具有血液相容性的嵌段聚酯-聚醚接枝共聚物的合成

本文研究了嵌段聚酯-聚醚膜经紫外光活化后,于水溶液中铈盐引发亲水性单体丙烯酰胺在其表面上接枝共聚合反应。同时对接枝物进行了证实和表征。并通过活体动物血液灌流实验表明,此接枝共聚物具有良好的血液相容性。     

SYNTHESIS OF IMINO-C-DISACCHARIDES RELATED TO SUCROSE[1]

Stabilised ylides 1 and 10, prepared from perbenzylated and peracetylated allyl C-glucopyranosides, respectively, were reacted with differently protected D-serinal; osmylation of the obtained α,β-unsaturated ketones 3 and 12, followed by intramolecular reductive amination, afforded different imino-C-disaccharides 14, 15, 18, and 19 related to sucrose.     

RAFT法合成两亲性嵌段共聚物PSt-b-PAA-b-PSt及其在离子液体[BMIM][PF_6]中的自组装

用三硫代碳酸二(α,α′-二甲基-α-乙酸)酯(BDATC)作为链转移剂,苯乙烯St作为第一单体,通过可逆加成-断裂链转移聚合(RAFT)方法合成出大分子链转移剂PSt-CTA,以丙烯酸AA作为第二共聚单体合成出3个不同嵌段比的两亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸-b-聚苯乙烯(PSt-b-PAA-b-PSt).通过傅里叶变换红外光谱(FTIR)和核磁共振氢谱(1H-NMR)确定了PSt-b-PAA-b-PSt结构,使用凝胶渗透色谱(GPC)测定了大分子引发剂PSt-CTA和嵌段共聚物PSt-b-PAA-b-PSt的分子量及分子量分布.将这3个不同嵌段比的两亲性嵌段共聚物在离子液体1-丁基-3-甲基咪唑六氟磷酸盐[BMIM][PF6]中进行自组装,用透射电子显微镜(TEM)观察聚合物在离子液体中自组装结构.研究发现,当PSt的链段长度固定时,胶束的自组装形态主要依赖于PAA链的长度.当PAA链段较长时,胶束呈球形;PAA链段变得较短时,胶束的形态则由球形转变为核壳结构,并且胶束形态在25℃至100℃之间不受温度影响.     

SYNTHESIS AND APPLICATION OF SPACER-MODIFIED L-FUCOSE ANALOGUES[1]

Starting from 6-O-tert-butyldimethylsilyl-2,3;4,5-di-O-isopropylidenealdehydo-D-galactose (1), the carbon backbone elongated GDP-L-fucose analogue 15 bearing a chromophore tag at the end of a spacer was synthesized. Additionally, the analogues of 3-L-fucosyllactose (29) and 2′-L-fucosyllactose (36), where the fucosyl moiety is marked by a five atom alkyl chain at C-5, were prepared as labeled oligosaccharides of human milk.     

SYNTHESIS AND CONFORMATIONAL INVESTIGATIONS OF SULFATED CARBOHYDRATES[1]

Starting from the finding that methyl 2,3,4,6-tetra-O-sulfonato-β-D-glucopyranoside (3) existed in a conformational equilibrium of the two chair conformers, the effect of sulfation on conformational equilibria was further investigated using a number of sulfated saccharides. Three sulfate groups on positions 3,4, and 6 or two on positions 2 and 3 were not sufficient to induce the conformational change as shown with methyl 2-amino-2-deoxy-3,4,6-tri-O-sulfonato-β-D-glucopyranoside. N-Sulfation of the amino group of the latter compound furnished an equilibrium of chair conformers with less ¹ C ₄ conformer content than for 3. The presence of persulfated methyl β-D-galactopyranoside in the usual ⁴ C ₁ conformation suggested the involvement of the 4-O-sulfate in the effect. Methyl 2,3,4-tri-O-sulfonato-β-D-xylopyranoside was found to prefer the “all-axial” ¹ C ₄ conformation demonstrating that O-sulfates facilitate 1,3-O/O-diaxial interactions better than ester groups and in particular benzoates. Also, sulfated 1,5-anhydro-D-glucitol occurred as a conformational mixture, the influence of the anomeric effect may thus have been overestimated in the previous discussion of this conformational effect.     

机理转移法合成聚丁二烯-b-聚(甲基丙烯酸N,N-二甲氨基乙酯)两亲性嵌段共聚物

将活性负离子聚合与原子转移自由基聚合(ATRP)技术相结合,运用机理转移法制备了一种两亲性材料聚丁二烯-b-聚(甲基丙烯酸N,N-二甲氨基乙酯)(PB-b-PDMAEMA)嵌段共聚物.首先通过负离子聚合方法设计合成聚丁二烯,用环氧丙烷封端,2-溴异丁酰溴作酯化剂,合成具有活性端基溴的聚丁二烯大分子引发剂(PB-B r),再用其引发亲水性单体DMAEMA进行原子转移自由基聚合,聚合动力学证实了该聚合反应具有典型的活性/可控自由基聚合的特征.通过差示扫描量热法(DSC)研究嵌段共聚物的微相分离行为.制备的大分子引发剂及两亲性嵌段共聚物经凝胶色谱、红外和核磁表征证实了预定的结构.     

SYNTHESIS AND CHARACTERIZATION OF WATER-SOLUBLE BLOCK COPOLYMERS WITH AN END-TAGGED NAPHTHALENE PROBE

Water-soluble A-B block copolymers of 2-perfluoroethyl-2-oxazoline or 2-pentyl-2-oxazoline as hydrophobic monomers and 2-methyl-2-oxazoline as hydrophilic monomer were prepared by means of the living cationic ring-opening polymerization. The polymerization was initiated with N-methyl-2-(1-naphthyl)-2-oxazolinium trifluoromethanesulfonate as fluorescence label followed by sequential addition of the hydrophobic and the hydrophilic monomer. The polymerization was monitored by ¹H NMR spectroscopy and gel permeation chromatography (GPC) measurements. The results revealed that fluorophilic block copolymers can be prepared by this method while lipohilic block copolymers are not accessible by this monomer sequence. Micelle formation of the fluorophilic block copolymers in aqueous solution was studied by means of steady-state fluorescence spectroscopy which confirmed strong intermolecular excimer formation of the terminal bounded naphthalene moiety. In chloroform as a good solvent for both blocks, only monomer fluorescence could be observed.     

单茂钛催化剂用于苯乙烯-乙烯嵌段共聚物的合成与表征

乙烯（Ｅ）与苯乙烯（Ｓ）的嵌段共聚合用自制的两种催化剂———茂基三呋喃甲氧基钛［ＣｐＴｉ（ＯＣＨ２Ｏ）３］和茂基三苄氧基钛［ＣｐＴｉ（ＯＣＨ２Ｐｈ）３］进行了研究．考察了促进剂三甲基铝（ＴＭＡ）及乙烯的预聚合时间对聚合结果的影响，发现不同的催化体系有不同的［ＴＭＡ］最佳值以及随着乙烯预聚合时间的延长总的催化效率降低．对嵌段共聚合产物用丁酮、四氢呋喃和氯仿连续萃取分离，得到四氢呋喃中的可溶级分即嵌段共聚物ＰＥ ｂ ｓＰＳ，它占总嵌段共聚合产物的４０ｗｔ％～６０ｗｔ％．对嵌段共聚物用ＤＳＣ、ＷＡＸＤ、ＦＴＩＲ和１３Ｃ ＮＭＲ等方法进行了表征．     

EFFICIENT SYNTHESIS OF POLYLACTOSAMINE STRUCTURES THROUGH REGIOSELECTIVE GLYCOSYLATIONS[1]

Di-, tri- and tetramers of β-(1→3)-linked N-acetyllactosamine residues have been synthesised as their methyl glycosides, to be used in ITC binding studies to various galectins. The synthetic strategy involves two types of regioselective glycosylations: couplings of a galactosyl donor to 3,4-diol N-tetrachlorophthalimido glucose acceptors to give the lactosamine monomer building blocks, and subsequent formation of the oligomers through consecutive couplings of lactosamine donors to 2′,3′,4′-lactosamine acceptors, with high selectivity for the desired products.     

A FACILE SYNTHESIS OF DIETHYL 1- ISOTHIOCYANO)ALKYLPHOSPHONATES[1]

Abstract

Novel, diethyl 1-(isothiocyano)alkylphosphonates 3 have been efficiently synthesized via a one-pot reaction of diethyl 1-azidoalkylphosphonates 1 with triphenylphosphine, followed by in situ transformation of thus formed phosphazenes 2 with carbon disulfide. Application of the title compounds in the synthesis of diethyl (N-phenylthioureido)- and (benzothiazol-2-ylamino)methylphosphonates was also described.     

4，4＇－偶氮二［4－氰基戊酰（对－二甲氨基）苯胺］作为引发剂的嵌段共聚物合成

４，４＇－偶氮二［４－氰基戊酰（对－二甲氨基）苯胺］作为引发剂的嵌段共聚物合成邱醒宇，魏峰，关宏宇，平学真（辽宁大学化学系，沈阳，１１００３６）关键词４，４＇－偶氮二［４－氰基戊酰（对－二甲氨基）苯胺］，多官能团引发剂，自由基聚合７０年代以来，陆续报...     

4，4＇－偶氮二［4－氰基戊酰（对－二甲氨基）苯胺］作为引发剂的嵌段共聚物合成

his paper describes a new polyfimctional inihator, 4,4'-azobis[4-cyanopentanoyl (p-dimethylandno)anilide] (ACPDA), for the the radical polymerization. It was obtained by the rcaction of 4,4'-azobis(4-cyanopentanoyl chloride) with p-amino-N, N-dimethylaniline' ACPDA contains two reaction centres with different reactvities that are azo-group and N, N-dimethylaniline-group. By the controlled different conditions this initator can be utilized to make block polymers.     

用SN型催化剂合成苯乙烯一丙烯嵌段共聚物的研究──Ⅰ．聚合条件对共聚合反应的影响

用稀土化合物改性的钛系载体催化剂（ＳＮ催化剂）进行苯乙烯和丙烯顺序嵌段共聚合（Ｓｅｑｕｅｎｔｉａｌｂｌｏｃｋｃｏｐｏｌｙｍｅｒｉｚａｔｉｏｎ）的研究．考察了苯乙烯预聚时间、单体比、外加给电子体（ＥＢ）、烷基铝浓度、催化剂浓度和聚合温度等条件对共聚合的影响．发现外加酯（ＥＢ）降低了共聚合反应催化活性，在ＥＢ／Ｔｉ摩尔比为５范围内，外酯有助于提高嵌段共聚物（ｉＰＳ—ｂ—ｉＰＰ）中ＰＳ段和ＰＰ段的等规度及增加苯乙烯链节含量．ＳＮ型催化剂对苯乙烯一丙烯嵌段共聚合有较高的催化活性，催化效率在１００ｇ聚合物／ｇ－Ｔｉ以上．共聚物通过溶剂革取分级除去均聚物后，所得嵌段共聚物中苯乙烯链节含量可在１５～８５ｍｏｌ％之间调节．其结构表征续见第ＩＩ报．     

SYNTHESIS OF NEW 2,3-UNSATURATED O-GLYCOSIDES THROUGH FERRIER REARRANGEMENT[1]

The synthesis of five new 2,3-unsaturated O-glycosides (3a—e) employing Ferrier's rearrangement with different catalysts, is reported.     

A SONOCHEMICAL PROTOCOL FOR THE SYNTHESIS OF PERMODIFIED CYCLODEXTRINS[1]

A series of O-peralkylated β- and γ-cyclodextrins, commonly used as stationary phases in high-resolution gas chromatography or as drug carriers, has been prepared both according to the usual methods and with sonocatalysis. The sonochemical protocol, using either a common cleaning bath or sonochemical apparatus, resulted in markedly improved yields, reaction times and reproducibility.     

SYNTHESIS AND CRYSTAL STRUCTURE OF A HETERODINUCLEAR COMPLEX OF PALLADIUM SILVER WITH BRIDGING BIS-( DIPHENYLPHOSPHINO ) METHANE [ 1 ]

<正> A heterodinuclear complex, trans- dicyano- palladium (Ⅱ)- bis [β- bis (diphenylphosphino)methane]-nitritosilver(Ⅰ),has been prepared by treatment of trans-(NC)2Pd(dppm)2 with AgNO2 and characterized by elementary analysis, ir, nmr, and X-ray crystal structure determination. AgPdC52H44N3O2P4,Mr= 1081. 12,monoclinic,space group P21/c,a=14. 745(7),b= 19. 208(7),c= 17. 486(6) A ,β=94. 99°(2) ,and Z = 4. The final R=0. 032 for 8673 unique reflections. In the molecule,the Pd -Ag distance is 3. 205 A. The palladium moiety has an approximately square planar geometry, and the silver moiety has a severely distorted tetrahedral geometry.     

SYNTHESIS AND REACTVITY OF N-[N-PHOSPHORAMIDO-1H-BENZIMIDAZOL-2-YL] IMIDATES

N-(-1H-Benzimidazol-2-yl) imidates 1a–c react with chlorophosphoramide to give the N-[-1-N,N,N′,N′-tetramethylphosphoramidoyl-1H-benzimidazol-2-yl]-imidates 2a–c or with dichlorophosphoramide to yield the bis[(N-1-benzimidazol-2-yl)-imidate] phosphoramide derivatives 3a–b. The reaction of compounds 2a–c toward primary amines is studied. The obtained amidine derivatives 4a–b were unambiguously characterized by different spectroscopic techniques (IR, ¹H, ¹³C, and ³¹P NMR, and in some cases MS).     

SYNTHESIS OF MESO-ARYLSUBSTITUTED CALIX[4]PYRROLES

Novel sterically hindered Ca1ix[4]pyrroles were synthesized by modified condensation of pyrrole with p-substituted acetophenone in decent yields. These compounds might serve as molecular receptors and starting materials for further derivate.     

双环[10,3,0]十五碳-1(12)-烯-13-酮系列化合物的合成

以多聚磷酸为催化剂,通过环十二碳烯和α,β-不饱和酸的反应,合成了十个双环[10.3.0]十五碳-1(12)-烯-13-酮系列化合物,研究了合成反应的条件及产物的分离提纯方法,并测定了它们的紫外光谱、红外光谱以及~1H核磁共振谱。