Adsorptive Voltammetry of Polyelectrolyte Complex Between 11‐Ferrocenyltrimethylundecylammonium and Polyanions at Carbon Paste Electrode

For polyelectrolyte complex between cationic surfactant and polyanion, the adsorptive voltammetry at carbon paste electrode using an electroactive cationic surfactant was examined. The adsorption state of the cationic surfactant in the complexes at CPE was estimated from the half‐height width of the oxidation waves. The half‐height width for poly(styrene sulfonate) was independent of the molecular weight, and was same as that for poly(vinyl sulfate). The half‐height width for heparin was broad and different from that of the vinyl polyanions. According to the analysis by Frumkin isotherm, the interaction between cationic surfactants was attractive in heparin complex at CPE, however, in the vinyl polyanion complexes at CPE the interaction was non‐cooperative as that predicted with the Langmuir isotherm. In spite of the same adsorption state, the concentration dependency of the peak current for poly(styrene sulfonate) was quite different from that for poly(vinyl sulfate). The concentration dependence indicated the reactive property of each polyanion on the association with the cationic surfactant in aqueous solution.     

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXVI Structural Studies in the Copper(I) Halide : Norbornadiene System

The structural characterizations of some copper(I) halide (CuX) adducts with norbornadiene (nbd) are recorded. CuCl : nbd (1:1)₄ (a redetermination), (2:1)_2(|), are systems both based around Cu₄Cl₄ cubane-type cluster arrays. CuBr : nbd (7:3)_(|)( 0.5 MeOH), a complex polymer with 3-symmetry, is believed to be the complex previously described as an adduct of 2:1 stoichiometry. Attempts to obtain an iodide counterpart have resulted in the definition of an ephemeral adduct CuI : MeCN (3:2)_(|). 0.5 C₇H₈ in which, remarkably, the nbd is uncoordinated; the complex is a polymer, related to the [AgX(quinoline)]_(|) (X = Cl, Br) saddle polymer.     

Zur Synthese von Human-Big-Gastrin I

The synthesis of the tetratriacontapeptide amide corresponding to the revised primary structure of human big gastrin I is described. For this purpose the fragments were designed in view of the maximum use of those utilized in our previous synthesis of human big gastrin I according to the first sequence proposal. Consequently the key tripeptide-Pro-Pro-His- (sequence 7–9) was prepared in suitably protected form to be used as amino or carboxyl component for assembly of the segments 1–9 and 1–14, respectively. Final condensation of the latter nona- and tetradecapeptide derivatives with the C-terminal segments 10–34 and 15–34 via the azide and the dicyclohexylcarbodiimide/N-hydroxysuccinimide procedure, respectively, leads to crude fully protected human big gastrin I. Upon deprotection by exposure to trifluoroacetic acid in presence of ethanedithiol-(1,2) as scavanger, ion exchange chromatography and partition chromatography, the desired tetratriacontapeptide amide was isolated in satisfactory yield with a high degree of purity. The identical immunological behaviour of the synthetic material, if compared with that of natural human big gastrin I, represents ulterior strong evidence for the correctness of the newly proposed structure for this putative prohormonal form of the gastrins.

Kurzmitteilung:Wünsch E., Wendlberger G., Mladenova-Orlinova L., Göhring W., Jaeger E., Scharf R., Gregory R. A., Dockray G. J., Hoppe-Seyler's Z. Physiol. Chem.362, 179 (1981).     

NMR studies of interionic interactions in N-methylformamide

The NMR chemical shifts of alkali and thallium(I) salts with various monovalent anions have been measured in N-methylformamide solution. Lithium-7 chemical shifts are virtually concentration and counter-ion independent, presumably due to an absence of direct cation-anion interactions. The sodium-23, potassium-39 and cesium-133 chemical shifts of the salts studied depend on the anion and vary linearly with the concentration. The observed behavior can be accounted for by the formation of collisional ion pairs. On the other hand, the thallium-205 chemical shifts of thallium(I) nitrate and perchlorate were anion-dependent and varied non-linearly with the salt concentration. These results are indicative of contact ion pair formation; formation constants were calculated to be 2.6±0.4 M ^–1 for TlNO ₃ and 1.7±0.5 M ^–1 for TlClO ₄ . The cesium-133 NMR spectra of several mixed electrolyte systems also have been measured in N-methylformamide solution. The¹³³Cs chemical shifts also change linearly with the concentrations of the salts added to 0.10 M CsI/NMF solutions. The influence of the anions on the chemical shifts is the same as that observed for cesium salts alone.     

Supramolecular Hybrids from Cyanometallate Complexes and Diblock Copolypeptide Amphiphiles in Water

The self-assembly of discrete cyanometallates has attracted significant interest due to the potential of these materials to undergo soft metallophilic interactions as well as their optical properties. Diblock copolypeptide amphiphiles have also been investigated concerning their capacity for self-assembly into morphologies such as nanostructures. The present work combined these two concepts by examining supramolecular hybrids comprising cyanometallates with diblock copolypeptide amphiphiles in aqueous solutions. Discrete cyanometallates such as [Au(CN)₂]⁻, [Ag(CN)₂]⁻, and [Pt(CN)₄]²⁻ dispersed at the molecular level in water cannot interact with each other at low concentrations. However, the results of this work demonstrate that the addition of diblock copolypeptide amphiphiles such as poly-(L-lysine)-block-(L-cysteine) (Lys_m-b-Cys_n) to solutions of these complexes induces the supramolecular assembly of the discrete cyanometallates, resulting in photoluminescence originating from multinuclear complexes with metal-metal interactions. Electron microscopy images confirmed the formation of nanostructures of several hundred nanometers in size that grew to form advanced nanoarchitectures, including those resembling the original nanostructures. This concept of combining diblock copolypeptide amphiphiles with discrete cyanometallates allows the design of flexible and functional supramolecular hybrid systems in water.     

Mixed-Valent Trinuclear CoIII-CoII-CoIII Complex with 1,3-Bis(5-chlorosalicylideneamino)-2-propanol

A mixed-valent trinuclear complex with 1,3-bis(5-chlorosalicylideneamino)-2-propanol (H₃clsalpr) was synthesized, and the crystal structure was determined by the single-crystal X-ray diffraction method at 90 K. The molecule is a trinuclear Co^III-Co^II-Co^III complex with octahedral geometries, having a tetradentate chelate of the Schiff-base ligand, bridging acetate, monodentate acetate coordination to each terminal Co³⁺ ion and four bridging phenoxido-oxygen of two Schiff-base ligands, and two bridging acetate-oxygen atoms for the central Co²⁺ ion. The electronic spectral feature is consistent with the mixed valent Co^III-Co^II-Co^III. Variable-temperature magnetic susceptibility data could be analyzed by consideration of the axial distortion of the central Co²⁺ ion with the parameters Δ = –254 cm⁻¹, λ = –58 cm⁻¹, κ = 0.93, tip = 0.00436 cm³ mol⁻¹, θ = –0.469 K, g_z = 6.90, and g_x = 2.64, in accordance with a large anisotropy. The cyclic voltammogram showed an irreversible reduction wave at approximately −1.2 V·vs. Fc/Fc⁺, assignable to the reduction of the terminal Co³⁺ ions.     

Discriminating between Parallel,Anti-Parallel and Hybrid G-Quadruplexes: Mechanistic Details on Their Binding to Small Molecules

G-quadruplexes (G4) are now extensively recognised as a peculiar non-canonical DNA geometry that plays a prime importance role in processes of biological relevance whose number is increasing continuously. The same is true for the less-studied RNA G4 counterpart. G4s are stable structures; however, their geometrical parameters may be finely tuned not only by the presence of particular sequences of nucleotides but also by the salt content of the medium or by a small molecule that may act as a peculiar topology inducer. As far as the interest in G4s increases and our knowledge of these species deepens, researchers do not only verify the G4s binding by small molecules and the subsequent G4 stabilisation. The most innovative studies now aim to elucidate the mechanistic details of the interaction and the ability of a target species (drug) to bind only to a peculiar G4 geometry. In this focused review, we survey the advances in the studies of the binding of small molecules of medical interest to G4s, with particular attention to the ability of these species to bind differently (intercalation, lateral binding or sitting atop) to different G4 topologies (parallel, anti-parallel or hybrid structures). Some species, given the very high affinity with some peculiar G4 topology, can first bind to a less favourable geometry and then induce its conversion. This aspect is also considered.     

一致空间的理想导集映射

本文介绍一致空间的理想导集映射,并对这些映射的像展开研究.同时,介绍I-Hurewicz有界性的概念,研究I-Hurewicz有界性的基础拓扑运算性质.最后,得到一致空间中I-Hurewicz有界性的一个等价刻画.     

Oxidation of Styrene to Benzaldehyde Catalyzed by Schiff Base Functionalized Triazolylidene Ni(II) Complexes

Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L₁NHC)₂](PF₆)₂; 3, [Ni-(L₂NHC)₂](PF₆)₂; 4, [Ni-(L₃NHC)](PF₆)₂; 7 and [Ni-(L₄NHC)](PF₆)₂; 8, (where L₁NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L₂NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L₃NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L₄NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle.     

Gold Nanoparticles as Effective ion Traps in Poly(dimethylsiloxane) Cross-Linked by Metal-Ligand Coordination

At this time, the development of advanced elastic dielectric materials for use in organic devices, particularly in organic field-effect transistors, is of considerable interest to the scientific community. In the present work, flexible poly(dimethylsiloxane) (PDMS) specimens cross-linked by means of ZnCl₂-bipyridine coordination with an addition of 0.001 wt. %, 0.0025 wt. %, 0.005 wt. %, 0.04 wt. %, 0.2 wt. %, and 0.4 wt. % of gold nanoparticles (AuNPs) were prepared in order to understand the effect of AuNPs on the electrical properties of the composite materials formed. The broadband dielectric spectroscopy measurements revealed one order of magnitude decrease in loss tangent, compared to the coordinated system, upon an introduction of 0.001 wt. % of AuNPs into the polymeric matrix. An introduction of AuNPs causes damping of conductivity within the low-temperature range investigated. These effects can be explained as a result of trapping the Cl⁻ counter ions by the nanoparticles. The study has shown that even a very low concentration of AuNPs (0.001 wt. %) still brings about effective trapping of Cl⁻ counter anions, therefore improving the dielectric properties of the investigated systems. The modification proposed reveals new perspectives for using AuNPs in polymers cross-linked by metal-ligand coordination systems.