Direct SNAr amination of fluorinated imidazo[4,5-c]pyridine nucleosides: efficient syntheses of 3-fluoro-3-deazaadenosine analogs

This paper describes the ready preparation of 3,6-difluoro-3-deazapurine (4,7-difluoroimidazo[4,5-c]pyridine). This novel base was glycosylated under mild conditions using three different ribose sugar analogs. 3,6-Difluoro-3-deazapurine ribonucleoside analogs underwent direct S_NAr amination reactions with liquid ammonia to give 3-fluoro-3-deazaadenosine analogs in excellent yield; in contrast, 6-chloro-3-fluoro-3-deazapurine nucleosides were inert under similar reaction conditions.     

A facile and improved synthesis of tubercidin and certain related pyrrolo[2,3-d]pyrimidine nucleosides by the stereospecific sodium salt glycosylation procedure

A simple synthesis of tubercidin ( 1 ), 7-deazaguanosine ( 2 ) and 2′-deoxy-7-deazaguanosine ( 14 ) has been accomplished using the sodium salt glycosylation procedure. Reaction of the sodium salt of 4-chloro- and 2-amino-4-chloro-pyrrolo[2,3-d]pyrimidine, 3 and 4 , respectively, with 1-chloro-2,3-0-isopropylidene-5-0-(t-butyl)dimethylsilyl-α-D-ribofuranose ( 5 ) gave the corresponding protected nucleosides 6n and 7 with β-anomeric configuration. Deprotection of 6 provided 8 , which on heating with methanolic ammonia gave tubercidin ( 1 ) in excellent yield. Functional group transformation of 7 , followed by deisopropylidenation gave 2-aminotubercidin ( 10 ) and 2-amino-7-β-D-ribofuranosylpyrrolo[2,3-d]pyrimidine-4(3H)-thione ( 11 ). Treatment of 7 with 1N sodium methoxide followed by exposure to aqueous trifluoroacetic acid, and ether cleavage furnished 7-deazaguanosine ( 2 ). 2′-Deoxy-7-deazaguanosine ( 14 ) and 2′-deoxy-7-deaza-6-thioguano-sine ( 18 ) were also prepared by using similar sequence of reactions employing 4 and 1-chloro-2-deoxy-3,5-di-O-p-toluoyl-α-D-erythro-pentofuranose ( 15 ).     

Substituted derivatives of [Fe2(CO)9] and [Ru2(CO)9] and their susceptibility to electrophilic attack: X-ray crystal structure of [Fe2(μ-Br)(CO)4{μ-(C6H5O)2PN(C2H5)P(OC6H5)2}2]PF6

Bis- and, in particular, tetra-substituted ditertiary phosphine and diphosphazane derivatives of [Fe₂(CO)₉] and [Ru₂(CO)₉], readily synthesised by reaction of the appropriate bidentate ligand with [Fe₂(CO)₉] and [Ru₃(CO)₁₂], respectively, are very susceptible to electrophilic attack by reagents such as halogens and protons; the solid state structure of one of the products [Fe₂(μ-Br)(CO)₄ {μ-(PhO)₂PN(Et)P(OPh)₂}₂]PF₆ has been determined by X-ray crystallography.     

磁性纳米颗粒固定化细菌纤维素酶的活性和稳定性

在氨水溶液中进行Fe+2和Fe+3离子共沉淀并水热处理后制得磁性纳米颗粒Fe3O4,通过戊二醛活化将纤维素酶固定于其上。采用基于响应面法的Box-Behnken法(BBD)优化了制备条件,如磁性纳米颗粒浓度、戊二醛浓度、酶浓度和交联时间。 BBD分析结果表明,用实验数据可合理调节二次模型。利用生成的基于统计数据的等高线评价了响应面的变化,以理解纳米颗粒和酶活性之间的关系。运用扫描电镜、X射线衍射和红外光谱表征了纳米颗粒上酶的尺寸、结构、形貌和结合情况。采用诸如pH值、温度、重复使用性和存储能力分析了固定化纤维素酶的活性和稳定性。发现固定后的纤维素酶表现出更好的稳定性和活性。     

Microwave-assisted catalyst-free synthesis of tetrasubstituted pyrroles using dialkyl acetylenedicarboxylates and monophenacylanilines

An efficient catalyst-free microwave-assisted synthesis of tetrasubstituted pyrroles using dialkyl acetylenedicarboxylates and substituted monophenacylanilines has been developed. Axial chirality has been noticed in some N-(α-naphthyl/2-isopropylphenyl)-2,3-dicarbethoxy-4-arylpyrroles, but not with N-aryl-2,3-dicarbethoxy-4-(α-naphthyl)pyrrole.     

Magnetohydrodynamic and heat transfer effects on the stagnation-point flow of an electrically conducting nanofluid past a porous vertical shrinking/stretching sheet in the presence of variable stream conditions

A steady two-dimensional magnetohydrodynamic stagnation-point flow of an electrically conducting fluid and heat transfer with thermal radiation of a nanofluid past a shrinking and stretching sheet is investigated numerically. The model used for the nanofluid incorporates the effects of the Brownian motion and thermophoresis. A similarity transformation is used to convert the governing nonlinear boundary-layer equations into coupled higher-order nonlinear ordinary differential equations. The result shows that the velocity, temperature, and concentration profiles are significantly influenced by the Brownian motion, heat radiation, and thermophoresis particle deposition.     

Local non-similarity solution to impact of chemical reaction on MHD mixed convection heat and mass transfer flow over porous wedge in the presence of suction / injection

Combined heat and mass transfer on free, forced, and mixed convection flow along a porous wedge with magnetic effect in the presence of chemical reaction is investigated. The flow field characteristics are analyzed by the Runge-Kutta-Gill scheme with the shooting method as well as the local non-similarity method up to the third level of truncation, which are used to reduce the governing partial differential equations into nine ordinary differential equations. The governing boundary layer equations are converted to a dimensionless form by Falkner-Skan transformations. Because of the effect of suction/injection on the wall of the wedge with buoyancy force and variable wall temperature, the flow field is locally non-similar. Numerical calculations up to the third order level of truncation are carried out as a special case for different values of dimensionless parameters. Effects of the magnetic field strength in the presence of chemical reaction with variable wall temperature and concentration on the dimensionless velocity, temperature and concentration profiles are shown graphically.     

Expanding the Potential of DNA for Binding and Catalysis: Highly Functionalized dUTP Derivatives That Are Substrates for Thermostable DNA Polymerases

The discovery of a simple structural motif allows for the enzymatic synthesis by polymerase chain reactions (PCR) of modified DNA (see reaction scheme) bearing side chains similar or even identical to those of several amino acids. Libraries of DNA functionalized with both cationic and anionic groups may now be readily prepared. R=I, HgCl; X=functional group.     

Soret and dufour effects on MHD free convective heat and mass transfer with thermophoresis and chemical reaction over a porous stretching surface: Group theory transformation

The group theoretic method is applied for solving the problem of the combined influence of the thermal diffusion and diffusion thermoeffect on magnetohydrodynamic free convective heat and mass transfer over a porous stretching surface in the presence of thermophoresis particle deposition with variable stream conditions. The application of one-parameter groups reduces the number of independent variables by one; consequently, the system of governing partial differential equations with boundary conditions reduces to a system of ordinary differential equations with appropriate boundary conditions. The equations along with the boundary conditions are solved numerically by using the Runge-Kutta-Gill integration scheme with the shooting technique. The impact of the Soret and Dufour effects in the presence of thermophoresis particle deposition with a chemical reaction plays an important role on the flow field.