Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

Molecular properties of hemicelluloses located in the surface and inner layers of hardwood and softwood pulps

The molecular properties of hemicelluloses located in the surface and inner layers of fibers present in hardwood and softwood pulps, together with the effects of different bleaching processes on these properties, have been investigated in this study. In order to separate the hemicelluloses located in these two layers, fibers were subjected to mechanical peeling and then separated by filtration into surface (filtrate) and inner layer materials. The materials thus obtained were characterized with respect to their polysaccharide compositions and uronic acid contents. The molar mass parameters of the hemicelluloses (extracted by alkali) were determined by employing size-exclusion chromatography in combination with off-line MALDI mass spectrometry. For all of the pulps examined, the relative content of xylan was found to be greater in the surface layer of the fiber than in the corresponding inner layer. The xylan polymers of the surface layer exhibited higher molar masses and lower frequencies of uronic acid side groups than did the xylans in the inner fiber layer. In connection with ozone treatment, hexenuronic acid residues in the surface layer xylan were removed to a greater extent than in the case of the inner layers, indicating a gradient for the reaction with ozone across the fiber wall. The xylan polymer remaining on the surface of the softwood pulps after completion of the chlorine dioxide bleaching process was predominantly uncharged.     

Der Einfluß des Zusatzes von Hemicellulosen auf die Fließeigenschaften von Weizenmehlteig

The water adsorption capacity of a dough consisting of wheat flour was increased linearly by the addition of water-insoluble hemicelluloses (xylane, mannane etc.) extracted from beech-wood pulp using soda lye (a by-product of viscose fiber production). The investigation of this finding by viscosity measurements revealed two reasons for the higher water uptake: 1) a higher kneading resistance of the dough, and 2) a gel-regeneration of the kneaded dough during the dough-rest.

Herrn Prof. Dr. Josef Schurz zum 60. Geburtstag gewidmet.     

Adsorption performance and stability of the modified straws and their extracts of cellulose,lignin, and hemicellulose for Pb2+: pH effect

Adsorption performance and stability of the carboxyl groups modified straws and their extracts of cellulose, lignin, and hemicellulose for Pb²⁺ were investigated, and the optimum pH range for Pb²⁺ adsorption was determined by considering both the stability and capacity of the modified biosorbents for the first time. Results showed that adsorption capacity and stability of the straws and extracts were both improved significantly after modification. Adsorption capacities of the modified straws and extracts followed the order: modified hemicellulose > modified lignin, modified straw > modified cellulose, while stability of them followed the reverse order. In the optimum pH range from 4.0 to 5.0, modified rape and cotton straw showed better stability than the modified maize straw, and total organic carbon (TOC) values determined from the two modified straws and extracts were lower than 5.0 mg L⁻¹ even after adsorption for 30 days, which reached the drinking water standard in China.     

Application of a depolymerization model for predicting thermochemical hydrolysis of hemicellulose

Literature data were collected and analyzed to guide selection of conditions for pretreatment by dilute acid and water-only hemicellulose hydrolysis, and the severity parameter was used to relate performance of different studies on a consistent basis and define attractive operating conditions. Experiments were then run to confirm performance with corn stover. Although substantially better hemicellulose sugar yields are observed when acid is added, costs would be reduced and processing operations simplified if less acid could be used while maintaining good yields, and understanding the relationship between operating conditions and yields would be invaluable to realizing this goal. However, existing models seldom include the oligomeric intermediates prevalent at lower acid levels, and the few studies that include such species do not account for the distribution of chain lengths during reaction. Therefore, the polymeric nature of hemicellulose was integrated into a kinetic model often used to describe the decomposition of synthetic polymers with the assumption that hemicellulose linkages are randomly broken during hydrolysis. Predictions of monomer yields were generally consistent with our pretreatment data, data reported in the literature, and predictions of other models, but the model tended to overpredict oligomer yields. These differences need to be resolved by gathering additional data and improving the model.     

Cellulose crystallinity and ordering of hemicelluloses in pine and birch pulps as revealed by solid-state NMR spectroscopic methods

Solid-state ¹³C NMR spectroscopy was used to determine the degree of cellulose crystallinity (CrI) in kraft, flow-through kraft and polysulphide–anthraquinone (PS–AQ) pulps of pine and birch containing various amounts of hemicelluloses. The applicability of acid hydrolysis and the purely spectroscopic proton spin-relaxation based spectral edition (PSRE) method to remove the interfering hemicellulose signals prior to the determination of CrI were also compared. For softwood pulps, the spectroscopic removal of hemicelluloses by PSRE was found to be more efficient than the removal of hemicelluloses by acid hydrolysis. In addition to that, the PSRE method also provides information on the associations between cellulose and hemicelluloses. On the basis of the incomplete removal of xylan from the cellulose subspectra by PSRE, the deposition of xylan on cellulose fibrils and therefore an ordered ultrastructure of xylan in birch pulps was suggested. The ordered structure of xylan in birch pulps was also supported by the observed change of xylan conformation after regeneration. Similarly, glucomannan in pine pulps may have an ordered structure. According to the ¹³C CPMAS measurements conducted after acid hydrolysis, the degree of cellulose crystallinity was found to be slightly lower in birch pulps than in the pine pulps. Any significant differences in cellulose crystallinity were not found between the pulps obtained by the various pulping methods. Only in pine PS–AQ pulp, the degree of cellulose crystallinity may be slightly lower than in the kraft pulps containing less hemicelluloses.     

The use of steamed hemicellulose as substrate in microbial conversions

The suitability of acid- and enzymatically hydrolyzed birch hemicellulose as biotechnical raw material was studied usingCluconobacter oxydans, Fusarium oxysporum, andCandida utilis for production of xylonic acid, ethanol, and SCP, respectively. The fermentabilities of both hydrolyzates were rather similar and inhibition was evident in all cases at xylose concentrations of 257–30 g/L and higher. Potential identified fermentation inhibitors were the lignin-derived compounds sinapyl alcohol, coniferyl alcohol, vanillin, and syringaldehyde and the sugar degradation products furfural and 5-hydroxymethyl furfural.     

Brazilian integrated sugarcane-soybean biorefinery: Trends and opportunities

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Glow discharge electrolysis plasma initiated synthesis of upconversion luminescent and temperature sensitive multifunctional hydrogel

In the present work, a novel multifunctional hydrogel that simultaneously possesses strong upconversion luminescence (UL) and temperature responsibility was fabricated based on the crosslinking of hemicellulose and ricinoleic acid capped NaYF₄:Yb/Er in the presence of Poly (N-isopropylacrylamide) (PNIPAM) and polyacrylamide (PAAm) aqueous solution by using glow discharge electrolysis plasma (GDEP) initiated technique. Its structure and properties were characterized by wide angle X-ray diffraction, FT-IR spectra, scanning electron microscopy, transmission electron microscope and fluorescence spectra. The obtained hydrogel exhibited reversibly temperature-dependent UL and highly enhanced sensibility. The luminescence intensity and transmittance of hydrogel showed a sharp decrease in the range of 32–35°C. Furthermore, the luminescence intensity of hydrogel was almost not weakened after five heating-cooling cycles, which may allow their use in remote control thermosensitive switch.     

新型半纤维素基磁性水凝胶的制备及性能

采用H₂O₂-Vc氧化还原体系引发半纤维素衍生物,以表面修饰的Fe₃O₄粒子作为磁性组分,利用接枝共聚方法制备了新型半纤维素基磁性水凝胶. 分别用傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)对水凝胶的结构及形貌进行了表征,利用X射线衍射(XRD)和振动样品磁强计(VSM)对水凝胶的晶型结构及磁性能进行了分析,发现Fe₃O₄粒子均匀分散在凝胶网络中,半纤维素基磁性水凝胶表现出良好的顺磁性. 考察了丙烯酸/半纤维素比例、Fe₃O₄粒子含量及交联剂用量对水凝胶溶胀性能的影响,并探讨了该水凝胶的溶胀机理,它在pH 8 缓冲溶液中的溶胀较好符合Fickian 和Schott 动力学模型. 通过SEM和溶胀性能分析表明,随着pH值的升高水凝胶的孔径增大,水凝胶的溶胀率逐渐增大. 制备的水凝胶被用于溶菌酶吸附研究,结果表明磁性凝胶的吸附量大于非磁性水凝胶,水凝胶的吸附行为符合Freundlich 和Temkin 等温模型.