Nitrobenzene oxidation of lignins from several plants of the family Gramineae

It was found based on results from alkaline nitrobenzene oxidation of natural and isolated dioxane lignins from several plants of the family Gramineae such as rice husks, rice straw, and corn and sorghum stems that the studied lignins consisted of three types of structural units with the predominance of guaiacyl structures.     

A study of the polysaccharides,hydrolysates, and sulfuric-acid lignin of cottonplant stems

A comparative investigation of the acid hydrolysis of the guza-paya [stems and bolls] and seed husks of the cotton plant has shown that the hydrolysates differ in their quantitative levels of monosaccharides, but in the pentose hydrolysates xylose predominates in both cases. The extracts after the preliminary enrichment of the raw material contain a large amount of xylose. The sulfuric-acid lignin obtained from the guza-paya contains a far smaller amount of unhydrolyzed polysaccharide and a larger amount of functional groups than the lignin from the husks.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 48–52, January–February, 1987.     

Composition of Inorganic Components of Oat Husks and Products of Their Chemical and Enzymatic Transformation

Samples of ash prepared from oat husks and products of their chemical and enzymatic processing in the bacterial nanocellulose production cycle were studied. Their elemental composition and content of the main substance, silicon dioxide, were determined, and the IR spectra and X-ray diffraction patterns were taken. The purest silica was prepared from the dry residue after enzymatic hydrolysis of the product of nitric acid treatment of oat husks, which allows comprehensive use of organic and inorganic components of the vegetable raw material.     

Surface Modification of Rice Husk Ash by Ethanol-assisted Milling to Reinforce the Properties of Natural Rubber/Butadiene Rubber Composites

Rice husk ash(RHA), obtained by pyrolysis of rice husks, can be used as a potential reinforcing filler for rubber composites. In this work, ball milling in ethanol(ethanol-assisted milling) was used to hydroxylate the surface of RHA, promoting the graft modification of bis-(γ-triethoxysilylpropyl)-tetrasulfide(Si69). The obtained modified RHA(RHA-EM-Si69) was filled into the natural rubber/butadiene rubber(NR/BR) composites, and the filler-rubber interactions were enhanced. In consequence, RHA-EM-Si69 filled NR/BR composites showed overall improvement in the mechanical properties compared with RHA filled NR/BR composites. The tear strength increased from 13.37 kN/m to 34.71 kN/m, and the tensile strength increased from 1.84 MPa to 7.75 MPa. Carbon black(N774) was also used for comparison under the same conditions. This method provides a potential for promoting the value of RHA in rubber industry.     

不同烟草生物质热解释放致香物质的研究

采用烟叶和烟梗为原料,使用热裂解气相色谱法对烟草的燃烧时间、燃烧温度进行控制,精确模拟实际烟草致香物质释放环境,精确捕获、并半定量物质,从而在实验室模拟、分析、研究烟草燃烧物中致香物质的组成和特点。研究分别考察了两种生物质在500℃、550℃下释放的致香物质组成。结果表明,烟梗、烟叶中元素组成中硫、氮两种元素含量低,而C/H比值两种烟草生物质均较高。两个热解温度下烟叶的热解产物中致香物质的含量均明显高于烟梗。升高热解温度均有利于获得更高相对含量的热解成分。烟叶热解产物中烯烃类物质相对含量比烟梗中多,而烟梗热解产物中酚类物质含量比烟叶中多。提高热解温度有利于酮类致香物质含量产生。     

Thermal degradation of rice husks on a pilot plant

This study is an attempt to establish the possibilities to obtain black rice husk ash (BRHA) and white rice husk ash (WRHA) via pyrolysis of wasted raw rice husks in a pilot plant fluidized-bed reactor at different conditions. The process course auto thermally, without outer fuel. The released heat may be used for steam obtaining or drying. The solid products obtained (BRHA or WRHA) are characterized using X-ray diffraction patterns, thermal analysis, and low temperature nitrogen adsorption. Using batch adsorption technique, the kinetics was studied and the adsorption capacities of crude oil and diesel fuel at different temperatures as well as some hydrocarbons at 298?K onto BRHA and WRHA are determined. It was established that BRHA have been higher adsorption capacity than WRHA. At a given temperature, BRHA sorbed more crude oil than diesel fuel. The results obtained showed that the material studied has high adsorption capacity and low cost and may successfully be used as an effective adsorbent to cleanup of bilge water and spills of oil and oil products in water basins. Because the saturated BRHA with crude oil, diesel fuel or different hydrocarbons are characterized with high calorific, they can be burnt in incinerators, industrial ovens or steam generators. By this way, we attain not only ecological but also economical effect.     

Cleavage by sodium in liquid ammonia of kenaf lignins and the biological activity of the cleavage products

The natural lignin of kenaf stems and fractions of the dioxane lignin of kenaf stems isolated previously were cleaved by sodium in liquid ammonia in order to study their structure. It was established that the kenaf lignins consist of three types of structural units: p-coumaryl, guaiacyl, and syringyl, with a predominance of the guaiacyl types. An antioxidation activity of the monomeric products of the degradation of the kenaf lignins has been found.     

Effects of the pyrolysis process on the oil sorption capacity of rice husk

Fixed bed slow pyrolysis experiments on rice husks were carried out in order to determine the effect of pyrolysis temperature upon: porous structure; surface morphology; phase composition; total amount, nature and distribution of the volatile compounds finely dispersed on the solid pyrolysis residues. The pyrolysis experiments were performed within the temperature range 250–700 °C. The sorption capacity of pyrolyzed rice husks for crude oil was determined. The results indicate that the increase in oil sorption capacity of rice husks after pyrolysis is the result of mutual influence of the above mentioned parameters. It was established that the oil sorption capacity was more strongly influenced by the porous structure of the adsorbents than by their phase composition and by the nature and amount of finely dispersed fluids. For achieving the purpose that was set in advance, the capabilities of: scanning electron microscopy, mercury porosimetry, Brunauer–Emmett–Teller method, Fourier transform infrared spectroscopy, gas-chromatography/mass spectrometric analysis, extraction and gravimetric analysis were used.     

Anionic graft polymerization of lithiated poly(2,6-dimethyl-1,4-phenylene ether)

Lithiated poly(2,6-dimethyl-1,4-phenylene ether) has been used as an initiator for the graft polymerization of isoprene, methyl methacrylate, hexamethylcyclotrisiloxane, and phenyl isocyanate with the use of toluene and tetrahydrofuran as solvents. The products were examined by gel-permeation chromatography for evidence of homopolymerization and graft polymerization. The composition of the graft copolymers was determined by NMR, and for isoprene and hexamethylcyclotrisiloxane, termination by trialkylchlorosilanes enabled chain lengths to be determined by NMR. The use of toluene gave rise to some homopolymerization, but with tetrahydrofuran, only hexamethylcyclotrisiloxane gave homopolymer. In all cases, graft copolymers were formed. With isoprene and methyl methacrylate, soluble graft copolymers were formed in good yield. In the former case approximately 60% 3,4 and 40% 1,4 addition was found. In the latter case 1,1-diphenylethylene was used to reduce crosslinking, in its absence, methyl methacrylate gave only crosslinked gels in tetrahydrofuran. Hexamethylcyclotrisiloxane added only one molecule per lithium on the polymer, the remainder giving homopolymer. Phenyl isocyanate gave some soluble graft copolymer in toluene, but only crosslinked products were obtained when tetrahydrofuran was used as reaction solvent.     

Depolymerization of xylan-derived products in an enzymatic membrane reactor

Rice husks were subjected to aqueous processing to obtain liquors containing xylan-derived products, which were assayed for composition. Liquors were diafiltered using 1 kDa ceramic membrane for purification purposes, and the retentate was concentrated using the same membrane. The molecular weight distribution of xylan-derived products in concentrated liquors was assayed by gel permeation chromatography. In order to achieve the one-step conversion of soluble, high molecular weight xylan-derived products into low molecular weight arabino-xylooligosaccharides (AXOS) and the recovery of low molecular weight AXOS, concentrated liquors were treated in a continuous enzymatic membrane reactor (EMR) with a commercial endoxylanase (Shearzyme 2X). Two operational modes were studied: in the first one, both enzymatic reaction and membrane operation began at the same time, whereas in the second case, permeation started when the reaction achieved a given conversion. Both operational modes are compared in terms of productivity.     

Identification of chemical ingredients of peanut stems and leaves extracts using UPLC‐QTOF‐MS coupled with novel informatics UNIFI platform

Peanut stems and leaves have been used traditionally as both herbal medicines and special food in Asia. In this study, the main functional compounds of peanut stems and leaves extracts were identified using UPLC separation coupled to high resolution mass spectrometry (QTOF‐MS), and a traditional medicine library. Three different extraction solvents (ethyl acetate, petroleum ether and n‐butanol) were evaluated to prepare the extracts of peanut stems and leaves. A total of 283 chemical compounds were identified in peanut stems and leaves extracts, of which 207 compounds are tentatively new identifications in Genus Arachis. The integration of data acquisition and processing with the traditional medicine library provides a simple, efficient process to effectively facilitate the identification of chemical ingredients in complex natural product extracts. The integrated workflow for separation, detection and identification of functional compounds in natural products using UPLC/QTOF‐MS greatly improves productivity for development of traditional herbal medicines. Copyright © 2016 John Wiley & Sons, Ltd.     

Development of a bionematicide with Paecilomyces lilacinus to control Meloidogyne incognita

Root-knot disease caused by Meloidogyne incognita is a matter of grave concern because it affects several economically important crop plants. The use of solid-state fermentation (SSF) may help to elaborate efficient formulations with fungi to be employed in the biologic control of nematodes. Attempts were made to select low-cost substrates for spore production of a strain of Paecilomyces lilacinus with known nematicide capacity. Coffee husks, cassava bagasse, and defatted soybean cake were utilized as substrates, and sugarcane bagasse was used as support. Fermentations were carried out in flasks covered with filter paper at 28°C for 10 d. The products obtained by SSF were evaluated for their nematicide activity in pot experiments containing one seedling of the plant Coleus inoculated with the nematode M. incognita. The plants were evaluated 2 mo after inoculation. Fermented products showed a reduction in the number of nematodes. The best results were obtained with defatted soybean cake, which showed almost 100% reduction in the number of nematodes; the reduction with coffee husk was 80% and with cassava bagasse was about 60%.     

Lignin of the fine-fibered cotton plant of variety S-6030 affected by fusarial wilt. II

A comparative study of the products of cleavage by sodium in liquid ammonia of the dioxane lignins (DLAs) from healthy and fusarial-wilt-affected stems of the fine-fibered cotton plant of variety S-6030 and a study of the PMR spectra of both lignins has shown that the DLA from the healthy stems is more highly condensed than the DLA of the stems affected by wilt. The main structures of DNA wilt are of the guaiacyl type. In the DLA from the affected stems, the amount of p-coumaryl structures had increased, which confirms the demethylating action of fusarial wilt on cotton-plant lignin.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 364–366, May–June, 1986.     

HIPS／MA接技共聚物对HIPS／PA1010共混体系的增容

制备了高抗冲聚苯乙烯和马来酸酐的接枝共聚物，利用红外光谱，电子能谱和动态力学谱对产物的结构进行了表征，并通过滴定法测定了接枝物中马来酸酐的含量。结果表明马来酸酐接技到了高抗冲聚苯乙烯中顺丁橡胶的分子链上，接技率为４．７％。研究了该接枝共聚物对ＰＡ１０１０／ＨＩＰＳ共混物的增容作用。电镜照片显示，随着共聚物中接枝物含量的增加，分散相相区尺寸明显减小，说明增容效果显著。测定了共混体系的拉伸行为，研究了     

Characterization of rice husks and the products of its thermal degradation in air or nitrogen atmosphere

Rice husk is a by-product of rice milling process and are a major waste product of the agricultural industry. They have now become a great source as a raw biomass material for manufacturing value-added silicon composite products, including silicon carbide, silicon nitride, silicon tetrachloride, pure silicon, zeolite, fillers of rubber and plastic composites, adsorbent and support of catalysts. The bulk and true densities of raw rice husk with different moisture and sizes were determined. The rice husk was subjected to pyrolysis in fluidized-bed reactor in air or nitrogen atmosphere. The products obtained were characterized by thermogravimetric and X-ray powder analysis, IR-spectroscopy, scanning electron microscopy and nitrogen adsorption at 77 K. The specific surface area of the products is comparable with this of γ-Al₂O₃. The kinetics of H₂SeO₃ adsorption out of aqueous solutions at 298 K was studied. The adsorption capacity of white rice husks ash was found to be higher than that of black rice husk ash and the adsorption kinetics obeyed the second order kinetic equation.     

超高效液相色谱-四极杆串联飞行时间质谱分析黄酮类化合物及小毛茛茎叶的成分

为了探索液相色谱-质谱联用(LC-MS)技术在快速识别中药及天然产物成分中的应用,以黄酮对照品为研究前体,药用植物小毛茛为研究对象,采用超高效液相色谱/二极管阵列检测器-电喷雾四极杆串联飞行时间质谱(UPLC/DAD-ESI/Q-TOF MS)分析了黄酮类化合物同系物及同分异构体的色谱、质谱特性。结果显示:黄酮氧苷和黄酮碳苷的紫外吸收光谱及二级质谱具有显著性差异,糖苷化位置同保留时间、二级质谱碎片及相对丰度具有相关性。将该方法应用于小毛茛茎叶醇提液的分析,结合其酸水解液的分析,解析了22个黄酮醇糖苷和3个苷元。方法简便,具有可操作性。     

Use of compatibilizers in polymer blends

Among the different ways of recycling plastic wastes, one of the techniques used consists in processing these products without any preliminary separation of the different plastic families. The bad performances of the obtained materials lead to the use of emulsifiers. The work described in this study concerns the synthesis of emulsifiers prepared by chemical modification of polymers with ozone. This reaction produces the formation of peroxides which are then used to initiate the grafting of comonomers. According to this method, we obtain graft copolymers usable as emulsifiers in the elaboration of polymer blends. Those graft copolymers prepared according to this method improve mechanical performances of polymer blends.     

Cleavage by sodium in liquid ammonia of kenaf lignins and the biological activity of the cleavage products

The natural lignin of kenaf stems and fractions of the dioxane lignin of kenaf stems isolated previously were cleaved by sodium in liquid ammonia in order to study their structure. It was established that the kenaf lignins consist of three types of structural units: p-coumaryl, guaiacyl, and syringyl, with a predominance of the guaiacyl types. An antioxidation activity of the monomeric products of the degradation of the kenaf lignins has been found.Institute of the Chemistry of Plant Substances of the Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 738–742, September–October, 1987.     

Use of modified rice husks as a natural solid adsorbent of trace metals: characterisation and development of an on-line preconcentration system for cadmium and lead determination by FAAS

The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l⁻¹ NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (2⁴) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min⁻¹ preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent), the system achieved a detection limit of 1.14 μg l⁻¹ and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min⁻¹ preconcentration flow rate, 300 μl elution volume and 1.0 mol l⁻¹ HNO₃ solution as eluent) from which a detection limit of 14.1 μg l⁻¹ and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used.     

A kinetic study on grafting of maleic anhydride onto a thermoplastic elastomer

Maleation of a thermoplastic elastomer, styrene-[ethylene-butylene]-styrene (SEBS) triblock copolymer, was carried out by a solution grafting reaction with maleic anhydride initiated by dicumyl peroxide. The reaction products from the graft reaction in xylene, commonly chosen as the solvent for maleation graft reactions, were identified using liquid chromatograph (LC), IR, and ¹³C-NMR. Side products from the graft reaction were identified by the LC analysis and, it was concluded that xylene affected the graft reaction through its active methyl groups. Reaction mechanisms were investigated by performing free radical kinetics analysis. The reaction orders and the apparent rate constant were estimated. It was concluded that a proper choice of the solvent might favor better graft efficiency. © 1993 John Wiley & Sons, Inc.