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1.
W Li  R Xu  L Zheng  J Du  Y Zhu  R Huang  H Deng 《Carbohydrate polymers》2012,90(4):1656-1663
Organic rectorite (OREC) was used to prepare intercalated composites with chitosan. The negatively charged cellulose acetate (CA) fibrous mats were modified with multilayers of the positively charged chitosan or chitosan-OREC intercalated composites and the negatively charged bovine serum albumin (BSA) via electrostatic layer-by-layer (LBL) self-assembly technique. The morphology and protein delivery properties of the resultant samples were investigated by regulating the number of deposition bilayers, the outermost layer and the composition of coating bilayers. The thickness of LBL films coated CA mats increased as the number of bilayers was increased and OREC was added. X-ray photoelectron spectroscopy indicated that chitosan and OREC were deposited on CA fibers. Small angle X-ray diffraction patterns showed that OREC was intercalated by chitosan. The in vitro BSA encapsulation and release experiments demonstrated that OREC could affect the degree of protein loading capacity and release efficiency of the LBL films coating.  相似文献   

2.
R Huang  Y Li  X Zhou  Q Zhang  H Jin  J Zhao  S Pan  H Deng 《Carbohydrate polymers》2012,90(2):957-966
N-(2-hydroxyl) propyl-3-trimethyl ammonium chitosan chloride (HTCC) was synthesized from chitosan (CS). Organic rectorite (OREC) added into cellulose acetate (CA) was used to fabricate electrospun nanofibrous mats with improved thermal properties, as a result of depositing multilayers of the positively charged HTCC-OREC composites and the negatively charged sodium alginate (ALG) via layer-by-layer (LBL) technique. The morphology was affected by the number of deposition bilayers and the component of the outmost layer. Observed from the field emission scanning electron microscopy (FE-SEM) images, the LBL structured nanofibrous mats had much larger fiber sizes than CA-OREC nanofibrous mats. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) results further confirmed that HTCC-OREC was assembled on nanofibrous mats. Additionally, cell experiments and MTT results demonstrated that OREC had little effect on the cytotoxicity of LBL template, but obviously affected both the cytotoxicity and the cell compatibility of LBL structured mats when OREC was in the deposition films.  相似文献   

3.
Pectin and cellulose are major components of most primary cell walls, yet little is known about the way in which they interact either during assembly or in subsequent functional performance of the wall. As a mimic of cell wall assembly, we studied the formation of molecular composites formed by deposition of cellulose from Acetobacter xylinus into pectin/calcium systems, and the molecular, architectural and mechanical properties of the composites obtained. The formation of interpenetrating cellulose/pectin composite networks (as envisaged in current models for primary cell walls) required a pre-existing, but not too strong, pectin network. For pectin either in solution or strongly networked, phase separation from cellulose occurred, providing two physical models for the formation of middle lamellae. Composite networks showed no evidence of direct molecular interaction between the components, but pectin networks became more aggregated following deposition of cellulose into them. The shear strength under small deformation conditions for cellulose/pectin composites was very similar to that of cellulose alone. In contrast, under uniaxial tension, extensibility was greatly increased and stiffness decreased. These major changes were due to the effect of pectin on cellulose network architecture at deposition, as they were maintained upon removal of the pectin component. These results show that the presence and physical state of pectin at the time of cellulose deposition in muro may be a significant determinant of subsequent extensibility without compromising strength.  相似文献   

4.
Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall.  相似文献   

5.
Rigid nanoscale polymer rods were prepared by grafting preformed amine-terminated poly(styrene) and poly(tert-butyl acrylate) onto oxidized cellulose microcrystals. Low polydispersity polymers, grown using atom transfer radical polymerization, were characterized and purified prior to cellulose attachment. Oxidation of the cellulose microcrystal led to the formation of carboxylic acids on the surface of the microcrystals. Covalent attachment of the polymers onto the cellulose microcrystals was achieved via a carbodiimide-mediated amidation reaction. The length and diameter of the polymer-cellulose composites increased upon surface modification. Typically, polymer-cellulose composites are synthesized by a grafting-from method because it can be difficult to obtain sufficient graft density using a grafting-to preparation. However, the composites reported here comprised 60-64% grafted polymer by mass. This degree of grafting-to allowed the composite to form stable suspensions in organic solvents.  相似文献   

6.
Pectins of varying structures were tested for their ability to interact with cellulose in comparison to the well-known adsorption of xyloglucan. Our results reveal that sugar beet (Beta vulgaris) and potato (Solanum tuberosum) pectins, which are rich in neutral sugar side chains, can bind in vitro to cellulose. The extent of binding varies with respect to the nature and structure of the side chains. Additionally, branched arabinans (Br-Arabinans) or debranched arabinans (Deb-Arabinans; isolated from sugar beet) and galactans (isolated from potato) were shown bind to cellulose microfibrils. The adsorption of Br-Arabinan and galactan was lower than that of Deb-Arabinan. The maximum adsorption affinity of Deb-Arabinan to cellulose was comparable to that of xyloglucan. The study of sugar beet and potato alkali-treated cell walls supports the hypothesis of pectin-cellulose interaction. Natural composites enriched in arabinans or galactans and cellulose were recovered. The binding of pectins to cellulose microfibrils may be of considerable significance in the modeling of primary cell walls of plants as well as in the process of cell wall assembly.  相似文献   

7.
Hu X  Ji J 《Biomacromolecules》2011,12(12):4264-4271
A convenient and simple route to multifunctional surface coatings via the alternating covalent layer-by-layer (LBL) assembly of p-nitrophenyloxycarbonyl group-terminated hyperbranched polyether (HBPO-NO(2)) and polyethylenimine (PEI) is described. The in situ chemical reaction between HBPO-NO(2) and PEI onto aminolyzed substrates was rapid and mild. Results from ellipsometry measurements, contact angle measurements, and ATR-FTIR spectra confirmed the successful LBL assembly of the building blocks, and the surface reactivity of the multilayer films with HBPO-NO(2) as the outmost layer was demonstrated by the immobilization of an amine-functionalized fluorophore. Furthermore, a biomimetic surface was achieved by surface functionalization of the multilayer films with extracellular matrix protein collagen to promote the adhesion and growth of cells. The studies on the drug loading and in vitro release behaviors of the multilayer films demonstrated their application potentials in local delivery of hydrophilic and hydrophobic therapeutic agents.  相似文献   

8.
A highly sensitive biosensor was developed based on bionanomultilyer with water-soluble carbon nanotubes (CNTs). The water-soluble poly(allylamine hydrochloride)-wrapped multiwall carbon nanotubes (PAH-MWNTs) can be obtained for the first time relying on the function of barbiturates, which provides a useful avenue for CNT application in material science and biosensor technology. Based on this, the PAH-MWNTs/horseradish peroxidase (HRP) bionanomultilayer was prepared via layer-by-layer (LBL) assembly. Electrochemical impedance spectroscopy, atomic force microscopy and UV-vis spectra were adopted to monitor the uniform LBL assembly of the homogeneous bionanomultilayer. The bionanomultilayer was used to construct a phenolic biosensor. Under the optimal conditions, the biosensor presented a linear response for catechol from 0.1 to 20.4muM, with a detection limit of 0.06muM. A series of phenolics were detected by the bionanomultilayer biosensor. The introduced MWNTs in the biosensor provided a suitable microenvironment to retain the HRP activity and acted as a transducer for amplifying the electrochemical signal of the product of the enzymatic reaction. So the developed bionanomultilayer biosensor exhibited a fast, sensitive and stable detection.  相似文献   

9.
- Model composites, produced using cellulose from stationary cultures of the bacterium Gluconoacetobacter xylinus and tamarind xyloglucan, were examined by wide-angle X-ray scattering (WAXS) and CP/MAS solid-state (13)C NMR spectroscopy. The dominant crystallite allomorph of cellulose produced in culture media with or without xyloglucan was cellulose I(alpha) (triclinic). The presence of xyloglucan in the culture medium reduced the cross-section dimensions of the cellulose crystallites, but did not affect the crystallite allomorph. However, when the composites were refluxed in buffer, the proportion of cellulose I(beta) allomorph increased relative to that of cellulose I(alpha). In contrast, cellulose I(alpha) remained the dominant form when cellulose, produced in the absence of xyloglucan, was then heated in the buffer. Hence the presence of xyloglucan has a profound effect on the formation of the cellulose crystallites by G. xylinus.  相似文献   

10.
Bacterial biofilms are communities of bacteria entangled in a self‐produced extracellular matrix (ECM). Escherichia coli direct the assembly of two insoluble biopolymers, curli amyloid fibers, and phosphoethanolamine (pEtN) cellulose, to build remarkable biofilm architectures. Intense curiosity surrounds how bacteria harness these amyloid‐polysaccharide composites to build biofilms, and how these biopolymers function to benefit bacterial communities. Defining ECM composition involving insoluble polymeric assemblies poses unique challenges to analysis and, thus, to comparing strains with quantitative ECM molecular correlates. In this work, we present results from a sum‐of‐the‐parts 13C solid‐state nuclear magnetic resonance (NMR) analysis to define the curli‐to‐pEtN cellulose ratio in the isolated ECM of the E. coli laboratory K12 strain, AR3110. We compare and contrast the compositional analysis and comprehensive biofilm phenotypes for AR3110 and a well‐studied clinical isolate, UTI89. The ECM isolated from AR3110 contains approximately twice the amount of pEtN cellulose relative to curli content as UTI89, revealing plasticity in matrix assembly principles among strains. The two parent strains and a panel of relevant gene mutants were investigated in three biofilm models, examining: (a) macrocolonies on agar, (b) pellicles at the liquid‐air interface, and (c) biomass accumulation on plastic. We describe the influence of curli, cellulose, and the pEtN modification on biofilm phenotypes with power in the direct comparison of these strains. The results suggest that curli more strongly influence adhesion, while pEtN cellulose drives cohesion. Their individual and combined influence depends on both the biofilm modality (agar, pellicle, or plastic‐associated) and the strain itself.  相似文献   

11.
In cellulosomes produced by Clostridium spp., the high-affinity interaction between the dockerin domain and the cohesin domain is responsible for the assembly of enzymatic subunits into the complex. Thus, heterologous expression of full-length enzymatic subunits containing the dockerin domains and of the scaffolding unit is essential for the in vitro assembly of a "designer" cellulosome, or a recombinant cellulosome with a specific function. We report the preparation of Clostridium cellulovorans recombinant cellulosomes containing the enzymatic subunit EngB and the scaffolding unit, mini-CbpA, containing a cellulose binding domain, a putative cell wall binding domain, and two cohesin units. The full-length EngB containing the dockerin domain was expressed by Bacillus subtilis WB800, which is deficient in eight extracellular proteases, to prevent the proteolytic cleavage of the enzymatic subunit between the catalytic and dockerin domains that was observed in previous attempts to express EngB with Escherichia coli. The assembly of recombinant EngB with the mini-CbpA was confirmed by immunostaining, a cellulose binding experiment, and native polyacrylamide gel electrophoresis analysis.  相似文献   

12.
The preparation of functionalized beads in the micrometer size range that can be used to probe the action of immobilized biomolecules on cell cultures during controlled periods of time is of fundamental importance in cell biology. However, the preparation and characterization of such particles is tedious because of their fast sedimentation. It is hence difficult to prepare such beads in a reproducible manner. This highlights the need to prepare an important batch of functionnalized particles and to store them under conditions where the loss of biological activity is minimized. The aim of this paper was to immobilize alkaline phosphatase (AP) as a model enzyme on the surface of Affi-gel heparin beads functionnalized by means of a layer-by-layer (LBL) film made of poly-l-glutamic (PGA) acid and poly-l-lysine (PLL). The enzyme has been adsorbed either on the top of the LBL film or embedded under five polyelectrolyte layers. When embedded, the enzyme was not released in buffer and retained more than 30% of its initial activity after 3 months of storage at 4 degrees C. However, when the enzyme was adsorbed on top of the LBL film, about 80% of the adsorbed enzyme was released in the buffer after a few days of storage. Longer storage did not lead to any further desorption and the remaining enzyme displayed the same evolution of its activity with time as the embedded enzyme. The time evolution of the enzyme activity on the beads is compared with that in solution alone and in the presence of PGA and PLL separately.  相似文献   

13.
This study demonstrates a polyelectrolyte-free method to fabricate controllable and stable all-MWNTs films via a covalent layer-by-layer (LBL) deposition. Aminated MWNTs and carboxylated MWNTs were prepared by surface functionalization, allowing the incorporation of MWNTs into highly tunable thin films through the formation of covalent amide bonds. Fourier transform infrared spectroscopy (FTIR) analysis demonstrated the formation of covalent linkages between MWNTs layers. Scanning electron microscopy (SEM) and ultraviolet-visible spectroscopy (UV-vis) were used to characterize the assembly process. Electrochemical studies indicated that the all-MWNTs film possessed a remarkable electrocatalytic activity toward dihydronicotinamide adenine dinucleotide (NADH) at relatively low potentials, without the need for redox mediators. The film thickness and the amount of assembled MWNTs were readily adjusted by simply changing the number of cycles in the LBL assembly process, which also effectively tuned the electrocatalytic activity of the film toward NADH. The film constructed with four bilayers showed a high sensitivity of 223.8μAmM(-1)cm(-2) and a detection limit of 1.5μM, with a fast response of less than 3s. Furthermore, the all-MWNTs film also showed good selectivity and excellent stability for the determination of NADH.  相似文献   

14.
Toward exploiting the attractive mechanical properties of cellulose I nanoelements, a novel route is demonstrated, which combines enzymatic hydrolysis and mechanical shearing. Previously, an aggressive acid hydrolysis and sonication of cellulose I containing fibers was shown to lead to a network of weakly hydrogen-bonded rodlike cellulose elements typically with a low aspect ratio. On the other hand, high mechanical shearing resulted in longer and entangled nanoscale cellulose elements leading to stronger networks and gels. Nevertheless, a widespread use of the latter concept has been hindered because of lack of feasible methods of preparation, suggesting a combination of mild hydrolysis and shearing to disintegrate cellulose I containing fibers into high aspect ratio cellulose I nanoscale elements. In this work, mild enzymatic hydrolysis has been introduced and combined with mechanical shearing and a high-pressure homogenization, leading to a controlled fibrillation down to nanoscale and a network of long and highly entangled cellulose I elements. The resulting strong aqueous gels exhibit more than 5 orders of magnitude tunable storage modulus G' upon changing the concentration. Cryotransmission electron microscopy, atomic force microscopy, and cross-polarization/magic-angle spinning (CP/MAS) 13C NMR suggest that the cellulose I structural elements obtained are dominated by two fractions, one with lateral dimension of 5-6 nm and one with lateral dimensions of about 10-20 nm. The thicker diameter regions may act as the junction zones for the networks. The resulting material will herein be referred to as MFC (microfibrillated cellulose). Dynamical rheology showed that the aqueous suspensions behaved as gels in the whole investigated concentration range 0.125-5.9% w/w, G' ranging from 1.5 Pa to 105 Pa. The maximum G' was high, about 2 orders of magnitude larger than typically observed for the corresponding nonentangled low aspect ratio cellulose I gels, and G' scales with concentration with the power of approximately three. The described preparation method of MFC allows control over the final properties that opens novel applications in materials science, for example, as reinforcement in composites and as templates for surface modification.  相似文献   

15.
Cellulose biosynthesis: current views and evolving concepts   总被引:10,自引:0,他引:10  
* AIMS: To outline the current state of knowledge and discuss the evolution of various viewpoints put forth to explain the mechanism of cellulose biosynthesis. * SCOPE: Understanding the mechanism of cellulose biosynthesis is one of the major challenges in plant biology. The simplicity in the chemical structure of cellulose belies the complexities that are associated with the synthesis and assembly of this polysaccharide. Assembly of cellulose microfibrils in most organisms is visualized as a multi-step process involving a number of proteins with the key protein being the cellulose synthase catalytic sub-unit. Although genes encoding this protein have been identified in almost all cellulose synthesizing organisms, it has been a challenge in general, and more specifically in vascular plants, to demonstrate cellulose synthase activity in vitro. The assembly of glucan chains into cellulose microfibrils of specific dimensions, viewed as a spontaneous process, necessitates the assembly of synthesizing sites unique to most groups of organisms. The steps of polymerization (requiring the specific arrangement and activity of the cellulose synthase catalytic sub-units) and crystallization (directed self-assembly of glucan chains) are certainly interlinked in the formation of cellulose microfibrils. Mutants affected in cellulose biosynthesis have been identified in vascular plants. Studies on these mutants and herbicide-treated plants suggest an interesting link between the steps of polymerization and crystallization during cellulose biosynthesis. * CONCLUSIONS: With the identification of a large number of genes encoding cellulose synthases and cellulose synthase-like proteins in vascular plants and the supposed role of a number of other proteins in cellulose biosynthesis, a complete understanding of this process will necessitate a wider variety of research tools and approaches than was thought to be required a few years back.  相似文献   

16.
Yan Mei  Chen Yao 《Biofouling》2014,30(3):313-322
In this work, antibacterial and anti-adhesive polymeric thin films were constructed on polyacrylonitrile (PAN) nanofibrous membranes in order to extend their applications. Polyhexamethylene guanidine hydrochloride (PHGH) as an antibacterial agent and heparin (HP) as an anti-adhesive agent have been successfully coated onto the membranes via a layer-by-layer (LBL) assembly technique confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), energy-dispersive spectroscopy (EDS) and scanning electron microscopy (SEM). The antibacterial properties of LBL-functionalized PAN nanofibrous membranes were evaluated using the Gram-positive bacterium Staphylococcus aureus and the Gram-negative Escherichia coli. Furthermore, the dependence of the antibacterial activity and anti-biofouling performance on the number of layers in the LBL films was investigated quantitatively. It was found that these LBL-modified nanofibrous membranes possessed high antibacterial activities, easy-cleaning properties and stability under physiological conditions, thus qualifying them as candidates for anti-biofouling coatings.  相似文献   

17.
LBL联合PBL的教学模式是一种"教为主导,学为主体,教与学并重"的综合教学方法。在临床医学专业的药理学教学中合理应用LBL联合PBL教学法,即采用LBL教学法讲授完理论知识后开设PBL病例讨论课。选取2011级五年制临床医学专业的学生为实验组,采用LBL联合PBL教学模式,2010级五年制临床医学专业的学生为对照组,采用传统LBL教学模式,对两组进行教学效果评估比较。结果显示与传统LBL教学法相比较,LBL联合PBL的教学法能显著提高学生的学习成绩,问卷调查分析结果显示LBL联合PBL的教学法能明显提高学生的综合能力。药理学授课中应用LBL联合PBL教学法充分调动了学生的积极性,培养了学生自主学习能力,分析问题、解决问题的能力和临床思维能力,对培养创新型医学人才具有重要意义。  相似文献   

18.
The structure of arabinan and galactan domains in association with cellulose microfibrils was investigated using enzymatic and alkali degradation procedures. Sugar beet and potato cell wall residues (called 'natural' composites), rich in pectic neutral sugar side chains and cellulose, as well as 'artificial' composites, created by in vitro adsorption of arabinan and galactan side chains onto primary cell wall cellulose, were studied. These composites were sequentially treated with enzymes specific for pectic side chains and hot alkali. The degradation approach used showed that most of the arabinan and galactan side chains are in strong interaction with cellulose and are not hydrolysed by pectic side chain-degrading enzymes. It seems unlikely that isolated arabinan and galactan chains are able to tether adjacent microfibrils. However, cellulose microfibrils may be tethered by different pectic side chains belonging to the same pectic macromolecule.  相似文献   

19.

Background

Polylactic acid (PLA) is considered to be a sustainable alternative to petroleum-based polymers for many applications. Using cellulose fiber to reinforce PLA is of great interest recently due to its complete biodegradability and potential improvement of the mechanical performance. However, the dispersion of hydrophilic cellulose fibers in the hydrophobic polymer matrix is usually poor without using hazardous surfactants. The goal of this study was to develop homogenously dispersed cellulose nanowhisker (CNW) reinforced PLA composites using whole milk casein protein, which is an environmentally compatible dispersant.

Results

In this study, whole milk casein was chosen as a dispersant in the PLA-CNW system because of its potential to interact with the PLA matrix and cellulose. The affinity of casein to PLA was studied by surface plasmon resonance (SPR) imaging. CNWs were functionalized with casein and used as reinforcements to make PLA composites. Fluorescent staining of CNWs in the PLA matrix was implemented as a novel and simple way to analyze the dispersion of the reinforcements. The dispersion of CNWs in PLA was improved when casein was present. The mechanical properties of the composites were studied experimentally. Compared to pure PLA, the PLA composites had higher Young’s modulus. Casein (CS) functionalized CNW reinforced PLA (PLA-CS-CNW) at 2 wt% filler content maintained higher strain at break compared to normal CNW reinforced PLA (PLA-CNW). The Young’s modulus of PLA-CS-CNW composites was also higher than that of PLA-CNW composites at higher filler content. However, all composites exhibited lower strain at break and tensile strength at high filler content.

Conclusions

The presence of whole milk casein improved the dispersion of CNWs in the PLA matrix. The improved dispersion of CNWs provided higher modulus of the PLA composites at higher reinforcement loading and maintained the strain and stress at break of the composites at relatively low reinforcement loading. The affinity of the dispersant to PLA is important for the ultimate strength and stiffness of the composites.
  相似文献   

20.
A series of conductive composites cellulose–polyaniline (PANI) were heterogeneously synthesized by chemical oxidative polymerization of aniline with native cellulose activated by various acids. The chemical structure and morphology of the composites were examined by FT-IR analysis and TEM. TGA was used to study their thermal properties. The composites prepared using the di-basic acids exhibited more favorable conductivity than the composites prepared using the monobasic acids. The content of PANI increased with increasing of activation time, and while the conductivity decreased because of the aggregation of PANI particles at the activation time range from 50 to 120 min. Both the PANI content and the electrical conductivity increased with an increase of the amount of aniline, and reached the maximum values at the 0.5 g aniline, respectively. The acids were able to successfully activate cellulose and lead to the improvement of the accessibility and reactivity of the O–H groups. The composites were highly stable compared to pure cellulose due to the safeguard from PANI slices. This work provided a facile method for the synthesis of cellulose–polyaniline conductive composites with excellent conductivity.  相似文献   

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