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.     

Fractionation of bagasse into cellulose, hemicelluloses, and lignin with ionic liquid treatment followed by alkaline extraction

Lignocellulose materials are potentially valuable resources for transformation into biofuels and bioproducts. However, their complicated structures make it difficult to fractionate them into cellulose, hemicelluloses, and lignin, which limits their utilization and economical conversion into value-added products. This study proposes a novel and feasible fractionation method based on complete dissolution of bagasse in 1-butyl-3-methylimidazolium chloride ([C(4)mim]Cl) followed by precipitation in acetone/water (9:1, v/v) and extraction with 3% NaOH solution. The ionic liquid [C(4)mim]Cl was easily recycled after concentration and treatment with acetonitrile. (1)H NMR analysis confirmed that there was no obvious difference between the recycled [C(4)mim]Cl and fresh material. Bagasse was fractionated with this method to 36.78% cellulose, 26.04% hemicelluloses, and 10.51% lignin, accounting for 47.17 and 33.85% of the original polysaccharides and 54.62% of the original lignin, respectively. The physicochemical properties of the isolated fractions were characterized by chemical analysis, high-performance anion exchange chromatography (HPAEC), gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), and (1)H and 2D (13)C-(1)H correlation (HSQC) nuclear magnetic resonance spectroscopy. The results showed that the acetone-soluble lignin and alkaline lignin fractions had structures similar to those of milled wood lignin (MWL). The easy extraction of the noncellulose components from homogeneous bagasse solution and amorphous regenerated materials resulted in the relatively high purity of cellulosic fraction (>92%). The hemicellulosic fraction was mainly 4-O-methyl-D-glucuronoxylans with some α-L-arabinofuranosyl units substituted at C-2 and C-3.     

Detection of sialylated phosphorylated kappa-casein glycomacropeptide electrophoresed on polyacrylamide gels and cellulose acetate strips by the thiobarbituric acid and malachite green dye reactions

A 64 amino acid residue sialylated phosphorylated glycomacropeptide (GMP) from bovine sweet whey can be detected as a Coomassie blue-staining peptide by electrophoresis on sodium dodecyl sulfate (SDS)-polyacrylamide gels. There is, however, limited information available concerning detection of GMP as a sialylated phosphorylated compound. Samples of GMP were electrophoresed on SDS-polyacrylamide gels or cellulose acetate strips (CAS). Immediately following electrophoresis, fractions obtained by cutting gels or strips were subjected to sialic acid determination by the thiobarbituric acid reaction and phosphorus determination by the malachite green dye reaction. Both determinations were found to be sensitive enough to detect approximately 20 and 40 microg of GMP in CAS and SDS gels, respectively. Further studies demonstrated that sialylated phosphorylated GMP can be detected on either SDS gels or CAS loaded with whey products or whey-added margarine residues.     

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。     

纤维素超低酸水解产物的分析

基于木质纤维素类生物质水解为人类提供乙醇等能源、化工产品的重要性，该文以定量滤纸模拟生物质的主要组分－纤维素，以其超低酸水解试验得到的最佳工况下液体产物和固体残渣为研究对象，通过高效液相色谱(HPLC)结合KS-802糖柱对产物质中糖的种类进行了划分，以GC-MS对副产物进行定性，并通过扫描电镜(SEM)及热重和工业分析元素分析对固体残渣作了从表观到内部的研究，发现纤维素超低酸水解主要生成纤维四糖、三糖和二糖等低聚糖和葡萄糖及果糖，反应副产物有糠醛、羟甲基糠醛、乙酰丙酸及一些小分子酮、醛类和酸类极性化合物，水解残渣已完全改变了原始形貌，热裂解活性增强，残留物中碳和灰分含量有较大增加，最后根据分析结果探讨了纤维素超低酸水解的反应途径，为木质纤维素类生物质水解技术的规模化利用打下基础。     

Heteronuclear single-quantum coherence nuclear magnetic resonance (HSQC NMR) characterization of acetylated fir (Abies sachallnensis MAST) wood regenerated from ionic liquid

An ionic liquid, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), was used to dissolve Japanese fir (Abies sachallnensis MAST) wood. Milled woods prepared by planetary ball-milling for 8 h dissolved completely in [Bmim]Cl at 100 °C in 2 h. The dissolved woods were then subjected to in situ acetylation, and the fully acetylated woods were regenerated from [Bmim]Cl. (1)H-(13)C correlation heteronuclear single-quantum coherence (HSQC) nuclear magnetic resonance (NMR) experiments were successfully conducted with the acetylated woods in dimethyl sulfoxide (DMSO)-d(6). The acetylated lignin and polysaccharide signals dispersed reasonably well on the 2D spectra. Characterization of the NMR signals for the whole cell-wall components, including lignin, cellulose, and hemicelluloses, was achieved by comparison with isolated lignin and commercial cellulose and hemicelluloses (arabinoxylan, galactomannan, and glucomannan). The procedure used here is applicable for the characterization of cell-wall components in various plant biomasses.     

Liquid chromatographic determination of medroxyprogesterone acetate in tablets

A reverse-phase liquid chromatographic method is described for the assay of medroxyprogesterone acetate in tablets. An octadecylsilane (C18) column with a mobile phase of methanol-0.01M dibasic ammonium phosphate (80 + 20 v/v, pH 7.2 +/- 0.1) and photometric detection at 254 nm separates medroxyprogesterone acetate from excipients. Detector responses were linear to concentrations of medroxyprogesterone acetate over the range 50-150 micrograms/mL (r = 0.999). Mean recovery of medroxyprogesterone acetate added to tablet excipients was 100.8%. Mean assay results were 101.3% (n = 3). The assay results are comparable to those obtained by the compendial liquid chromatographic method.     

Predicting bioavailability of PAHs in soils to wheat roots with triolein-embedded cellulose acetate membranes and comparison with chemical extraction

Triolein-embedded cellulose acetate membrane (TECAM) was buried in 15 field-contaminated soils in parallel with the cultivation of wheat to predict bioavailability of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene to wheat roots, and the method was compared with chemical extraction methods. Although a good linear relationship was found between PAH concentrations in chemical extractants and wheat roots, the percentage of PAH in soil removed by chemical extraction was much higher than the corresponding percentage removed by wheat roots. In contrast to chemical extraction, a nearly 1:1 relationship was found between the amount of each PAH taken up by TECAMs and wheat roots (r(2) = 0.798-0.925, P < 0.01). Furthermore, the uptake of PAHs by TECAMs and wheat roots had the same pathway of passive transport via the soil solution. Moreover, TECAM caused minimal disturbance to the soil and was easy to deploy. Therefore, TECAM is believed to be a useful tool to predict bioavailability of PAHs to wheat roots grown in contaminated soils.     

Isolation and characterization of cellulose obtained from ultrasonic irradiated sugarcane bagasse

Cell walls of sugarcane bagasse were first delignified with chlorite followed by ultrasonic irradiation and then by two-step sequential extractions at 23 degrees C with 15 and 18% KOH for 2 h, 15 and 18% NaOH for 2 h, 8 and 10% KOH for 12 h, and 8 and 10% NaOH for 12 h and by a single one-stage isolation with 10% KOH for 16 h and with 10% NaOH for 16 h, which released 79.4, 81.8, 83.6, 85.7, 61.5, and 65.6% of the original hemicelluloses, and subsequently yielded 50.7, 49.5, 48.6, 47.8, 57.2, and 55.4% of the cellulose, respectively. The six cellulosic preparations were free of bound lignin and had a purity of 77.1-90.1% with the intrinsic viscosity (eta), viscosity average degree of polymerization, and molecular weight (M(w)) ranging from 534.1 to 631.6 mL g(-1), from 1858.1 to 2238.2 mL g(-1), and from 301000 to 362600 g mol(-1), respectively. The structural features of the isolated six cellulosic samples were comparatively examined by Fourier transform infrared and cross-polarization/magic angle spinning (13)C NMR spectroscopy and X-ray diffraction, and their thermal stability was investigated by using thermogravimetric analysis. It was found that all of the cellulosic preparations have the typical cellulose I structure but the crystallinity of the SCB cellulose was lower than that of flax, cotton, and kenaf.     

Efficient sugar release by the cellulose solvent-based lignocellulose fractionation technology and enzymatic cellulose hydrolysis

Efficient liberation of fermentable soluble sugars from lignocellulosic biomass waste not only decreases solid waste handling but also produces value-added biofuels and biobased products. Industrial hemp, a special economic crop, is cultivated for its high-quality fibers and high-value seed oil, but its hollow stalk cords (hurds) are a cellulosic waste. The cellulose-solvent-based lignocellulose fractionation (CSLF) technology has been developed to separate lignocellulose components under modest reaction conditions (Zhang, Y.-H. P.; Ding, S.-Y.; Mielenz, J. R.; Elander, R.; Laser, M.; Himmel, M.; McMillan, J. D.; Lynd, L. R. Biotechnol. Bioeng. 2007, 97 (2), 214- 223). Three pretreatment conditions (acid concentration, reaction temperature, and reaction time) were investigated to treat industrial hemp hurds for a maximal sugar release: a combinatorial result of a maximal retention of solid cellulose and a maximal enzymatic cellulose hydrolysis. At the best treatment condition (84.0% H3PO4 at 50 degrees C for 60 min), the glucan digestibility was 96% at hour 24 at a cellulase loading of 15 filter paper units of cellulase per gram of glucan. The scanning electron microscopic images were presented for the CSLF-pretreated biomass for the first time, suggesting that CSLF can completely destruct the plant cell-wall structure, in a good agreement with the highest enzymatic cellulose digestibility and fastest hydrolysis rate. It was found that phosphoric acid only above a critical concentration (83%) with a sufficient reaction time can efficiently disrupt recalcitrant lignocellulose structures.     

Self-assembly and paclitaxel loading capacity of cellulose-graft-poly(lactide) nanomicelles

A series of amiphiphilic cellulose-based graft copolymers (MCC-g-PLA) with various molecular factors were synthesized in ionic liquid BmimCl and characterized by FT-IR, (1)H NMR, (13)C NMR, XRD, and TGA. Their solubility in a variety of solvents was compared. The prepared MCC-g-PLA copolymers can self-assemble into spherical nanomicelles (10-50 nm) in aqueous solution. The self-assembly behaviors of the MCC-g-PLA copolymers were systematically investigated by fluorescence probe. Furthermore, the hydrophobic antitumor drug paclitaxel (PTX) was successfully encapsulated into the MCC-g-PLA micelles. The drug encapsulation efficiency and loading content were found to be as high as 89.30% (w/w) and 4.97%, respectively. Results in this study not only suggest a promising cellulose-based antitumor drug carrier but also provide information for property-directed synthesis of the cellulose graft PLA copolymers.     

Evaluation of residual levels of benomyl, methyl parathion, diuron, and vamidothion in pineapple pulp and bagasse (Smooth cayenne)

The objective of this research was to study the residual levels of benomyl, methyl parathion, diuron, and vamidothion in pineapple bagasse and pulp. Benomyl (benlate), methyl parathion (Folidol 600), diuron (Krovar), and Vamidothion (Kilval 300) were applied pre-harvest to pineapples (smooth cayenne). After harvesting, the fruits were washed (100 ppm sodium hypochlorite) and the pulp was separated from the sub-products (peel, core, tops, and tails). The pulp was not submitted to any heat treatment. The sub-products and the juice expressed from them, were submitted to a blanching process (95 degrees C for 1 min). After separating the juice, the bagasse and pulp were analyzed for residues of diuron and benomyl by high performance liquid chromatography, and for residues of vamidothion and methyl parathion by gas chromatography using a TSD detector. No residues of benomyl, diuron, vamidothion, or methyl parathion were detected in the pulp within the quantification limits of the methods (0.1 mg/kg, 0.1 mg/kg, 0.005 mg/kg, and 0.005 mg/kg, respectively). Only methyl parathion (0.052 mg/kg) and vamidothion (0.021 mg/kg) were detected in the bagasse. The presence of these residues in the bagasse was probably due to the action of the wax found in the peel, which prevented the methyl parathion and vamidothion from dissolving in the juice. According to these results, the pulp was fit for human consumption, as far as pesticide residues were concerned, and the bagasse was fit for animal feed and similar applications, because the residual levels found were below the limits established for these compounds.     

Formiate and acetate in wet deposition at Pallanza (NW Italy) in relation to major ion concentrations

Weekly samples of wet deposition were collected at Pallanza (NW Italy) from January 1987 to December 1988. Their chemistry is characterized by high mineral acidity, with a median pH value of 4.26; only in 2 out of 62 samples was pH higher than 6.0. Sulphate, nitrate and ammonium are the main ions. Formiate and acetate showed a volume weighted average of 7 and 4 μeq L^?1, respectively; the values for the dissociated forms are 5 and 1 μeq L^?1, respectively. The contribution of formiate and acetate (dissociated form) to the total ionic concentration is about 2%, while the contribution to free hydrogenion is about 13%, mainly deriving from formic acid. Seasonal variations in concentration and the relationships between organic acid and other ions indicate that the photolysis of isoprenoid compounds released into the atmosphere from vegetation is a significant source for formic acid. In the case of acetic acid there is a contribution from anthropogenic emissions, more marked during the winter period.     

Growth of the earthworm Eisenia foetida on microorganisms and cellulose

The growth of Eisenia foetida (Savigny) (200–300 mg live weight) was measured on mixtures of inorganic salts, vitamins, and cellulose upon a base of ashed loam or sand. High concentrations of inorganic salts, exceeding an ionic conductivity of about 8mS cm^?1 were detrimental, and lower concentrations failed to promote growth.Hatchlings (5 mg live wt) grew to 233 ± 14 mg (SE) on 22 species of bacteria (100 mg dry wt) at 24±1°C, in 8 weeks. There were no significant differences in growth on Gram-negative versus Gram-positive bacteria. Human pathogens were no less nutritive than non-pathogenic species.There was no growth on 6 of 19 species of fungi. Only 31% weight (70 ± 16 mg) was gained per unit weight of fungi as per unit weight of bacteria (100 mg dry microbial biomass).Worms grew as well (274 ± mg) on three species of protozoa as on 22 bacterial species. Growth on any microorganisms tested was less than on activated sludge.E. foetida doubled in weight on the fungus Coriolus hirsutus with the addition of sand or ashed loam. With either of these two forms of grit and microorganisms there was no growth. For growth, a combination of carbohydrate (cellulose), microorganisms and grit appeared necessary. Lyophilized microorganisms had to be washed free of ionic conductivity (and presumably organic residues) from their culture medium for earthworms to grow favorably.     

小麦秸秆纤维素均相醚化制备羧甲基纤维素工艺优化

为了利用小麦秸秆通过均相反应制备羧甲基纤维素(CMC,carboxymethyl cellulose),采用氢氧化钠和过氧化氢回流加热法制备小麦秸秆纤维素。以加入氧化锌的氢氧化钠/尿素/硫脲体系为溶剂,采用冻融循环法溶解小麦秸秆纤维素,利用正交试验获得了该溶解体系的最佳组成。在溶解了小麦秸秆纤维素的氢氧化钠/尿素/硫脲/氧化锌的体系中,以氯乙酸钠为醚化剂制备CMC,并对其进行红外光谱分析和取代度(degree of substitution,DS)测定。结果表明:在固液比为1∶20 g/mL,质量分数为10%NaOH,反应温度为85℃,回流3.5 h和固液比为1∶30 g/m L,质量分数为3%H_2O_2,反应温度为85℃,回流3 h处理小麦秸秆,纤维素提取率最高为84.61%,同时能较好的脱除半纤维素和木质素;最佳溶解体系为:质量分数为7%NaOH,11%硫脲,5%尿素,0.05%氧化锌,0℃时,最大溶解度为2.880 1 g。红外光谱试验表明小麦秸秆纤维素与微晶纤维素特征吸收峰基本一致,醚化反应生成的CMC与商品CMC的特征吸收峰基本一致。CMC的取代度受纤维素用量、温度和氯乙酸钠与纤维素葡萄糖单元(AGU,anhydroglucose unit)的摩尔比影响,随纤维素用量和氯乙酸钠与纤维素AGU的摩尔比增大而提高,随醚化温度的增加先增大(55℃)后降低。研究结果为以小麦秸秆为原料,经NaOH和H_2O_2处理获得纤维素,溶解在加入氧化锌的氢氧化钠/尿素/硫脲体系中,与氯乙酸钠经过均相醚化反应合成取代度较高的CMC提供参考。     

Reverse-phase liquid chromatographic determination of dexamethasone acetate and cortisone acetate in bulk drug substance and dosage forms: collaborative study

A reverse-phase liquid chromatographic method for determination of dexamethasone acetate and of cortisone acetate was subjected to an interlaboratory study by 8 collaborators for each steroid acetate. Bulk drug substance, suspensions, and tablets were assayed. Bulk drug or dosage form is dissolved in an acetonitrile-buffer mixture and analyzed by an external standard method. The steroid acetate is resolved from extraneous components by reverse-phase chromatography and detected at 254 nm. The sample solutions are stable for at least 72 h. For dexamethasone acetate, coefficients of variation were 0.9 and less than or equal to 3.1% for the bulk drug substance and the suspensions, respectively. For cortisone acetate, coefficients of variation were 0.7% for bulk material, less than or equal to 2.0% for suspensions, and less than or equal to 2.5% for tablets. All dosage forms were commercial formulations. The 2 methods have been adopted official first action.     

Development of a rapid and sensitive SPE-LC-ESI MS/MS method for the determination of chloramphenicol in seafood

A method based on liquid chromatography-tandem mass spectrometry was developed and validated for the qualitative and quantitative detection of chloramphenicol (CAP) in seafood samples. The analysis of CAP residues in seafood is important because CAP can cause serious acute reactions in humans, including aplastic anemia and leukemia. The proposed methodology includes a cleanup solid-phase extraction procedure with high recovery efficiency (>90%). Chromatographic separation of CAP and the internal standard (IS) was carried out on a C(18) column, followed by mass spectrometric detection using electrospray ionization in the negative-ion mode. The precursor/product ion transitions 321-->257 (CAP) and 354-->290 (IS) were monitored. Statistical evaluation of this multiple reaction monitoring mass spectrometric procedure reveals good linearity, accuracy, and inter- and intraday precisions. The limit of detection was 0.1 ng/mL, and the limit of quantification for CAP in seafood samples is 0.02 microg/kg. Application in seafood samples allowed the detection of CAP in low parts per billion levels.     

Highly Efficient Removal of Cu(II) from Aqueous Solution by Using Graphene Oxide

Chemical reagents used by the textile industry are very diverse in their composition, ranging from inorganic compounds to polymeric compounds. Strong color is the most notable characteristic of textile effluents, and a large number of processes have been employed for color removal. In recent years, attention has been directed toward various natural solid materials that are able to remove pollutants from contaminated water at low cost, such as sugarcane bagasse. Cell immobilization has emerged as an alternative that offers many advantages in the biodegradation process, including the reuse of immobilized cells and high mechanical strength, which enables metabolic processes to occur under adverse conditions of pH, sterility, and agitation. Support treatment also increases the number of charges on the surface, thereby facilitating cell immobilization processes through adsorption and ionic bonds. Polyethyleneimine (PEI) is a polycationic compound known to have a positive effect on enzyme activity and stability. The aim of the present study was to investigate a low-cost alternative for the biodegradation and bioremediation of textile dyes, analyzing Saccharomyces cerevisiae immobilization in activated bagasse for the promotion of Acid Black 48 dye biodegradation in an aqueous solution. A 1 % concentration of a S. cerevisiae suspension was evaluated to determine cell immobilization rates. Once immobilization was established, biodegradation assays with free and immobilized yeast in PEI-treated sugarcane bagasse were evaluated for 240 h using UV–vis spectrophotometry. The analysis revealed significant relative absorbance values, indicating the occurrence of biodegradation in both treatments. Therefore, S. cerevisiae immobilized in sugarcane bagasse is very attractive for use in biodegradation processes for the treatment of textile effluents.     

细菌纤维素水悬浮液的流变特性

为能更好地指导细菌纤维素作为增稠剂应用于食品工业,进一步了解细菌纤维素水悬浮液的流变学特性,该研究首先用原子力显微镜观察了细菌纤维素水悬浮液中纤维素的形态结构和直径,然后以羧甲基纤维素溶液为对照,分别从静态和动态2方面着手,用物性测定仪和流变仪测定细菌纤维素水悬浮液的稠度、黏性指数、剪切应力、表观黏度,剪切应力和表观黏度与剪切速率的关系等特性指标。分析了稠度、黏性指数、剪切应力、表观黏度与悬浮液中细菌纤维素质量分数的关系,比较了细菌纤维素水悬浮液与羧甲基纤维素溶液的差别,结果显示:细菌纤维素的直径为60~80 nm;细菌纤维素水悬浮液中的纤维素相互缠结,呈现散乱分布的网状结构,纤维素可聚集形成平行或螺旋状的纤维束;细菌纤维素水悬浮液在质量分数为0.4%~1.2%时的稠度和黏性指数远高于相同质量分数的羧甲基纤维素钠溶液,且与质量分数呈显著的正相关关系(P0.05,R20.95);在较低剪切速率0.02~10 s-1下,悬浮液的表观黏度随剪切速率的增加呈缓慢下降的趋势,出现剪切稀化现象;当剪切应力达到屈服应力时悬浮液才发生流动,且剪切应力与剪切速率呈正相关(P0.05,R20.99),流动特性指数为1,细菌纤维素悬浮液为非牛顿流体的宾汉塑性流体。因此细菌纤维素水悬浮液做为增稠剂应用于食品工业时具有宾汉塑性流体的特征。     

Preparation of deoxynivalenol (vomitoxin) from field-inoculated corn

A process was developed for production of gram quantities of deoxynivalenol (DON) from corn that had been inoculated in the field with Fusarium graminearum and was estimated to contain 400-500 mg DON/kg. Steps in the purification procedure included extraction with methanol-water (1 + 1), partition from an aqueous solution into ethyl acetate by using a hydrophilic matrix, defatting, Florisil column chromatography, methylene chloride-water partition, semipreparative liquid chromatography (LC), and crystallization from ethyl acetate. The average yield of crystalline DON produced by this method (or with minor variations) was 281 mg/kg.