ELASTIC BEHAVIOR OF PROTEIN-LIKE SINGLE CHAIN

The conformational properties and elastic behaviors of protein-like single chains in the process of tensile elongation were investigated by means of Monte Carlo method. The sequences of protein-like single chains contain two types of residues: hydrophobic (H) and hydrophilic (P). The average conformations and thermodynamics statistical properties of protein-like single chains with various elongation ratio λ were calculated. It was found that the mean-square end-to-end distance r increases with elongation ratio,λ. The tensor eigenvalues ratio of : decreases with elongation ratio λ for short (HP)x protein-like polymers, however, the ratio of : increases with elongation ratioλ,especially for long (H)x sequence. Average energy per bond increases with elongation ratioλ, especially for(H)x protein-like single chains. Helmholtz free energy per bond also increases with elongation ratioλ. Elastic force (f), energy contribution to force (fU) and entropy contribution to force (fs) for different protein-like single chains were also calculated.These investigations may provide some insights into elastic behaviors of proteins.     

Poly（meta-phenylene） Derivative with Rigid Twisted Biphenyl Units in Backbone： Synthesis, Structural Characterization, Photophysical Properties and Electroluminescence

A soluble poly(meta-phenylene)derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction.The polymer is soluble in common organic solvents,and the number-average molecular weight is about 6500.The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones;it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound.The π-π transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm.Furthermore,the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 nm.The ultraviolet-emitting electroluminescence(EL)device with the single layer structure shows EL λmax of the derivative at 370 nm.     

Synthesis and Structure of MnCl2(HDpyF) (HDpyF = N,N′‐di(2‐pyridyl)formamidine): New Crystallographic Disorder and Bonding Mode of the HDpyF Ligand

The reaction of N,N′‐di(2‐pyridyl)formamidine (HDpyF) with MnCl₂‐4H₂O afforded the complex MnCl₂(HDpyF), which was characterized by X‐ray crystallography. The HDpyF ligand chelates to the Mn(II) center through the first and the third nitrogen atoms to form a six‐membered ring, leaving the second and the fourth nitrogen atoms uncoordinated. The HDpyF ligand is crystallographically disordered such that two different molecules can be solved. The neutral HDpyF ligand adopts the new s‐cis‐syn‐s‐trans conformation.     

STRUCTURE EVOLUTION OF POLYMER CHAINS FOR NECKING FORMATION IN HIGH-SPEED FIBER SPINNING PROCESS

Finite element method is used to simulate the high-speed melt spinning process,based on the equation system proposed by Doufas et al.Calculation predicts a neck-like deformation,as well as the related profiles of velocity,diameter, temperature,chain orientation,and crystallinity in the fiber spinning process.Considering combined effects on the process such as flow-induced crystallization,viscoelasticity,filament cooling,air drag,inertia,surface tension and gravity,the simulated material flow behaviors are consistent with those observed for semi-crystalline polymers under various spinning conditions.The structure change of polymer coils in the necking region described by the evolution of conformation tensor is also investigated.Based on the relaxation mechanism of macromolecules in flow field different types of morphology change of polymer chains before and in the neck are proposed,giving a complete prospect of structure evolution and crystallization of semi-crystalline polymer in the high speed fiber spinning process.     

Synthesis of 3,4-di-O-acylated glucose-derived furanoid sugar amino acids (Gaa): conformational analysis of a Leu-enkephalin analog containing di-O-myristoylated Gaa

3,4-Di-O-acylated derivatives 1-3 of a glucose-derived furanoid sugar amino acid (Gaa) were synthesized as novel peptide building blocks to study their effects on peptide conformation. Structural analysis of the di-O-myristoylated Gaa 3-containing Leu-enkephalin analog 4 by various NMR techniques and constrained molecular dynamics (MD) simulation studies established a well-defined β-turn structure in DMSO-d₆ with an intramolecular hydrogen bond between PheNH → TyrCO.     

Enantiomerically pure 4-amino-1,2,3-trihydroxybutylphosphonic acids

(1S,2R,3S)-, (1R,2R,3S)- and (1S,2R,3R)-4-amino-1,2,3-trihydroxybutylphosphonic acids were synthesised. The synthetic strategy involved preparation of the respective 4-azido-2,3-O-isopropylidene-l-threose or -d-erythrose, addition of dialkyl phosphites, separation of C-1 epimeric O,O-dibenzyl phosphonates, the reduction of azides and the removal of the protecting groups. The (2R,3S) and (2R,3R) configurations in the final products were secured by employing diethyl l-tartrate and d-isoascorbic acid as starting materials. The stereochemical course of the addition to the carbonyl groups in 4-azido-2,3-O-isopropylidene-l-threose or -d-erythrose followed that established earlier for 2,3-O-isopropylidene-d-glyceraldehyde and similar (3:1-4:1) diastereoselectivities were achieved.     

On the synthesis and chiroptical properties of the tri- and tetragalloylquinic acids

Summary A synthesis of the potential pharmaceutical agents 3,4,5-trigalloylquinic acid and 1,3,4,5-tetragalloylquinic acid is described. It involves three steps starting from commercially available quinic acid and provides overall yields of about 15%. The acylation of benzyl or 4-nitrobenzyl quinate with tribenzylgalloyl chloride is the key step. It leads selectively to the triacyl product in the case of benzyl quinate and can be either stopped at the triacyl stage or driven to the tetraacyl derivative in the case of the 4-nitrobenzyl quinate. From the chiroptical properties of the two compounds their stereochemistry was derived by means of the benzoate rule.

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Zu Synthese und chiroptischen Eigenschaften der Tri- und Tetragalloylchinasäuren

Zusammenfassung Eine Synthese von 3,4,5-Trigalloylchinasäure und 1,3,4,5-Tetragalloylchinasäure. die potentielle Pharmaka darstellen, wird beschrieben. Sie umfaßt drei Stufen, welche ausgehend von kommerziell erhältlicher Chinasäure Gesamtausbeuten um 15% ergeben. Die entscheidende Stufe dabei ist die Acylierung von Benzyl- oder 4-Nitrobenzylchinat mit Tribenzylgalloylchlorid. Sie führt im Falle des Benzylchinats selektiv zum Triacylprodukt und kann im Fall des 4-Nitrobenzylchinats entweder auf der Stufe des Triacylderivates abgebrochen oder bis zum Tetraacylprodukt durchgezogen werden. Aus den chiroptischen Eigenschaften der beiden Verbindungen wurde ihre Stereochemie abgeleitet.

     

Conformational studies of 3,4-dideoxy furanoid sugar amino acid containing analogs of the receptor binding inhibitor of vasoactive intestinal peptide

Conformational analysis of vasoactive intestinal peptide (VIP) receptor binding inhibitor Leu¹-Met²-Tyr³-Pro⁴-Thr⁵-Tyr⁶-Leu⁷-Lys⁸1 by various NMR techniques and constrained molecular dynamics (MD) simulation studies revealed that the molecule had a turn structure involving its Tyr³-Pro⁴-Thr⁵-Tyr⁶ moiety with intramolecular hydrogen bond between Tyr⁶NH→Tyr³CO. In order to mimic the structure of 1, peptidomimetic analogs 2-4 were synthesized using conformationally constrained scaffolds of 3,4-dideoxy furanoid sugar amino acids (2S,5R)-ddSaa1 5 and its enantiomer (2R,5S)-ddSaa2 6. All these analogs displayed well defined three-dimensional structures akin to that found in 1. Peptides 2 and 3, which differed only in the sugar amino acid stereochemistry, show propensity of structures with identical intramolecular hydrogen bonds between ThrNH→MetCO. A similar structure with a hydrogen bond between TyrNH→MetCO was observed in 4.     

蒙特卡洛模拟退火与距离限制相结合的方法在多肽溶液构象分析中的应用

多维核磁共振技术的飞速发展议得其在生物大分子结构测定方面的应用已经达到可以与【射线晶体学并驾齐驱的地步．蛋白质结构堆积紧密，较适合于用核磁共振方法给出确定的结构．与蛋白质不同的是多肽的柔性较大，在溶液中可能存在多种构象，核磁共振实验给出的只是平均信息＊．利用核磁，（振数据构建分子结构模型常用的方法有距离几何、分子动力学等，在由核磁共振NOESZ得到的距离信息足够多时可以给出较好的结果问．由于多肽本身的特点：柔性较大，由核磁共振得到的距离信息较少等，利用距离几何、分子动力学方法进行构象搜索时容易陷入…     

用胆甾型苯并—15—冠—5气相色谱固定相分离乳酸和乳酸乙酯光学异构体

胆甾型苯并－１５－冠－５（简称ＣＨ－Ｂ－１５－Ｃ－５）在不同温度范围内的相态不同，在同一温 度范围内因处理方式不同而物性亦相去甚远，用其作成的ＧＣ固定相兼具气固色谱（ＧＳＣ）、 普通气液色谱（ＧＬＣ）和冠醚液晶气液色谱（ＣＬ－ＧＬＣ）多种功能。用该固定相在不同条件下对 乳酸和乳酸乙酯光学异构体混合物的分高效果进行了比较研究，并探讨了手性拆分机理。