Umsetzungen von ω-alkenylsubstituierten Zirconocendichloridkomplexen mit n-Alkyllithiumverbindungen in Gegenwart von Alkenen bzw. Alkinen

The reaction of ω-alkenyl substituted zirconocene dichloride complexes with two equivalents of n-butyllithium is strongly influenced in the presence of alkenes and alkynes. Metallacyclic zirconocene complexes of novel structures are obtained. The additives alkenes and alkynes compete with the ω-alkenyl substituents and the intermediate 1-butene for the formation of a metallacyclic structure. The reaction of ω-alkenyl substituted zirconocene dichloride complexes with two equivalents of ethyllithium and n-hexyllithium gives analogous reactions and metallacycles as with n-butyllithium.     

SOLVERSTAT: a new utility for multipurpose analysis. An application to the investigation of dioxygenated Co(II) complex formation in dimethylsulfoxide solution

A new utility for multipurpose analysis, SOLVERSTAT, taking advantage of the versatility of spreadsheets is here described. By means of this tool advanced statistical tests have introduced in Microsoft Excel Solver thus allowing regression diagnostic and discrimination between different models. The utility is here applied to the determination, by UV-Vis spectroscopy, of the stability constant for the uptake of molecular dioxygen by the 1:2 complex of Co(II) with N,N′-dimethylethylenediamine (dmen) in the aprotic solvent dimethylsulfoxide (dmso) at 298 K and in a medium adjusted to 0.1 mol dm⁻³ with Et₄NClO₄. The reliability of the model and parameters obtained are discussed and the results compared with those obtained by Dynafit, a different software package, and by independent voltammetric measurements. The validity of SOLVERSTAT has been also examined applying it to the discrimination between different models already discussed in the literature.     

Characterization of antithrombin III from human plasma by two-dimensional gel electrophoresis and capillary electrophoretic methods

The isoforms distribution of the glycoprotein antithrombin III (ATIII) derived from human plasma was investigated by means of isoelectric focusing (IEF) in polyacrylamide gels with immobilized pH gradients (IPG) and two-dimensional gel electrophoresis (2-DE) as well as capillary electrophoretic methods. It turned out that the presence of high concentrations of chaotropics (urea, thiourea) and zwitterionic detergents (3-[(3-cholamidepropyl)dimethylammonio]-1-propanesulfonate (CHAPS)) was decisive for attaining good resolution of the protein isoforms. Resolution by IPG-IEF was obtained with excellent reproducibility and pI differences down to 0.01 pH units could be distinguished. ATIII-alpha and ATIII-beta-fractions preseparated by heparin affinity chromatography showed an analogous but shifted spot pattern consisting each of one major and three minor isoforms. The main isoforms of ATIII-alpha and ATIII-beta exhibit pI values of 5.18 and 5.32, respectively, both values determined in the presence of high concentrations of urea. The pI difference of 0.14 pH units correspond to the effect of two sialic acids absent in ATIII-beta. The formation and occurrence of ATIII dimers and trimers turned out to be dependent on the sample preparation. The results obtained by 2-DE were compared with those of capillary zone electrophoresis (CZE) and capillary IEF (CIEF). Quantitative analysis regarding the CZE separated isoforms of plasma derived ATIII yielded a content of about 70% ATIII-alpha main isoform and about 6.6% of ATIII-beta. The pI values of ATIII determined by CIEF with internal calibration were in fair agreement with the pI values of the main isoforms achieved with 2-DE.     

Multi-selective one dimensional proton NMR experiments for rapid screening and binding affinity measurements

High-throughput ligand-based proton NMR screening performed in the presence of a spy molecule and a control molecule is a valuable tool for identifying drug leads. A limitation of the technique is represented by the severe overlap encountered in the screening of large chemical mixtures. An approach for overcoming this overlap problem is the use of multi-selective R(1) filtered and COSY or TOCSY experiments. Application of this methodology to compounds binding to the Sudlow site I of human serum albumin is presented. The screening is performed by simply monitoring the intensity of two signals. The precise measurement of the relative intensity of the two resonances permits determination of the binding constant of the NMR-hit. For a simple competition binding mechanism, the rapidly-derived NMR binding constants are in good agreement with the values derived from full-titration ITC and fluorescence spectroscopy measurements.     

Electrochemically induced ring-closing of photochromic 1,2-dithienylcyclopentenes

An unprecedented combination of photochromism and electrochromism is observed for two 1,2-bis(dithienyl)cyclopentene derivatives; the ring-opening reactions are photochemically driven while the ring-closing reactions can be triggered by electrochemical oxidation.     

Artificial metalloenzymes for enantioselective catalysis based on biotin-avidin

Homogeneous and enzymatic catalysis offer complementary means to generate enantiomerically pure compounds. Incorporation of achiral biotinylated rhodium-diphosphine complexes into (strept)avidin yields artificial metalloenzymes for the hydrogenation of N-protected dehydroamino acids. A chemogenetic optimization procedure allows one to produce (R)-acetamidoalanine with 96% enantioselectivity. These hybrid catalysts display features reminiscent both of enzymatic and of homogeneous systems.     

Long‐Term Photostability in Terephthalate Metal–Organic Frameworks

Prolonged (weeks) UV/Vis irradiation under Ar of UiO‐66(Zr), UiO66 Zr‐NO₂, MIL101 Fe, MIL125 Ti‐NH₂, MIL101 Cr and MIL101 Cr(Pt) shows that these MOFs undergo photodecarboxylation of benzenedicarboxylate (BDC) linker in a significant percentage depending on the structure and composition of the material. Routine characterization techniques such as XRD, UV/Vis spectroscopy and TGA fail to detect changes in the material, although porosity and surface area change upon irradiation of powders. In contrast to BCD‐containing MOFs, zeolitic imidazolate ZIF‐8 does not evolve CO₂ or any other gas upon irradiation.     

Individual‐Molecule Perspective Analysis of Chemical Reaction Networks: The Case of a Light‐Driven Supramolecular Pump

The first study in which stochastic simulations of a two‐component molecular machine are performed in the mass‐action regime is presented. This system is an autonomous molecular pump consisting of a photoactive axle that creates a directed flow of rings through it by exploiting light energy away from equilibrium. The investigation demonstrates that the pump can operate in two regimes, both experimentally accessible, in which light‐driven steps can be rate‐determining or not. The number of photons exploited by an individual molecular pump, as well as the precision of cycling and the overall efficiency, critically rely on the operating regime of the machine. This approach provides useful information not only to guide the chemical design of a self‐assembling molecular device with desired features, but also to elucidate the effect of the environment on its performance, thus facilitating its experimental investigation.     

Structural and thermal study of asymmetric α-dioxime complexes of Co(III) with Cl and methyl-pyridines

Two new cobalt(III)-chelates, trans-bis(methyl-ethyl-dioximato)-chloro-β-picoline-cobalt (III) (1), and trans-bis(methyl-ethyl-dioximato)-chloro-3,4-lutidine-cobalt (III) (2) were obtained by oxidizing a mixture of CoCl₂, methyl-ethyl-dioxime and amines: β-picoline (3-methyl-pyridine) for (1) and 3,4-lutidine (3,4-dimethyl-pyridine) for (2). The crystal structure of (1) was determined by single crystal XRD (monoclinic, space group P2₁/c (No. 14) with a = 8.391(3) Å, b = 14.421(5) Å, c = 18.383(8) Å, β = 114.57(2)°, R = 0.0499), while both (1) and (2) were studied by middle and far FTIR spectroscopy, electrospray ionization (ESI) MS, powder XRD and thermal analysis (TG/DTA-MS). Melting of the related complexes 1 and 2 at 219 and 184 °C, respectively, results in an immediate chemical degradation of their whole structure and tarring of ligands.