Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Synthesis of Thiourea Derivatives on Soluble Polymeric Support

A modified poly(ethylene glycol) (PEG) has been developed as the soluble polymeric supports for liquid phase synthesis of novel thiourea derivatives.In each step of the sequence,the PEG-bound products were precipitated in cold Et2O and the unreacted materials and by-products were removed by simple filtration.The progress of reaction,purity of the isolation and the structure of the PEG-bound products were easily monitored by TLC,IR and ^1H NMR spectra.Representative thiourea derivatives were obtained in moderate yields with excellent purity from this modified PEG-bound product by the cleavage with 50% TFA/H2O.     

A novel phosphoramidite method for automated synthesis of oligonucleotides on glass supports for biosensor development

Two protocols for functionalization of glass supports with hexaethylene glycol (HEG)-linked oligonucleotides were developed. The first method (standard amidite protocol) made use of the 2-cyanoethyl-phosphoramidite derivative of 4,4′-dimethoxytrityl-protected HEG. This was first coupled to the support by standard solid-phase phosphoramidite chemistry followed by extension with a thymidylic acid icosanucleotide. Stepwise addition of the linker phosphoramidite graduated at 1% (relative to the total sites available) perstep at 50°C resulted in an optimal yield of immobilized oligonucleotides at a density of 2.24 × 10¹⁰ strands/mm². This observed loading maximum lies well below the theoretical maximum loading owing to nonspecific adsorption of HEG on the glass and subsequent blocking of reactive sites. Surface loadings as high as 3.73 × 10¹⁰/mm² and of excellent sequence quality were achieved with a reverse amidite protocol. The support was first modified into a 2-cyanoethyl-N,N-diisopropylphosphoramidite analog followed by coupling with 4,4′-dimethoxytrityl-protected HEG. This protocol is conveniently available when using a conventional DNA synthesizer. The reverse amidite protocol allowed for control of the surface loading at values suitable for subsequent analytical applications that make use of immobilized oligonucleotides as probes for selective hybridization of sample nucleic acids of unknown sequence and concentration.     

STUDY ON 1-HEXENE POLYMERIZATION BASED ON ZIEGLER-NATTA CATALYSTS WITH DOPED SUPPORT

A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.     

Universal system for liquid stationary phase classification on the basis of thermodynamical data

Summary Equations modifying Rohrschneider's relationship between I and thermodynamical characteristics values are derived. Polarity in chromatography is discussed as a possibility of stationary phases or absorbents to enter into intermolecular interactions and is determined on the basis of the partial molar free energies of solution (G) of six test substances. A simple method for the calculation of stationary phase polarity in terms of G from retention indices and McReynolds constants is given. Equations are presented for the calculation of stationary phase selectivity utilizing G data tabulated for selected test substances. The thermodynamical basis of selecting a reference phase for a unified system expressing the selectivity of stationary phases which can also be applied for adsorbents is suggested. The energy equivalent to an index unit, G_i.u., is discussed.     

Porous ceramic bed supports for fused silica packed capillary columns used in liquid chromatography

Porous ceramic bed supports for fused silica packed capillary columns utilized in liquid chromatography were prepared by polymerizing solutions containing potassium silicate in-situ within a column to create a mechanically stable, rugged, and easily constructed termination. The effect of the bed support length on efficiency, and comparisons to glass wool bed supports, were considered in terms of column efficiencies and hydrodynamic variables. Results obtained indicate better performance for the ceramic bed support.     

Improving resins for solid phase synthesis: incorporation of 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene

The preparation, characterisation and application of a series of non-grafted polystyrene (PS) resins containing a styrenic methoxypoly(ethylene glycol) (MPEG) derivative is presented. These novel PS-MPEG resins were designed to balance swelling and solvation with improved handling. The monomer, 1-[2-(2-methoxyethoxy)ethoxy]-4-vinyl-benzene, contained an inert phenyl ether linkage designed to provide broad chemical compatibility and stability, yet imparting all the favourable properties of the PEG group into the new resin, whilst maintaining a high loading capacity. The synthetic performance of the new resins compared very favourably to those of TentaGel™, ArgoGel™ and aminomethyl PS.     

直接甲醇燃料电池阳极电催化剂

直接甲醇燃料电池作为未来清洁的动力能源，由于具有下列优点：操作温度低(<100℃)、燃料易储存和运输、能量效率高、污染低和燃料启动快而受到人们广泛的关注。阳极电催化剂是直接甲醇燃料电池最重要的组成部分。本文综述了近三年来直接甲醇燃料电池阳极电催化剂最新的研究进展，主要对催化剂制备方法、新型碳载体材料、催化剂类型作了详细的评述，展望了未来甲醇电催化氧化催化剂的发展，指出了电催化剂面临的问题。     

Catalytic conversions of chloroolefins over iron oxide nanoparticles 2. Isomerization of dichlorobutenes over iron oxide nanoparticles stabilized on the surface of ultradispersed poly(tetrafluoroethylene)

Nanosized iron oxides stabilized on the surface of ultradispersed poly(tetrafluoroethylene) (UPTFE) granules were synthesized by the thermal destruction of iron formate in boiling bed of UPTFE on the surface of heated mineral oil. The particle size of nanoparticles (∼6 nm) containing 5, 10, and 16 wt.% Fe depends weakly on the temperature of synthesis and iron to polymer ratio. The metal state is determined by the synthesis conditions. The nanoparticles synthesized at 280 °C consist mainly of the Fe₃O₄ and Fe₂O₃ phases. The samples obtained at 320 °C also contain iron(II) oxide. The catalytic properties of the obtained samples were tested in dichlorobutene isomerization. Unlike isomerization on the iron oxide nanoparticles supported on silica gel, reaction over the UPTFE supports proceeds without an induction period. The sample with 10 wt.% Fe containing magnetically ordered γ-Fe₂O₃ nanoparticles possesses the highest catalytic activity. Fast electron exchange between the iron ions in different oxidation states and high defectiveness of the nanoparticles contribute, most likely, to the catalytic activity. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1383–1390, June, 2005.