Synthesis of New Macrocyclic Polyaza Compounds Containing 1-Methylpyrazole

New macrocyclic polyaza compoundscontaining the 1-methylpyrazole moiety are synthesizedin high yield by [2+2]dipodal condensation andreduction. The ring contracted structure of the Schiffbase has been elucidated by NMR. Two of thesemacrocycles form dinuclear complexes with copper andsilver. Macrocyclic Schiff base 5a extracts74.5% silver from aqueous to organic phase.     

新型多重氮杂杯[4]芳烃衍生物的合成

对叔丁基杯[4]芳烃-1,3-二醛基衍生物1与水杨酰肼、烟酰肼、异烟酰肼反应, 合成了具有开链结构新型杯[4]多重氮杂衍生物2a～2c, 产率分别为88%, 85%和90%. 化合物1与乙二酰肼、丙二酰肼、己二酰肼反应, 得到具有桥联结构的新型杯[4]多重氮杂衍生物3a～3c, 产率分别为86%, 89%和90%. 新化合物的结构经元素分析、质谱、核磁共振谱等表征证实, 杯[4]芳烃单元均为1,3-取代且采取锥式构象.     

Coordination chemistry of a new tetranucleating 26-membered polyaza macropolycyclic ligand and a novel phenolate/phthalazine-bridged copper(II) and zinc(II) complexes

The novel phenol and phthalazine-based symmetric compartmental 26-membered polyaza macropolycyclic ligand LH₂, was synthesised, incorporating 2,6-diformyl-p-cresol and 1,4-dihydrazinophthalazine via 1:1 condensation. Its coordination behaviour with Cu^II and Zn^II ions was investigated. The tetranuclear complexes [M₄μ(Cl₂)(L)Cl₄]·2H₂O exhibited aremarkably high stability, suggesting that, along with the large number of nitrogen donors available for metal binding, deprotonated phenolic functions were also involved in binding the metal ion. Incorporation of the bridging units into the macrocyclic cavity influenced electronic communications between the metal ions.     

Revealing interactions between polyaza pyridinophane compounds and DNA/RNA polynucleotides by SERS spectroscopy

Surface‐enhanced Raman scattering spectroscopy (SERS) in the near‐infrared region had been applied to study interactions of polyaza pyridinophanes with single stranded RNA and double stranded DNA and RNA polynucleotides. Studied compounds, PYPOD and PHENPOD, differed in the central aromatic moiety, pyridine and phenanthroline, respectively, which linked two cyclic amines. An intense scattering was obtained from molecules adsorbed onto the silver nanoparticles, showing nonlinear concentration dependence in the 6.5 × 10⁻⁸−6.5 × 10⁻⁵ M range. New bands in spectra of PYPOD/polynucleotide and PHENPOD/polynucleotide mixtures were assigned to vibrational modes of polynucleotide moieties involved in interactions. SERS spectra of both polyaza pyridinophanes with single stranded RNA polynucleotides indicated hydrogen bonding between the small molecules and the nucleic bases of poly A, poly C and poly U, whereas an interaction of only PYPOD with poly G was suggested. SERS spectra implied that both compounds bound into the minor groove of the helical poly dAdT–poly dAdT polynucleotide, while none of polyaza pyridinophanes interacted with the grooves of the poly dGdC–poly dGdC polynucleotide. Nevertheless, intensity ratios suggested intercalation of the phenanthroline moiety of the PHENPOD molecules into the double helix of the guanine‐cytosine polynucleotide. Spectral features also indicated binding of the PYPOD molecules within the major groove of the double stranded RNA analog. Copyright © 2014 John Wiley & Sons, Ltd.     

若干多氮双核银(Ⅰ)大环化合物的合成和电化学

本文在硝酸银存在下,用二乙撑三胺、三（2－氨基乙基）胺分别和以间苯二醛为母体的二醛缩合,得到了系列双核银（Ⅰ）和多氮环合物和穴合物。对所得产物进行了表征,并利用循环伏安法对配合物的电化学进行了研究。探讨了环空腔大小及取代基不同对配合物中银（Ⅰ）电化学行为的影响。