Burger, Christian; Hsiao, Benjamin S.; Chu, Benjamin

    2012-02-01

    Cellulose nascent crystals extracted from biomass (wood pulp, jute and cotton)by combined chemical and mechanical treatments are low cost, environmentally friendly and high performance materials to form the barrier layer in ultrafiltration membranes. This research project is aimed at using the synchrotron X-ray scattering methods to characterize the nascent crystalline nanofibers in different formats. The SAXS (Small Angle X-ray Scattering) data of cellulose nanofiber suspensions was analyzed and the polydisperse ribbon model with rectangular cross section fit the data well. The 2D and 3D simulations of WAXD (Wide Angle X-ray Diffraction) pattern of jute cellulose fibers solved the contents ratio of cellulose I-alpha and I-beta and Hermans' orientation parameter P2.

  14. Synergism of cellulases from Trichoderma reesei in the degradation of cellulose

    SciTech Connect

    Henrissat, B.; Driguez, H.; Viet, C.; Schuelein, M.

    1985-08-01

    The action of cellobiohydrolases I and II (CBHI and CBHII) and endoglucanases I and II (EGI and EGII) purified from Trichoderma reesei was evaluated against various substrates. CBHI degraded the ..beta..-D-glucan from barley in a typical endo pattern. With cellulose substrates, the synergism between CBHI and endoglucanase I or II depended on the structural and ultrastructural features of the substrate. This effect, unrelated to endo-exo cooperation, was found with substrates of intermediate crystallinity whereas weak or no synergism was recorded with cellulose microcrystals or the soluble carboxy-methyl cellulose derivative. Synergistic degradation of cellulose was also recorded with mixtures of CBHI and CBHII. On the other hand, synergism between endoglucanases and CBHII followed the pattern expected for an endo-exo cooperation. These results presented support evidence for multiple types of cooperation between the cellulolytic enzymes. 30 references, 7 figures, 1 table.

  15. Bionanocomposite films based on plasticized PLA-PHB/cellulose nanocrystal blends.

    PubMed

    Arrieta, M P; Fortunati, E; Dominici, F; López, J; Kenny, J M

    2015-05-05

    Optically transparent plasticized poly(lactic acid) (PLA) based bionanocomposite films intended for food packaging were prepared by melt blending. Materials were plasticized with 15wt% of acetyl(tributyl citrate) (ATBC) to improve the material processability and to obtain flexibile films. Poly(hydroxybutyrate) (PHB) was used to increase PLA crystallinity. The thermal stability of the PLA-PHB blends was improved by the addition of 5 wt% of cellulose nanocrystals (CNC) or modified cellulose nanocrystals (CNCs) synthesized from microcrystalline cellulose. The combination of ATBC and cellulose nanocrystals, mainly the better dispersed CNCs, improved the interaction between PLA and PHB. Thus, an improvement on the oxygen barrier and stretchability was achieved in PLA-PHB-CNCs-ATBC which also displayed somewhat UV light blocking effect. All bionanocomposite films presented appropriate disintegration in compost suggesting their possible applications as biodegradable packaging materials.

  16. Cellulose acetate from oil palm empty fruit bunch via a one step heterogeneous acetylation.

    PubMed

    Wan Daud, Wan Rosli; Djuned, Fauzi Muhammad

    2015-11-05

    Acetone soluble oil palm empty fruit bunch cellulose acetate (OPEFB-CA) of DS 2.52 has been successfully synthesized in a one-step heterogeneous acetylation of OPEFB cellulose without necessitating the hydrolysis stage. This has only been made possible by the mathematical modeling of the acetylation process by manipulating the variables of reaction time and acetic anhydride/cellulose ratio (RR). The obtained model was verified by experimental data with an error of less than 2.5%. NMR analysis showed that the distribution of the acetyl moiety among the three OH groups of cellulose indicates a preference at the C6 position, followed by C3 and C2. XRD revealed that OPEFB-CA is highly amorphous with a degree of crystallinity estimated to be ca. 6.41% as determined from DSC. The OPEFB-CA films exhibited good mechanical properties being their tensile strength and Young's modulus higher than those of the commercial CA.

  17. Hybrid composite thin films composed of tin oxide nanoparticles and cellulose

    NASA Astrophysics Data System (ADS)

    Mahadeva, Suresha K.; Nayak, Jyoti; Kim, Jaehwan

    2013-07-01

    This paper reports the preparation and characterization of hybrid thin films consisting of tin oxide (SnO2) nanoparticles and cellulose. SnO2 nanoparticle loaded cellulose hybrid thin films were fabricated by a solution blending technique, using sodium dodecyl sulfate as a dispersion agent. Scanning and transmission electron microscopy studies revealed uniform dispersion of the SnO2 nanoparticles in the cellulose matrix. Reduction in the crystalline melting transition temperature and tensile properties of cellulose was observed due to the SnO2 nanoparticle loading. Potential application of these hybrid thin films as low cost, flexible and biodegradable humidity sensors is examined in terms of the change in electrical resistivity of the material exposed to a wide range of humidity as well as its response-recovery behavior.

  18. Steam pretreatment of agricultural residues facilitates hemicellulose recovery while enhancing enzyme accessibility to cellulose.

    PubMed

    Chandra, Richard P; Arantes, Valdeir; Saddler, Jack

    2015-06-01

    The origins of lignocellulosic biomass and the pretreatment used to enhance enzyme accessibility to the cellulosic component are known to be strongly influenced by various substrate characteristics. To assess the impact that fibre properties might have on enzymatic hydrolysis, seven agricultural residues were characterised before and after steam pretreatment using a single pretreatment condition (190°C, 5min, 3% SO2) previously shown to enhance fractionation and hydrolysis of the cellulosic component of corn stover. When the fibre length, width and coarseness, viscosity, water retention value and cellulose crystallinity were monitored, no clear correlation was observed between any single substrate characteristic and the substrate's ease of enzymatic hydrolysis. However, the amount of hemicellulose that was solubilised during pretreatment correlated (r(2)=0.98) with the effectiveness of enzyme hydrolysis of each pretreated substrate. Simons's staining, to measure the cellulose accessibility, showed good correlation (r(2)=0.83) with hemicellulose removal and the extent of enzymatic hydrolysis.

  19. Spider Silk-CBD-Cellulose Nanocrystal Composites: Mechanism of Assembly

    PubMed Central

    Meirovitch, Sigal; Shtein, Zvi; Ben-Shalom, Tal; Lapidot, Shaul; Tamburu, Carmen; Hu, Xiao; Kluge, Jonathan A.; Raviv, Uri; Kaplan, David L.; Shoseyov, Oded

    2016-01-01

    The fabrication of cellulose-spider silk bio-nanocomposites comprised of cellulose nanocrystals (CNCs) and recombinant spider silk protein fused to a cellulose binding domain (CBD) is described. Silk-CBD successfully binds cellulose, and unlike recombinant silk alone, silk-CBD self-assembles into microfibrils even in the absence of CNCs. Silk-CBD-CNC composite sponges and films show changes in internal structure and CNC alignment related to the addition of silk-CBD. The silk-CBD sponges exhibit improved thermal and structural characteristics in comparison to control recombinant spider silk sponges. The glass transition temperature (Tg) of the silk-CBD sponge was higher than the control silk sponge and similar to native dragline spider silk fibers. Gel filtration analysis, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and cryo-transmission electron microscopy (TEM) indicated that silk-CBD, but not the recombinant silk control, formed a nematic liquid crystalline phase similar to that observed in native spider silk during the silk spinning process. Silk-CBD microfibrils spontaneously formed in solution upon ultrasonication. We suggest a model for silk-CBD assembly that implicates CBD in the central role of driving the dimerization of spider silk monomers, a process essential to the molecular assembly of spider-silk nanofibers and silk-CNC composites. PMID:27649169

  20. Spider Silk-CBD-Cellulose Nanocrystal Composites: Mechanism of Assembly.

    PubMed

    Meirovitch, Sigal; Shtein, Zvi; Ben-Shalom, Tal; Lapidot, Shaul; Tamburu, Carmen; Hu, Xiao; Kluge, Jonathan A; Raviv, Uri; Kaplan, David L; Shoseyov, Oded

    2016-09-18

    The fabrication of cellulose-spider silk bio-nanocomposites comprised of cellulose nanocrystals (CNCs) and recombinant spider silk protein fused to a cellulose binding domain (CBD) is described. Silk-CBD successfully binds cellulose, and unlike recombinant silk alone, silk-CBD self-assembles into microfibrils even in the absence of CNCs. Silk-CBD-CNC composite sponges and films show changes in internal structure and CNC alignment related to the addition of silk-CBD. The silk-CBD sponges exhibit improved thermal and structural characteristics in comparison to control recombinant spider silk sponges. The glass transition temperature (Tg) of the silk-CBD sponge was higher than the control silk sponge and similar to native dragline spider silk fibers. Gel filtration analysis, dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and cryo-transmission electron microscopy (TEM) indicated that silk-CBD, but not the recombinant silk control, formed a nematic liquid crystalline phase similar to that observed in native spider silk during the silk spinning process. Silk-CBD microfibrils spontaneously formed in solution upon ultrasonication. We suggest a model for silk-CBD assembly that implicates CBD in the central role of driving the dimerization of spider silk monomers, a process essential to the molecular assembly of spider-silk nanofibers and silk-CNC composites.

  1. Surface esterification of cellulose nanofibers by a simple organocatalytic methodology.

    PubMed

    Avila Ramírez, Jhon Alejandro; Suriano, Camila Juan; Cerrutti, Patricia; Foresti, María Laura

    2014-12-19

    Bacterial cellulose nanofibers were esterified with two short carboxylic acids by means of a simple and novel organic acid-catalyzed route. The methodology proposed relayed on the use of a non-toxic biobased α-hydroxycarboxylic acid as catalyst, and proceeded under moderate reaction conditions in solventless medium. By varying the esterification interval, acetylated and propionized bacterial cellulose nanofibers with degree of substitution (DS) in the 0.02-0.45 range could be obtained. Esterified bacterial cellulose samples were characterized by means of Solid-State CP/MAS (13)C Nuclear Magnetic Resonance spectroscopy (CP/MAS (13)C NMR), Fourier Transform Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and chosen hydrophobicity test assays. TGA results showed that the esterified nanofibers had increased thermal stability, whereas XRD data evidenced that the organocatalytic esterification protocol did not alter their crystallinity. The analysis of the ensuing modified nanofibers by NMR, FTIR, XRD and TGA demonstrated that esterification occurred essentially at the surface of bacterial cellulose microfibrils, something highly desirable for changing their surface hydrophilicity while not affecting their ultrastructure.

  2. Modeling the minimum enzymatic requirements for optimal cellulose conversion

    NASA Astrophysics Data System (ADS)

    den Haan, R.; van Zyl, J. M.; Harms, T. M.; van Zyl, W. H.

    2013-06-01

    Hydrolysis of cellulose is achieved by the synergistic action of endoglucanases, exoglucanases and β-glucosidases. Most cellulolytic microorganisms produce a varied array of these enzymes and the relative roles of the components are not easily defined or quantified. In this study we have used partially purified cellulases produced heterologously in the yeast Saccharomyces cerevisiae to increase our understanding of the roles of some of these components. CBH1 (Cel7), CBH2 (Cel6) and EG2 (Cel5) were separately produced in recombinant yeast strains, allowing their isolation free of any contaminating cellulolytic activity. Binary and ternary mixtures of the enzymes at loadings ranging between 3 and 100 mg g-1 Avicel allowed us to illustrate the relative roles of the enzymes and their levels of synergy. A mathematical model was created to simulate the interactions of these enzymes on crystalline cellulose, under both isolated and synergistic conditions. Laboratory results from the various mixtures at a range of loadings of recombinant enzymes allowed refinement of the mathematical model. The model can further be used to predict the optimal synergistic mixes of the enzymes. This information can subsequently be applied to help to determine the minimum protein requirement for complete hydrolysis of cellulose. Such knowledge will be greatly informative for the design of better enzymatic cocktails or processing organisms for the conversion of cellulosic biomass to commodity products.

  3. Cellulose Synthesis in Agrobacterium tumefaciens

    SciTech Connect

    Alan R. White; Ann G. Matthysse

    2004-07-31

    We have cloned the celC gene and its homologue from E. coli, yhjM, in an expression vector and expressed the both genes in E. coli; we have determined that the YhjM protein is able to complement in vitro cellulose synthesis by extracts of A. tumefaciens celC mutants, we have purified the YhjM protein product and are currently examining its enzymatic activity; we have examined whole cell extracts of CelC and various other cellulose mutants and wild type bacteria for the presence of cellulose oligomers and cellulose; we have examined the ability of extracts of wild type and cellulose mutants including CelC to incorporate UDP-14C-glucose into cellulose and into water-soluble, ethanol-insoluble oligosaccharides; we have made mutants which synthesize greater amounts of cellulose than the wild type; and we have examined the role of cellulose in the formation of biofilms by A. tumefaciens. In addition we have examined the ability of a putative cellulose synthase gene from the tunicate Ciona savignyi to complement an A. tumefaciens celA mutant. The greatest difference between our knowledge of bacterial cellulose synthesis when we started this project and current knowledge is that in 1999 when we wrote the original grant very few bacteria were known to synthesize cellulose and genes involved in this synthesis were sequenced only from Acetobacter species, A. tumefaciens and Rhizobium leguminosarum. Currently many bacteria are known to synthesize cellulose and genes that may be involved have been sequenced from more than 10 species of bacteria. This additional information has raised the possibility of attempting to use genes from one bacterium to complement mutants in another bacterium. This will enable us to examine the question of which genes are responsible for the three dimensional structure of cellulose (since this differs among bacterial species) and also to examine the interactions between the various proteins required for cellulose synthesis. We have carried out one

  4. Microbial diversity of cellulose hydrolysis.

    PubMed

    Wilson, David B

    2011-06-01

    Enzymatic hydrolysis of cellulose by microorganisms is a key step in the global carbon cycle. Despite its abundance only a small percentage of microorganisms can degrade cellulose, probably because it is present in recalcitrant cell walls. There are at least five distinct mechanisms used by different microorganisms to degrade cellulose all of which involve cellulases. Cellulolytic organisms and cellulases are extremely diverse possibly because their natural substrates, plant cell walls, are very diverse. At this time the microbial ecology of cellulose degradation in any environment is still not clearly understood even though there is a great deal of information available about the bovine rumen. Two major problems that limit our understanding of this area are the vast diversity of organisms present in most cellulose degrading environments and the inability to culture most of them.

  5. Ultrasonic dyeing of cellulose nanofibers.

    PubMed

    Khatri, Muzamil; Ahmed, Farooq; Jatoi, Abdul Wahab; Mahar, Rasool Bux; Khatri, Zeeshan; Kim, Ick Soo

    2016-07-01

    Textile dyeing assisted by ultrasonic energy has attained a greater interest in recent years. We report ultrasonic dyeing of nanofibers for the very first time. We chose cellulose nanofibers and dyed with two reactive dyes, CI reactive black 5 and CI reactive red 195. The cellulose nanofibers were prepared by electrospinning of cellulose acetate (CA) followed by deacetylation. The FTIR results confirmed complete conversion of CA into cellulose nanofibers. Dyeing parameters optimized were dyeing temperature, dyeing time and dye concentrations for each class of the dye used. Results revealed that the ultrasonic dyeing produced higher color yield (K/S values) than the conventional dyeing. The color fastness test results depicted good dye fixation. SEM analysis evidenced that ultrasonic energy during dyeing do not affect surface morphology of nanofibers. The results conclude successful dyeing of cellulose nanofibers using ultrasonic energy with better color yield and color fastness results than conventional dyeing.

  6. High magnetic field quantum transport in Au nanoparticle-cellulose films.

    PubMed

    Turyanska, L; Makarovsky, O; Patanè, A; Kozlova, N V; Liu, Z; Li, M; Mann, S

    2012-02-03

    We report the magneto-transport properties of cellulose films comprising interconnected networks of gold nanoparticles (Au NPs). Cellulose is a biopolymer that can be made electrically conducting by cellulose regeneration in Au NP dispersions. The mechanism of electronic conduction in the Au-cellulose films changes from variable range hopping to metallic-like conduction with decreasing resistivity. Our experiments in high magnetic fields (up to 45 T) reveal negative magnetoresistance in the highly resistive films. This is attributed to the spin polarization of the Au NPs and the magnetic field induced suppression of electron spin flips during spin-polarized tunneling in the NP network.

  7. Effects of acid impregnated steam explosion process on xylose recovery and enzymatic conversion of cellulose in corncob.

    PubMed

    Fan, Xiaoguang; Cheng, Gang; Zhang, Hongjia; Li, Menghua; Wang, Shizeng; Yuan, Qipeng

    2014-12-19

    Corncob residue is a cellulose-rich byproduct obtained from industrial xylose production via dilute acid hydrolysis processes. Enzymatic hydrolysis of cellulose in acid hydrolysis residue of corncob (AHRC) is often less efficient without further pretreatment. In this work, the process characteristics of acid impregnated steam explosion were studied in conjunction with a dilute acid process, and their effects on physiochemical changes and enzymatic saccharification of corncob residue were compared. With the acid impregnated steam explosion process, both higher xylose recovery and higher cellulose conversion were obtained. The maximum conversion of cellulose in acid impregnated steam explosion residue of corncob (ASERC) reached 85.3%, which was 1.6 times higher than that of AHRC. Biomass compositional analysis showed similar cellulose and lignin content in ASERC and AHRC. XRD analysis demonstrated comparable crystallinity of ASERC and AHRC. The improved enzymatic hydrolysis efficiency was attributed to higher porosity in ASERC, measured by mercury porosimetry.

  8. A comparison of cellulose nanocrystals and cellulose nanofibres extracted from bagasse using acid and ball milling methods

    NASA Astrophysics Data System (ADS)

    Rahimi Kord Sofla, M.; Brown, R. J.; Tsuzuki, T.; Rainey, T. J.

    2016-09-01

    This study compared the fundamental properties of cellulose nanocrystals (CNC) and cellulose nanofibrils (CNF) extracted from sugarcane bagasse. Conventional hydrolysis was used to extract CNC while ball milling was used to extract CNF. Images generated by scanning electron microscope and transmission electron microscope showed CNC was needle-like with relatively lower aspect ratio and CNF was rope-like in structure with higher aspect ratio. Fourier-transformed infrared spectra showed that the chemical composition of nanocellulose and extracted cellulose were identical and quite different from bagasse. Dynamic light scattering studies showed that CNC had uniform particle size distribution with a median size of 148 nm while CNF had a bimodal size distribution with median size 240 ± 12 nm and 10 μm. X-ray diffraction showed that the amorphous portion was removed during hydrolysis; this resulted in an increase in the crystalline portion of CNC compared to CNF. Thermal degradation of cellulose initiated at a much lower temperature, in the case of the nanocrystals while the CNF prepared by ball milling were not affected, indicating higher thermal stability.

  9. Porous cellulose spheres: Preparation, modification and adsorption properties.

    PubMed

    Ma, Xiaofei; Liu, Congzhi; Anderson, Debbie P; Chang, Peter R

    2016-12-01

    Porous cellulose spheres (PCS) were fabricated by precipitating the spheres from a cellulose ionic liquid solution, followed by freezing, solvent exchange, and drying. PCS had low crystallinity and a large surface area that facilitated modification with trisodium trimetaphosphate (STMP) to introduce phosphate ester groups into the porous structure of the heterogeneous system. The STMP-modified PCS (SPCS) were used to remove heavy metal ions from aqueous solution. With increasing STMP dosage, the adsorption capacity of SPCS obviously improved due to chelation between Pb(2+) and phosphate ester groups. The kinetic adsorption and isotherm data matched the pseudo-second order model and the Langmuir model well. The maximum adsorption capacity reached 150.6 mg g(-1) for SPCS. SPCS were competitive with other absorbents because the phosphate ester groups and porous structure contributed to Pb(2+) adsorption. Moreover, SPCS can be regenerated with ethylenediamine tetraacetic acid disodium salt (EDTA) solution for repetitious adsorption of Pb(2+).

  10. Isolation and characterization of cellulose nanofibrils from arecanut husk fibre.

    PubMed

    C S, Julie Chandra; George, Neena; Narayanankutty, Sunil K

    2016-05-20

    The isolation of cellulose nanofibres from arecanut husk was achieved by a chemo-mechanical method thereby opening up a means for utilizing a waste product more effectively. The chemical processes involved alkali treatment, acid hydrolysis, and bleaching. The mechanical fibrillation was performed via grinding and homogenization. The chemical constituents at different stages of treatment of fibres were analyzed according to the ASTM standards. Morphological characterization was done using the scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The isolated nanofibers had an average diameter of below 10 nanometres and a very high aspect ratio in the range 120-150. Fourier transform infrared spectroscopy (FT-IR) showed the effective removal of the non cellulosic components. The crystallinity was increased with successive treatments as shown by the X-ray diffraction analysis (XRD). The TGA studies revealed a good thermal stability for the isolated nanofibres.

  11. Nanostructural reorganization of bacterial cellulose by ultrasonic treatment.

    PubMed

    Tischer, Paula C S Faria; Sierakowski, Maria Rita; Westfahl, Harry; Tischer, Cesar Augusto

    2010-05-10

    In this work, bacterial cellulose was subjected to a high-power ultrasonic treatment for different time intervals. The morphological analysis, scanning electron microscopy, and atomic force microscopy revealed that this treatment changed the width and height of the microfibrillar ribbons and roughness of their surface, originating films with new nanostructures. Differential thermal analysis showed a higher thermal stability for ultrasonicated samples with a pyrolysis onset temperature of 208 degrees C for native bacterial cellulose and 250 and 268 degrees C for the modified samples. The small-angle X-ray scattering experiments demonstrated that the treatment with ultrasound increased the thickness of the ribbons, while wide-angle X-ray scattering experiments demonstrated that the average crystallite dimension and the degree of crystallinity also increased. A model is proposed where the thicker ribbons and crystallites result from the fusion of neighboring ribbons due to cavitation effects.

  12. Regenerated cellulose scaffolds: Preparation, characterization and toxicological evaluation.

    PubMed

    de Araújo Júnior, Adalberto M; Braido, Guilherme; Saska, Sybele; Barud, Hernane S; Franchi, Leonardo P; Assunção, Rosana M N; Scarel-Caminaga, Raquel M; Capote, Ticiana S O; Messaddeq, Younès; Ribeiro, Sidney J L

    2016-01-20

    Regenerated cellulose scaffolds (RCS) may be used as alloplastic materials for tissue repair. In this work, the RCS were obtained by viscose process and characterized by scanning electron microscopy (SEM), wide angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetry analysis (TG). In vitro enzymatic degradation assay and toxicological assays were also evaluated. The physicochemical characterizations revealed the formation of a porous material with distinct thermal profile and crystallinity compared to pristine cellulose pulp. Enzymatic degradation assay revealed that lysozyme showed a mildest catalytic action when compared to cellulase, Tricoderma reesei (Tr). Nevertheless, both enzymes were efficient for degrading the RCS. RCS did not show cytotoxicity, mutagenic or genotoxic effects. The systematically characterization of this work suggests that RCS presented distinct features that make it a viable material for future studies related to the development of scaffolds for biological applications.

  13. Preparation and characterization of nano-cellulose with new shape from different precursor.

    PubMed

    Maiti, Sonakshi; Jayaramudu, J; Das, Kunal; Reddy, Siva Mohan; Sadiku, Rotimi; Ray, Suprakas Sinha; Liu, Dagang

    2013-10-15

    Three different precursor materials - 1. China cotton, 2. South African cotton, 3. Waste tissue papers were used to produce nano-cellulose by acid hydrolysis route. No chemical pretreatment has been done for the production of nano-cellulose from these precursors. Prepared nano-cellulose and their corresponding precursor materials were characterized by transmission electron microscopy (TEM), particle size analysis, X-ray diffraction (XRD) study, thermo gravimetric analysis (TGA), differential scanning calorimetric (DSC) analysis and Fourier transformed infra red (FTIR) spectroscopy. A comparative study of the characteristics was done with the properties of raw materials and with that of nano-cellulose. Shape and size of the nano cellulose generally depends on nature of the precursor and hydrolysis condition. Morphology study of nano-cellulose from different sources revealed range of length from 50 to 200 nm and diameter from 10 to 90 nm. Higher thermal stability and crystallinity of nano-cellulose were observed compared to that of precursor from TGA/DSC study.

  14. The adsorption of xyloglucan on cellulose: effects of explicit water and side chain variation.

    PubMed

    Zhang, Qiong; Brumer, Harry; Ågren, Hans; Tu, Yaoquan

    2011-11-29

    The interaction between para-crystalline cellulose and the cross-linking glycan xyloglucan (XG) plays a central role for the strength and extensibility of plant cell walls. The coating of XGs on cellulose surfaces is believed to be one of the most probable interaction patterns. In this work, the effects of explicit water and side chain variation on the adsorption of XGs on cellulose are investigated by means of atomistic molecular dynamics simulations. The adsorption properties are studied in detail for three XGs on cellulose Iβ 1-10 surface in aqueous environment, namely GXXXGXXXG, GXXLGXXXG, and GXXFGXXXG, which differ in the length and composition of one side chain. Our work shows that when water molecules are included in the theoretical model, the total interaction energies between the adsorbed XGs and cellulose are considerably smaller than in vacuo. Furthermore, in water environment the van der Waals interactions prevail over the electrostatic interactions in the adsorption. Variation in one side chain does not have significant influence on the interaction energy and the binding affinity, but does affect the equilibrium structural properties of the adsorbed XGs to facilitate the interaction between both the backbone and the side chain residues with the cellulose surface. Together, this analysis provides new insights into the nature of the XG-cellulose interaction, which helps to further refine current molecular models of the composite plant cell wall.

  15. Hydrated fractions of cellulosics probed by infrared spectroscopy coupled with dynamics of deuterium exchange.

    PubMed

    Driemeier, Carlos; Mendes, Fernanda M; Ling, Liu Yi

    2015-08-20

    This article presents a novel method to selectively probe the non-crystalline, hydrated fractions of cellulosic biomass. The method is based on time-resolved infrared spectra analyzed to provide information on spectral and dynamical features of deuterium exchange (OH → OD) in D2O atmosphere. We assign deuterium exchange spectral regions (700-3800 cm(-1)) and explore changes due to relative humidity, different cellulosic samples, and infrared polarization. Here, two results are highlighted. First, a wide range of celluloses isolated from plants show remarkable spectral similarities whatever the relative amounts of cellulose and xylan. This result supports an inherent type of hydrated disorder which is mostly insensitive to the molecular identities of the associated polysaccharides. Second, polarized infrared analysis of cotton reveals hydrated cellulose having chains preferentially aligned with those of crystals, while the hydroxyls of hydrated cellulose present much more randomized orientation. Our results provide new insights on molecular and group orientation and on hydrogen bonding in hydrated fractions of cellulosic biomass.

  16. Cellulose functionalization via high-energy irradiation-initiated grafting of glycidyl methacrylate and cyclodextrin immobilization

    NASA Astrophysics Data System (ADS)

    Desmet, Gilles; Takács, Erzsébet; Wojnárovits, László; Borsa, Judit

    2011-12-01

    Cotton-cellulose was functionalized using gamma-irradiation-induced grafting of glycidyl methacrylate (GMA) to obtain a hydrophobic cellulose derivative with epoxy groups suitable for further chemical modification. Two grafting techniques were applied. In pre-irradiation grafting (PIG) cellulose was irradiated in air and then immersed in a GMA monomer solution, whereas in simultaneous grafting (SG) cellulose was irradiated in an inert atmosphere in the presence of the monomer. PIG led to a more homogeneous fiber surface, while SG resulted in higher grafting yield but showed clear indications of some GMA-homopolymerization. Effects of the reaction parameters (grafting method, absorbed dose, monomer concentration, solvent composition) were evaluated by SEM, gravimetry (grafting yield) and FTIR spectroscopy. Water uptake of the cellulose decreased while adsorption of a pesticide molecule increased upon grafting. The adsorption was further enhanced by β-cyclodextrin immobilization during SG. This method can be applied to produce adsorbents from cellulose based agricultural wastes.

  17. Studies of cellulose binding by cellobiose dehydrogenase and a comparison with cellobiohydrolase 1.

    PubMed Central

    Henriksson, G; Salumets, A; Divne, C; Pettersson, G

    1997-01-01

    The binding isotherm to cellulose of cellobiose dehydrogenase (CDH) from Phanerochaete chrysosporium has been compared with that of cellobiohydrolase 1 (CBH 1) from Trichoderma reesei. CDH binds more strongly but more sparsely to cellulose than does CBH 1. In a classical Scatchard analysis, a better fit to a one-site binding model was obtained for CDH than for CBH 1. The binding of both enzymes decreased in the presence of ethylene glycol, increased in the presence of ammonium sulphate and was unaffected by sodium chloride. Attempts to localize the cellulose-binding site on CDH have also been made by exposing enzymically digested CDH to cellulose and isolating the cellulose-bound peptides. The results suggest that the cellulose-binding site is located internally in the amino acid sequence of CDH. PMID:9210407

  18. Hybrid nanocomposite based on cellulose and tin oxide: growth, structure, tensile and electrical characteristics

    NASA Astrophysics Data System (ADS)

    Mahadeva, Suresha K.; Kim, Jaehwan

    2011-10-01

    A highly flexible nanocomposite was developed by coating a regenerated cellulose film with a thin layer of tin oxide (SnO2) by liquid-phase deposition. Tin oxide was crystallized in solution and formed nanocrystal coatings on regenerated cellulose. The nanocrystalline layers did not exfoliate from cellulose. Transmission electron microscopy and energy dispersive x-ray spectroscopy suggest that SnO2 was not only deposited over the cellulose surface, but also nucleated and grew inside the cellulose film. Current-voltage characteristics of the nanocomposite revealed that its electrical resistivity decreases with deposition time, with the lowest value obtained for 24 h of deposition. The cellulose-SnO2 hybrid nanocomposite can be used for biodegradable and disposable chemical, humidity and biosensors.

  19. Screening of cellulases for biofuel production: online monitoring of the enzymatic hydrolysis of insoluble cellulose using high-throughput scattered light detection.

    PubMed

    Jäger, Gernot; Wulfhorst, Helene; Zeithammel, Erik U; Elinidou, Efthimia; Spiess, Antje C; Büchs, Jochen

    2011-01-01

    A new prospective cellulase assay simultaneously combining high-throughput, online analysis and insoluble cellulosic substrates is described. The hydrolysis of three different insoluble cellulosic substrates, catalysed by a commercial cellulase preparation from Trichoderma reesei (Celluclast), was monitored using the BioLector - allowing online monitoring of scattered light intensities in a continuously shaken microtiter plate. Cellulase activities could be quantitatively assayed using the BioLector. At low cellulase/cellulose ratios, the Michaelis-Menten parameters of the cellulase mixture were mainly affected by the crystallinity index of the cellulose. Here, the apparent maximum cellulase activities inversely correlated with the crystallinity index of the cellulose. At high cellulase/cellulose ratios the particle size of the cellulose, defining the external surface area accessible to the cellulases, was the key determining factor for cellulase activity. The developed technique was also successfully applied to evaluate the pH optimum of cellulases. Moreover, the non-hydrolytic deagglomeration of cellulose particles was investigated, for the first time, using high-throughput scattered light detection. In conclusion, this cellulase assay ideally links high-throughput, online analysis and realistic insoluble cellulosic substrates in one simple system. It will considerably simplify and accelerate fundamental research on cellulase screening.

  20. MICROBIAL FERMENTATION OF ABUNDANT BIOPOLYMERS: CELLULOSE AND CHITIN

    SciTech Connect

    Leschine, Susan

    2009-10-31

    Clostridium papyrosolvens. We discovered that C. papyrosolvens produces a multiprotein, multicomplex cellulase-xylanase enzyme system that hydrolyzes crystalline cellulose, and we have described this system in detail.

  1. Anomalous scaling law of strength and toughness of cellulose nanopaper

    PubMed Central

    Zhu, Hongli; Zhu, Shuze; Jia, Zheng; Parvinian, Sepideh; Li, Yuanyuan; Vaaland, Oeyvind; Hu, Liangbing; Li, Teng

    2015-01-01

    The quest for both strength and toughness is perpetual in advanced material design; unfortunately, these two mechanical properties are generally mutually exclusive. So far there exists only limited success of attaining both strength and toughness, which often needs material-specific, complicated, or expensive synthesis processes and thus can hardly be applicable to other materials. A general mechanism to address the conflict between strength and toughness still remains elusive. Here we report a first-of-its-kind study of the dependence of strength and toughness of cellulose nanopaper on the size of the constituent cellulose fibers. Surprisingly, we find that both the strength and toughness of cellulose nanopaper increase simultaneously (40 and 130 times, respectively) as the size of the constituent cellulose fibers decreases (from a mean diameter of 27 μm to 11 nm), revealing an anomalous but highly desirable scaling law of the mechanical properties of cellulose nanopaper: the smaller, the stronger and the tougher. Further fundamental mechanistic studies reveal that reduced intrinsic defect size and facile (re)formation of strong hydrogen bonding among cellulose molecular chains is the underlying key to this new scaling law of mechanical properties. These mechanistic findings are generally applicable to other material building blocks, and therefore open up abundant opportunities to use the fundamental bottom-up strategy to design a new class of functional materials that are both strong and tough. PMID:26150482

  2. CHITINASE-LIKE1/POM-POM1 and Its Homolog CTL2 Are Glucan-Interacting Proteins Important for Cellulose Biosynthesis in Arabidopsis[W][OA

    PubMed Central

    Sánchez-Rodríguez, Clara; Bauer, Stefan; Hématy, Kian; Saxe, Friederike; Ibáñez, Ana Belén; Vodermaier, Vera; Konlechner, Cornelia; Sampathkumar, Arun; Rüggeberg, Markus; Aichinger, Ernst; Neumetzler, Lutz; Burgert, Ingo; Somerville, Chris; Hauser, Marie-Theres; Persson, Staffan

    2012-01-01

    Plant cells are encased by a cellulose-containing wall that is essential for plant morphogenesis. Cellulose consists of β-1,4-linked glucan chains assembled into paracrystalline microfibrils that are synthesized by plasma membrane–located cellulose synthase (CESA) complexes. Associations with hemicelluloses are important for microfibril spacing and for maintaining cell wall tensile strength. Several components associated with cellulose synthesis have been identified; however, the biological functions for many of them remain elusive. We show that the chitinase-like (CTL) proteins, CTL1/POM1 and CTL2, are functionally equivalent, affect cellulose biosynthesis, and are likely to play a key role in establishing interactions between cellulose microfibrils and hemicelluloses. CTL1/POM1 coincided with CESAs in the endomembrane system and was secreted to the apoplast. The movement of CESAs was compromised in ctl1/pom1 mutant seedlings, and the cellulose content and xyloglucan structures were altered. X-ray analysis revealed reduced crystalline cellulose content in ctl1 ctl2 double mutants, suggesting that the CTLs cooperatively affect assembly of the glucan chains, which may affect interactions between hemicelluloses and cellulose. Consistent with this hypothesis, both CTLs bound glucan-based polymers in vitro. We propose that the apoplastic CTLs regulate cellulose assembly and interaction with hemicelluloses via binding to emerging cellulose microfibrils. PMID:22327741

  3. Changes in the molecular-size distribution of insoluble celluloses by the action of recombinant Cellulomonas fimi cellulases.

    PubMed Central

    Kleman-Leyer, K M; Gilkes, N R; Miller, R C; Kirk, T K

    1994-01-01

    Specific patterns of attacks of cotton, bacterial cellulose and bacterial microcrystalline cellulose (BMCC) by recombinant cellulases of Cellulomonas fimi were investigated. Molecular-size distributions of the celluloses were determined by high-performance size-exclusion chromatography. Chromatography of cotton and bacterial celluloses revealed single major peaks centered over progressively lower molecular-mass positions during attack by endoglucanase CenA. In advanced stages, a second peak appeared at very low average size (approx. 11 glucosyl units); ultimate weight losses were approximately 30%. The isolated catalytic domain of CenA, p30, gave results very similar to those with complete CenA. CenA did not effectively depolymerize or solubilize BMCC significantly. Molecular-size distributions of cotton and bacterial cellulose incubated with endoglucanases CenB or CenD exhibited one major peak regardless of incubation time; low-molecular-mass fragments did not accumulate. Weight losses were 40 and 35% respectively. The single peak shifted to lower-molecular-mass positions as incubation continued, but high-molecular-mass material persisted. CenB and CenD readily attacked and solubilized BMCC (approx. 70%). We conclude that CenA attacks cellulose by preferentially cleaving completely through the cellulose microfibrils at the amorphous sites, and much more slowly by degrading the crystalline surfaces. Conversely, CenB and CenD cleave the amorphous regions much less efficiently while vigorously degrading the surfaces of the crystalline regions of the microfibrils. PMID:8092998

  4. Changes in Molecular Size Distribution of Cellulose during Attack by White Rot and Brown Rot Fungi

    PubMed Central

    Kleman-Leyer, Karen; Agosin, Eduardo; Conner, Anthony H.; Kirk, T. Kent

    1992-01-01

    The kinetics of cotton cellulose depolymerization by the brown rot fungus Postia placenta and the white rot fungus Phanerochaete chrysosporium were investigated with solid-state cultures. The degree of polymerization (DP; the average number of glucosyl residues per cellulose molecule) of cellulose removed from soil-block cultures during degradation by P. placenta was first determined viscosimetrically. Changes in molecular size distribution of cellulose attacked by either fungus were then determined by size exclusion chromatography as the tricarbanilate derivative. The first study with P. placenta revealed two phases of depolymerization: a rapid decrease to a DP of approximately 800 and then a slower decrease to a DP of approximately 250. Almost all depolymerization occurred before weight loss. Determination of the molecular size distribution of cellulose during attack by the brown rot fungus revealed single major peaks centered over progressively lower DPs. Cellulose attacked by P. chrysosporium was continuously consumed and showed a different pattern of change in molecular size distribution than cellulose attacked by P. placenta. At first, a broad peak which shifted at a slightly lower average DP appeared, but as attack progressed the peak narrowed and the average DP increased slightly. From these results, it is apparent that the mechanism of cellulose degradation differs fundamentally between brown and white rot fungi, as represented by the species studied here. We conclude that the brown rot fungus cleaved completely through the amorphous regions of the cellulose microfibrils, whereas the white rot fungus attacked the surfaces of the microfibrils, resulting in a progressive erosion. PMID:16348694

  5. Amorphous and Ultradisperse Crystalline Materials,

    DTIC Science & Technology

    The book sums up experimental and theoretical findings on amorphous and ultradisperse crystalline materials , massive and film types. Present-day... crystalline materials of metallic systems are presented. Emphasis is placed on inorganic film materials.

  6. Stable Aqueous Foams from Cellulose Nanocrystals and Methyl Cellulose.

    PubMed

    Hu, Zhen; Xu, Richard; Cranston, Emily D; Pelton, Robert H

    2016-12-12

    The addition of cellulose nanocrystals (CNC) greatly enhanced the properties of methylcellulose (MC) stabilized aqueous foams. CNC addition decreased air bubble size, initial foam densities and drainage rates. Mixtures of 2 wt % CNC + 0.5 wt % MC gave the lowest density foams. This composition sits near the onset of nematic phase formation and also near the overlap concentration of methylcellulose. More than 94% of the added CNC particles remained in the foam phase, not leaving with the draining water. We propose that the nanoscale CNC particles bind to the larger MC coils both in solution and with MC at the air/water interface, forming weak gels that stabilize air bubbles. Wet CNC-MC foams were sufficiently robust to withstand high temperature (70 °C for 6 h) polymerization of water-soluble monomers giving macroporous CNC composite hydrogels based on acrylamide (AM), 2-hydroxyethyl methacrylate (HEMA), or polyethylene glycol diacrylate (PEGDA). At high temperatures, the MC was present as a fibrillar gel phase reinforced by CNC particles, explaining the very high foam stability. Finally, our CNC-MC foams are based on commercially available forms of CNC and MC, already approved for many applications. This is a "shovel-ready" technology.

  7. Catalytic decomposition of cellulose under biological conditions

    PubMed Central

    Halliwell, G.

    1965-01-01

    1. The catalytic decomposition of undegraded cellulose in the form of cotton fibres is described with hydrogen peroxide at 0·4–0·04% (w/v) concentration in the presence of ferrous salts at pH3–5. 2. Complete solubilization of 5mg. of cotton fibres occurred in about 7 days in the presence of 0·4% hydrogen peroxide and 0·2mm-ferrous sulphate at the optimum pH4·2–4·3. 3. With 0·4% hydrogen peroxide the most rapid decomposition of cellulose was confined to ferrous sulphate concentrations of approx. 2–0·02mm. If the concentrations of the reagents were decreased in proportion extensive breakdown occurred but much more slowly. 4. In the primary stages of breakdown cotton fibres were disintegrated to very short fibres. These were subsequently solubilized, but there was little accumulation of soluble material. Organic matter was lost from solution as the reaction progressed. 5. Other naturally occurring cellulose-containing materials, such as grass, straw, hay and sawdust, were also disintegrated and solubilized by hydrogen peroxide and ferrous sulphate. PMID:14333565

  8. Hydrolysis of ionic cellulose to glucose.

    PubMed

    Vo, Huyen Thanh; Widyaya, Vania Tanda; Jae, Jungho; Kim, Hoon Sik; Lee, Hyunjoo

    2014-09-01

    Hydrolysis of ionic cellulose (IC), 1,3-dimethylimidazolium cellulose phosphite, which could be synthesized from cellulose and dimethylimidazolium methylphosphite ([Dmim][(OCH3)(H)PO2]) ionic liquid, was conducted for the synthesis of glucose. The reaction without catalysts at 150°C for 12h produced glucose with 14.6% yield. To increase the hydrolysis yield, various acid catalysts were used, in which the sulfonated active carbon (AC-SO3H) performed the best catalytic activity in the IC hydrolysis. In the presence of AC-SO3H, the yields of glucose reached 42.4% and 53.9% at the reaction condition of 150°C for 12h and 180°C for 1.5h, respectively; however the yield decreased with longer reaction time due to the degradation of glucose. Consecutive catalyst reuse experiments on the IC hydrolysis demonstrated the catalytic activity of AC-SO3H persisted at least through four successive uses.

  9. Liquid crystalline composites containing phyllosilicates

    DOEpatents

    Chaiko; David J.

    2007-05-08

    The present invention provides barrier films having reduced gas permeability for use in packaging and coating applications. The barrier films comprise an anisotropic liquid crystalline composite layer formed from phyllosilicate-polymer compositions. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while remaining transparent. Because of the ordering of the particles in the liquid crystalline composite, barrier films comprising liquid crystalline composites are particularly useful as barriers to gas transport.

  10. Crystalline oxides on silicon.

    PubMed

    Reiner, James W; Kolpak, Alexie M; Segal, Yaron; Garrity, Kevin F; Ismail-Beigi, Sohrab; Ahn, Charles H; Walker, Fred J

    2010-07-20

    This review outlines developments in the growth of crystalline oxides on the ubiquitous silicon semiconductor platform. The overall goal of this endeavor is the integration of multifunctional complex oxides with advanced semiconductor technology. Oxide epitaxy in materials systems achieved through conventional deposition techniques is described first, followed by a description of the science and technology of using atomic layer-by-layer deposition with molecular beam epitaxy (MBE) to systematically construct the oxide-silicon interface. An interdisciplinary approach involving MBE, advanced real-space structural characterization, and first-principles theory has led to a detailed understanding of the process by which the interface between crystalline oxides and silicon forms, the resulting structure of the interface, and the link between structure and functionality. Potential applications in electronics and photonics are also discussed.

  11. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, Rayford G.; Dosch, Robert G.

    1993-01-01

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  12. Liquid Crystalline Polymers

    DTIC Science & Technology

    1990-02-28

    Liquid crystalline polymers (LCPs); fibers ; thermotropic; lyotropic; processing; rheology; nonlinear optical (4L-" properties* blends* Q2 P- USTRACT...CowMnue on reverse if , cevwy and identify by block number) The remarkable mechanical properties and thermal stability of fibers fabricated from liquid...control of orientation falls short of allowing manipula- tion of macroscopic orientation (except for the case of uniaxial fibers ). This report

  13. Crystalline titanate catalyst supports

    DOEpatents

    Anthony, R.G.; Dosch, R.G.

    1993-01-05

    A series of new crystalline titanates (CT) are shown to have considerable potential as catalyst supports. For Pd supported catalyst, the catalytic activity for pyrene hydrogenation was substantially different depending on the type of CT, and one was substantially more active than Pd on hydrous titanium oxide (HTO). For 1-hexene hydrogenation the activities of the new CTs were approximately the same as for the hydrous metal oxide supports.

  14. Cellulose Derivatives for Water Repellent Properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this poster presentation, we will discuss the synthesis and structural characterizations of nitro-benzyl cellulose (1), amino-benzyl cellulose (2) and pentafluoro –benzyl cellulose (3). All cellulose derivatives are synthesized by etherification process in lithium chloride/N,N-dimethylacetamide h...

  15. Cellulose Derivatives for Water Repellent Properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Synthesis and structural characterizations of nitro-benzyl cellulose, amino-benzyl cellulose and pentafluoro –benzyl cellulose were carried out. Cellulose derivatives were synthesized by etherification process in lithium chloride/N,N-dimethylacetamide homogeneous solution. Nitrobenzylation was effec...

  16. 21 CFR 172.868 - Ethyl cellulose.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ethyl cellulose. 172.868 Section 172.868 Food and... Multipurpose Additives § 172.868 Ethyl cellulose. The food additive ethyl cellulose may be safely used in food in accordance with the following prescribed conditions: (a) The food additive is a cellulose...

  17. 21 CFR 172.868 - Ethyl cellulose.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ethyl cellulose. 172.868 Section 172.868 Food and... Multipurpose Additives § 172.868 Ethyl cellulose. The food additive ethyl cellulose may be safely used in food in accordance with the following prescribed conditions: (a) The food additive is a cellulose...

  18. 21 CFR 172.868 - Ethyl cellulose.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ethyl cellulose. 172.868 Section 172.868 Food and... Multipurpose Additives § 172.868 Ethyl cellulose. The food additive ethyl cellulose may be safely used in food in accordance with the following prescribed conditions: (a) The food additive is a cellulose...

  19. 21 CFR 573.420 - Ethyl cellulose.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Ethyl cellulose. 573.420 Section 573.420 Food and... Listing § 573.420 Ethyl cellulose. The food additive ethyl cellulose may be safely used in animal feed in accordance with the following prescribed conditions: (a) The food additive is a cellulose ether...

  20. 21 CFR 172.868 - Ethyl cellulose.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethyl cellulose. 172.868 Section 172.868 Food and... Multipurpose Additives § 172.868 Ethyl cellulose. The food additive ethyl cellulose may be safely used in food in accordance with the following prescribed conditions: (a) The food additive is a cellulose...

  1. Sono-assisted TEMPO oxidation of oil palm lignocellulosic biomass for isolation of nanocrystalline cellulose.

    PubMed

    Rohaizu, R; Wanrosli, W D

    2017-01-01

    Highly stable and dispersible nanocrystalline cellulose (NCC) was successfully isolated from oil palm empty fruit bunch microcrystalline cellulose (OPEFB-MCC), with yields of 93% via a sono-assisted TEMPO-oxidation and a subsequent sonication process. The sono-assisted treatment has a remarkable effect, resulting in an increase of more than 100% in the carboxylate content and a significant increase of approximately 39% in yield compared with the non-assisted process. TEM images reveal the OPEFB-NCC to have rod-like crystalline morphology with an average length and width of 122 and 6nm, respectively. FTIR and solid-state (13)C-NMR analyses suggest that oxidation of cellulose chain hydroxyl groups occurs at C6. XRD analysis shows that OPEFB-NCC consists primarily of a crystalline cellulose I structure. Both XRD and (13)C-NMR indicate that the OPEFB-NCC has a lower crystallinity than the OPEFB-MCC starting material. Thermogravimetric analysis illustrates that OPEFB-NCC is less thermally stable than OPEFB-MCC but has a char content of 46% compared with 7% for the latter, which signifies that the carboxylate functionality acts as a flame retardant.

  2. Assemblies of Cellulose Nanocrystals

    NASA Astrophysics Data System (ADS)

    Kumacheva, Eugenia

    The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and different types of nanoparticles (NPs), including dye-labeled latex NPs, carbon dots and plasmonic NPs was experimentally studied in aqueous suspensions and in solid films. In mixed CNC-NP suspensions, phase separation into an isotropic NP-rich and a chiral nematic CNC-rich phase took place; the latter contained a significant amount of NPs. Drying the mixed suspension resulted in CNC-NP films with planar disordered layers of NPs, which alternated with chiral nematic CNC-rich regions. In addition, NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of NPs in the anisotropic phase, led to the films having close-to-uniform fluorescence, birefringence, and circular dichroism properties.

  3. Radiation degradation of cellulose

    NASA Astrophysics Data System (ADS)

    Leonhardt, J.; Arnold, G.; Baer, M.; Langguth, H.; Gey, M.; Hübert, S.

    The application of straw and other cellulose polymers as feedstuff for ruminants is limited by its low digestibility. During recent decades it was attempted to increase the digestibility of straw by several chemical and physical methods. In this work some results of the degradation of gamma and electron treated wheat straw are reported. Complex methods of treatment (e.g. radiation influence and influence of lyes) are taken into consideration. In vitro-experiments with radiation treated straw show that the digestibility can be increased from 20 % up to about 80 %. A high pressure liquid chromatography method was used to analyze the hydrolysates. The contents of certain species of carbohydrates in the hydrolysates in dependence on the applied dose are given.

  4. Magnetic cellulose-derivative structures

    DOEpatents

    Walsh, M.A.; Morris, R.S.

    1986-09-16

    Structures to serve as selective magnetic sorbents are formed by dissolving a cellulose derivative such as cellulose triacetate in a solvent containing magnetic particles. The resulting solution is sprayed as a fine mist into a chamber containing a liquid coagulant such as n-hexane in which the cellulose derivative is insoluble but in which the coagulant is soluble or miscible. On contact with the coagulant, the mist forms free-flowing porous magnetic microspheric structures. These structures act as containers for the ion-selective or organic-selective sorption agent of choice. Some sorption agents can be incorporated during the manufacture of the structure. 3 figs.

  5. Magnetic cellulose-derivative structures

    DOEpatents

    Walsh, Myles A.; Morris, Robert S.

    1986-09-16

    Structures to serve as selective magnetic sorbents are formed by dissolving a cellulose derivative such as cellulose triacetate in a solvent containing magnetic particles. The resulting solution is sprayed as a fine mist into a chamber containing a liquid coagulant such as n-hexane in which the cellulose derivative is insoluble but in which the coagulant is soluble or miscible. On contact with the coagulant, the mist forms free-flowing porous magnetic microspheric structures. These structures act as containers for the ion-selective or organic-selective sorption agent of choice. Some sorbtion agents can be incorporated during the manufacture of the structure.

  6. Thermophilic degradation of cellulosic biomass

    NASA Astrophysics Data System (ADS)

    Ng, T.; Zeikus, J. G.

    1982-12-01

    The conversion of cellulosic biomass to chemical feedstocks and fuel by microbial fermentation is an important objective of developing biotechnology. Direct fermentation of cellulosic derivatives to ethanol by thermophilic bacteria offers a promising approach to this goal. Fermentations at elevated temperatures lowers the energy demand for cooling and also facilitates the recovery of volatile products. In addition, thermophilic microorganisms possess enzymes with greater stability than those from mesophilic microorganisms. Three anaerobic thermophilic cocultures that ferment cellulosic substrate mainly to ethanol have been described: Clostridium thermocellum/Clostriidium thermohydrosulfuricum, C. thermocellum/Clostridium thermosaccharolyticum, and C. thermocellum/Thermoanaerobacter ethanolicus sp. nov. The growth characteristics and metabolic features of these cocultures are reviewed.

  7. Sucrose synthase affects carbon partitioning to increase cellulose production and altered cell wall ultrastructure.

    PubMed

    Coleman, Heather D; Yan, Jimmy; Mansfield, Shawn D

    2009-08-04

    Overexpression of the Gossypium hirsutum sucrose synthase (SuSy) gene under the control of 2 promoters was examined in hybrid poplar (Populus alba x grandidentata). Analysis of RNA transcript abundance, enzyme activity, cell wall composition, and soluble carbohydrates revealed significant changes in the transgenic lines. All lines showed significantly increased SuSy enzyme activity in developing xylem. This activity manifested in altered secondary cell wall cellulose content per dry weight in all lines, with increases of 2% to 6% over control levels, without influencing plant growth. The elevated concentration of cellulose was associated with an increase in cell wall crystallinity but did not alter secondary wall microfibril angle. This finding suggests that the observed increase in crystallinity is a function of altered carbon partitioning to cellulose biosynthesis rather than the result of tension wood formation. Furthermore, the augmented deposition of cellulose in the transgenic lines resulted in thicker xylem secondary cell wall and consequently improved wood density. These findings clearly implicate SuSy as a key regulator of sink strength in poplar trees and demonstrate the tight association of SuSy with cellulose synthesis and secondary wall formation.

  8. Cellulose Nanofibers from Softwood, Hardwood, and Tunicate: Preparation-Structure-Film Performance Interrelation.

    PubMed

    Zhao, Yadong; Moser, Carl; Lindström, Mikael E; Henriksson, Gunnar; Li, Jiebing

    2017-04-10

    This work reveals the structural variations of cellulose nanofibers (CNF) prepared from different cellulose sources, including softwood (Picea abies), hardwood (Eucalyptus grandis × E. urophylla), and tunicate (Ciona intestinalis), using different preparation processes and their correlations to the formation and performance of the films prepared from the CNF. Here, the CNF are prepared from wood chemical pulps and tunicate isolated cellulose by an identical homogenization treatment subsequent to either an enzymatic hydrolysis or a 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. They show a large structural diversity in terms of chemical, morphological, and crystalline structure. Among others, the tunicate CNF consist of purer cellulose and have a degree of polymerization higher than that of wood CNF. Introduction of surface charges via the TEMPO-mediated oxidation is found to have significant impacts on the structure, morphology, optical, mechanical, thermal, and hydrophobic properties of the prepared films. For example, the film density is closely related to the charge density of the used CNF, and the tensile stress of the films is correlated to the crystallinity index of the CNF. In turn, the CNF structure is determined by the cellulose sources and the preparation processes. This study provides useful information and knowledge for understanding the importance of the raw material for the quality of CNF for various types of applications.

  9. Preparation and Characterization of Cellulose Nanocrystals from the Bio-ethanol Residuals

    PubMed Central

    Du, Lanxing; Wang, Jinwu; Zhang, Yang; Qi, Chusheng; Wolcott, Michael P.; Yu, Zhiming

    2017-01-01

    This study was to explore the conversion of low-cost bio-residuals into high value-added cellulose nanocrystals. Two enzymatic hydrolyzed residuals (i.e., HRMMW and HRSPW) were collected from two different bio-ethanol producing processes—hydrolyzing medium-milled wood (MMW) and hydrolyzing acid sulfite pretreated wood (SPW), respectively. The results showed that both residuals contained over 20 wt % glucan with a crystallinity of about 30%, confirming the existence of cellulose in a well-organized structure in two bio-residuals. The cellulose nanocrystals (CNCs) were successfully extracted by first bleaching the hydrolyzed residuals to remove lignin and then hydrolyzing them with sulfuric acid. The resulting CNCs displayed the flow birefringence under two crossed polarizers. Compared with CNCs from microfibrillated cellulose (CNCMCC), HRMMW and its resulted CNC present the smallest particle size and aspect ratio. CNCMCC had the larger particle size, aspect ratio, and higher z-potential value, CNCSPW presented a similar morphology to CNCMCC, and had the largest aspect ratio. The CNCMCC enhanced its high crystallinity to 85.5%. However, CNCMMW and CNCSPW had a better thermal stability and higher activation energy as well as onset temperature and maximum decomposition temperature. As a result, the CNCs from bio-ethanol residuals are valued and promising cellulose nanoparticle resources. PMID:28336885

  10. Effect of Late Planting and Shading on Cellulose Synthesis during Cotton Fiber Secondary Wall Development

    PubMed Central

    Chen, Ji; Lv, Fengjuan; Liu, Jingran; Ma, Yina; Wang, Youhua; Chen, Binglin; Meng, Yali; Zhou, Zhiguo; Oosterhuis, Derrick M.

    2014-01-01

    Cotton-rapeseed or cotton-wheat double cropping systems are popular in the Yangtze River Valley and Yellow River Valley of China. Due to the competition of temperature and light resources during the growing season of double cropping system, cotton is generally late-germinating and late-maturing and has to suffer from the coupling of declining temperature and low light especially in the late growth stage. In this study, late planting (LP) and shading were used to fit the coupling stress, and the coupling effect on fiber cellulose synthesis was investigated. Two cotton (Gossypium hirsutum L.) cultivars were grown in the field in 2010 and 2011 at three planting dates (25 April, 25 May and 10 June) each with three shading levels (normal light, declined 20% and 40% PAR). Mean daily minimum temperature was the primary environmental factor affected by LP. The coupling of LP and shading (decreased cellulose content by 7.8%–25.5%) produced more severe impacts on cellulose synthesis than either stress alone, and the effect of LP (decreased cellulose content by 6.7%–20.9%) was greater than shading (decreased cellulose content by 0.7%–5.6%). The coupling of LP and shading hindered the flux from sucrose to cellulose by affecting the activities of related cellulose synthesis enzymes. Fiber cellulose synthase genes expression were delayed under not only LP but shading, and the coupling of LP and shading markedly postponed and even restrained its expression. The decline of sucrose-phosphate synthase activity and its peak delay may cause cellulose synthesis being more sensitive to the coupling stress during the later stage of fiber secondary wall development (38–45 days post-anthesis). The sensitive difference of cellulose synthesis between two cultivars in response to the coupling of LP and shading may be mainly determined by the sensitiveness of invertase, sucrose-phosphate synthase and cellulose synthase. PMID:25133819

  11. Effect of late planting and shading on cellulose synthesis during cotton fiber secondary wall development.

    PubMed

    Chen, Ji; Lv, Fengjuan; Liu, Jingran; Ma, Yina; Wang, Youhua; Chen, Binglin; Meng, Yali; Zhou, Zhiguo; Oosterhuis, Derrick M

    2014-01-01

    Cotton-rapeseed or cotton-wheat double cropping systems are popular in the Yangtze River Valley and Yellow River Valley of China. Due to the competition of temperature and light resources during the growing season of double cropping system, cotton is generally late-germinating and late-maturing and has to suffer from the coupling of declining temperature and low light especially in the late growth stage. In this study, late planting (LP) and shading were used to fit the coupling stress, and the coupling effect on fiber cellulose synthesis was investigated. Two cotton (Gossypium hirsutum L.) cultivars were grown in the field in 2010 and 2011 at three planting dates (25 April, 25 May and 10 June) each with three shading levels (normal light, declined 20% and 40% PAR). Mean daily minimum temperature was the primary environmental factor affected by LP. The coupling of LP and shading (decreased cellulose content by 7.8%-25.5%) produced more severe impacts on cellulose synthesis than either stress alone, and the effect of LP (decreased cellulose content by 6.7%-20.9%) was greater than shading (decreased cellulose content by 0.7%-5.6%). The coupling of LP and shading hindered the flux from sucrose to cellulose by affecting the activities of related cellulose synthesis enzymes. Fiber cellulose synthase genes expression were delayed under not only LP but shading, and the coupling of LP and shading markedly postponed and even restrained its expression. The decline of sucrose-phosphate synthase activity and its peak delay may cause cellulose synthesis being more sensitive to the coupling stress during the later stage of fiber secondary wall development (38-45 days post-anthesis). The sensitive difference of cellulose synthesis between two cultivars in response to the coupling of LP and shading may be mainly determined by the sensitiveness of invertase, sucrose-phosphate synthase and cellulose synthase.

  12. Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations.

    PubMed

    Wang, Tuo; Yang, Hui; Kubicki, James D; Hong, Mei

    2016-06-13

    The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D (13)C-(13)C correlation spectra of uniformly (13)C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose (13)C chemical shifts differ significantly from the (13)C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing, and hydrogen bonding from celluloses of other organisms. 2D (13)C-(13)C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Celluloses f and g are well mixed chains on the microfibril surface, celluloses a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of

  13. Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations

    PubMed Central

    Wang, Tuo; Yang, Hui; Kubicki, James D.; Hong, Mei

    2017-01-01

    The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D 13C-13C correlation spectra of uniformly 13C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose 13C chemical shifts differ significantly from the 13C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing and hydrogen bonding from celluloses of other organisms. 2D 13C-13C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Cellulose f and g are well mixed chains on the microfibril surface, cellulose a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of bacterial, algal

  14. Power generation from cellulose using mixed and pure cultures of cellulose-degrading bacteria in a microbial fuel cell.

    PubMed

    Hassan, Sedky H A; Kim, Yong Seong; Oh, Sang-Eun

    2012-10-10

    Microbial fuel cells (MFCs) have been used to generate electricity from various organic compounds such as acetate, glucose, and lactate. We demonstrate here that electricity can be produced in an MFC using cellulose as the electron donor source. Tests were conducted using two-chambered MFCs, the anode medium was inoculated with mixed or pure culture of cellulose-degrading bacteria Nocardiopsis sp. KNU (S strain) or Streptomyces enissocaesilis KNU (K strain), and the catholyte in the cathode compartment was 50mM ferricyanide as catholyte. The power density for the mixed culture was 0.188 mW (188 mW/m(2)) at a current of 0.5mA when 1g/L cellulose was used. However, the power density decreased as the cellulose concentration in the anode compartment decreased. The columbic efficiencies (CEs) ranged from 41.5 to 33.4%, corresponding to an initial cellulose concentration of 0.1-1.0 g/L. For the pure culture, cellobioase enzyme was added to increase the conversion of cellulose to simple sugars, since electricity production is very low. The power densities for S and K strain pure cultures with cellobioase were 162 mW/m(2) and 145 mW/m(2), respectively. Cyclic voltammetry (CV) experiments showed the presence of peaks at 380, 500, and 720 mV vs. Ag/AgCl for the mixed bacterial culture, indicating its electrochemical activity without an external mediator. Furthermore, this MFC system employs a unique microbial ecology in which both the electron donor (cellulose) and the electron acceptor (carbon paper) are insoluble.

  15. TRICHOME BIREFRINGENCE and Its Homolog AT5G01360 Encode Plant-Specific DUF231 Proteins Required for Cellulose Biosynthesis in Arabidopsis1[W][OA

    PubMed Central

    Bischoff, Volker; Nita, Silvia; Neumetzler, Lutz; Schindelasch, Dana; Urbain, Aurélie; Eshed, Ravit; Persson, Staffan; Delmer, Deborah; Scheible, Wolf-Rüdiger

    2010-01-01

    The Arabidopsis (Arabidopsis thaliana) trichome birefringence (tbr) mutant has severely reduced crystalline cellulose in trichomes, but the molecular nature of TBR was unknown. We determined TBR to belong to the plant-specific DUF231 domain gene family comprising 46 members of unknown function in Arabidopsis. The genes harbor another plant-specific domain, called the TBL domain, which contains a conserved GDSL motif known from some esterases/lipases. TBR and TBR-like3 (TBL3) are transcriptionally coordinated with primary and secondary CELLULOSE SYNTHASE (CESA) genes, respectively. The tbr and tbl3 mutants hold lower levels of crystalline cellulose and have altered pectin composition in trichomes and stems, respectively, tissues generally thought to contain mainly secondary wall crystalline cellulose. In contrast, primary wall cellulose levels remain unchanged in both mutants as measured in etiolated tbr and tbl3 hypocotyls, while the amount of esterified pectins is reduced and pectin methylesterase activity is increased in this tissue. Furthermore, etiolated tbr hypocotyls have reduced length with swollen epidermal cells, a phenotype characteristic for primary cesa mutants or the wild type treated with cellulose synthesis inhibitors. Taken together, we show that two TBL genes contribute to the synthesis and deposition of secondary wall cellulose, presumably by influencing the esterification state of pectic polymers. PMID:20388664

  16. Oxidized Cellulose with Different Carboxyl Content: Structure and Properties before and after Beating

    NASA Astrophysics Data System (ADS)

    Vendula, Hejlová; Miloslav, Milichovský

    Our recent studies concentrated in investigating influence of beating oxidized cellulose, with different carboxyl content, on changing their basic properties (degree of polymerization, WRV - water resistant value and X-ray diffraction). Cellulose samples of oxidized cellulose were beated by toroidal beating machine. Cellulose consists of both amorphous and crystalline regions. Cellulose consists of linear chains of poly[ß-1,4-D- anhydroglucopyranose] (C6nH10n + 2O5n + 1 (n = degree of polymerization of glucose)), which crystallize through hydrogen bonding between the chains and has cellobiose as repeat unit. Oxidized cellulose is preparing by oxidation of cellulose in the C6 position of the glucopyranose units to carboxylic group (-COOH) and polyanhydroglukuronic acid (PAGA) is arised. An other option is oxidation with sodium hypochlorite with catalytic amounts of sodium bromide and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) under various conditions. Beating and refining or mechanical treatment of fibers in water is an important step in using pulps for papermaking. It is an energy intensive process. The purpose of the treatment is to modify fiber properties to obtain the most desirable paper machine runnability and product properties. End of beating pulps was characterized by position, when all beated pulps under mixture passed through of riddle (about sizes mesh of 50). During beating of samples about different ratio of oxidation it was found, that samples with higher contents of COOH groups in starting pulp are characterized by a significantly lower specific beating energy consumption needed to achieving the same sizes of particles. X-ray analyse shows that for non-beated oxidized cellulose was perceptible high share amorphous contents compared with beated oxidized cellulose.

  17. Reinforcement effect of poly(butylene succinate) (PBS)-grafted cellulose nanocrystal on toughened PBS/polylactic acid blends.

    PubMed

    Zhang, Xuzhen; Zhang, Yong

    2016-04-20

    Poly(butylene succinate) (PBS)/polylactic acid (PLA) blends modified with dicumyl peroxide (DCP) were reinforced by PBS-g-cellulose nanocrystal (CNC) through melt mixing. PBS-g-CNC was prepared through in situ polymerization and its structure was confirmed by FTIR, (13)C NMR, XPS and GPC analysis after saponification. The morphological analysis of PBS/PLA/PBS-g-CNC composites before and after etched by CH2Cl2 shows that the addition of DCP and PBS-g-CNC could decrease the size of PBS as a dispersed phase in PLA matrix and improve the dispersion of PBS-g-CNC in both PBS and PLA phases, which could affect the crystallization and mechanical properties of composites. The crystallinity of PLA α'-phase crystal in PBS/PLA/PBS-g-CNC composites is increased obviously by the addition of PBS-g-CNC, leading to an increase of the crystallinity of the composites. PBS/PLA blends modified by DCP have high Notched Izod impact strength and moduli, and the values are increased by the addition of PBS-g-CNC. Both storage modulus and glass translation temperature of PBS/PLA blend are increased by DCP and PBS-g-CNC, which is proved by DMA results, showing a weak molecular segment mobility of PBS/PLA matrix. The addition of DCP decreases the crystallization temperature and crystallinity of PBS/PLA composite, but increases the thermal stability of composites, mostly because of the crosslink effect of DCP on PBS/PLA matrix.

  18. Isolation and Properties of Cellulose Nanofibrils from Coconut Palm Petioles by Different Mechanical Process

    PubMed Central

    Li, Dagang; Zhu, Nanfeng

    2015-01-01

    In this study, cellulose nanofibrils (CNFs) were successfully isolated from coconut palm petiole residues falling off naturally with chemical pretreatments and mechanical treatments by a grinder and a homogenizor. FTIR spectra analysis showed that most of hemicellulose and lignin were removed from the fiber after chemical pretreatments. The compositions of CNFS indicated that high purity of nanofibrils with cellulose contain more than 95% was obtained. X-ray diffractogram demonstrated that chemical pretreatments significantly increased the crystallinity of CNFs from 38.00% to 70.36%; however, 10-15 times of grinding operation followed by homogenizing treatment after the chemical pretreatments did not significantly improve the crystallinity of CNFs. On the contrary, further grinding operation could destroy crystalline regions of the cellulose. SEM image indicated that high quality of CNFs could be isolated from coconut palm petiole residues with chemical treatments in combination of 15 times of grinding followed by 10 times of homogenization and the aspect ratio of the obtained CNFs ranged from 320 to 640. The result of TGA-DTG revealed that the chemical-mechanical treatments improved thermal stability of fiber samples, and the CNFs with 15 grinding passing times had the best thermal stability. This work suggests that the CNFs can be successfully extracted from coconut palm petiole residues and it may be a potential feedstock for nanofiber reinforced composites due to its high aspect ratio and crystallinity. PMID:25875280

  19. Isolation and properties of cellulose nanofibrils from coconut palm petioles by different mechanical process.

    PubMed

    Xu, Changyan; Zhu, Sailing; Xing, Cheng; Li, Dagang; Zhu, Nanfeng; Zhou, Handong

    2015-01-01

    In this study, cellulose nanofibrils (CNFs) were successfully isolated from coconut palm petiole residues falling off naturally with chemical pretreatments and mechanical treatments by a grinder and a homogenizor. FTIR spectra analysis showed that most of hemicellulose and lignin were removed from the fiber after chemical pretreatments. The compositions of CNFS indicated that high purity of nanofibrils with cellulose contain more than 95% was obtained. X-ray diffractogram demonstrated that chemical pretreatments significantly increased the crystallinity of CNFs from 38.00% to 70.36%; however, 10-15 times of grinding operation followed by homogenizing treatment after the chemical pretreatments did not significantly improve the crystallinity of CNFs. On the contrary, further grinding operation could destroy crystalline regions of the cellulose. SEM image indicated that high quality of CNFs could be isolated from coconut palm petiole residues with chemical treatments in combination of 15 times of grinding followed by 10 times of homogenization and the aspect ratio of the obtained CNFs ranged from 320 to 640. The result of TGA-DTG revealed that the chemical-mechanical treatments improved thermal stability of fiber samples, and the CNFs with 15 grinding passing times had the best thermal stability. This work suggests that the CNFs can be successfully extracted from coconut palm petiole residues and it may be a potential feedstock for nanofiber reinforced composites due to its high aspect ratio and crystallinity.

  20. Preparation and characterization of nanocrystalline cellulose from Acacia mangium and its reinforcement potential.

    PubMed

    Jasmani, Latifah; Adnan, Sharmiza

    2017-04-01

    Acacia mangium, a fast growing tree is widely planted in Malaysia. Converting Acacia wood into nanocellulose could create new value added products for forest-based industry. Nanocrystalline cellulose (NCC) was prepared from Acacia mangium wood pulp via 64wt% sulfuric acid hydrolysis. Prior to acid hydrolysis, Acacia mangium was subjected to pulping followed by bleaching in order to remove non-cellulosic fragments. Acid hydrolysis was carried out on bleached pulp to produce the needle-like NCC with 79% crystallinity and aspect ratio of 26. The resulting NCC was mixed with PVA as a reinforcement material. Incorporation of 2% NCC improved the tensile of the NCC-PVA film by 30%.

  1. Cellulose and cellobiose. Adventures of a wandering organic chemist in theoretical chemistry

    SciTech Connect

    Baluyut, John

    2012-04-03

    The energies arising from the rotation of free hydroxyl groups in the central glucose residue of a cellulose crystalline assembly, calculated using RHF, DFT, and FMO2/MP2 methods, will be presented. In addition, interactions of this central glucose residue with some of the surrounding residues (selected on the basis of the interaction strengths) are analyzed. The mechanism of acid-catalyzed hydrolysis of cellobiose, which is the repeating unit of cellulose. Energies corresponding to the different steps of this mechanism calculated using RHF and DFT are compared with those previously reported using molecular dynamics calculations and with experimental data.

  2. Cellulose pretreatments of lignocellulosic substrates

    NASA Technical Reports Server (NTRS)

    Weil, J.; Westgate, P.; Kohlmann, K.; Ladisch, M. R.; Mitchell, C. A. (Principal Investigator)

    1994-01-01

    Cellulose in inedible plant materials, forestry residues, and municipal wastes must be pretreated to disrupt its physical structure, thereby making its hydrolysis to glucose practical. Developments since 1991 are summarized.

  3. Preparation and characterization of aminobenzyl cellulose by two step synthesis from native cellulose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Synthesis and structural characterizations of nitro- and amino-benzyl cellulose were carried out. Cellulose derivatives were synthesized by etherification. Nitrobenzylation produced 80% yield by treating a mixture of microcrystalline cellulose, 4-dimethyl aminopyridine and 4-nitrobenzyl chloride at ...

  4. Chromophores in lignin-free cellulosic materials belong to three compound classes. Chromophores in cellulosics, XII

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The CRI (chromophore release and identification) method isolates well-defined chromophoric substances from different cellulosic matrices, such as highly bleached pulps, cotton linters, bacterial cellulose, viscose or lyocell fibers, and cellulose acetates. The chromophores are present only in extrem...

  5. Swelling and dissolution of cellulose in amine oxide/water systems

    SciTech Connect

    Chanzy, H.; Noe, P.; Paillet, M.; Smith, P.

    1983-01-01

    The swelling behavior and the dissolution process of various cellulosic fibers, both native and regenerated, in N-methylmorpholine N-oxide (MMNO), dimethylethanolamine N-oxide (DMEAO), and mixtures thereof were studied in the presence of various amounts of water. The principal tools in this investigation were optical microscopy and wide-angle X-ray scattering (WAXS). The two amine oxides could either dissolve or only swell cellulose, depending on the water concentration, which was found to be of critical importance. Three domains of water concentration were found important. When only a few percent water was present, cellulose fibers, such as ramie, cotton, rayon, etc., dissolved readily without noticeable swelling in the amine oxide/water system brought above its melting point. At a relatively high water concentration (e.g., 18% w/w for MMNO), the cellulose fibers exhibited an extensive swelling (up to sevenfold increase in the fiber diameter) but no dissolution. In that case, the removal of the swelling agent showed that the initial native cellulose fibers were converted into an unoriented cellulose II structure. With still greater water content (e.g., 20% and more for MMNO or 15% for DMEAO), only partial swelling was observed, and the native cellulose fibers recovered their initial oriented cellulose I structure after removal of the swelling medium. X-ray investigations provided no evidence forthe formation of cellulose/solvent complexes in the swollen fibers. A relatively large decrease of the cellulose I (110) reflection was found in the WAXS patterns of the gels. This is interpreted as due to a preferential cleavage of the cellulose crystals along the corresponding plane when the cellulose fibers are exposed to the swelling forces of the amine oxide/water systems. 29 references, 13 figures, 1 table.

  6. Comparison of the properties of cellulose nanocrystals and cellulose nanofibrils isolated from bacteria, tunicate, and wood processed using acid, enzymatic, mechanical, and oxidative methods.

    PubMed

    Sacui, Iulia A; Nieuwendaal, Ryan C; Burnett, Daniel J; Stranick, Stephan J; Jorfi, Mehdi; Weder, Christoph; Foster, E Johan; Olsson, Richard T; Gilman, Jeffery W

    2014-05-14

    This work describes the measurement and comparison of several important properties of native cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs), such as crystallinity, morphology, aspect ratio, and surface chemistry. Measurement of the fundamental properties of seven different CNCs/CNFs, from raw material sources (bacterial, tunicate, and wood) using typical hydrolysis conditions (acid, enzymatic, mechanical, and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation), was accomplished using a variety of measurement methods. Atomic force microscopy (AFM), transmission electron microscopy (TEM), and 13C cross-polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy were used to conclude that CNCs, which are rodlike in appearance, have a higher crystallinity than CNFs, which are fibrillar in appearance. CNC aspect ratio distributions were measured and ranged from 148±147 for tunicate-CNCs to 23±12 for wood-CNCs. Hydrophobic interactions, measured using inverse gas chromatography (IGC), were found to be an important contribution to the total surface energy of both types of cellulose. In all cases, a trace amount of naturally occurring fluorescent compounds was observed after hydrolysis. Confocal and Raman microscopy were used to confirm that the fluorescent species were unique for each cellulose source, and demonstrated that such methods can be useful for monitoring purity during CNC/CNF processing. This study reveals the broad, tunable, multidimensional material space in which CNCs and CNFs exist.

  7. Microwave-assisted rapid synthesis and characterization of CaF₂ particles-filled cellulose nanocomposites in ionic liquid.

    PubMed

    Deng, Fu; Fu, Lian-Hua; Ma, Ming-Guo

    2015-05-05

    In this article, we try to compound cellulose/alkali earth metal fluorides (MF2, M=Ca, Mg, Sr, Ba) nanocomposites via microwave-assisted ionic liquid method, wherein cellulose/CaF2 and cellulose/MgF2 were successfully synthesized through this method while cellulose/SrF2 and cellulose/BaF2 could not be synthesized. We focused on the synthesis of cellulose/CaF2 and investigated the influences of the different time and different temperature for the synthesis of cellulose/CaF2 nanocomposites. The influence of different heating methods such as oil-bath heating method was also studied. Ionic liquid ([Bmim][BF4]) was used for dissolving microcrystalline cellulose and providing the source of fluoride ionic and the alkali earth metal nitrate (Ca(NO3)2, Mg(NO3)2, Sr(NO3)2, and Ba(NO3)2) was used as the reaction initiator. They were investigated by X-ray powder diffraction (XRD), Fourier transform infrared spectrometry (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TG), derivative thermogravimetric (DTG), and energy-dispersive X-ray spectra (EDS). The different heating modes have influence on the morphology and property. The different temperature and heating time also have a certain influence on the morphology and crystallinity of calcium fluoride.

  8. Cellulose supplementation early in life ameliorates colitis in adult mice

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Decreased consumption of dietary fibers, such as cellulose, has been proposed to promote the emergence of inflammatory bowel diseases (Crohn disease and ulcerative colitis) where intestinal microbes are recognized to play an etiologic role. However, it is not known if transient fiber consumption dur...

  9. Effects of CMC addition on bacterial cellulose production in a biofilm reactor and its paper sheets analysis.

    PubMed

    Cheng, Kuan-Chen; Catchmark, Jeffrey M; Demirci, Ali

    2011-03-14

    Bacterial cellulose (BC) can be grown into any desired shape such as pellicles, pellets, and spherelike balls, depending on the cultivation method, additives, and cell population. In this study, Acetobacter xylinum (ATCC 700178) was grown in the production medium with different concentrations of carboxylmethylcellulose (CMC) and were evaluated for BC production by using a PCS biofilm reactor. The results demonstrated that BC production was enhanced to its maximum (∼13 g/L) when 1.5% of CMC was applied, which was 1.7-fold higher than the result obtained from control culture. The major type of the produced BC was also switched from BC pellicle to small pellets. The ratio of BC pellets in suspension increased from 0 to 93%. Fourier transform infrared (FTIR) spectroscopy demonstrated that CMC was incorporated into BC during fermentation and resulted in the decreased crystallinity and crystal size. The X-ray diffraction (XRD) patterns indicated that CMC-BC exhibited both lower crystallinity (80%) and crystal size (4.2 nm) when compared with control samples (86% and 5.3 nm). The harvested BC was subjected to paper formation and its mechanical strength was determined. Dynamic mechanical analysis (DMA) results demonstrated that BC paper sheets exhibited higher tensile strength and Young's modulus when compared with regular paper.

  10. Cellulose triacetate doped with ionic liquids for membrane gas separation

    NASA Astrophysics Data System (ADS)

    Lam, Benjamin Fatt Soon

    The doping of cellulose triacetate (CTA) with imidazolium based ionic liquids (ILs) is investigated in order to reduce the polymer crystallinity and enhance the affinity with CO2, thus increasing CO2 permeability and CO2/light gas selectivity. CTA membranes doped with [emim] BF4 or [emim] DCA were prepared, and the effect of the ILs loading on properties, such as crystallinity, density, degradation temperature, glass transition temperature, and gas transport properties, has been determined. In general, doping with IL reduces the crystallinity in CTA, increasing gas solubility, diffusivity and permeability. The ILs doping also increases CO 2/CH4 solubility selectivity and CO2/N2 permeability selectivity, due to the affinity of these ILs with CO2, instead of light gases such as CH4 and N2. This study provides a mechanistic understanding of interaction of ILs and CTA, and demonstrates an effective route in manipulating the morphology and gas transport properties of semi crystalline polymers by doping with ILs.

  11. Molecular Modeling and Imaging of Initial Stages of Cellulose Fibril Assembly: Evidence for a Disordered Intermediate Stage

    PubMed Central

    Haigler, Candace H.; Grimson, Mark J.; Gervais, Julien; Le Moigne, Nicolas; Höfte, Herman; Monasse, Bernard; Navard, Patrick

    2014-01-01

    The remarkable mechanical strength of cellulose reflects the arrangement of multiple β-1,4-linked glucan chains in a para-crystalline fibril. During plant cellulose biosynthesis, a multimeric cellulose synthesis complex (CSC) moves within the plane of the plasma membrane as many glucan chains are synthesized from the same end and in close proximity. Many questions remain about the mechanism of cellulose fibril assembly, for example must multiple catalytic subunits within one CSC polymerize cellulose at the same rate? How does the cellulose fibril bend to align horizontally with the cell wall? Here we used mathematical modeling to investigate the interactions between glucan chains immediately after extrusion on the plasma membrane surface. Molecular dynamics simulations on groups of six glucans, each originating from a position approximating its extrusion site, revealed initial formation of an uncrystallized aggregate of chains from which a protofibril arose spontaneously through a ratchet mechanism involving hydrogen bonds and van der Waals interactions between glucose monomers. Consistent with the predictions from the model, freeze-fracture transmission electron microscopy using improved methods revealed a hemispherical accumulation of material at points of origination of apparent cellulose fibrils on the external surface of the plasma membrane where rosette-type CSCs were also observed. Together the data support the possibility that a zone of uncrystallized chains on the plasma membrane surface buffers the predicted variable rates of cellulose polymerization from multiple catalytic subunits within the CSC and acts as a flexible hinge allowing the horizontal alignment of the crystalline cellulose fibrils relative to the cell wall. PMID:24722535

  12. Preparation and characterization of transparent PMMA-cellulose-based nanocomposites.

    PubMed

    Kiziltas, Esra Erbas; Kiziltas, Alper; Bollin, Shannon C; Gardner, Douglas J

    2015-01-01

    Nanocomposites of polymethylmethacrylate (PMMA) and cellulose were made by a solution casting method using acetone as the solvent. The nanofiber networks were prepared using three different types of cellulose nanofibers: (i) nanofibrillated cellulose (NFC), (ii) cellulose nanocrystals (CNC) and (iii) bacterial cellulose from nata de coca (NDC). The loading of cellulose nanofibrils in the PMMA varied between 0.25 and 0.5 wt%. The mechanical properties of the composites were evaluated using a dynamic mechanical thermal analyzer (DMTA). The flexural modulus of the nanocomposites reinforced with NDC at the 0.5 wt% loading level increased 23% compared to that of pure PMMA. The NFC composite also exhibited a slightly increased flexural strength around 60 MPa while PMMA had a flexural strength of 57 MPa. The addition of NDC increased the storage modulus (11%) compared to neat PMMA at room temperature while the storage modulus of PPMA/CNC nanocomposite containing 0.25 and 0.5 wt% cellulose increased about 46% and 260% to that of the pure PMMA at the glass transition temperature, respectively. Thermogravimetric analysis (TGA) indicated that there was no significant change in thermal stability of the composites. The UV-vis transmittance of the CNF nanocomposites decreased by 9% and 27% with the addition of 0.25 wt% CNC and NDC, respectively. This work is intended to spur research and development activity for application of CNF reinforced PMMA nanocomposites in applications such as: packaging, flexible screens, optically transparent films and light-weight transparent materials for ballistic protection.

  13. Cellulose Deficiency Is Enhanced on Hyper Accumulation of Sucrose by a H+-Coupled Sucrose Symporter1[OPEN

    PubMed Central

    Yeats, Trevor H.; Sorek, Hagit

    2016-01-01

    In order to understand factors controlling the synthesis and deposition of cellulose, we have studied the Arabidopsis (Arabidopsis thaliana) double mutant shaven3 shaven3-like1 (shv3svl1), which was shown previously to exhibit a marked cellulose deficiency. We discovered that exogenous sucrose (Suc) in growth medium greatly enhances the reduction in hypocotyl elongation and cellulose content of shv3svl1. This effect was specific to Suc and was not observed with other sugars or osmoticum. Live-cell imaging of fluorescently labeled cellulose synthase complexes revealed a slowing of cellulose synthase complexes in shv3svl1 compared with the wild type that is enhanced in a Suc-conditional manner. Solid-state nuclear magnetic resonance confirmed a cellulose deficiency of shv3svl1 but indicated that cellulose crystallinity was unaffected in the mutant. A genetic suppressor screen identified mutants of the plasma membrane Suc/H+ symporter SUC1, indicating that the accumulation of Suc underlies the Suc-dependent enhancement of shv3svl1 phenotypes. While other cellulose-deficient mutants were not specifically sensitive to exogenous Suc, the feronia (fer) receptor kinase mutant partially phenocopied shv3svl1 and exhibited a similar Suc-conditional cellulose defect. We demonstrate that shv3svl1, like fer, exhibits a hyperpolarized plasma membrane H+ gradient that likely underlies the enhanced accumulation of Suc via Suc/H+ symporters. Enhanced intracellular Suc abundance appears to favor the partitioning of carbon to starch rather than cellulose in both mutants. We conclude that SHV3-like proteins may be involved in signaling during cell expansion that coordinates proton pumping and cellulose synthesis. PMID:27013021

  14. Relationship between length and degree of polymerization of TEMPO-oxidized cellulose nanofibrils.

    PubMed

    Shinoda, Ryuji; Saito, Tsuguyuki; Okita, Yusuke; Isogai, Akira

    2012-03-12

    The influence of 2,2,6,6-tetrametylpiperidine-1-oxyl (TEMPO)-mediated oxidation of wood cellulose and the mechanical disintegration of oxidized cellulose in water on degree of polymerization determined by viscosity measurement (DP(v)) and the apparent length of the TEMPO-oxidized cellulose nanofibrils (TOCNs) was investigated. DP(v) values decreased from 1270 to 500-600 with increasing addition of NaClO in the TEMPO-mediated oxidation stage. The DP(v) values were further decreased by mechanical fibrillation in water. There is a linear relationship between the average fibril length and DP(v); the lengths of TOCNs can be approximated from DP(v) using 0.5 M copper ethylenediamine as a solvent of both the cellulose and oxidized celluloses in TOCNs. Based on the cellulose fibril models and TEMPO oxidation mechanism, the depolymerization behavior of TOCNs is tentatively explained in terms of distribution of disordered regions in wood cellulose fibrils and formation of C6-aldehydes in cellulose fibrils during TEMPO-mediated oxidation.

  15. Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites.

    PubMed

    Fortunati, E; Peltzer, M; Armentano, I; Torre, L; Jiménez, A; Kenny, J M

    2012-10-01

    The aim of this paper is to report the impact of the addition of cellulose nanocrystals on the barrier properties and on the migration behaviour of poly(lactic acid), PLA, based nano-biocomposites prepared by the solvent casting method. Their microstructure, crystallinity, barrier and overall migration properties were investigated. Pris