溶胶-凝胶法制备木质素碳基固体酸及其催化α-蒎烯水合反应性能研究

以造纸黑液中提取的硫酸盐木质素为原料,通过溶胶-凝胶法合成了木质素水凝胶,再经过真空干燥、炭化及浓硫酸磺化合成木质素碳基固体酸,采用傅里叶变换红外光谱（FT-IR）、场发射扫描电子显微镜（SEM）、BET比表面积法、Boehm滴定法等手段对其进行表征分析,并将其应用于催化α-蒎烯水合反应以合成α-松油醇。结果表明,采用溶胶-凝胶法制备的木质素碳基固体酸具有丰富的孔隙结构和良好的催化性能,其比表面积可达281.25 m²/g,α-蒎烯的转化率为93.1%,α-松油醇产率为40.4%,选择性为43.4%。催化剂循环使用5次后,α-蒎烯的转化率降至86.7%,α-松油醇产率降至32.6%,催化性能下降的根本原因在于其表面磺酸基团的脱落。     

基于螺旋挤压-GVL/水/酸两步预处理的溶解浆联产糠醛和木质素

针对目前溶解浆生产过程中存在的半纤维素和木质素利用率低、溶解浆质量有待提升等问题,本研究基于螺旋挤压耦合γ-戊内酯（GVL）/水/酸预处理,提出绿色环保的溶解浆联产糠醛和木质素的工艺。结果表明,桉木经螺旋挤压-GVL/水/酸两步预处理（150 ℃下反应1.5 h）,蒸煮用碱量8%,漂白工艺OQP₁P₂,制备出α-纤维素含量为96.5%、白度为84.0%的高品质溶解浆;水解液分离木质素后,以甲基异丁基酮（MIBK）/H₂O-NaCl为催化体系,商业离子交换树脂为催化剂,于180 ℃下催化木糖水解液2 h,糠醛最大得率为96.0%;GVL木质素S/G比为4.81,保留一定含量的β-O-4键（22.6%）。经物料衡算,每100 g桉木可生产37.2 g溶解浆、6.2 g糠醛（理论值10.2 g）和16.4 g的GVL木质素。     

广西10种野生竹材的化学组分分析及木质素结构表征

本研究采用NREL法、硫醇酸解法、凝胶渗透色谱法（GPC）以及二维核磁（2D NMR）等分析检测手段对广西10种野生竹材纤维原料的化学成分与分离木质素的结构进行了表征。结果表明,10种野生竹材的纤维素含量为37.09%~44.21%,半纤维素含量为17.16%~23.32%,木质素含量为21.73%~25.81%;所有竹材分离木质素均为GSH型,基本结构单元均以S型和G型为主,H型结构单元含量均不高于5%;木质素结构单元间的主要连接键方式为β-O-4、β-β与β-5,其中β-O-4含量占主要侧链连接的80%以上、占总芳环总量的47.41%~52.07%;此外,木质素中还存在与阿魏酸和对香豆酸的酯键连接。综合分析,撑篙竹在10种竹材中最适合用于生物质精炼、木质素降解以及制浆造纸等领域的开发利用,耳垂竹、大绿竹次之。     

13C-2H双同位素示踪法研究未漂硫酸盐浆中残余木质素的化学结构

采用¹³C和²H分别标记裸子植物的木质素和碳水化合物,研究未漂硫酸盐浆中残余木质素的化学结构。向银杏（Ginkgo）植株中投入木质素前驱物松伯醇葡萄糖苷-[α-¹³C]、多糖前驱物D-葡萄糖-[6-²H₂]及苯丙氨酸解氨酶（Phenylalanine Ammonialyas,PAL）的阻诘剂羧甲氧基胺半盐酸盐（AOA）,获得双同位素标记的木材。将其制备的硫酸盐浆通过酶水解法分离得到纤维素酶解木质素（CEL）,通过碱抽提纯化得到碱溶性CEL（CEL-Alk）。利用¹³C NMR对其结构进行分析,发现蒸煮前,天然银杏木质部中木质素结构单元间主要以β—1、β—5、β—O—4结构为主,少量木质素与多糖类物质以缩醛键连接。硫酸盐浆残余木质素中主要有β—5、β—1等缩合结构,部分木质素通过缩醛键与多糖类物质相连。¹H NMR差示光谱显示,木质素单元Cα与葡萄糖或甘露糖之间形成了苯甲醚键连接。结果表明,银杏纤维中的木质素-碳水化合物复合体（LCC）中缩醛键和苯甲醚键结构在硫酸盐法蒸煮过程中较稳定。     

不同催化剂对麦草组分乙醇溶剂热分离效果的影响

高效清洁的纤维生物质组分分离技术是生物质深度精炼和高值化利用的前提。乙醇溶剂高温热分解是一项极具前景的生物质组分高效分离技术,催化剂的加入可以明显加快脱木质素效率。本研究在麦草乙醇溶剂热分离过程中加入催化剂,探讨了催化剂乙酸、MgCl_2、H_3PO_4以及3种催化剂与H_2O_2组成的二元催化体系对麦草组分分离效果的影响。结果表明,H_2O_2的加入对乙酸、MgCl_2催化半纤维素的脱除有明显的提高,而对木质素的脱除影响不显著; H_2O_2的添加对于H_3PO_4催化来说,木质素脱除率有明显的上升,而半纤维素脱除率则保持较高水平。当反应温度190℃、催化剂浓度0. 02 mol/L、H_3PO_4/H_2O_2质量比为5∶5时,木质素脱除率由单独H_3PO_4催化的80. 99%增加到88. 64%;半纤维素脱除率为68. 99%。     

马尾松树皮在离子液体中的溶解及组分分离研究

针对目前树皮组分难以有效利用的问题,以离子液体1-烯丙基-3-甲基咪唑氯盐（［Amim］Cl）为溶剂,对球磨后的马尾松（Pinus massoniana L.）树皮进行溶解,随后以NaOH溶液及乙醇为沉淀剂,对树皮中的纤维素、木质素和半纤维素组分进行分级分离。结果表明,球磨24 h后的马尾松树皮在100℃、溶解5 h的条件下,能够在离子液体中完全溶解;再生后树皮中纤维素的晶型由I型转变为II型,结晶度降低,但再生后树皮主要化学成分与原料相同。采用1% NaOH溶液及乙醇溶液处理溶解后的树皮可有效分离得到纤维素、木质素和半纤维素,分离后各组分的化学结构未发生明显改变。离子液体经5次循环再利用后,其回收率依旧可以保持90%以上。     

乙二醇抑制DES预处理过程中木质素缩合程度的研究

利用氯化胆碱/草酸和氯化胆碱/草酸/乙二醇2种低共熔溶剂（DES）体系预处理竹粉以分馏提取木质素,并通过多种表征手段探究木质素的结构变化。结果表明,在110 ℃反应180 min的条件下,氯化胆碱/草酸二元DES体系提取的木质素（二元DES木质素）中β-O-4芳基醚键的相对含量仅为0.26/Ar,氯化胆碱/乙二醇/草酸三元DES体系提取的木质素（三元DES木质素）此值则为0.43/Ar。同时,二元DES木质素中的缩合结构（β-β,β-5=3.11/Ar）及缩合的芳环C—C连接（Aromatic C—C=2.18/Ar）多于三元DES木质素（β-β,β-5=2.02/Ar,Aromatic C—C=1.99/Ar）。利用超声辅助三元DES体系预处理过程,发现反应20 min后木质素脱除率即可达76.0%。采用水相电位滴定法测定不同反应条件下的三元DES木质素的酚羟基和羧基含量;并提出乙二醇在三元DES体系预处理竹粉过程中抑制木质素缩合的机理,证实乙二醇与对香豆酸和阿魏酸反应生成了酯化的木质素结构。     

不同木质素对酶蛋白的吸附影响及酶活变化研究

通过3,5-二硝基水杨酸（DNS）和对硝基苯基-β-D-吡喃葡萄糖苷（pNPG）比色法,研究对比碱法和水溶预处理桉木得到的两种不同木质素对不同酶蛋白（纤维素酶、聚木糖酶和β-葡萄糖苷酶）的吸附和脱附影响差异,以及木质素吸附对不同酶蛋白活性的抑制影响。两种木质素对不同酶蛋白吸附实验表明,温度对碱木质素吸附酶蛋白能力的影响大于二甲苯磺酸钠（SXS）木质素,被吸附的酶蛋白更容易从SXS木质素上脱附下来;木质素吸附会显著降低酶活,升高温度可以提高木质素对酶蛋白的吸附能力,但会抑制酶活。     

牛膝多糖降血糖活性成分的分离鉴定

研究牛膝多糖与降血糖活性的关系。牛膝粉碎后先经乙醇提取,再用热水提取,水提液减压浓缩后经醇沉得到牛膝水提醇沉物。采用链脲佐菌素（streptozocin,STZ）诱导方法建立小鼠糖尿病模型,每日给药牛膝各分离组分,连续给药8周,通过测定小鼠血糖、糖化血红蛋白,检测牛膝中具有降血糖活性的组分。采用DEAE、HW-55F、Sephacryl S-400等凝胶色谱柱对具有降血糖活性的牛膝多糖组分进一步分离。运用Sephadex G-100凝胶色谱、飞行时间质谱（time of flight mass spectrometer,TOF-MS）、气相色谱（gas chromatography,GC）、核磁共振（nuclear magnetic resonance,NMR）等手段鉴定多糖纯度、测定相对分子质量、分析结构。结果表明,牛膝的水提醇沉物能显著降低糖尿病小鼠的空腹血糖（fasting plasma glucose,FPG）和糖化血红蛋白（HbA1c）浓度（P＜0.05）。将水提醇沉部分进一步分离得到具有降血糖活性的牛膝多糖,并鉴定其纯度为均一多糖,相对分子质量为1 800.5,该多糖由1分子葡萄糖和10分子果糖组成,以葡萄糖分子为起点,与果糖C₂相连,果糖之间以β-1,2 糖苷键连接形成主链,支链连接在果糖的C₆上,该研究明确了牛膝中具有降血糖活性的多糖分子结构。     

乙酸强化水热预水解对相思木半纤维素溶出及组分与结构的影响

在170℃下,分别采用水热预水解法和1.0%（质量分数）乙酸强化水热预水解法抽提相思木,通过乙醇沉淀法回收预水解液中的半纤维素,分析了乙酸对预水解液中溶解半纤维素的化学组分及含量、乙醇沉淀半纤维素回收率及其组分和结构的影响。结果表明,乙酸可显著提高预水解液中低聚糖和总糖含量;在170℃下预处理35 min时,乙醇沉淀半纤维素回收率最大;离子色谱和紫外光谱分析结果表明,乙酸强化水热预水解乙醇沉淀半纤维素的化学组分与水热预水解乙醇沉淀半纤维素相同,但木糖和木素含量较高,而阿拉伯糖和半乳糖含量偏低;凝胶色谱分析结果表明,乙酸强化水热预水解乙醇沉淀半纤维素平均分子质量低于水热预水解乙醇沉淀半纤维素;核磁共振分析结果表明,乙酸强化水热预水解乙醇沉淀半纤维素聚木糖主链上残留阿拉伯糖支链较少,有明显木素 碳水化合物复合体（LCC）存在。     

Reliable identification of grapevine rootstock varieties using RAPD PCR on woody samples

Since grapevine ( Vitis spp .) rootstock material is being traded increasingly as disbudded woody material a lack of distinctive morphological features on such material necessitates an alternative and reliable means of identification. Methods described here were developed for rapid and efficient extraction of DNA from woody samples rich in phenolic compounds and polysaccharides, and for subsequent identification of varieties by RAPD PCR. Using these methods, and with the application of only one selected RAPD primer, we were able to differentiate sixteen rootstock varieties, including the seven varieties most commonly used in Germany. Problems commonly encountered with reproducibility of RAPD patterns were avoided by choosing primers with a dinucleotide sequence and a high G/C content that allowed a rather high annealing temperature of 45°C. Methods described here should also be useful for other horticultural crops, especially those with woody tissues rich in phenolic compounds and polysaccharides.     

An internet compendium of analytical methods and spectroscopic information for monomers and additives used in food packaging plastics

An internet website (http://cpf.jrc.it/smt/) has been produced as a means of dissemination of methods of analysis and supporting spectroscopic information on monomers and additives used for food contact materials (principally packaging). The site which is aimed primarily at assisting food control laboratories in the European Union contains analytical information on monomers, starting substances and additives used in the manufacture of plastics materials. A searchable index is provided giving PM and CAS numbers for each of 255 substances. For each substance a data sheet gives regulatory information, chemical structures, physico-chemical information and background information on the use of the substance in particular plastics, and the food packaging applications. For monomers and starting substances (155 compounds) the infra-red and mass spectra are provided, and for additives (100 compounds); additionally proton NMR are available for about 50% of the entries. Where analytical methods have been developed for determining these substances as residual amounts in plastics or as trace amounts in food simulants these methods are also on the website. All information is provided in portable document file (PDF) format which means that high quality copies can be readily printed, using freely available Adobe Acrobat Reader software. The website will in future be maintained and up-dated by the European Commission's Joint Research Centre (JRC) as new substances are authorized for use by the European Commission (DG-ENTR formerly DGIII). Where analytical laboratories (food control or other) require reference substances these can be obtained free-ofcharge from a reference collection housed at the JRC and maintained in conjunction with this website compendium.     

Aroma characterization of various apricot varieties using headspace–solid phase microextraction combined with gas chromatography–mass spectrometry and gas chromatography–olfactometry

The characterization of the aromatic profile of several apricot cultivars with molecular tracers in order to obtain objective data concerning the aromatic quality of this fruit was undertaken using headspace–solid phase microextraction (HS–SPME). Six apricot cultivars were selected according to their organoleptic characteristics: Iranien, Orangered, Goldrich, Hargrand, Rouge du Roussillon and A4025. The aromatic intensity of these varieties measured by HS–SPME–Olfactometry were defined and classified according to the presence and the intensity of grassy, fruity and apricot like notes. In the six varieties, 23 common volatile compounds were identified by HS–SPME–GC–MS. Finally, 10 compounds, ethyl acetate, hexyl acetate, limonene, β-cyclocitral, γ-decalactone, 6-methyl-5-hepten-2-one, linalool, β-ionone, menthone and (E)-hexen-2-al were recognized by HS–SPME–GC–O as responsible of the aromatic notes involved in apricot aroma and considered as molecular tracers of apricot aromatic quality which could be utilized to discriminate apricot varieties.     

Tests of potential functional barriers for laminated multilayer food packages. Part I: Low molecular weight permeants

The advent of the functional barrier concept in food packaging has brought with it a requirement for fast tests of permeation through potential barrier materials. In such tests it would be convenient for both foodstuffs and materials below the functional barrier (sub-barrier materials) to be represented by standard simulants. By means of inverse gas chromatography, liquid paraffin spiked with appropriate permeants was considered as a potential simulant of sub-barrier materials based on polypropylene (PP) or similar polyolefins. Experiments were performed to characterize the kinetics of the permeation of low molecular weight model permeants (octene, toluene and isopropanol) from liquid paraffin, through a surrogate potential functional barrier (25 μm-thick oriented PP) into the food simulants olive oil and 3% (w/v) acetic acid. These permeation results were interpreted in terms of three permeation kinetic models regarding the solubility of a particular model permeant in the post-barrier medium (i.e. the food simulant). The results obtained justify the development and evaluation of liquid sub-barrier simulants that would allow flexible yet rigorous testing of new laminated multilayer packaging materials.     

Chlorohydrins of bisphenol A diglycidyl ether (BADGE) and of bisphenol F diglycidyl ether (BFDGE) in canned foods and ready-to-drink coffees from the Japanese market

BADGE.2HCl and BFDGE.2HCl were determined in 28 samples of ready-to-drink canned coffee and 18 samples of canned vegetables (10 corn, 5 tomatoes and 3 others), all from the Japanese market. HPLC was used as the principal analytical method and GCMS for confirmation of relevant LC fractions. BADGE.2HCl was found to be present in one canned coffee and five samples of corn, BFDGE.2HCl in four samples of canned tomatoes and in one canned corn. No sample was found which exceeded the 1mg/kg limit of the EU for the BADGE chlorohydrins. However the highest concentration was found for the sum of BFDGE.2HCl and BFDGE.HCl.H₂O at a level of 1.5mg/kg. A Beilstein test confirmed that all cans containing foods contaminated with BADGE.2HCl or BFDGE.2HCl had at lest one part coated with a PVC organosol.     

European priorities for research to support legislation in the area of food contact materials and articles

A strong science base is required to underpin the planning and decision-making process involved in determining future European community legislation on materials and articles in contact with food. Significant progress has been made in the past 5 years in European funded work in this area, with many developments contributing to a much better understanding of the migration process, and better and simpler approaches to food control. In this paper this progress is reviewed against previously identified work-areas (identified in 1994) and conclusions are reached about future requirements for R&D to support legislation on food contact materials and articles over the next 5 or so years.     

Analysis of benzo[a]pyrene in spiked fatty foods by second derivative synchronous spectrofluorimetry after microwave-assisted treatment of samples

A simple, rapid and inexpensive method has been developed for the determination of benzo[a     

The development of reference materials for paralytic shellfish poisoning toxins in lyophilized mussel. II: Certification study

This paper describes the second part of a project undertaken to develop certified mussel reference materials for paralytic shellfish poisoning toxins. In the first part two interlaboratory studies were undertaken to investigate the performance of the analytical methodology for several PSP toxins, in particular saxitoxin and decarbamoyl-saxitoxin in lyophilized mussels, and to set criteria for the acceptance of results to be applied during the certification exercise. Fifteen laboratories participated in this certification study and were asked to measure saxitoxin and decarbamoyl-saxitoxin in rehydrated lyophilized mussel material and in a saxitoxin-enriched mussel material. The participants were allowed to use a method of their choice but with an extraction procedure to be strictly followed. The study included extra experiments to verify the detection limits for both saxitoxin and decarbamoyl-saxitoxin. Most participants (13 of 15) were able to meet all the criteria set for the certification study. Results for saxitoxin.2HCl yielded a certified mass fraction of <0.07 mg/kg in the rehydrated lyophilized mussels. Results obtained for decarbamoyl-saxitoxin.2HCl yielded a certified mass fraction of 1.59+/-0.20 mg/kg. The results for saxitoxin.2HCl in enriched blank mussel yielded a certified mass fraction of 0.48 +/- 0.06 mg/kg. These certified reference materials for paralytic shellfish poisoning toxins in lyophilized mussel material are the first available for laboratories to test their method for accuracy and performance.     

Announcing a new international peer-reviewed journal:Food Science and Human Wellness now accepting manuscript submission in English

<正>We are pleased to announce the launch of a new international peer-reviewed journal-Food Science and Human Wellness,ISSN 2213-4530,which is an open access journal,produced and hosted by Elsevier B.V.on behalf of Beijing Academy of Food Sciences.Food Science and Human Wellness is an international peer-reviewed English journal that provides a forum for the dissemination of the