Plumbocenes with sec- und tert-Alkyl Substituents

[(C₅H₂tBu₃-1,2,4)₂Pb] ( 1 ), [(C₅HiPr₄)₂Pb] ( 2 ), and [(C₅iPr₅)₂Pb] ( 3 ) have been obtained from PbCl₂ and Li(C₅H₂tBu₃-1,2,4), Na(C₅HiPr₄) and Na(C₅iPr₅), respectively. 3 exists as a 1 : 1 mixture of meso- 3 and rac- 3 which interconvert at elevated temperature via one-at-a-time rotation of isopropyl groups with ΔG^# = 73.0 ± 1.5/73.7 ± 1.5 kJ/mol at 348 K. 3 is slightly bent in the solid state with an angle of 170(1)° between the ring normals.     

Polystyrene resins cross-linked with di- or tri(ethylene glycol) dimethacrylates as supports for solid-phase peptide synthesis

Polystyrene resins cross-linked with di(ethylene glycol) dimethacrylate (DEGDMA) and tri(ethylene glycol) dimethacrylate (TEGDMA), DEGDMA-PS and TEGDMA-PS, were synthesized by suspension copolymerization. Four functionalized resins, chloromethyl resin, 4-hydroxymethylphenoxymethyl resin (Wang resin), 4-methylbenzhydrylamine resin (MBHA resin) and 2-chlorotrityl chloride resin, were prepared from DEGDMA-PS and TEGDMA-PS. DEGDMA-PS and TEGDMA-PS showed high reactivity in the functionalization reactions in comparison with Merrifield resin (polystyrene cross-linked with divinylbenzene, DVB-PS). DEGDMA-PS-Wang resin and TEGDMA-PS-Wang resin were used as the solid-phase support for the synthesis of a difficult sequence, the fragment of acyl carrier protein 65-74. The yields of the crude peptide synthesized using DEGDMA-PS-Wang resin, TEGDMA-PS-Wang resin and DVB-PS-Wang resin were 92.3%, 91.6% and 78.8%, respectively. The purities of the crude peptides were 85.7%, 88.1% and 73.3%, respectively.     

Exploring of tri-allelic SNPs using pyrosequencing and the SNaPshot methods for forensic application

Tri-allelic single nucleotide polymorphisms (SNPs) are potential forensic markers for DNA analysis. Currently, only a limited number of tri-allelic SNP loci have been proved to be fit for forensic application. In this study, we aimed to develop an effective method to select and genotype tri-allelic SNPs based on both Pyrosequencing (PSQ) and the SNaPshot methods. 50 candidate SNPs were chosen from NCBI's dbSNP database and were analyzed by PSQ. The results revealed that 20 SNPs were tri-allelic and were located on 16 autosomal chromosomes. Then 20 SNP loci were combined in one multiplex polymerase chain reaction to develop a single base extension (SBE)-based SNP-typing assay. A total of 100 unrelated Chinese individuals were genotyped by this assay and allele frequencies were estimated. The total discrimination power was 0.999999999975 and the cumulative probability of exclusion was 0.9937. These data demonstrated that the strategy is a rapid and effective method for seeking and typing tri-allelic SNPs. In addition, the 20 tri-allelic SNP multiplex typing assay may be used to supplement paternity testing and human identification.     

Enhancement of Electrochemiluminescence of Porous Silicon with Tri‐n‐propylamine as Co‐reactant

Visible light emission can be stimulated by applying a cyclic bias to a porous silicon/tri‐n‐propylamine (PS/TPrA) solid/liquid system. With the presence of 2.5 mM TPrA, the electrochemiluminescence intensity of the in situ formed PS electrode is 450 times higher than the blank solution. An applied voltage as low as 1.2 V is capable of generating light emission, indicating that current‐induced chemical reactions are an aid to the generation of charge carriers. A mechanism involving oxidation of TPrA followed by hole injection is proposed. The system also shows good ECL stability. In addition, the ECL emission can be inhibited by diphenols rather than phenol.     

Zur Kenntnis der Kristallstruktur von Melem C6N7(NH2)3

On the Crystal Structure of Melem C₆N₇(NH₂)₃ Single crystals of melem ( 1 ) were grown from both DMSO‐solutions and the gas phase. The structure of melem ( 1 ) was solved by single‐crystal X‐ray diffraction (P2₁/c, Z = 4, a = 741.66(15), b = 862.28(17), c = 1335.9(3) pm, β = 99.91(3)° R1 = 0.037 for 1098 reflections). The structure determination by X‐ray powder diffraction, which has been previously conducted, is in agreement with our data. The increased quality of the structural information allows for a more detailed understanding of the hydrogen bonding network.     

Carbonylation of terminal alkynes catalysed by Pd complexes in combination with tri(2-furyl)phosphine and methanesulfonic acid

Pd(OAc)₂ in combination with tri(2-furyl)phosphine and methanesulfonic acid is an efficient catalyst for the alkoxycarbonylation of 1-alkynes. Fairly good reaction rates are obtained under mild conditions (50–80°C and P(CO)=20 bar) with high regioselectivity (ca. 95%) towards the formation of 2-substituted acrylic ester.     

含三(2-吡啶甲基)胺识别体的荧光化学敏感器核磁共振谱分析

采用二维核磁共振谱技术对新型丹磺酰胺和1,8-萘酰亚胺荧光化学敏感器的结构进行了测定。应用'H—'HCOSY、HSQC、HMBC等二维相关核磁谱对化合物的C和H进行了正确的归属。     

A comparative study of coordination between host polymers and Li ions in UV-cured gel polymer electrolytes

Crosslinked gel polymer electrolytes are prepared via free radical photo-polymerization of 1,6-hexanediol diacrylate (HDDA) or tri(ethylene glycol) diacrylate (TEGDA) with 1 M LiClO₄ dissolved in a solvent mixture of ethylene carbonate (EC) and propylene carbonate (PC). TEGDA-based gel polymer electrolytes containing a polar moiety of ethylene oxide exhibit relatively high ionic conductivities over a temperature range from − 15 to 65 °C in comparison to those based on HDDA. The coordination structure between polar moieties of a polymer backbone and Li⁺ ions is examined using a Fourier transform infrared (FT-IR) spectroscopy. The results of FT-IR analyses manifest that the CO and COC groups of TEGDA-based polymer matrix form the complex with Li⁺ ions.     

SYNTHESIS AND POLYMERIZATION OF TRI(2-PYRIDYL)METHYL METHACRYLATE

A novel methacrylate monomer with bulky side group, tri(2-pyridyl)methyl methacrylate(Tr2PyMA), was synthesized and polymerized. The polymer obtained by radical polymerization exhibits highisotactic tacticity.     

B(C6F5)3在有机化学及高分子化学中的应用研究进展

B(C6F5)3与传统的Lewis酸相比,具有化学性质稳定、酸性强、使用方便等优点,被称为非传统的Lewis酸。B(C6F5)3的应用领域已经从最初的烯烃聚合共催化剂向有机化学及高分子化学的其它各个领域发展。B(C6F5)3催化的反应与传统Lewis酸催化的反应在反应机理及反应结果上均有很大的不同。本文主要综述B(C6F5)3近年来在有机化学及高分子化学中的应用研究成果。