Chemoselective Modification of Vinyl DNA by Triazolinediones

A new method for the post‐synthetic modification of nucleic acids was developed that involves mixing a phenyl triazolinedione (PTAD) derivative with DNA containing a vinyl nucleobase. The resulting reactions proceeded through step‐wise mechanisms, giving either a formal [4+2] cycloaddition product, or, depending on the context of nucleobase, PTAD addition along with solvent trapping to give a secondary alcohol in water. Catalyst‐free addition between PTAD and the terminal alkene of 5‐vinyl‐2′‐deoxyuridine (VdU) was exceptionally fast, with a second‐order rate constant of 2×10³ m ⁻¹ s⁻¹. PTAD derivatives selectively reacted with VdU‐containing oligonucleotides in a conformation‐selective manner, with higher yields observed for G‐quadruplex versus duplex DNA. These results demonstrate a new strategy for copper‐free bioconjugation of DNA that can potentially be used to probe nucleic acid conformations in cells.     

以聚乙二醇-b-聚四乙烯基吡啶为模板制备聚联苯胺微/纳米颗粒及其电容特性

以两亲性嵌段共聚物聚乙二醇-b-聚四乙烯基吡啶(PEO-b-P4VP)为模板制备聚联苯胺微/纳米颗粒,调节模板剂胶束溶液pH,得到了一系列形貌和尺寸可控的聚联苯胺微/纳米颗粒。利用红外光谱、核磁共振、透射电镜、循环伏安、恒电流放电、交流阻抗等测试对材料的结构和性能进行了表征。模板法合成的聚联苯胺为平均直径小于200nm的亚微米至纳米级棒状颗粒,其直径随着模板剂胶束溶液pH的降低而增加。所得聚联苯胺颗粒均显示了一定的电化学活性,当电流密度为1A/g时,聚联苯胺的比电容量达到306.3F/g,经过长时间的充放电测试,不同条件下合成的聚联苯胺的容量衰减率均很小,表现出良好的循环稳定性且各样品电化学性能呈现出随着直径的减小而增强的趋势。     

Initial lamellar thickness dependency of recrystallization behavior of poly(4‐methyl‐1‐pentene)

The isothermal crystallization and subsequent melting process in semicrystalline poly(4‐methyl‐1‐pentene) were investigated via temperature‐dependent small‐ and wide‐angle X‐ray scattering and Flash DSC techniques. In a phase diagram of inversed crystalline lamellar thickness and temperature, the crystallization and melting lines can be described by two linear dependencies of different slopes and different limiting temperatures at infinite lamellar thickness. Upon subsequent heating, recrystallization lines with different slopes were observed for samples with different lamellar thickness, indicating changes in surface free energy difference between stabilized crystallites and mesomorphic phase. The surface free energy of native crystallites with extended‐chain conformation decreased with increasing lamellar thickness due to a more ordered surface region and less chain ends which changes cooperatively with mesomorphic phase. The surface free energy of stabilized crystallites remained unchanged for all lamellar thickness. Therefore, the recrystallization lines with different slopes are consequences of changes in surface free energy of mesomorphic phase. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 219–224     

One-Pot Palladium-Catalyzed Ligand- and Metal-Oxidant-Free Aerobic Oxidative Isocyanide Insertion Leading to 2-Amino-substituted-4(3H)-quinazolinones

An efficient, ligand- and metal-oxidant-free, one-pot, cascade aerobic oxidative, palladium-catalyzed, multicomponent reaction has been developed through isocyanide insertion of less active secondary amide and aromatic amine, which leads to 2-amino-substituted-4(3H)-quinazolinones. This approach proves to be one of the simplest methods for the synthesis of this class of valuable bioactive heterocyclic scaffolds.     

Scrupulous recognition of biologically important acids by fluorescent “turn off-on” mechanism of thaicalix reduced silver nanoparticles

Water dispersible silver nanoparticles(AgNps) were prepared using thiacalix[4]arene tetrahydrazide(TCTH) as a reducing and stabilizing agent.TCTH-AgNps were characterized by surface plasmon resonance(SPR),transmission electron microscopy(TEM) and energy dispersive X-ray(EDX).Relatively uniform 20 nm spherical particles of TCTH-AgNps were efficiently formed over a pH range of 5-9 and from 10-40 ℃.The interaction behavior of TCTH-AgNps with different amino acids was investigated using spectrophotometry and spectrofluorimetry.Among the amino acids tested,only tryptophan and histidine showed fluorescence quenching and fluorescence enhancement,respectively.The linear detection range by Stern-Volmer plot was 5 nmol/L to 0.48 μmol/L for tryptophan and 4 nmol/L to 0.54 μmol/L for histidine.TCTH-AgNps were able to effectively reduce the levels of gram-positive bacteria,gram-negative bacteria,and fungi.These properties argue for the potential use of TCTH-AgNps as detectors of histidine and tryptophan and as antibiotics.     

Conformational properties of propargyloxy-calix[4]arene tricarboxamides: NMR and DFT studies on the O-through-the-annulus rotation

The size limit of substituents allowing O-through-the-annulus rotation of substituted calix[4]arenes was further extended to the propargyloxy group in 24-propargyloxy-25,26,27-tris(N,N-dimethylcarbamoylmethoxy)-p-tert-butylcalix[4]arene by demonstrating its free but slow motion affording equilibrium between the partial cone and 1,2-alternate conformers. The effect of solvent and upper rim substituents R¹ on the conformational inversion was investigated by means of ¹H NMR. The rotational isomerisation of the parent (R¹ = H) analogue could not unambiguously be detected. The experimental results were supported by comprehensive density functional theory studies.