Reactivity of green tea catechins with formaldehyde

In the reaction of green tea catechins with formaldehyde at room temperature (25°C), tea catechins were found to have reactivity. In particular, (-)-epicatechin gallate and (-)-epigallocatechin gallate, which have a galloyl moiety at the C-3 position, showed higher reactivity than (+)-catechin, (-)-epicatechin, or (-)-epigallocatechin. Reactivity of various kinds of simple phenolic compounds and flavonoids with formaldehyde was also examined. Among these compounds, only phloroglucinol showed reactivity to the same degree as that of nongalloylated catechins. These results suggest that factors for reactivity with formaldehyde at room temperature may be the presence of a phloroglucinolic A-ring structure and the absence of the electron-attractive group such as a carbonyl group in Cring. The comparison of the reactivity of 3-O-acylated catechins with that of 3-O-galloylated catechins indicated that only a galloyl group effectively enhanced reactivity with formaldehyde.     

Accumulation of flavanols in yellowing beech leaves from forest decline sites

Beech leaves were sampled during two consecutive years from three sites characterized by forest decline. Both monomeric and oligomeric flavanols from green and yellowing leaves were determined quantitatively by reversed-phase, high-performance liquid chromatography (HPLC) combined with a chemical reaction detection technique (CRD). Yellowing leaves generally contained more than twice the quantity of flavanols than normal green leaves. The monomeric flavanols, epicatechin and (+)-catechin, comprised up to 80% of the total flavanol fraction. Histochemical staining with p-dimethylaminocinnamaldehyde was used to determine local deposition of flavanols, including insoluble oligomeric flavanols, in leaf tissues. The yellowing leaves stained intensely, whereas the green leaves stained lightly. Flavanol staining was strongest in the spongy parenchyma followed by the palisade cells. The upper epidermis stained more intensely than the lower epidermis. A 4-day treatment of small leaf pieces (5 x 5 mm) with 0.04 mM paraquat resulted in browning of the leaf pieces. The browning reaction was prevented when the paraquat treatment was carried out in the presence of 0.16 mM (+)-catechin, indicating an antioxidative property for this flavanol.     

Color development of proanthocyanidins in vanillin-hydrochloric acid reaction

The influence of proanthocyanidin (PA) structures contained in bark on color development in the vanillin-hydrochloric acid (V-HCl) method used widely as a quantitative method for measuring PA were examined. The maximal absorption wavelength was different in terms of the bark from which the PA was obtained. Phenyl nucleus (resorcinol, phloroglucinol) constituting the A-ring of PA reacts with vanillin to produce the color. The maximal absorption wavelengths of the solutions from synthesized procyanidin and profisetinidin were 500 and 540 nm, respectively, indicating that the color tone differs in the V-HCl method based on the hydroxylation patterns of the A-ring. The colored solution of (+)-catechin with vanillin was dialyzed, and the resulting product (C-VC) was analyzed by gel permeation chromatography and ¹H nuclear magnetic resonance. It was found that C-VC was a polymer complex consisting of 9mol (+)-catechin moieties and 10mol vanillin moieties. It was presumed that the cationized vanillin molecules that do not combine with (+)-catechin play an important role on color development in the presence of C-VC.This study was presented at the 44th and 45th Annual Meetings of The Japan Wood Research Society, Nara and Tokyo, April 1994 and April 1995     

木质素模型化合物香草醛Mannich反应及其产物化学结构表征

以木质素模型化合物香草醛、二乙醇胺及多聚甲醛为原料,1,4-二氧杂环己烷为溶剂,通过Mannich反应合成了香草醛胺基多元醇,研究了物料配比、反应温度、时间及溶剂用量等因素对Mannich反应的影响。实验结果表明:反应物料按物质的量比n(香草醛)∶n(甲醛)∶n(二乙醇胺)1∶1∶1,甲醛与二乙醇胺60℃反应2 h生成1,3-氧氮杂环戊烷,再将其滴入香草醛中,80℃反应3 h,二氧六环溶剂用量为100 mL/mol(以香草醛的物质的量计),二乙醇胺的转化率最高可达到84.92%。采用HPLC、LC-MS、FT-IR及1H NMR表征了香草醛胺基多元醇的化学结构,相对分子质量269。     

Isolation of (+)-catechin and a new polyphenolic compound in Bengal catechu

Methanol extractives from the red heartwood of Bengal catechu (Acacia catechu) contained (+)-catechin as a major component making up 0.3% of the wood. A new polyphenolic compound with a (+)-homo-iso-catechin structure and having catechol and phloroglucinol moieties constituted 0.005% of the wood, and probably its epimeric compound in trace amounts, were also found.This report was presented at the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1999 and the 44th Lignin Symposium, Gifu, October 1999     

薯莨及红根皮单宁组分的研究(凝缩类单宁组分研究之四)

从薯莨(Dioscorea cirrhosa)块茎及红根(Rosa spp.)根皮提取物中分离出来的单宁,通过各种降解反应及波谱方法研究,均判定为原花青定。其中的终端单元及延伸单元,都由(+)-儿茶素及(-)-表儿茶素组成,但(-)-表儿茶素单元在薯莨原花青定中占大部分,(+)-儿茶素单元在红根原花青定中占大部分。     

木麻黄及山槐树皮单宁组分的研究(凝缩类单宁组分研究之二)

从木麻黄(Casuarina equisetifolia)及山槐(Albizzia kalkora)树皮提取物中分离出来的水溶性单宁,通过各种降解反应及波谱方法研究,判定均为原花青定,且二者在化学组成上十分相似,它们的终端单位均由各占一半左右的(+)—儿茶素及(-)—表儿茶素组成,二者的比例为6:4。延伸单元亦均由(+)—儿茶素与(-)—表儿茶素组成,而以(-)—表儿茶素占绝大部分,二者的比例约为3:7。它们的分子中,2,3—反式与2,3—顺式单元的比例约为2:8。木麻黄和山槐树皮单宁的平均聚合度分别为12和14。     

Water sorption mechanisms of commercial wood adhesive films

As water moves inside the wood, the gluelines might act as barriers that are potentially leading to local moistening. Even low amounts of water may influence the mechanical performance of glued wood products. Dynamic vapor sorption analysis was performed to assess the sorption processes of six commercial wood adhesives. Vapor sorption isotherms were compared with vapor uptake dynamics. Phenol–resorcinol–formaldehyde showed high moisture uptake of 18 %, while vapor diffusion speed was low. Fish glue showed a water uptake of 45 % at otherwise moderate vapor uptake speed. Melamine–formaldehyde resin gained 22 % water, and polyvinyl acetate absorbed 10 %. The latter was also the fastest vapor absorbing adhesive. Polyurethane only absorbed 3.5 % of moisture at medium uptake speed. Mechanisms of water diffusion seem to be driven by (1) the available free volume in the polymer and (2) the interacting ionic groups of the polymer chain. While the free volume could be linked to the accumulated moisture, the ionic group interaction might determine the measured vapor diffusion dynamics.     

落叶松树皮单宁组分的研究(凝缩类单宁组分研究之一)

从兴安落叶松(Larix gmelini)树皮提取物中分离出来的水溶性单宁,通过花色素反应、硫解反应、间苯三酚反应、~(13)C-核磁共振、旋光、紫外光谱和红外光谱等方法研究,判定为原花青定。落叶松树皮原花青定的终端单元由(+)—儿茶素及(—)—表儿茶素组成,二者的比例为8:2,延伸单元由(+)—儿茶素及(—)—表儿茶素组成,二者的比例约为3:7,水溶性单宁分子的平均聚合度约为8。     

Radical scavenging capacity of Agrimonia eupatoria and Agrimonia procera

The antioxidant activity of Agrimonia eupatoria (Agrimony) and Agrimonia procera (Fragrant agrimony) extracts was assessed by measuring in DPPH radical scavenging and ABTS(+) radical decolourisation reaction systems. Radical scavenging capacity of agrimony extracts varied in a wide range (9.1-97.5% in DPPH reaction and 6.7-79.5% in ABTS reaction) depending on the polarity of the solvent used to obtain the extract.     

Isolation of a novel catechin from Bergenia rhizomes that has pronounced lipase-inhibiting and antioxidative properties

An aqueous ethanol extract of Bergenia crassifolia rhizomes strongly inhibited human pancreatic lipase activity and increased scavenging of DPPH free radicals in vitro. Chromatographic separation of this extract led to isolation of the hydrolysable tannins (+)-catechin 3,5-di-O-gallate () and (+)-catechin 3-O-gallate (). This is the first report of the isolation of compound 1 from plant material. This compound strongly inhibited human pancreatic lipase (with an IC₅₀ value of 0.42 μg/ml) and exhibited a remarkable free radical-scavenging ability (with an SC₅₀ value of 1.04 μg/ml). The chemical structures of 1 and 2 were elucidated using MS, NMR and chemical approaches.     

日本落叶松新鲜松针的化学成分及其抗氧化活性研究

研究了日本落叶松新鲜松针的化学成分及其抗氧化活性.采用Sephadex LH-20柱色谱及薄层色谱等方法进行分离,从其95%乙醇提取物乙酸乙酯溶性部分中分到7种化合物,经波谱分析及理化性质化合物分别鉴定为:儿茶素(1)、表儿茶素(2)、没食子儿茶素(3)、异鼠李素-3-O-葡萄糖苷(4)、紫云英苷(5)、2"-O-鼠李糖牡荆黄苷(6)和cedrusin (7).7种化合物均首次从该植物中分得.经DPPH试验,测定了核酸溶性部分、二氯甲烷溶性部分、乙酸乙酯溶性部分、水溶性部分、粗提物及分得化合物的抗氧化活性.其中乙酸乙酯溶性部分及化合物1～3具有很强的抗氧化活性.     

Investigation of the free radical scavenging activity of Ginkgo biloba L. leaves

The free radical scavenging activity of methanolic, ethanolic and aqueous extracts from Ginkgo biloba leaves, has been determined by EPR (electron paramagnetic resonance) using the DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging method. The investigation has also included selected constituents of G. biloba leaves, protocatechuic and p-coumaric acids, quercetin, rutin, isoginkgetin and (+)-catechin.     

Contribution of lignin to the reactivity of wood in chemical modifications II: influence of delignification on reaction with vaporous formaldehyde

Participation of lignin in the reaction between vapor-phase formaldehyde and wood was examined by using gradually delignified wood meal. A fi rst-order rate equation was successfully applied to the weight gain data. From the estimated reaction parameters such as rate constant, k, and ultimate weight gain, a, the reactivity toward formaldehyde was discussed among wood components, and compared with that for acetylation. k decreased monotonously with progress of the elimination of lignin, suggesting that the reaction rate of lignin is dominant over that of whole wood, and the decrease in the ratio of lignin retarded the reaction of wood as a whole. On the other hand, a increased with decreasing lignin content. This may be attributable to the enhanced reactivity of the remaining lignin due to some structural changes and to the increase in the number of reactive sites in polysaccharides as a result of their exposure accompanying the elimination of lignin. The dependencies of k and a on the lignin content were not similar to the case for acetylation, probably because of the difference in the reaction phase. In vapor-phase formaldehyde treatment, the remaining lignin reacts as it is, whereas in liquid-phase acetylation it would undergo rearrangement or swelling of the structure in the reaction solution.     

光催化提高黑荆树单宁与甲醛反应能力研究

为提高黑荆树单宁与甲醛反应能力,以纳米TiO 2为催化剂对黑荆树单宁进行紫外光催化降解。以降解物的甲醛结合量为指标,分析催化剂用量对黑荆树单宁降解产物甲醛反应能力的影响。采用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)测定黑荆树单宁和具有最大甲醛结合量黑荆树单宁降解产物的分子量和聚合度。采用傅里叶转换红外光谱(FT-IR)对黑荆树单宁及具有最大甲醛结合量黑荆树单宁降解产物的官能团进行表征。结果表明,催化剂用量对降解物甲醛结合量的影响较大,当紫外光功率为400 W、溶液初始质量浓度为60 g/L、反应温度为(35±5)℃、纳米TiO 2添加量为4%(质量分数,以黑荆树单宁质量计)、降解时间为10 h时,降解物的甲醛结合量达到最大值(1.13 g/g),超过了苯酚和间苯二酚的甲醛结合量(0.89 g/g和0.94 g/g),有替代苯酚和间苯二酚与甲醛反应制备木材用胶黏剂的潜能。MALDI-TOF MS分析表明,黑荆树单宁的聚合度和分子量均有明显地下降趋势,降解物分子量分布集中于低分子量部分。FT-IR分析表明,单宁结构中连接棓酰基的醚键、棓儿茶素的苯环骨架、芳醚键、单元间C—C连接键均被破坏。以上结果表明,可通过紫外光催化降解调控黑荆树单宁的化学组成并降低其聚合度和分子量,获得的降解物具有良好的甲醛反应能力。     

低甲醛释放量刨花板用脲醛树脂结构的研究(英文)

本文通过~(13)C NMR研究了脲醛树脂合成新工艺中不同反应阶段时的脲醛树脂的化学结构。研究结果表明脲醛树脂的化学结构主要受甲醛/尿素的摩尔比,pH值、反应温度和反应时间的影响。对脲醛树脂中主要的官能团:游离甲醛、亚甲基、亚甲基醚、Uron等相互关系也进行了研究。指出了生产低甲醛释放量,高力学性能刨花板用脲醛树脂中主要官能团的最佳含量。     

用不脱水低摩尔脲醛树脂制造低游离甲醛刨花板与中密度纤维板

试验结果表明差示扫描量热仪 (DSC)能够测得NLFS - 1型捕捉剂与甲醛反应 ,并且这种捕捉剂能够捕捉脲醛树脂胶中的大部分游离甲醛 ,其捕捉量与树脂的摩尔比或游离甲醛量有关。对于低摩尔比 ,不脱水脲醛树脂刨花板和中密度纤维板 ,仅用 5 %捕捉剂就能获得较高的捕捉能力。这些板的游离甲醛释放量均能达到欧洲E1级或国标GB -T11718- 1999A级标准。刨花板后期热处理 ,对板的内结合强度提高明显 ,但板的甲醛释放量略有增加     

天然黄酮Mannich碱衍生物的合成及生物活性研究

以柚皮苷和橙皮苷为原料,经碘/吡啶脱氢,O-甲基化和糖苷水解等反应,分别合成了2种天然黄酮芹菜素-5,4'-二甲醚(1)和木犀草素-5,3',4'-三甲醚(2)。然后以1和2为底物,分别与甲醛、二级胺在酸性醇溶剂中发生微波协助的Mannich反应,对黄酮8-位进行胺甲基化修饰,合成了15个新型黄酮Mannich碱衍生物3~17。所合成的化合物经~1H NMR、~(13) C NMR和MS等进行了结构确证,并采用细胞计数Kit-8(CCK-8)法测试了化合物1~17对子宫颈癌Hela细胞的体外抑制活性。结果表明,化合物1、2、7、9、10、12和17对Hela细胞增殖具有明显的抑制活性,其中化合物10、12和17的半数抑制浓度(IC_(50))分别为16.13、29.04和9.14μmol/L,活性高于阳性对照药物顺铂(IC_(50)为41.25μmol/L)。     

木材工业用胶粘剂发展前景

本文综述了国外近年来对新型合成胶粘剂（包括低毒性脲醛树脂胶粘剂,阻燃、防腐胶粘剂和异氰酸脂胶粘剂）、利用再生资源制各胶粘剂（包括木素、单宁和碳水化合物）和“非传统粘合”技术的研究进展。作者认为,今后发展趋势是对现有合成树脂胜粘荆进行改性并向高性能发展;开发原料来源丰富、成本低廉、性能更优的新型非甲醛系合成胶粘剂;充分利用再生资源制胶和开发“非传统粘合”技术。     

固体核磁共振法对低甲醛释放脲醛树脂化学结构的研究

在采用液体核磁对3种低甲醛释放脲醛树脂化学构造进行分析的基础上,利用13CCP/MASNMR对脲醛树脂固化产物的化学结构进行了研究.结果表明,不同固化体系下,3种低甲醛释放脲醛树脂胶黏剂的固化历程不同,固化后树脂的结构有所差别.不添加固化剂时,脲醛树脂的固化交联反应程度低,固化产物中羟甲基含量高,甲醛释放量也随之增加.加入固化剂后,促进了羟甲基的固化交联反应,脲醛树脂固化产物中羟甲基含量普遍降低.3种固化体系下,UF-3羟甲基含量最高;在氯化铵为固化剂的条件下,UF-2羟甲基含量最低,为0.0582;不添加固化剂和复合固化体系条件下,UF-1羟甲基含量最低,分别为0.0784和0.0713.不同固化体系对不同种类脲醛树脂的固化效果不同,固化后树脂的结构不同,其力学性能和甲醛释放能力也不同.