STRUCTURE, MOLECULAR WEIGHT AND BIOACTIVITIES OF (1→3)-β-D- GLUCANS AND ITS SULFATED DERIVATIVES FROM FOUR KINDS OF LENTINUS EDODES

Lentinan samples, (1→3)-β-D-glucans containing 4.6-15.2 wt% proteins, coded as L-I1, L-I2, L-I3 and L-I4 (L-I)were isolated from four kinds of Lentinus edodes. These glucans were treated with acetone to remove the protein in order to obtain free protein glucans coded as LNP-I1, LNP-I2, LNP-I3 and LNP-I4 (LNP-I). The free-protein polysaccharides were sulfated to give derivatives (S-LNP-I) with degree of substitution (DS) from 0.4-0.8. The structural features and weight- average molecular weight (Mw) of the samples were investigated by using infrared spectroscopy, elemental analysis,13C-NMR, size exclusion chromatography combined with laser light scattering (SEC-LLS) and viscometry. The effects of structure and conformation of the polysaccharides on antitumor activities were assayed in vivo (Sarcoma 180 solid tumors)and in vitro (Sarcoma 180, HL-60, MCF-7 and Vero tumors). The results indicated that the predominant species of the samples L-I and LNP-I in 0.2 mol/L NaCl aqueous solution existed as triple-helical chains with high rigidity and in dimethyl sulfoxide (DMSO) as single-flexible chains. Interestingly, the antitumor activities of LNP-I are lower than those of the native glucans (L-I), whereas their sulfated derivatives have higher inhibition ratio against Sarcoma 180 than LNP-I. The results reveal that the binding of protein, sulfated modification and the triple helix conformation are important factors in the enhancement of the antitumor activities of polysaccharides on the whole.     

CRITICAL CONCENTRATIONS OF α(1→3)-D-GLUCAN FROM LENTINUS EDODES IN NaOH AQUEOUS SOLUTION

Critical concentrations of α-(1→3)-D-glucan L-FV-Ⅱ from Lentinus edodes were studied by viscometry andfluorescence probe techniques. The dependence of the reduced viscosity on concentration of the glucan in 0.5 mol/L NaOHaqueous solutions with or without urea showed two turning points corresponding to the dynamic contact concentration c_s andthe overlap concentration c~* of the polymer. The values of c_s and c~* were found to be 1×10~(-3) g cm~(-3) and 1.1×10~(-2) g cm~(-3),respectively, for L-FV-Ⅱ in 0.5 mol/L NaOH aqueous solutions. The two critical concentrations of L-FV-Ⅱ in 0.5 mol/LNaOH aqueous solutions were also found to be 1.2×10~(-3) g cm~(-3) fbr c_s and 9.2×10~(-3) g cm~(-3) for c~* from the concentrationdependence of phenanthrene fluorescence intensities. The overlap concentration c~* of L-FV-Ⅱ in 0.5 mol/L NaOH aqueoussolutions was lower than that of polystyrene with same molecular weight in benzene, owing to the fact that polysaccharidetends to undergo aggregation caused by intermolecular hydrogen bonding. A normal viscosity behavior of L-FV-Ⅱ in 0.5 mol/L urea/0.5 mol/L NaOH aqueous solutions can still be observed in an extremely low concentration range at 25℃.     

Highly Efficient Regio- and Stereoselective Synthesis of β-（1 →6）-Branched β-（1 →3）-Linked Glucohexaose and Its Analogue

A β-（1→）6）-branched β-（1→）3）-linked glucohexaose （1） and its lauryl glycoside （2）, present in many biologically active polysaccharides from traditional herbal medicines such as Ganoderma lucidum, Schizophyllum commune and Lentinus edodes, were highly efficiently synthesized. Coupling of 2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl- （1--）3）-2-O-benzoyl-4,6-O-benzylidene-a-D-glucopyranosyl trichloroacetimidate （7） with 3,6-branched acceptors 8 and 12 gave β-（1→）3）-linked pentasaccharides （9） and （13）, then via simple chemical transformation 4＇,6＇-OH pentasaccharide acceptors 10 and 14 were obtained. Regio- and stereoselective coupling of 3 with 10 and 14 gave β-（1→）3）-linked hexasaccharides （11） and （15） as the major products. Deprotection of 11 and 15 provided the target sugar 1 and 2. Thus, a new method for the preparation of this kind of compounds was developed.     

3-D-（β-D-吡喃葡萄糖-1-基）-6-（4-卤代苯基）哒嗪的合成与表征

利用6-(4-卤代苯基)-3(2H)-哒嗪酮的银盐(2)与2，3，4，6-四-O-乙酰基-1-溴-1-脱氧-α-D-吡喃葡萄糖(3)发生Koenig’s-knorr反应，合成了3-0-(2，3，4，6-四-O-乙酰基-β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(4)，4用干燥的氨气在0℃～-5℃下处理脱乙酰基保护基得相应的3-O-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)哒嗪(5)。其结构经元素分析，IR及1H NMR证实。     

具有β-(1→6)-半乳吡喃糖骨架和α-L-(1→3)-阿拉伯呋喃糖侧链的阿拉伯半乳寡糖的简易合成

4-Methoxyphenyl glycoside of β-D-Galp-(1→6)-[α-L-Araf-(1→3)-]β-D-Galp-(1→6)-β-D-Galp-(1→6)-{β-D-Galp-(1→6)-[α-L-Araf-(1→3)-]β-D-Galp-(1→6)-β-D-Galp-(1→6)-}2β-D-Galp-(1→6)-[α-L-Araf-(1→)3)-]β-D-Galp-(1→)6)-β-D-Galp was synthesized with 2,3,4,6-tetra-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (1), 6-O-acetyl-2,3,4-tri-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate (11), 4-methoxyphenyl 3-O-allyl-2,4-tri-O-benzoyl-β-D-galactopyranoside (2),isopropyl 3-O-allyl-2,4-tri-O-benzoyl--thio-β-D-galactopyranoside (12),4-methoxyphenyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside (5), and 2,3,5-tri-O-benzoyl-α-L-arabinofuranosyl trichloroacetimidate (8) as the key synthons.     

PREPARATION AND STRUCTURE OFFIVE DERIVATIVES OFβ-(1→3)-D-GLUCAN ISOLATED FROM PORIA COCOS SCLEROTIUM*

A new solvent of cellulose (1.5 mol/L NaOH/0.5 mol/L urea aqueous solution) was used as one of the homogeneous reaction media of polysaccharides for methylation, hydroxyethylation and hydroxypropylation. A water insoluble β-(1→3)-D-glucan, sample PCS3-Ⅱ, isolated from fresh sclerotium of Poria cocos was sulfated in dimethyl sulfoxide (Me2SO), carboxymethylated in NaOH, isopropanol solution, as well as methylated, hydroxyethylated and hydroxypropylated in the new solvent system, respectively, to obtain five water-soluble derivatives coded as S-PCS3-Ⅱ, C-PCS3-Ⅱ, M-PCS3-Ⅱ, HE-PCS3-Ⅱand HP-PCS3-Ⅱ. Their chemical structure and distribution of substitution were characterized by infrared spectroscopy (IR), elementary analysis (EA), ^1H-NMR, ^13C-NMR, 2D-COSY, 2D-TOCSY and 2D-^1H-detected ^1H ^13C HMQC spectra. The results reveal that the relative reactivity of hydroxyl groups of the β(1→3)-D-glucan is in the order C-6 ＞ C-4 ＞ C-2 on the whole. The substitution of the samples S-PCS3-Ⅱ, C-PCS3-Ⅱ and M-PCS3-Ⅱ occurred mainly at C-6 position and secondly at C-4 and C-2 positions, and that of HE-PCS3-Ⅱ occurred at C-6 and C-4 positions and of HP-PCS3-Ⅱ almost completely occurred at C-6 position. The degrees of substitution (DS) obtained from ^13C-NMR range from 0.23 to 1.27. The water solubility of the derivatives is in the order S-PCS3-Ⅱ ＞ C-PCS3-Ⅱ ＞ M-PCS3-Ⅱ ＞ HE-PCS3-Ⅱ ＞ HP-PCS3-Ⅱ. This work provides a novel and nonpolluting process for the methylation, hydroxyethylation and hydroxypropylation of β-(1→3)-D-glucan.     

Synthesis, Structure and Biological Activities of 2-（1H- 1,2,3-Benzotriazol-1 -yl ）-1-（ 4- methylphenyl ）-2-（1H-1,2,4-triazol-l-yl）-1-ethanone

The title compound was synthesized and characterized by IR, ^1H NMR, elemental analysis and single crystal X-ray diffraction analysis. Its biological activities were also tested. The results show that the title compound reveals inhibiting activities towards wheat gibberellin, apple ringspot, tomato early blight, peanut cercospora arachidicola and stem wilt of asparagus.     

Synthesis and Crystal Structure of 1-（Trifluoromethyl）-1-（propioloyl）-（E）-3-oxo-（2-thienyl）-（2-naphthylamine）

1INTRODUCTIONTheSchiffbasesderivedfromb-diketonesandaliphaticamineshavebeenshowntoexistastheketo-amines.However,ifsubstituentseitherattheketooraminogrouparearomatic,itmaybeexpectedtheenoliminewillbethefavoredtautomericform[1].Recently,someSchiffbasesderivedfromTTA(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione)andPMBPhavebeenstudiedbyWang[2]andYu[3]etal.Inordertostudytherelationshipbetweenthestructuresandperformancesofthesecompounds,thetitlecom-poundwillbereportedherein.2EXPERIMENT…     

聚辛烯-1Mark-Houwink常数的确定及其分子量分布研究

本文用GPC结合特性粘度的方法,对聚辛烯-1四氢呋喃体系的Mark-Houmink常数进行订定。数据处理采用了Weiss法和流体力学平均分子量(?)_x两种方法,α值分别为0.701和0.625,相对误差10％左右,所得Mark-Hon-Wink方程Weiss法为:[η]_(THF)~(25℃)=3.89×10~(-4)[M]~(0.701)(?)_x法为[η]_(THF)~(℃25)=4.14×10~(-4)M~(0'625)。本文还研完了聚合反应条件对聚辛烯-1分子量及分子量分布的影响。发现三种TiCl_3为主催化剂,三乙基铝为助催化剂时,其GPC谱图均为双峰型,两个峰的比例随聚合反应条件不同而变化。表明聚合体系至少有两种不同性质的活性中心,有着不同的形成和增长速率。     

1-(2-羟基-3,5-二硝基苯基)-3-[4-(苯基偶氮)苯基]-三氮烯与锌的显色反应及其应用

研究了 1 (2 羟基 3,5 二硝基苯基 ) 3 [4 (苯基偶氮 )苯基 ] 三氮烯 (HDNPAPT)与锌(Ⅱ )的显色条件。在乳化剂OP存在下的氢氧化钠介质中 ,在 5 2 5nm波长处 ,锌与HDNPAPT形成稳定的 1∶2的红色配合物 ,表观摩尔吸光系数ε52 5=9.15× 10 4 L·mol- 1·cm- 1,锌 (Ⅱ )浓度在 0～ 10 μg/ 2 5ml范围内符合比耳定律。方法已应用于人发、面粉中微量锌的测定 ,结果满意     

1—羟基—2（1H）—吡啶硫酮及其甲基衍生物与Cr（Ⅲ）配合物的合成和性质

Edrissi认为Cr(Ⅲ)与1-羟基-2(1H)-吡啶硫酮(HPT)的甲基衍生物不能给出任何反应,并且将与HPT的配合物注明为绿色溶液。本文在过去工作的基础上合成了S-(1-氧化-2-吡啶基)硫代苯甲酸酯(PTB)和3-CH_3-PTB;并合成了3个铬配合物。通过元素分析,紫外-可见,红外光谱,摩尔电导和TG-DTA-DTG作了表征。探讨了形成机理并研究了抑菌活性。     

碳笼（C_（60）／C_（70））载体钕系催化聚合丁二烯的研究 Ⅱ．聚合物分子量及其微观结构

碳笼（Ｃ_（６０）／Ｃ_（７０））载体钕系催化聚合丁二烯的研究Ⅱ．聚合物分子量及其微观结构赵春英，陈滇宝，仲崇祺，柳润平，徐玲，唐学明（青岛化工学院高分子材料系青岛２６６０４２）关键词球笼钕催化剂，聚丁二烯，分子量及其分布，微观结构目前，稀土催化双烯烃...     

1-氧代-4(取代)-2,6,7-三氧杂-1-磷杂双环[2,2,2]辛烷晶体结构研究

具有双环笼状结构的磷酸酯类化合物的合成始于60年代。由于其分子呈高度对称的笼状结构及其衍生物具有很强的生物活性而且作用机理独特,引起人们普遍的关注。某些衍生物可用作杀菌剂,杀螨剂,除草剂,灭火剂,树脂稳定剂等等.由于此类化合物的生理作用机理不同于常用的有机磷农药.因此,可能会成为潜在的农药新途径。对此类化合物的晶体结构的测定,至今只有有限文献报导,为了研究其分子结构与化学性质及生物活性的关系,本文分析了四个磷氧杂双环磷酸酯类化合物的晶体结构,其合成方法已有报导。     

新试剂1-(4-安替比林)-3-(4-溴苯基)-三氮烯的合成及其与镉的显色反应研究

新试剂１－（４－安替比林）－３－（４－溴苯基）－三氮烯的合成及其与镉的显色反应研究佘志刚（广东药学院药学系广州５１０２２４）龚楚儒（湖北师范学院化学系黄石４３５００２关键词镉，１－（４－安替比林）－３－（４－溴苯基）－三氮烯，合成，显色反应中图分类号...     

Synthesis of propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4-di-O-(2s-methylbutyryl)-α-L-rhamnopyranosyl]-(1→2)=(3-O-acetyl-β-D-glucopyranosyl)-(1→2)-βp-D-fucopyranoside,the tetrasaccharide moiety of Tricolorin A

Propyl O-(α-L-rhamnopyranosyl)-(1→3)-[2,4di-O-(2s-methylbutyryl)-α-L-rhamnopyranosyl]-(1→2)-(3-O-acetyl-β-glucopyranosyl)-(1→2)-β-D-fucopyranoside (1), the tetrasaccharide moiety of Ricolorin A, was synthesized in total 23 steps with a longest linear sequence of 10 steps, and overall yield of 3.7% from D-Glucose. The isomerization of the dioxolane-type benzylidene in the prance of NIS/AgOTf was observed. Tetrasaccharide 1 exhibited no activity against the cultured P388 cell as Tricolorin A did.     

Die Hydrolyse des 1, 1, 3, 3-Tetrakis(dimethylamino)-1λ5, 3λ5-diphosphets

Hydrolysis of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵, 3λ⁵ -diphosphete Hydrolysis of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵, 3λ⁵ -diphosphet ( 2 ) yields in the first step Bis(dimethylamino)phosphorylmethyliden-methyl-bis(dimethylamino)phosphorane ( 5 ). In the second step Bis(dimethylamino)phosphoryl-methyl(dimethylamino)phosphosphonylmethylen ( 6 ) is the main product of hydrolysis. In addition small amounts of methylphosphonic-bis(dimethylamide) ( 7 ) are formed. Properties, nmr and mass spectra of 5 and 6 are described, their mechanism of formation is discussed.     

新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯的合成及其与汞的显色反应研究

合成了新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯(DCNPNPT),测定了试剂的亚氨基离解常数pKa＝9．2。在TritonX-100存在下,pH9．8～11．0范围内,试剂与Hg2+形成14黄色型配合物,用双波长法测得其表观摩尔吸光系数为2．27×105L·mol-1·cm-1。汞含量在0～10μg／25ml范围内符合比耳定律,用此法测定了天然水和实验室废水中微量汞含量,结果满意。