竹材及其磺化化机浆木素结构与发色基团特性研究

研究了白夹竹及其磺化化机浆ＭＷＬ的结构与发色基团的特性，并把两者进行了对比。从而了解了木素特性及其磺化预处理后的变化。由１３Ｃ－ＮＭＲ谱和硝基苯氧化证明，竹料木素是ＧＳＨ型木素。竹料制成浆后，木素的分子量有很大降低，对香豆酸酯含量下降。醌式结构是木素中最主要的发色基团，制成浆后醌式结构有很大的增加。     

Chemical and in vivo evaluation of a brown midrib mutant of Zea mays. II. Nuclear magnetic resonance spectra of digested and undigested alkali lignins and undigested dimethyformamide lignins

Nuclear magnetic resonance (n.m.r.) spectra were obtained on the alkali lignins extracted from Tr and bm₁ cornstalks, before and after digestion by sheep, and on the dimethylformamide lignins (DMFL) from undigested cornstalks. Differences due to solvent extraction, plant genotype and digestion were apparent. The bm¹ corn lignin has a higher degree of cross linking of the propane side chain of the lignin molecule than Tr corn lignin, a factor which may be significant in determining the effect of lignin on digestibility. The main effect of digestion was to increase the degree of cross-linking of the propane side chain, especially with the Tr lignin. Alkali lignin n.m.r. spectra were considerably different from DMFL n.m.r. spectra. For example over 40% of the total bm DMFL protons were highly shielded protons but these were virtually absent in the alkali lignins. These highly shielded protons cannot be explained by the presence of ferulic and p-coumaric acids in DMFL.     

Comparative characterisation of dioxane-soluble lignins released by ball milling and by sheep digestion from forage grasses

Faecal soluble lignin (FSL), extracted from the faeces of sheep that received orchardgrass and timothy, were compared with 90% dioxane-soluble lignins released by ball milling (MHL) and by subsequent enzymatic hydrolysis (EHL) from the same grasses. FSL contained much less carbohydrate and esterified p-coumaric and ferulic acids than MHL and EHL. Although no considerable differences were found in the yields of vanillin and syringaldehyde produced by nitrobenzene oxidation, the molar ratio of syringaldehyde to vanillin was higher for FSL than for MHL and EHL. Such differences in chemical properties among the lignin preparations were confirmed by ¹³C-NMR spectroscopy. FSL had a lower molecular size compared with MHL and EHL. Results indicated that syringyl-rich lignin fragments with less phenolic acid esters, probably depolymerisation products of the grass lignins, were released by digestion in sheep from the forage grasses.     

An investigation of lignin extraction from dietary fibre using acetyl bromide

Acetyl bromide is a suitable reagent for the extraction of lignins from woody material and grasses but lignins present in vegetables do not give the expected absorbance spectrum. Treatment of the vegetable fibre with either organic solvents or dilute acid or the removal of protein and hemicellulose does not alter the absorbance spectrum of lignins present in vegetables. All methods used for lignin extraction are quantitatively consistent and show only a trace of lignin to be present in vegetable fibre.     

漆酶/天然介体体系漂白硫酸盐竹浆的机理研究

对硫酸盐竹浆包含漆酶/天然介体漂白段的全无氯(TCF)漂白各段的残余木素进行了GPC、TGA、FT-IR、1H-NMR和t3C-NMR分析,主要探讨漆酶/天然介体体系(LMS)漂白的机理.分析表明,随漂白的进行,竹浆残余木素的总体变化趋势为分子质量降低;经LMS处理后,竹浆残余木素的热稳定性变差,更易在较低温度下热解;竹浆木素为GSH型,结构单元以G为主,苯丙烷单元之间的连接以β-O-4′为主,此外还有β-1′和β-5′连接.原浆木素中的羟基以酚羟基为主,苯丙烷单元中S的含量(以物质的量计,下同)少于1/3;O段残余木素中,脂肪族羟基比酚羟基多,且有少量-COOH、-OCH3被脱除,苯丙烷单元中G＞H＞S;LMS段残余木素中的羟基以脂肪族羟基为主,S单元含量增加,H单元含量减少,争1′连接增加,β-5′连接很少.     

Determination of lignin in herbaceous plants by an improved acetyl bromide procedure

A modified acetyl bromide procedure is proposed for the spectrophotometric determination of lignin in herbaceous plants. The digestion with 25 % acetyl bromide (AcBr) in acetic acid at 70°C is improved by including 4 % perchloric acid in the digesting solutions. This allows for more rapid, complete digestion and the use of coarser samples. On the basis of infrared spectra and nitrobenzene oxidation data for milled sample lignins, the value of 20.0 g^?1 litre cm^?1 for the specific absorption coeficient of AcBr-treated lignins of herbaceous plant samples gave lignin values which were consistent with nitrobenzene oxidation data, but were higher than those obtained by the acid detergent lignin method and the earlier AcBr method proposed for grasses. The lower lignin values obtained in the latter methods are considered to be due to partial lignin solubilisation in the sulphuric acid digestion.     

蓝莓花青素的抗氧化活性对比及其稳定性分析

本文研究不同提取工艺对蓝莓花青素抗氧化活性的影响,以及对微波波辅助提取得到的蓝莓花青素的稳定性进行了分析。通过1,1-二苯基-2-苦肼基(DPPH·)、羟基自由基(·OH)、超氧自由基(O2-·)等体外抗氧化实验评价不同提取工艺所提取的蓝莓花青素抗氧化活性,并分析光照、pH、温度、葡萄糖以及有机酸对蓝莓花青素保存率的影响。结果显示,乙醇浸取法、丙酮浸取法和微波辅助提取法的蓝莓花青素的得率分别为4.46%、4.41%和4.92%。蓝莓花青素的体外抗氧化活性在0.25~4.0 mg/mL范围内有浓度依赖性,微波辅助提取法获得的蓝莓花青素浓度为4.0 mg/mL时,DPPH·清除率、·OH清除率和O2-·清除率分别为86.59%、56.85%和88.65%,均显著高于乙醇浸提法、丙酮浸提法(p<0.05)。蓝莓花青素在强光、碱性、高温及抗坏血酸存在的环境下较为不稳定,而葡萄糖和柠檬酸则对蓝莓花青素的稳定性有一定的保护作用。     

Bestimmung der phenolischen Hydroxylgruppen in Ligninen und Ligninfraktionen durch Aminolyse und FTIR-Spektroskopie

The quantitative analysis of phenolic OH groups is of interest for the characterization of isolated lignins when evaluating the extent to which lignin has been changed. While aminolysis is a very accurate if elaborate chemical method, the evaluation of the aliphatic and aromatic IR ester bands of acetylated lignins at 1745 and 1765 cm^?1 permits a quick, easy and reliable determination of the phenolic hydroxyl groups. The excellent correlation between the two methods was proved for 35 different lignins and lignin fractions of different molecular weights.     

大豆秸秆和毛竹碱木素的逐级分离及性状表征

采用酸析法分别对大豆秸秆和毛竹的硫酸盐制浆黑液中的碱木素按不同pH值进行逐级分离,探讨了黑液中碱木素在酸析过程中的溶出规律;采用凝胶渗透色谱(GPC)、红外光谱(FT-IR)、动态光散射(DLS)对不同条件下酸析得到的各级碱木素进行分析与比较。结果表明,逐级分离后,各级碱木素的相对分子质量分布变窄,分子质量有相当程度的重叠;随着pH值的降低,各级碱木素的粒径逐渐减小,相对分子质量及其多分散性也逐渐减小,说明酸析法是分离不同分子质量碱木素的一种有效方法。     

微波辅助涂膜技术对竹笋保藏性的影响

为了解决竹笋采后不耐保藏的问题,研究微波辅助涂膜技术对竹笋保藏性的影响。对比微波辅助涂膜、微波不涂膜、直接涂膜、直接冷藏4种处理方式,4℃避光贮藏60d,定期检测竹笋质量损失率、呼吸强度、硬度、PAL活性、POD活性、粗纤维含量、木质素含量及总糖含量等指标。结果表明,微波辅助涂膜处理在各项指标上均优于其他处理,可明显降低PAL活性、POD活性和呼吸强度,抑制竹笋的纤维化,保持竹笋良好的外观品质,贮藏期达50d以上。     

葵花籽壳木质素的结构分析及抗氧化活性

以葵花籽壳为原料,采用醋酸法提取木质素,并利用凝胶渗透色谱、紫外光谱、傅里叶变换红外光谱、核磁共振氢谱和热重分析对提取的木质素进行结构表征,并对提取木质素的抗氧化活性进行评价。结果表明:醋酸法木质素提取率为70.12%(相对于Klason木质素),纯度达到88.54%,结合少量的碳水化合物(2.92%)。葵花籽壳木质素为GS型木质素,含有较高的愈创木基结构单元(G),结构单元之间的连接键以β-O-4结构为主,重均分子质量(M_w)、数均分子质量(M_n)和多分散度(M_w/M_n)分别为2 977、1 931 D和1.54。葵花籽壳醋酸提取的木质素主要降解温度在200~400℃之间,最大失质量速率为0.32%/℃。抗氧化活性研究表明,木质素清除1,1-二苯基-2-三硝基苯肼自由基指数值为1.54,显著高于商业合成抗氧化剂二丁基羟基甲苯(0.94),具有很好地应用于食品及其他工业做抗氧化剂的前景。     

毛葱水溶性多糖的超声波微波协同法提取工艺优化及结构分析

以毛葱为原料,利用超声波微波协同法提取毛葱水溶性多糖。以多糖得率为考察指标,在单因素试验的基础上,通过响应面分析方法确定毛葱水溶性多糖提取的最佳工艺为液料比17∶1(mL/g)、超声波功率360 W、微波功率200 W、协同时间16 min,此条件下毛葱水溶性多糖得率为(11.92±0.13)%。溶解性实验结果表明:该毛葱水溶性多糖可溶于水,不溶于有机溶剂;显色反应实验结果表明:该毛葱水溶性多糖含有糖醛酸,但不含淀粉及酚类物质。紫外光谱分析显示该毛葱水溶性多糖无明显的核酸和蛋白质的特征吸收峰,傅里叶变换红外光谱分析显示该毛葱水溶性多糖具有多糖类的特征吸收峰。高效凝胶渗透色谱法分析该毛葱水溶性多糖的重均分子质量,可初步得出该毛葱水溶性多糖不是由均一组分构成的。     

Comparative study of Caribbean pine (Pinus caribaea L.) wood and bark dioxane lignin

The objective of this paper was to depict some differences between Caribbean pine bark and wood lignin. Gas chromotography (GC) of nitrobenzene oxidation products of extracted wood and bark meals and of corresponding dioxane lignins was performed. The isolated lignins were submitted to IR and UV spectrometry, gel permeation chromatography and differential thermo-gravimetry. The data obtained indicate differences in the contents of condensed bis-guaiacyl structures in the lignins. Contents of phenolic hydroxyl and α-carbonyl groups in both lignins do not markedly differ. There are also certain differences in the thermostability and the molecular weights of compared dioxane lignin preparations.     

A comparison of some chemical and physical properties of alkali lignins from grass and lucerne hays before and after digestion by sheep

The chemical and physical properties of alkali lignins from a grass hay and a lucerne hay were studied, before and after digestion by sheep. A greater proportion of the total grass lignins was dissolved by alkali than with the lucerne lignins but digestion increased this proportion with both species. Of the lignin dissolved by alkali, less of it was precipitated on acidification when faeces (50–70%) were compared with the undigested hays (86–92%). Extraction of lignins with boiling alkali produced a lignin with the smallest amount of amino acids but considerably altered the chemical structure as revealed by nuclear magnetic resonance (n.m.r.). Trypsin treatment of a cooler alkali extract was less effective in reducing amino acid contamination but did not alter the structure. Compared with the grass alkali lignins, the lucerne lignins had more total but fewer aromatic protons, fewer groups reacting with N-2,6-trichloro-p-benzoquinone imine, ionisable hydroxyl groups and fewer methoxyl groups. On Sephadex G-200 gel chromatography, three peaks were apparent with the lucerne, but only two with grass lignins. Both plant lignins showed large amounts of highly shielded n.m.r. protons but there were more with lucerne. Infrared spectra suggested that they were probably due to methyl groups. Digestion had very little effect on the n.m.r., ultraviolet or infrared spectra or the molecular weight distribution of the isolated lignins. It may have reduced the numbers of groups, reacting with N-2,6-trichloro-p-benzoquinone imine with the grass and two maize samples examined, but appeared to have the opposite effect with the lucerne.     

杨木自催化乙醇制浆废液中有机酸的分析

针对杨木自催化乙醇法蒸煮废液成分复杂、副产物价值高等特点,对废液中的有机酸进行分析。首先制取杨木自催化乙醇制浆废液,对分离出木素的废液用乙醚萃取,将萃取物用气相色谱-质谱联用检测仪进行定性分析。结果表明,废液中的各成分复杂而且都很微量,主要是一些酸、酯、低分子木素等,约25种,其中乙酸和甲酸含量较高。其次对杨木自催化乙醇法蒸煮废液减压蒸馏至无液体来分离木素,对全部馏分采用容量分析的方法测得总酸含量为0.043 mol/L,同时用气相色谱定量测得乙酸含量为1.864 g/L、甲酸含量为0.665 g/L。     

Optimization of extraction process for phenolic acids from black cohosh (Cimicifuga racemosa) by pressurized liquid extraction

An investigation to optimize the extraction of phenolic acids from black cohosh using a pressurized liquid extractor system was studied with the aim of developing a generalized approach for sample preparation of phenolic compounds from plant matrices. Operating parameters such as solvent composition, solid‐to‐solvent ratio, temperature, particle size distribution, and number of extraction cycles were identified as main variables that influence extraction efficiency. A mixture of methanol and water (60:40 v/v) was found to be the best solvent for total phenolics (TP) and individual phenolic acids. The four phenolic acids extracted from black cohosh were identified by HPLC and LC‐MS as caffeic acid, ferulic acid, sinapic acid and isoferulic acid. Over 96% of the measured phenolics were extracted in first two cycles. The extraction efficiency for black cohosh with MeOH:H₂O (60:40 v/v) was found to be maximum at a solid‐to‐solvent ratio of 80 mg ml^?1. TP content of the extract was found to increase with temperature up to 90 °C. Particle size was found to have a large impact on extraction efficiency of TP. Samples with particle size between 0.25 mm and 0.425 mm provided optimum extraction of phenolics from black cohosh. Published in 2005 for SCI by John Wiley & Sons, Ltd.     

Evaluation of starch analysis methods for feed samples

The objectives of this work were to evaluate the efficacies of commercial starch analyses and of starch analysis extraction and gelatinisation procedures. In Study 1, accuracy and specificity of commercially available starch analyses were evaluated with six co‐operating laboratories (five commercial, one university). Results from 11 test samples showed three laboratories with recoveries of purified starch of 92 g kg⁻¹ or less. Three and four laboratories had inflated values when samples contained glucose or sucrose, respectively. Analyses appeared to have good specificity for glucose. Incompleteness of starch detection and interference by non‐starch carbohydrates can affect commercially available analyses. In Study 2, extraction with 80:20 ethanol/water (v/v; 80EtOH) or 90:10 ethanol/water (v/v; 90EtOH) to remove low‐molecular‐weight carbohydrates, and gelatinisation with heat, alkali (KOH), 6 M urea or 8 M urea were evaluated. Extraction with 80EtOH or 90EtOH reduced interference from non‐starch carbohydrates. Gelatinisation with heat was adequate for good recoveries of starch glucose for both control (non‐extracted) and 80EtOH‐extracted samples; gelatinisation with alkali was required for 90EtOH‐extracted samples. Recoveries of pure starch samples were greatest with no extraction and heat gelatinisation. 80EtOH extraction with heat gelatinisation appears to be an adequate preparation method when removal of low‐molecular‐weight carbohydrates is desired. © 2000 Society of Chemical Industry     

Microwave-assisted extraction of phenolic compounds from tea residues under autohydrolytic conditions

Phenolic compounds were extracted from three kinds of tea residues (green, oolong and black tea residues) by microwave-assisted extraction in water under autohydrolytic conditions without using any catalyst or organic solvent. Productions of phenolic compounds were enhanced by microwave heating at 230 °C. The main phenolic constituent in the extract from green tea residue was pyrogallol (24.6%) which was estimated to be originated from degradations of catechins. Derivatives of guaiacyl units of lignin such as dihydroconiferyl alcohol (10.3%) and vanillin (8.1%) were, however, the main constituents in oolong tea residue. In the case of black tea residue, derivatives of both catechins and lignin were comparably extracted. These phenolic compounds are interesting as a bio-based chemical feedstock such as phenolic precursors and antioxidants.     

Conventional and Microwave-Assisted Extraction of Mucilage from <Emphasis Type="Italic">Opuntia ficus-indica</Emphasis> Cladodes: Physico-Chemical and Rheological Properties

Cactus pear cladodes processing has potential value for mainstream industries and is equally important for marginal rural communities in arid regions. This work is focused on physico-chemical and rheological properties of Opuntia ficus-indica (OFI) peeled cladodes extracted by conventional method “CE” and using microwave-assisted extraction “MAE.” MAE gave the highest yield extraction (8.13 %, w/w) within the lowest extraction time (500 W/7 min) and provided more protein (×1.03) and carbohydrates (×1.51) than CE. The monosaccharides detected by gas chromatography were arabinose, galactose, rhamnose, xylose, and galacturonic acid. The dialyzed mucilage solution characterized by SEC/MALS/VD/DRI (size-exclusion chromatography coupled with online multi-angle light scattering, viscometer detectors, and differential refractive index) revealed fractions with molecular weight (M _w ) ranging from 15.3–15.7?×?10⁶ g mol^?1 for the CE extracts and about 16.7–17.5?×?10⁶ g mol^?1 for the MAE extracts. Dynamic oscillatory testing has been used to study the rheological properties of mucilage solution within the concentration of 0.50–3.00 % (w/v) at 25 °C. The rheological profiles of CE and MAE showed similar behavior. At low frequency and low mucilage concentration (<2.00 %), the viscous component (G") predominated over the elastic component (G'), while for higher frequencies, the behavior is reversed (G'?>?G"). If safely controlled, alternative energies like microwaves could extract soluble polymers with comparable properties to commercial ones, conventionally extracted.     

微波辅助提取巴旦木蛋白工艺优化及其功能性质研究

本文采用微波辅助碱溶酸沉法提取巴旦木中的蛋白质,在单因素实验基础上,采用L₁₆（45）正交试验设计,研究微波预处理功率、微波预处理时间、提取液pH、提取温度和料液比对巴旦木蛋白提取率的影响。结果表明,微波辅助提取巴旦木蛋白的最佳工艺条件为:微波功率400 W、微波时间180 s、提取液pH 9.5、提取温度50 ℃和料液比1:25 g/mL,在此条件下测出的巴旦木蛋白提取率达到46.69%。相较于未经微波辅助提取的巴旦木蛋白,微波处理后蛋白的溶解性、持水性、持油性、乳化性和起泡性分别提升了15.35%、26.07%、26.22%、30.61%和20.53%,而乳化稳定性和泡沫稳定性分别降低了1.05%和13.29%,研究表明,微波处理有助于提高巴旦木蛋白的提取率并改善功能性质。