Adsorption of heavy metals by a porous bioadsorbent from lignocellulosic biomass reconstructed in an ionic liquid

A novel porous bioadsorbent for metal ion binding (Pd(2+) and Cd(2+)) was successfully prepared from lignocellulosic biomass in ionic liquid by homogeneous succinoylation and sequent chemical cross-linking. The morphology of the bioadsorbent and the interaction between bioadsorbent and metal ions was revealed by scanning electron microscopy and Fourier transform infrared spectroscopy. Results showed that the adsorption mechanism of the bioadsorbent was an ion exchange. A lower dose of cross-linker or higher carboxyl content increased the adsorption capacities of Pd(2+) and Cd(2+). The adsorption capacities of Pd(2+) and Cd(2+) remarkably increased as the pH of metal ion solutions increased. The pores in the bioadsorbent greatly favored the diffusion and adsorption of metal ions, and the adsorption equilibrium time was about 50 min. The adsorption of metal ions could be well explained by the Langmuir model, and the maximum adsorption capacities of Pd(2+) and Cd(2+) were 381.7 and 278.6 mg/g.     

Antioxidant and antimicrobial effects of extracts from hydrolysates of lignocellulosic materials

The antioxidant and antimicrobial activities of ethyl acetate extracts obtained from acid hydrolysates of several lignocellulosic materials (Eucalyptus globulus wood, barley bran, corn cobs, and corn leaves) were evaluated. The minimum inhibitory and bactericide concentrations (MIC and MBC, respectively) were determined against a selection of bacteria and yeasts. Extracts from Eucalyptus wood hydrolysates were the most active for inhibiting bacteria and yeast growth, with MIC in the range of 10(2)--5 x 10(3) microg/mL and MBC in the range of 10(3)--0(5) microg/mL. Bacteriogenic and bacteriostatic activities of extracts from Eucalyptus wood and barley bran acid hydrolysates were slightly higher than those of corn cobs and leaves. Both the radical scavenging capacity and the inhibition of the beta-carotene bleaching caused by extracts were determined and compared with those of synthetic antioxidants. The antioxidant activity of extracts increased with their concentrations in the media, the stronger properties corresponding to those obtained from Eucalyptus wood hydrolysates.     

Detection of pork and lard as adulterants in processed meat: liquid chromatographic analysis of derivatized triglycerides

A new method is described for detection of pork and lard as adulterants in processed beef and mutton mixtures. The unsaturated triglycerides in the fat are ozonized and then derivatized. The mixture of derivatized and saturated triglycerides is analyzed by liquid chromatography using a reverse-phase column and a UV detector. Pork fat has larger amounts of triglyceride containing saturated fatty acid at the C-2 position than does the fat of other meat. The ratio of triglyceride containing saturated fatty acid vs triglyceride containing unsaturated fatty acid at the same (C-2) position (SSU/SUS) in a sample is compared with those of pure meats. The presence of pork in the sample causes the ratio to increase compared with ratios for pure beef or mutton. The increase in the SSU/SUS ratio is significant for the addition of 1% pork in beef. In the case of mutton, the addition of 3% pork causes a noticeable change. The method is reliable and is also applicable to samples containing only fat. Processing (heating or cooking) does not affect the ratios.     

超声波辅助离子液体组合物直接制备微藻生物柴油

微藻生物柴油能够解决目前植物原料生物柴油面临的耕地不足、气候变化影响产量并引起农作物价格上涨等突出问题,但传统微藻生物柴油生产过程能源与化学品消耗大,将微藻油脂的提取-酯交换耦合成一个单元,具有较大应用潜力。该研究采用小球藻、甲醇为原料,离子液体组合物作为提取剂、催化剂,超声波辅助催化微藻直接提取-酯交换制备生物柴油。考察超声波频率、超声波功率、离子液体类型、离子液体用量、反应温度、反应时间、醇油摩尔比等因素对酯交换率的影响,并与传统水浴加热机械搅拌法比较,结果表明,超声波和离子液体对生物柴油的制备有协同促进作用,离子液体具有催化、提取与增溶的作用,能较好地消除醇油界面接触,超声波的引入强化了传质传热过程,与传统加热方式水浴加热机械搅拌法相比,可以缩短酯交换反应的时间,降低反应温度,减少离子液体、甲醇的用量。离子液体[BMIM][HCOO]为提取剂,微藻油脂提取率最高;酸性离子液体催化效果明显高于碱性离子液体,离子液体[SO3H- BMIM][HSO4]为催化剂,微藻油脂转化率最高。当超声波功率240W,频率28kHz,甲醇用量和藻粉质量比为6∶1,离子液体组合物和藻粉质量比为5∶1,离子液体[BMIM][HCOO]与[SO3H-BMIM][HSO4]体积比为12∶1,反应温度为50 ℃,超声反应时间50 min条件下,生物柴油的转化率可达69.6%。该方法将离子液体溶解提取性能、催化性能及超声波的空化效应相结合,将油脂的提取与油脂的转酯化合二为一,不需先从微藻粉中提取油脂,缩短了工艺,能够实现含油微藻到生物柴油的一步转化。     

棉秆纤维素在离子液体中溶解及分离的工艺参数

离子液体是纤维素的新型绿色溶剂,是可以进行纤维素均相反应的非衍生化溶剂。为解决纤维素生产加工过程复杂且污染严重问题,试验探讨了棉秆纤维素在离子液体溴代N-乙基吡啶中的溶解性能,采用红外光谱等手段对棉秆纤维素在离子液体中溶解和再生前后的结构变化进行了分析,并探讨了离子液体的回收。结果表明,未经活化的棉秆纤维素可直接溶解于离子液体而不发生其他衍生化反应。溶解的较优条件是：溶解温度为120℃,分离方式为冷至室温加冷水,溶解时间为30 min,水液比为 1∶2;棉秆所得水洗不溶物质量均可稳定在0.41 g左右,离子液体可以循环使用多次且活性没有明显降低。     

Preparation and characterization of phthalated cellulose derivatives in room-temperature ionic liquid without catalysts

Homogeneous modification of cellulose, isolated with 10% KOH from delignified sugarcane bagasse, was performed in room-temperature ionic liquid 1-allyl-3-methylinidazolium chloride with phthalic anhydride in the absence of catalyst. The results showed the degree of substitution of phthalated cellulosic derivatives, ranging from 0.10 to 0.73, increased with the increment of reaction temperature, reaction time, and the molar ratio of phthalic anhydride/anhydroglucose units in cellulose under the conditions given. The products were characterized by FT-IR and solid-state CP/MAS 13C NMR spectroscopy as well as thermal analysis, and the results revealed that the phthalation reaction at C-6, C-2, and C-3 positions of the cellulose all occurred. The thermal stability of the phthalated cellulose was found to decrease upon chemical modification. However, this thermal stability of the phthalated cellulose over 200 degrees C is rather satisfactory.     

Influence of glycosidic linkages and molecular weight on the fermentation of maltose-based oligosaccharides by human gut bacteria

A structure-function study was carried out to increase knowledge of how glycosidic linkages and molecular weights of carbohydrates contribute toward the selectivity of fermentation by gut bacteria. Oligosaccharides with maltose as the common carbohydrate source were used. Potentially prebiotic alternansucrase and dextransucrase maltose acceptor products were synthesized and separated into different molecular weights using a Bio-gel P2 column. These fractions were characterized by matrix-assisted laser desorption/ionization time-of-flight. Nonprebiotic maltooligosaccharides with degrees of polymerization (DP) from three to seven were commercially obtained for comparison. Growth selectivity of fecal bacteria on these oligosaccharides was studied using an anaerobic in vitro fermentation method. In general, carbohydrates of DP3 showed the highest selectivity towards bifidobacteria; however, oligosaccharides with a higher molecular weight (DP6-DP7) also resulted in a selective fermentation. Oligosaccharides with DPs above seven did not promote the growth of "beneficial" bacteria. The knowledge of how specific structures modify the gut microflora could help to find new prebiotic oligosaccharides.     

木质纤维素生物质厌氧发酵沼渣热化学转化利用研究进展

厌氧发酵技术可以将木质纤维素生物质转化为沼气,并伴随副产物沼渣产生。随着大型沼气工程的发展,大量沼渣排放已成为厌氧发酵技术推广应用的主要限制因素之一,亟须对沼渣进行快速有效处理。其中,沼渣的热化学转化利用符合大型沼气工程发展趋势,是当前的研究热点之一。首先分析木质纤维素沼渣的原料特性与热化学转化潜力;再对沼渣成型燃料、热解以及水热炭化等领域的研究现状进行分析,着重对沼渣衍生产物特性、热化学转化过程中存在的问题以及与厌氧发酵结合的潜在优势等方面进行讨论;最后,对沼渣热化学转化的发展趋势进行了展望。木质纤维素生物质厌氧发酵与沼渣热化学转化结合的应用模式研究对大型沼气工程推广应用具有一定的科学意义。     

Molecular affinity and permeability of different molecular weight chitosan membranes

Membranes were prepared from chitosan with different molecular weights by a casting method. The molecular affinity and permeability of the membranes for sodium chloride, glucose, tyrosine, and bovine serum protein were measured at 4 degrees C and pH 7. The molecular permeability of the chitosan membranes was inversely related to molecular weight. All prepared membranes showed a molecular affinity to bovine serum protein. The higher the molecular weight of chitosan membrane, the higher the affinity and the lower permeability of the membrane to bovine serum protein.     

Stability and emulsifying capacity of biosurfactants obtained from lignocellulosic sources using Lactobacillus pentosus

Lactobacillus pentosus grown on sugars from agricultural residues produces biosurfactants with emulsifying properties that could facilitate the bioremediation of hydrocarbon contaminated sites. The biosurfactans obtained after growing L. pentosus cells on distilled grape marc hydrolyzates gave values of relative emulsion volume (EV) close to 50%, being stable after 72 h when gasoline or kerosene were employed. These EV values were higher than those achieved using commercial surfactin (14.1% for gasoline and 27.2% for kerosene). Moreover, assays carried out with kerosene showed that L. pentosus produced biosurfactants from distilled grape marc hydrolyzates with the highest stabilizing capacity value (ES) to maintain the emulsion (99%) followed by biosurfactants produced from hazelnut shell hydrolyzates (97%). These data are comparable with those obtained using sodium dodecyl sulfate, SDS (87.7%), whereas surfactin only gave an ES value of 65.4%. Consequently, this work shows that utilization of low-cost feedstock agricultural residues as substrates for producing biosurfactants/bioemulsifiers is possible thus removing obstacles for the wide-scale industrial application of biosurfactants/bioemulsifiers.     

离子液体提取山楂绿原酸的工艺优化

绿原酸是许多植物中的活性成分,因其有显著的药理活性和生物活性而被广泛关注,选择合适的提取溶剂、提取方法和工艺参数是绿原酸得以进一步应用的重要环节。该文以离子液体为溶剂,采用超声辅助方法提取山楂中的绿原酸,首先选择离子液体种类,再通过单因素试验确定离子液体浓度、提取时间和固液比3个主要因素的参数,并用响应面法分析法优化提取工艺参数。结果表明,优化工艺为以离子液体1-乙基咪唑盐酸盐[EIm]Cl的水溶液为提取溶剂,当其浓度为1.19 mol/L,固液比为1∶19.67 g/mL,每次提取时间为42.83 min时,理论的绿原酸提取率为4 179.48μg/g,获得工艺参数的回归模型。验证试验绿原酸提取率为4 128.28μg/g,与模型符合很好。另外,因离子液体的价格昂贵、难降解和不可预知的毒性,进行了离子液体和目标物质的分离操作,在酸性条件下,以乙酸乙酯为反萃取剂萃取出绿原酸,其得率为提取液中质量分数的96.3%;离子液体通过减压蒸馏、在65℃烘干后循环使用,提取率达到第1次的92.96%。此外,试验考察了离子液体与普通溶剂比较,在提取率上和循环使用上具有明显优势,是一种高效、绿色萃取溶剂。     

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

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.     

Optimization of simultaneous saccharification and fermentation for the production of ethanol from lignocellulosic biomass

Simultaneous saccharification and fermentation (SSF) of alkaline hydrogen peroxide pretreated Antigonum leptopus (Linn) leaves to ethanol was optimized using cellulase from Trichoderma reesei QM-9414 (Celluclast from Novo) and Saccharomyces cerevisiae NRRL-Y-132 cells. Response surface methodology (RSM) and a three-level four-variable design were employed to evaluate the effects of SSF process variables such as cellulase concentration (20-100 FPU/g of substrate), substrate concentration (5-15% w/v), incubation time (24-72 h), and temperature (35-45 degrees C) on ethanol production efficiency. Cellulase and substrate concentrations were found to be the most significant variables. The optimum conditions arrived at are as follows: cellulase = 100 FPU/g of substrate, substrate = 15% (w/v), incubation time = 57.2 h, and temperature = 38.5 degrees C. At these conditions, the predicted ethanol yield was 3.02% (w/v) and the actual experimental value was 3.0% (w/v).     

酸性离子液体催化麦秸液化及其产物分析

为降低有机酸催化剂对设备的腐蚀,提高秸秆类生物质原料的利用率,该文以合成的1-甲基-3-(4-磺酸基丁基)咪唑硫酸氢盐离子液体为催化剂,乙醇为溶剂,考察小麦秸秆的液化过程,并对离子液体的结构进行傅里叶红外光谱和核磁共振表征,对液化后的残渣和液相产物进行傅里叶红外光谱、热重和气质联用分析。试验和表征结果表明:合成的1-甲基-3-(4-磺酸基丁基)咪唑硫酸氢盐离子液体对秸秆液化具有较优的催化性能,在反应温度为200℃、反应时间为60 min、离子液体用量为26%的条件下,液化率可达85.5%,同时乙酰丙酸乙酯的得率为9.97%,在液化产物中的相对百分含量为29.9%;液化产物中包含有醛、酮、酯、酸和酚类等含氧化合物,其中酚类化合物主要源于木质素的降解,其他化合物则主要源于半纤维素和纤维素的降解。研究结果为开发利用低腐蚀性环保型催化剂催化液化秸秆制备高品位化学品提供理论依据。     

pH memory of immobilized lipase for (+/-)-menthol resolution in ionic liquid

Magnetic DEAE-GMA-EDMA microspheres were prepared via suspension polymerization and used for the immobilization of Candida rugosa lipase by ion exchange. The effect of pH values on the immobilization of lipase was investigated. Resolution of (+/-)-menthol in the hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate was performed by immobilized lipase-catalyzed enantioselective esterification with propionic anhydride as acyl donor. The effects of pH condition at lipase immobilization on the conversion and enantioselectivity were investigated. As a result, pH memory of the immobilized lipase for catalyzing (+/-)-menthol resolution in the ionic liquid was observed. Better conversion and the best enantioselectivity were obtained with the immobilized lipase prepared at pH 5.0. Under the condition, (-)-menthyl propionate with enantiomeric excess of >90% was obtained. Moreover, the enantioselectivity of the immobilized lipase decreased gradually with increasing pH value.     

Pyrolysis-GC-MS analysis of the formation and degradation stages of charred residues from lignocellulosic biomass

The structural transformations undergone by lignocellulosic biomass (freeze-dried rye grass, Lolium rigidum) subjected to progressive isothermal heating (burning at 350 degrees C under oxidizing conditions for 30, 45, 60, 75, and 90 s) have been monitored by Curie-point pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). The pyrograms suggest that even charred residues after severe heating (carbon loss ca. 50%) still contain substantial concentrations of some resistant plant structural components. Several trends were observed when monitoring the relative concentrations of the different groups of pyrolysis compounds released during successive charring stages: (i) the tetrapyrrole moiety of chlorophylls is rapidly destroyed as indicated by the decreasing yields of pyrroles and pyrrolines, whereas the phytol backbone is comparatively more resistant, leading to phytadienes after dehydration and reduction; (ii) the increasing yields of imidazoles from progressively heated samples (maximum at 45 s stage) suggest accumulation of newly formed nitrogen-containing compounds that may survive natural fires; (iii) the lignin backbone shows a relative resistance, the yields of aromatic products pointing to progressive demethoxylation; and, (iv) a selective accumulation of recalcitrant alkyl material occurred, which is interpreted as the result of thermal condensation of hydrocarbons and fatty acids into macromolecular materials in the charred residue. In terms of the intensity of the isothermal heating, the yields of the different classes of alkyl compounds follow the order phytadienes < fatty acids < alkanes < wax esters < sterols.     

Production of chlamydospores and conidia by Trichoderma spp in liquid and solid growth media

Isolates of Trichoderma spp grew and produced chlamydospores as well as conidia in molasses-corn steep liquor (M-CSL), sucrose nitrate (SN), and glucose tartrate (GT) media. In M-SCL, isolates of T. hamatum, T. viride, and T. harzianum formed 10.4, 5.9 and 1.1 × 10⁸ chlamydospores g^?1 dry weight of mycelium. Fewer chlamydospores formed in SN and GT. Although T. harzianum formed the least number of chlamydospores, it produced the highest number of conidia in all three media. Molasses-corn steep liquor was superior to SN or GT in supporting development of both spore types. Spore production was not influenced by initial pH of the media or by continuous maintenance of the media at pH 4 or 7. Equal numbers of chlamydospores were formed in liquid media incubated in shake or static culture. Conidia formation, however, was stimulated in static culture. Chlamydospores and conidia of several naturally occurring isolates and induced biotypes of Trichoderma spp were abundantly produced on a variety of solid substrates moistened with liquid nutrients or water, preferably at pH 4. Bran, cornmeal, and peanut hull meal were better than eight other solid substrates for production of chlamydospores and conidia. A u.v.-induced, benomyl-resistant biotype of T. viride (T-1-R9) formed 22 × 10⁷ and 18 × 10⁸ chlamydospores and conidia, respectively, g^?1 of bran-SN. The ratio of conidia to chlamydospores was always greater in solid than liquid media. In solid media, 10 times more conidia than chlamydospores were formed, whereas in liquid only two or three times more were formed. Chlamydospores from liquid and solid fermentations were viable (ca 80%) and fresh chlamydospores germinated well (ca 75%) on nutrient agar. Although dried chlamydospores were viable, as determined with tetrazolium bromide, their germination on agar was poor (ca 8%).     

Reverse phase liquid chromatographic assay for calcium pantothenate in multivitamin preparations and raw materials

A reverse phase liquid chromatographic (LC) method has been developed for the assay of calcium pantothenate in commercial multivitamin tablet formulations and raw materials. The assay was validated according to the Pharmaceutical Manufacturers Association Quality Control HPLC Committee guidelines. The chromatographic system includes a C-18 column and a mobile phase consisting of 0.25M sodium phosphate buffer, pH 2.5, and acetonitrile (97 + 3 v/v). The column effluent is monitored by UV detection at 205 nm. The sample preparation involves only extraction in water followed by filtration. The method is stability-indicating with a detection limit of approximately 50 ng/mL of the calcium pantothenate in the samples. The system is linear from at least 0.02 to 0.10 mg/mL. The mean recovery of spiked placebos ranged from 98.7 to 99.8%. The within-day precision of the assay on finished products (N = 6) ranged from 0.3 to 2.0% CV. A system suitability criterion for resolution is based on the separation between calcium pantothenate and 2 closely eluting compounds, saccharin and a saccharin degradation product, 2-sulfamoylbenzoic acid.     

Lipase-catalyzed esterification of ferulic Acid with oleyl alcohol in ionic liquid/isooctane binary systems

Lipase-catalyzed synthesis of ferulic acid oleyl alcohol ester in an ionic liquid (IL)/isooctane system was investigated. Considerable bioconversion and volumetric productivity were achieved in inexpensive 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF(6)]) and 1-methyl-3-octylimidazolium hexafluorophosphate ([Omim][PF(6)]) mediated systems, and thus, the two types of ILs were selected for further optimization of variables. The results showed that, before reaching a maximum, the increase of ferulic acid concentration, temperature, or enzyme dosage led to an increase in volumetric productivity. Variations of the ratios of IL/isooctane and concentrations of oleyl alcohol also profoundly affected the volumetric productivity. To a higher extent, [Hmim][PF(6)]/isooctane and [Omim][PF(6)]/isooctane show similar reaction behaviors. Under the optimized reaction conditions (60 °C, 150 mg of Novozym 435 and 100 mg of molecular sieves), up to 48.50 mg/mL productivity of oleyl feruleate could be achieved for the [Hmim][PF(6)]/isooctane (0.5 mL/1.5 mL) system with a substrate concentration of ferulic acid of 0.08 mmol/mL and oleyl alcohol of 0.32 mmol; while an optimum volumetric productivity of 26.92 mg/mL was obtained for the [Omim][PF(6)]/ isooctane (0.5 mL/1.5 mL) system under a similar reaction condition other than the substrate concentrations of ferulic acid at 0.05 mmol/mL and oleyl alcohol at 0.20 mmol.     

Improved solvent extraction procedure and high-performance liquid chromatography-evaporative light-scattering detector method for analysis of polar lipids from dairy materials

A normal-phase high-performance liquid chromatography-evaporative light-scattering detector method employing dichloromethane, methanol, and acetic acid/triethylamine buffer as the mobile phase was developed for analysis of polar lipids (PLs). This method was applicable for analysis of PLs from both dairy materials and soy lecithin. All of the PLs of interest such as glycolipids, phospholipids, and sphingomyelin were well separated with a total run time of 22.5 min and without necessitating the removal of neutral lipids beforehand. Peak retention times were stable, and the method was reproducible. In this study, a modified method of using solvents for extraction of PLs from dairy matrices was also investigated. The modified method offered higher extraction efficiency, consumed less time, and in some cases saved solvent use.