Numerical simulation of laminar flow past a circular cylinder

The present paper focuses on the analysis of two- and three-dimensional flow past a circular cylinder in different laminar flow regimes. In this simulation, an implicit pressure-based finite volume method is used for time-accurate computation of incompressible flow using second order accurate convective flux discretisation schemes. The computation results are validated against measurement data for mean surface pressure, skin friction coefficients, the size and strength of the recirculating wake for the steady flow regime and also for the Strouhal frequency of vortex shedding and the mean and RMS amplitude of the fluctuating aerodynamic coefficients for the unsteady periodic flow regime. The complex three dimensional flow structure of the cylinder wake is also reasonably captured by the present prediction procedure.     

Syntheses,X-ray,MS, NMR and CD structure determination of nickel(II) complexes of Schiff bases of (S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide and aromatic α-amino acids

A preparative procedure for the synthesis of an important chiral synthon of side-chain protected tyrosine was developed and optimised for the minimisation of nickel salts waste. While preparing a similar side-chain protected tryptophan synthon, an unexpected low stability was found of the Boc-protective group of the tryptophan aromatic nitrogen during purification on silica gel. X-ray crystal structure determination, tandem mass spectrometry (MS/MS) and NMR were applied for the elucidation of the structures of the prepared complexes and by-products. Stereochemistry of products of α-methylation of the complexes was assessed using a model tyrosine-derived compound.     

Scission induced by circular shear and heat conduction in an elastomeric cylinder

Constitutive equations for the thermo-mechanics of elastomeric materials generally assume that they do not undergo microstructural change. A constitutive theory is discussed here which accounts for such changes arising from continuous scission of macromolecular junctions of elastomeric networks due to deformation and high temperatures and the subsequent cross-linking of molecules into new networks with new reference states. The total stress is the superposition of the stresses in the remainder of the original network and in each subsequently formed network. Each network acts as a temperature-dependent non-linear elastic material. The interaction of this material response with inhomogeneous deformation and temperature fields is studied for finite circular shear of a cylinder. Numerical results illustrate how the mechanical response of the cylinder depends on the temperature dependence of both the scission–cross-linking process and the properties of the elastic networks.     

Reconstitution of apomyoglobin with bile pigments

Summary Apomyoglobin was reconstituted with bile pigments of the verdinoid, 2,3-dihydroverdinoid, pterobilinoid, and violinoid type. Absorption and circular dichroism data as well as formation constants of the complexes were measured. From these results it was concluded that chromophore binding and induced chirality of these pigments are mainly governed by a lipophilic region opposite to the propionic side chain(s) and the asymmetric position of the hydrogen bonding acceptors of the propionic acid side chain(s) at the entrance of the protein pocket.Dedicated to Prof. Dr. A. Eschenmoser on occasion of his 65th birthday     

Corroborating study on the absolute configurations of trigochinins A–C

Trigochinins A–C (1–3) are three highly oxygenated daphnane-type diterpenes isolated from Trigonostemon chinensis. Their structures with the absolute configurations were initially assigned by a combination of spectroscopic data, X-ray crystallography (Mo Kα radiation) study and CD analysis. In the current study, the absolute configurations of trigochinins A–C were confirmed by single crystal X-ray diffraction (Cu Kα radiation) study, CD spectral analogy, and theoretical ECD study by using quantum chemical TDDFT calculations.     

中厚度圆浮板自由振动的一个解析解

本文提出了常水深环境下中厚度圆浮板自由振动的一个解析解.分析中考虑了板横向剪切变形的影响和横截面转动惯性效应,利用空气中中厚度圆板的振型叠加和势流理论,导得了浮板系统频率方程的解析式.由此可看出Y.Tanaka得到的圆形薄浮板的解是本文的特例.最后数值计算还给出了水深和钢缆刚度与频率的关系曲线.并指出了h/a在什么范围可以略去剪切变形和转动惯量的影响.     

Foldamers of bifunctional diketopiperazines displaying a β-bend ribbon structure

The synthesis of two oligomers, of a bifunctional diketopiperazine scaffold DKP-1, formally derived from the cyclization of l-aspartic acid and (S)-2,3-diaminopropionic acid, is reported. A trimeric and a tetrameric structure were prepared by solution-phase peptide synthesis (Boc strategy). Conformational analysis of these derivatives was carried out by a combination of ¹H NMR spectroscopy, CD spectroscopy, and molecular modeling, and revealed the formation of β-bend ribbon involving 10-membered H-bonded rings and a reverse turn of the growing peptide chain.     

Study on the absolute configuration of (−)-palau’amine

The absolute stereochemistry of the immunosuppressive pyrrole-imidazole alkaloid (−)-palau’amine from the marine sponge Stylotella aurantium is analyzed by CD spectroscopy. With the help of a series of model compounds it is shown that the CD spectrum of (−)-palau’amine can be explained based on the assumption that the pyrrolopyrazinone partial structure is planar in 2,2,2-trifluoroethanol (TFE). Surprisingly, the natural product (−)-dibromophakellin shows the opposite Cotton effect, despite exhibiting the same absolute configuration.     

新型Salen型配合物的合成和表征及轴向配位热力学

采用金属模板法合成了四个新型Salen型单、双核金属配合物,并用元素分析、核磁共振(1HNMR)、电喷雾质谱(ESI-MS)、傅里叶变换红外光谱(FT-IR)等手段进行了表征.使用紫外-可见(UV-Vis)光谱滴定法和圆二色(CD)光谱研究了主体金属镍配合物与咪唑类含氮小分子的轴向配位反应热力学性质.结果表明:主体与咪唑(Im)和N-甲基咪唑(N-MeIm)的配位数是2,而与2-Et-4-MeIm和2-MeIm的配位数是1;轴配体系的热力学数据显示主体与咪唑类配体的平衡常数按K苓(Im)K苓(N-MeIm)K苓(2-Et-4-MeIm)K苓(2-MeIm)顺序依次减小;测得的△rHm苓和△rSm苓数据表明该轴向配位反应为放热、熵增加过程.     

包结法拆分1,1'-联-2-萘酚:包结物的晶体结构及CD光谱

以D/L-缬氨醇为原料,通过二步反应得到价廉易得的拆分剂碘化(R)/(S)-N,N,N-三甲基-1-羟基-3-甲基-2-丁铵,采用包结拆分法,成功实现了对1,1′-联-2-萘酚(BINOL)的拆分.对具有(R)-构型的季铵盐与(R)-BINOL在甲醇中所形成包结物的晶体结构分析结果表明:I-离子桥联主体(拆分剂)的醇羟基和客体(BINOL)的酚羟基形成O-H…I-氢键,以及相邻层的主客体分子之间的C-H…O氢键相互作用是在包结物中实现手性识别的关键.同时对两个包结物的溶液和固体圆二色(CD)光谱进行了研究.