Hydrolysis of Microcrystalline Cellulose to Produce Fermentable Monosaccharides by Plasma Acid

Plasma acid was obtained by treating distilled water with a dielectric barrier discharge (DBD) at atmospheric pressure. The tentative relationship between discharge conditions and pH value of the plasma acid was investigated. In order to optimize the hydrolysis conditions of microcrystalline cellulose with the plasma acid, an orthogonal experiment was carried out and the colorimetric determination of 3,5-dinitro-salicylic acid was applied to measure the concentration of total reduced sugar (TRS). The results showed that the pH value of the plasma acid was related to the discharge time. The acidity of the plasma acid was maintained for several hours and then faded gradually. The microcrystalline cellulose was hydrolyzed effectively by the plasma acid and the optimal hydrolysis conditions were as follows: pH 1.42 of the plasma acid, hydrolysis temperature of 80°C and hydrolysis time of 60 min. Under these conditions, the microcrystalline cellulose with polymerization degree of 200–300 was hydrolyzed completely to produce monosaccharides, including xylose and glucose with the mole ratio of 1:35, as shown by high-performance liquid chromatography (HPLC) analysis. Moreover, the hydrolysis of luffa cellulose with polymerization degree of 500–600 was also carried out. The luffa cellulose was hydrolyzed completely to produce monosaccharides including xylose, mannose and glucose with mole ratio of 6.7:1:218. Therefore, it could be concluded that the main hydrolysis product of both types of cellulose was glucose. The glucose yield of microcrystalline cellulose was 46%, whereas for luffa cellulose it was 41%. This method was an environmentally friendly and effective method to hydrolyze cellulose.     

Studies on the electrochemical and dopamine sensing properties of AgNP-modified carboxylated cellulose nanocrystal-doped poly(3,4-ethylenedioxythiophene)

Ionics - Carboxylated cellulose nanocrystals (CNCC) were synthesized by treating microcrystalline cellulose with ammonium persulfate. Silver nanoparticles (AgNPs) were prepared on the surface of...     

纳米纤维素碱法制备及光谱性质

在纳米尺寸范围操控纤维素分子,由此创制出具有优异功能的新纳米材料是纤维素科学的前沿领域。纳米纤维素作为一种可再生生物材料已成为国内外研究热点,研究开发新型的简单、绿色、低能耗、快速、高效的纳米纤维素制备方法显得尤为重要。该研究采用简易可行的碱性水解法制备得到粒径较小且分散性较好的纳米纤维素。同时采用了电子显微镜、X射线粉末衍射仪和傅里叶红外光谱仪对所制备纳米纤维素进行了表征,研究了其结构与谱学性质。所制备样品为准球形纳米纤维素,颗粒尺寸约为20～40 nm,样品仍属于纤维素Ⅰ型,结晶度为79.71%,晶粒平均尺寸为3～6 nm。结果表明,碱水解法制备纳米纤维素方法具有简易可行、得率高的优点,研究可为纳米纤维素的高效制备提供一条新途径。     

Chemical physics of cellulose nitration

The physical mechanisms responsible for the kinetics of nitration of cellulose raw materials of different origin have been studied. It has been shown that the main nitration rate-limiting factor is the speed of untwisting of supercoiled cellulose fibers. This process limits the penetration of nitrating agents into microcrystalline regions and, thus, the total reaction rate. The constructed physical model provides an adequate explanation of all the experimentally observed features of the cellulose nitration process, particularly as a function of cellulose origin (cotton, flax, wood) and preparation/treatment methods (sulfite, sulfate, bleached, refined with sulfurous or boric acids or acetone). The theoretical results have been tested in practice.     

Processing and characterization of new thermoset nanocomposites based on cellulose whiskers

In the present study, the processing and the mechanical properties of new thermoset nanocomposites prepared from aqueous suspensions of microcrystalline cellulose fillers and epoxy are described. The nature of cellulose fibers, which display a large aspect ratio and the ability to associate by means of H-bonds implies that the processing method chosen in this study avoids the problem of a high level of viscosity of the epoxy reactive system-whiskers mixture. The reinforcing effect of this type of natural fiber in an epoxy matrix is mainly shown from the dynamic mechanical properties in the rubbery state. This unusual reinforcement is due to (i) the strong interactions existing between the cellulose whiskers and the epoxy network and, (ii) the creation of a percolating network linked by H-bonds between cellulose fibers. The existence of such a percolation effect is evidenced from the analysis of the rubbery shear modulus of nanocomposites based on various volume fractions of whiskers with mechanical modeling such as Halpin-Kardos and percolation approaches.     

Pretreatment combining ultrasound and sodium percarbonate under mild conditions for efficient degradation of corn stover

Ultrasound (US) can be used to disrupt microcrystalline cellulose to give nanofibers via ultrasonic cavitation. Sodium percarbonate (SP), consisting of sodium carbonate and hydrogen peroxide, generates highly reactive radicals, which cause oxidative delignification. Here, we describe a novel pretreatment technique using a combination of US and SP (US–SP) for the efficient saccharification of cellulose and hemicellulose in lignocellulosic corn stover. Although US–SP pretreatment was conducted under mild condition (i.e., at room temperature and atmospheric pressure), the pretreatment greatly increased lignin removal and cellulose digestibility. We also determined the optimum US–SP treatment conditions, such as ultrasonic power output, pretreatment time, pretreatment temperature, and SP concentration for an efficient cellulose saccharification. Moreover, xylose could be effectively recovered from US–SP pretreated biomass without the formation of microbial inhibitor furfural.     

Investigation of Novel Quantum Dots/Proteins/Cellulose Bioconjugate Using NSOM and Fluorescence

We investigated the engineered bioconjugate of cadmium selenide core/zinc sulfide shell, (CdSe)ZnS, quantum dots (QDs) with genetically modified proteins using fluorescence spectroscopy, near-field scanning optical microscopy (NSOM) and spectroscopy (NSOS). The protein polymer was allowed to self-assemble to the bacterial microcrystalline cellulose surface through the cellulosic binding domain. Results from the sample containing the QDs/protein/cellulose assemblies suggest that QDs were arrayed along the cellulose surface. The spectroscopic change of spectroscopic properties of the QDs upon bioconjugation, indicating the interaction among the immobilized QDs and between the constructed protein and QDs.     

Effect of compatibilizers on the crystallization kinetics of cellulose-filled high density polyethylene

High density polyethylene (HDPE) is a ubiquitous material with versatile properties. It is produced and used in greater volume than any other thermoplastic. HDPE is often filled with a variety of materials for various applications. Glass fiber and wood flour are two common fillers for HDPE. This study investigated microcrystalline cellulose (MCC) as a filler in HDPE. The use of compatibilizers, or coupling agents, was investigated as a means of improving the dispersion of the cellulose filler in the HDPE matrix and the mechanical properties of the resulting composites. One compatibilizer was shown to improve the strength of the resulting composite. The stiffness was unaffected, as expected. Thermal properties were measured by means of differential scanning calorimetry. Analysis of the crystallization kinetics indicated that the Avrami coefficient was altered by the filler and was also modified by the presence of the compatibilizer. The presence of cellulose and/or compatibilizer increased the matrix degree of crystallinity. The two compatibilizers studied did not behave similarly and may have different mechanisms of compatibilization.     

Sono-assisted TEMPO oxidation of oil palm lignocellulosic biomass for isolation of nanocrystalline cellulose

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 6 nm, respectively. FTIR and solid-state ¹³C-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 ¹³C-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.     

Copper and copper oxide nanoparticles in a cellulose support studied using anomalous small-angle X-ray scattering

Microcrystalline cellulose is a porous natural material which can be used both as a support for nanoparticles and as a reducer of metal ions. Cellulose supported nanoparticles can act as catalysts in many reactions. Cu, CuO, and Cu₂O particles were prepared in microcrystalline cellulose by adding a solution of copper salt to the insoluble cellulose matrix and by reducing the copper ions with several reducers. The porous nanocomposites were studied using anomalous small angle X-ray scattering (ASAXS), X-ray absorption spectroscopy, and X-ray diffraction. Reduction of Cu²⁺ with cellulose in ammonium hydrate medium yielded crystalline CuO nanoparticles and the crystallite size was about 6–20 nm irrespective of the copper concentration. The size distribution of the CuO particles was determined with ASAXS measurements and coincided with the crystallite sizes. Using sodium borohydrate or hydrazine sulfate as a reducer both metallic Cu and Cu₂O nanoparticles were obtained and the crystallite size and the oxidation state depended on the amount of reducer.     

Effects of Replacement of Part of the Silica Reinforcement with Hybrid Modified Microcrystalline Cellulose on the Properties of their Rubber Composites

Hybrid modified microcrystalline cellulose (HMCC), with SiO₂ nanoparticles being in-situ loaded on the surface of microcrystalline cellulose (MCC), was obtained through a sol-gel process of tetraethoxysilane (TEOS) by using ammonia as catalyst. HMCC was characterized by thermogravimetric analysis and scanning electron microscopy. The results showed that the spherical nano-SiO₂ particles had been loaded successfully on the surface of the MCC with a loading ratio of approximately 10%. Then the HMCC was used in high vinyl solution-polymerized styrene butadiene rubber (SSBR)/silica compounds to replace part of the silica, and its effects on the physio-mechanical and dynamic mechanical properties of the vulcanizates were investigated. The results showed that the HMCC samples had improved physio-mechanical properties and lower heat build-up than that of MCC ones. Dynamic mechanical analysis (DMA) showed that the tanδ value of the compounds decreased at 60°C while increased obviously at 0°C, which meant that the tires would have improved wet-skid resistance while maintaining low rolling resistance when HMCC was used in tire tread compounds. As observed from scanning electron microscopy (SEM) photos, the sizes of the HMCC were in-situ decreased from 20–90 µm to 0.5–10 µm during the processing of the rubber compounds. Compared with MCC, the interfacial adhesion between HMCC and rubber was also improved greatly.     

EPR investigation of some gamma-irradiated excipients

The results of electron paramagnetic resonance (EPR) studies on some excipients: lactose, microcrystalline cellulose (avicel), starch, dioxosilane (aerosil), talc and magnesium stearate before and after gamma-irradiation are reported. Before irradiation, all samples are EPR silent except talc. After gamma-irradiation, they show complex spectra except magnesium stearate, which is EPR silent. Studies show the influence of gamma-irradiation on EPR spectra and stability of gamma-induced radicals. Analysis of the EPR spectrum of gamma-irradiated talc shows that this material is radiation insensitive. Only lactose forms stable-free radicals upon gamma sterilization and can be used for identification of radiation processing for a long time period thereafter.     

Preparation of nanocrystalline cellulose via ultrasound and its reinforcement capability for poly(vinyl alcohol) composites

Rod-shaped nanocrystalline cellulose (NCC) was prepared from microcrystalline cellulose (MCC) using the purely physical method of high-intensity ultrasonication. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction was used for the characterization of the morphology and crystal structure of the material. The thermal properties were investigated using thermogravimetric analysis. The reinforcement capabilities of the obtained NCC were investigated by adding it to poly(vinyl alcohol) (PVA) via the solution casting method. The results revealed that the prepared NCC had a rod-shaped structure, with diameters between 10 and 20 nm and lengths between 50 and 250 nm. X-ray diffraction results indicated that the NCC had the cellulose I crystal structure similar to that of MCC. The crystallinity of the NCC decreased with increasing ultrasonication time. The ultrasonic effect was non-selective, which means it can remove amorphous cellulose and crystalline cellulose. Because of the nanoscale size and large number of free-end chains, the NCC degraded at a slightly lower temperature, which resulted in increased char residue (9.6-16.1%), compared with that of the MCC (6.2%). The storage modulus of the nanocomposite films were significantly improved compared with that of pure PVA films. The modulus of PVA with 8 wt.% NCC was 2.40× larger than that of pure PVA.     

Study of solid–liquid interface in water dispersions of microcrystalline celluloses

Interaction on the solid–liquid surface in dispersions of microcrystalline cellulose (MCC) with various particle sizes has been studied by means of rheological methods. It was shown that the MCC dispersions possess shear-thinning rheological properties. An inversely proportional relationship between the average particle size of the MCC particles and the viscosity of the dispersions was discovered. This phenomenon is explained by the decrease of water mobility with increase in the specific surface of the MCC particles. Irreversible closing of the MCC pores reduces the viscosity of water dispersions. Addition of some water-soluble polymers leads to a considerable increase in viscosity due to formation of macromolecular net composed of solid particles.     

X射线荧光光谱法直接测定油页岩中微量元素

本文提出用微晶纤维素与GSD等国家一级系列标样按不同比例混合制备标准样品。油页岩样品不经前处理,直接粉末法压片,经验系数法校正元素间效应,直接测定油页岩中V、Co、Ni、Cr、Cu、Zn、Sr、Ba和Rb等元素的X射线荧光光谱法。样品分析结果与ICP-AES法分析结果基本一致,本法具有简单、准确、实用的特点。     

Solid state NMR study of dietary fiber powders from aronia, bilberry, black currant and apple

13C CPMAS NMR spectra of dietary fiber powders from aronia (chokeberry), bilberry, black currant and apple were recorded. The spectra are complex owing to superposition of resonances from different polysaccharides and polyphenolic compounds. Standard, dipolar dephased and the TH(1rho) partially relaxed spectra enabled the identification of several constituents: microcrystalline cellulose, pectins, lignins, cutin-like polymers and condensed tannins. The fiber powders obtained from berries contain significant amounts of anthocyanins, as indicated by their dark violet color, but not verified by chemical shifts. The anthocyanin-rich extract from aronia berries and its major components, cyanidin-3-O-galactoside and (-)epicatechin were also studied.     

Viscoelastic characterization of compacted pharmaceutical excipient materials by analysis of frequency-dependent mechanical relaxation processes

A newly developed method for determining the frequency-dependent complex Young's modulus was employed to analyze the mechanical response of compacted microcrystalline cellulose, sorbitol, ethyl cellulose and starch for frequencies up to 20 kHz. A Debye-like relaxation was observed in all the studied pharmaceutical excipient materials and a comparison with corresponding dielectric spectroscopy data was made. The location in frequency of the relaxation peak was shown to correlate to the measured tensile strength of the tablets, and the relaxation was interpreted as the vibrational response of the interparticle hydrogen and van der Waals bindings in the tablets. Further, the measured relaxation strength, holding information about the energy loss involved in the relaxation processes, showed that the weakest material in terms of tensile strength, starch, is the material among the four tested ones that is able to absorb the most energy within its structure when exposed to external perturbations inducing vibrations in the studied frequency range. The results indicate that mechanical relaxation analysis performed over relatively broad frequency ranges should be useful for predicting material properties of importance for the functionality of a material in applications such as, e.g., drug delivery, drug storage and handling, and also for clarifying the origin of hitherto unexplained molecular processes.     

制备生物炭的结构特征及炭化机理的XRD光谱分析

XRD光谱分析是研究物质内部结晶结构物质的重要手段。利用X射线技术分析了不同物料来源和制备方式对生物炭结晶结构特征及其炭化机理。结果表明：生物炭均含有d₁₀₁和d₀₀₂晶面衍射峰类石墨微晶纤维素炭,但炭化后析出的盐分随不同物料,差异较大,如牛粪、蓖麻粕以及糠醛渣的CaCO₃含量要高于其他生物炭,而仅牛粪与蓖麻粕含有CaMg(CO₃)₂。随温度升高,玉米秸秆炭中半纤维素优先分解,然后为纤维素石墨微晶化,结晶度提高,向更稳定的碳化合物转化。其中的矿物盐分随着炭化裂解温度升高,由稀土类氧化物→醋酸盐类物质→碳酸盐类物质逐步析出,CaCO₃的含量也随之增多。不同炭化方法的炭化机理不同,先干燥后炭化可促进半纤维素的分解,高温微波处理则是强烈震荡,主要促进物质多键断裂分解,碳酸盐类物质析出相对较少。通过X射线衍射分析可以很好研究生物炭内部结构结晶特征,可有效反映其炭化过程裂解机理。     

Nanocomposites of magnetic cobalt nanoparticles and cellulose

Polymeric matrices with stabilized metallic nanoparticles constitute an important class of nanostructured materials, because polymer technology allows fabrication of components with various electronic, magnetic and mechanical properties. The porous cellulose matrix has been shown to be a useful support material for platinum, palladium, silver, copper and nickel nanoparticles. In the present study, nanosized cobalt particles with enhanced magnetic properties were made by chemical reduction within a microcrystalline cellulose (MCC) matrix. Two different chemical reducers, NaBH₄ and NaH₂PO₂, were used, and the so-formed nanoparticles were characterized with X-ray absorption spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These experimental techniques were used to gain insight into the effect of different synthesis routes on structural properties of the nanoparticles. Magnetic properties of the nanoparticles were studied using a vibrating sample magnetometer. Particles made via the NaBH₄ reduction were amorphous Co-B or Co oxide composites with diminished ferromagnetic behaviour and particles made via the NaH₂PO₂ reduction were well-ordered ferromagnetic hcp cobalt nanocrystals.     

氢化硅薄膜的晶化机理研究

采用PECVD工艺制备了非晶,微晶和多形硅薄膜,研究了电极间热梯度对氢化硅薄膜结构的影响.根据拉曼光谱得到了微晶硅的晶化率,并在椭偏仪中用BEMA模型验证了其准确性.根据理论模型研究了热梯度对微晶和多形硅薄膜沉积机理的影响.研究薄膜厚度对晶化率的影响表明微晶薄膜底端和表面之间存在晶化梯度,而多形硅薄膜中无晶化梯度存在.采用Tauc-Lorentz模型拟合得到薄膜的结构参数表明非晶硅薄膜的致密度和有序度低,而多形硅和微晶硅薄膜的有序度、致密度相近,且明显高于非晶硅. 关键词： 氢化硅 晶化 热梯度 结构