Synthesis,structures and magnetic properties of four 3D heterometallic cobalt(II)–barium(II) coordination polymers

Four heterometallic complexes, namely {[CoBa(2,5-pdc)₂(H₂O)₃]_n·2nH₂O} (1), [CoBa(2,5-pdc)₂(H₂O)₄]_n (2), [CoBa(2,5-pdc)₂(H₂O)₅]_n (3) and [CoBa₂(2,5-pdc)₃(μ₂-H₂O)₂(H₂O)₄]_n (4) (2,5-H₂pdc?=?pyridine-2,5-dicarboxylic acid), have been hydrothermally synthesized and characterized both structurally and magnetically. All four complexes exhibit 3D frameworks, in which the Co(II) centers are chelated by pyridine nitrogen and carboxyl oxygen atoms in a five-membered ring. The Ba(II) centers are chelated and bridged by carboxyl oxygen atoms to extend the structures into 3D frameworks. The networks of the complexes can be controlled via rationally choosing the appropriate ligand and tuning the ratio of the two types of metal centers. The magnetic properties of complexes 1, 2 and 4 have been investigated from 2 to 300 K.     

Synthesis,characterization, DNA binding,topoisomerase I inhibition,and antiproliferation activities of (di-<Emphasis Type="Italic">tert</Emphasis>-butylbipyridine) platinum(II) complexes

Two mononuclear Pt(II) complexes, Pt(dbbpy)Cl₂ (1) and [Pt(dbbpy)₂](PF₆)₂ (2) (dbbpy?=?4,4′-ditertbutyl-2,2′-biyridine) were synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, ¹H NMR, and ESI–MS. Their binding affinities for both double-stranded (DS) calf thymus DNA (ct-DNA) and G-quadruplex DNA (HT21 and BCL-2) were investigated. In addition to structural differences, complex 1 displayed higher binding affinity for DS ct-DNA, whereas positively charged complex 2 was selective for binding to G-quadruplex DNA over DS DNA. The time-dependent cleavage of supercoiled circular plasmid pBR322 DNA by 1 was observed using agarose gel electrophoresis, whereas complex 2 hardly cleaved DS DNA. Stabilization of G-quadruplex HT21 DNA by both complexes was assessed by PCR stop assays. Both complexes exhibited moderate activities for inhibition of topoisomerase I as well as modest antiproliferation activities toward cancer cells in CKK-8 assays.     

A Metal–Organic Framework with Cooperative Phosphines That Permit Post‐Synthetic Installation of Open Metal Sites

PCM‐101 is a phosphine coordination material comprised of tris(p‐carboxylato)triphenylphosphine and secondary pillaring groups coordinated to [M₃(OH)]⁵⁺ nodes (M=Co, Ni). PCM‐101 has a unique topology in which R₃P: sites are arranged directly trans to one another, with a P???P separation distance dictated by the pillars. Post‐synthetic coordination of soft metals to the P: sites proceeds at room temperature to provide X‐ray quality crystals that permit full structural resolution. Addition of AuCl groups forces a large distortion of the parent framework. In contrast, CuBr undergoes insertion directly between the trans‐P sites to form dimers that mimic solution‐phase complexes, but that are geometrically strained due to steric pressure exerted by the MOF scaffold. The metalated materials are active in heterogeneous hydroaddition catalysis under mild conditions, yielding different major products compared to their molecular counterparts.     

Structure and conformation of DAB dendrimers in solution via multidimensional NMR techniques.

NOESY-HSQC 3D-NMR and NOESY 2D-NMR techniques have been used on a 750 MHz spectrometer to study the chain conformations of different generation DAB dendrimers (poly[propylene imine] dendrimers) in chloroform and benzene solutions. The high-field multidimensional NMR techniques provided the chemical shift dispersion needed to resolve all of the unique resonances in the dendrimers. By studying the NOE interactions among dendritic chain protons, information about through space interactions between protons on different parts of the dendrimer chain is obtained, which is directly related to the conformation of the dendrimer. These experiments also give further proof of the chemical shift assignments obtained from the HMQC-TOCSY 2D and 3D NMR experiments. The concentration effects on chemical shifts have also been observed, revealing information about the interactions between solvent and different parts of dendrimer molecules. These studies clearly show for DAB dendrimers, that folded chain conformations can occur in nonpolar solvents such as benzene and extended chain conformations are predominant in polar solvents such as chloroform.     

BaO-B2O3-GeO2(BaO≤50 mo1％)三元系相图的研究

本文用X射线衍射及差热分析等方法, 研究了BaO-B_2O_3-GeO_2(BaO≤50 mol％)三元系的室温截面相图。发现了一个新的三元化合物Ba_3B_6Ge_2O_(16)(3BaO·3B_2O_3·2GeO_2)。并且研究了BaB_2O_4-Ba_3B_6Ge_2O_(16), BaGeO_3-Ba_3B_6Ge_2O_(16), BaB_2O_4-BaGeO_3三个二元系相图。它们都是共晶体系, 共晶温度分别为937±3 ℃、879±3 ℃875±3 ℃; 共晶组分分别为(BaO)_(0.42)(B_2O_3)_(0.42)(GeO_2)_(0.16), (BaO)_(0.42)(B_2O_3)_(0.24)(GeO_2)_(0.34), (BaO)_(0.50)(B_2O_3)_(0.27)(GeO_2)_(0.23)。这三个二元系组成一个三元共晶体系, 其三元共晶温度为870±3 ℃, 共晶组分为(BaO)_(0.46)(B_2O_3)_(0.27)(GeO_2)_(0.27)。     

Fast atom bombardment induced ring rupture of silatranes

During a comparison study of the fast atom bombardment (FAB) and electron impact mass spectra of 1-organyl-2,9,10-trioxa-6-aza-1-silatricyclo[4.3.3.0^1,6]dodecanes, an unusual ion peak at m/z 164 was noticed in the FAB spectra. Accurate mass measurement indicated that m/z 164 corresponds to protonated 1-[N,N-bis(2-hydroxyethyl)amino]-1-propanol (BHAP), which is produced by a ring-rupture reaction. Further experiment showed that the intensity of the [BHAP + H]⁺ ion peak increased markedly as the 7keV Ar⁰ bombardment proceeded, suggesting a FAB-induced reaction. The possible mechanism is also discussed.     

One step synthesis of Fe4.4Ni17.6Se16 coupled NiSe foam as self-supported,highly efficient and durable oxygen evolution electrode

The development of cost-effective, durable and high-efficient oxygen evolution reaction (OER) electrocatalysts is an extremely critical technology for the large-scale industrial water electrolysis. Here, a new strategy is proposed to significantly enhance the electrocatalytic activity by forming a hybrid electrode of NiSe and Fe_4.4Ni_17.6Se₁₆ through direct selenization of porous iron-nickel (FeNi) alloy foam via thermal selenization process. The obtained self-supported Fe_4.4Ni_17.6Se₁₆/NiSe hybrid (FNS/NiSe) foam displays outstanding durability and remarkable catalytic activity in 1.0 M KOH with low overpotentials of 242 and 282 mV to achieve the current densities of 100 and 500 mA cm^?2, respectively. To the best of our knowledge, it exceeds most of the reported OER electrocatalysts in alkaline electrolytes.     

Chemically modified electrode based on poly[tetra(4-aminophenyl)porphyrin] as a pH sensor

A chemically modified platinum electrode with coated poly[tetra(4-aminophenyl)porphyrin] has been used as a potentiometric pH sensor. It gives a linear response over the pH range 1.5-13.7 with a slope of 55 mV/pH (at 20 degrees ). The sensor has fair resistance to erosion of hydrofluoric acid and to interference of a coexisting redox couple. The sensor can be used for pH determination and end-point indication for potentiometric titration of hydrofluoric acid with sodium hydroxide. The a.c. impedance of the polymer membrane has also been studied.