Specific Interaction of Coproporphyrin I with Antibodies in Water and Reverse Micelles: Dimerization of Antibodies Affects Antigen Binding Site

The antigen-antibody interaction between coproporphyrin I and anti-coproporphyrin antibodies was studied by a fluorescence method in water and a reverse micellar system: n-octane/Aerosol OT. Coproporphyrin fluorescence was quenched, and coproporphyrin emission maximum was shifted to the long-wavelength region after binding to the antibodies or Fab-fragments. The mechanism of this quenching is static, most probably, by a tryptophan residue (or maybe lysine or methionine). Apparent dynamic quenching, in this case, arises from protein backbone motion. A special kind of antibody Fab-Fab dimerization was proposed.     

Cis‐trans Isomerism in Copper(II) Complexes with N‐acyl Thiourea Ligands

The N‐acyl thiourea complexes bis[N,N‐diethyl‐N′‐(p‐nitrobenzoyl)‐thioureato]copper(II) ( 1a,1b ) and bis(N,N‐diphenyl‐N′‐benzoylthioureato)copper(II) ( 2a,2b ) crystallize in each case in two modifications. X‐ray structural analysis shows that 1a and 1b are cis‐trans isomers. This is very unusual for N‐acyl thioureato complexes because with exception of one platinum(II) complex up to now only cis complexes have been found. In contrast X‐ray structural analysis of both forms 2a and 2b of the other complex shows no cis‐trans pair. Both modifications are cis complexes. In solution both isomers of the copper(II) complexes are observable by EPR spectroscopy.     

Synthesis and Properties of Hyperbranched Polyimides Combined with Silica

Summary: The novel hyperbranched polyimide - silica hybrid materials containing theoretically 16 wt% of an inorganic phase were prepared via a sol-gel process. An amine terminated polyimide precursor (hyperbranched polyamic acid) was prepared from commercially available monomers 4,4′,4″-triaminotriphenylmethane and 4,4′-oxydiphthalic anhydride in molar ratio 1:1. Tetramethoxysilane and/or 3-glycidoxypropyltrimethoxysilane (also used as a coupling agent) were used as silica precursors. During thermal exposition the polyimide precursor was transformed to hyperbranched polyimide and hydrolyzed alkoxy groups reacted mutually to form silica. The final products were self-standing films, whose structure was characterized by using IR and ¹³C and ²⁹Si solid state NMR spectroscopy. The influence of the amount of silica and/or coupling agent on their structure and thermal properties was described.     

New dirhenium(III) compounds bridged by carboxylate ligands: N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] and Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2)

The solvothermal reaction of (N(C(4)H(9))(4))(2)[Re(2)Cl(8)] with trifluoroacetic acid and acetic anhydride leads to the new rhenium trifluoroacetate dimer N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1) and to the rhenium carbonyl dimer Re(2)(mu(2)-Cl)(2)(CO)(8) as the rhenium-reduced byproduct. The reaction of the precursor complex, N(C(4)H(9))(4)[Re(2)(OOCCF(3))Cl(6)] (1), with the organometallic carboxylic acid (CO)(6)Co(2)HCCCOOH leads to the cluster of clusters compound Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2), which has the dimer structure of Re(2)(OOCR)(4)Cl(2). Cyclic voltammetric measurements show that Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) has one reduction centered on the dirhenium core and a reduction centered on the cobalt atoms. DFT calculations have been used to rationalize the observed displacements of the voltammetric signals in Re(2)(OOCCCHCo(2)(CO)(6))(4)Cl(2) (2) compared to the parent ligand (CO)(6)Co(2)HCCCOOH and rhenium pivalate.     

A novel copper cobalt inorganometallic cluster. Synthesis,structure and bonding analysis of Cu(3)[mu(2)-(CCHCo(2)(CO)(6))](3)

The reaction of the organometallic carboxylic acid HOOCCCHCo(2)(CO)(6) with copper(II) methoxide leads to a new inorganometallic cluster; Cu(3)[mu(2)-(CCHCo(2)(CO)(6))](3). This cluster has a triangular core of copper(I) centers surrounded by three CCHCo(2)(CO)(6) fragments. The structure of the cluster has short Cu-Cu and Cu-Co distances (average 2.500 and 2.540 A, respectively). DFT calculations provide a rationalization of the peculiar bonding in this cluster.     

Method development for compositional analysis of low molecular weight poly(vinyl acetate) by matrix-assisted/laser desorption-mass spectrometry and its application to analysis of chewing gum

The influence of the sample preparation parameters (the choice of the solvent and of the matrix:analyte ratio) was investigated and optimal conditions were established for MALDI mass spectrometry analysis of the pristine low molecular weight polyvinyl acetate (PVAc). It was demonstrated that comparison of polymer’s and solvent’s Hansen solubility parameters could be used as a guide when choosing the solvent for MALDI sample preparation. The highest intensity PVAc signals were obtained when ethyl acetate was used as a solvent along with the lowest matrix–analyte ratio (2,5-dihydroxybenzoic acid was used as a matrix in all experiments). The structure of the PVAc was established with high accuracy using the matrix-assisted laser desorption/ionization-Fourier transform mass spectrometry (MALDI-FTMS) analysis. It was demonstrated that PVAc undergoes unimolecular decomposition by losing acetic acid molecules from its backbone under the conditions of FTMS measurements. Number and weight average molecular weights as well as polydispersity indices were determined with both MALDI-TOF and MALDI-FTMS methods. The sample preparation protocol developed was applied to the analysis of a chewing gum and the molecular weight and structure of the polyvinyl acetate present in the sample were established. Thus, it was shown that optimized MALDI mass spectrometry could be used successfully for characterization of polyvinyl acetate in commercially available chewing gum.     

Synthesis and EPR/UV/Vis‐NIR Spectroelectrochemical Investigation of a Persistent Phosphanyl Radical Dication

The reaction of the bis(imidazoliumyl)‐substituted P^I cation [(2‐Im^Dipp)P(4‐Im^Dipp)]⁺ ( 10 ⁺) (2‐Im=imidazolium‐2‐yl; 4‐Im=imidazolium‐4‐yl; Dipp=2,6‐di‐isopropylphenyl) with trifluoromethanesulfonic acid (HOTf) or methyl trifluoromethylsulfonate (MeOTf) yields the corresponding protonated [(2‐Im^Dipp)PH(4‐Im^Dipp)]²⁺ ( 11 ²⁺) and methylated [(2‐Im^Dipp)PMe(4‐Im^Dipp)]²⁺ ( 12 ²⁺) dications, respectively. EPR/UV/Vis‐NIR spectroelectrochemical investigation of the low‐coordinated P^I cation 10 ⁺ predicted a stable and “bottleable” P‐centered radical dication [(2‐Im^Dipp)P(4‐Im^Dipp)]^2+. ( 13 ^2+.). The reaction of 10 ⁺ with the nitrosyl salt NO[OTf] yields the persistent phosphanyl radical dication 13 ^2+. as triflate salt in crystalline form. Quantum chemical investigation revealed an exceptional high spin density at the P atom.     

External electric field effect on electronic properties and charge transfer in CoI2/NiI2 spinterface

Electronic structure and spin-related properties of CoI₂/NiI₂ heterostructure were studied by means of density functional theory. It was shown that the electronic structure at the Fermi level can be characterized by a band gap. The effect of the external electric field on charge transfer and electronic properties of the CoI₂/NiI₂ interface was investigated, and it was found that band gap width depends on the strength of the applied electric field, switching its nature from semiconducting to a half-metallic one. An easy control of the electronic properties and promising spin-polarized nature of the CoI₂/NiI₂ spinterface allows the heterostructure to be used in spin-related applications.     

A Novel Coordination Polymer Based on Decavanadate Units Linked by Copper(II) Ethylenediamine Complexes

Summary: A novel coordination polymer[{Cu(en)₂}(V₁₀O₂₈)]_n · 2n[Cu(en)₂(H₂O)] · 2n(H₃BO₃) · 2n(H₂O) was obtained by hydrothermal reaction. The compound crystallizes in the monoclinic crystal system, in the C2/c space group, with a = 26.490 (3) Å; b = 11.6558 (11) Å; c = 19.8426 (19) Å; β = 124.011 (1)°; V = 5078.6(8) ų. The solid structure is formed by polymeric chains, [Cu(en)₂(H₂O)]²⁺ cations, and boric acid and water solvate molecules, stabilized through a multiple hydrogen bond network.     

The stabilization of charged states at phenazine-like units in polyaniline under p-doping: an in situ ATR-FTIR spectroelectrochemical study

The structure and stabilization of charged states during p-doping of polyaniline (PANI) were studied by in situ ATR-FTIR spectroelectrochemistry. The role of phenazine-like units in several copolymers of aniline and a phenazine derivative (3,7-diamino-5-phenylphenazinium chloride, phenosafranine) was investigated by spectroelectrochemistry. PANI and three copolymers with different aniline to phenosafranine ratio were electrochemically prepared. FTIR spectra of as-prepared polymers as well as in situ FTIR spectra during the oxidation of the polymers give evidence of the presence of phenazine-like units in the structure of electrochemically prepared PANI, as shown by vibrations of the phenazine rings. New bands corresponding to the in-plane and out-of-plane C-H vibration of 1,2,4-trisubstituted benzene nuclei in the phenazine skeleton are found at 1033, 957, 880, 766 and 681 cm(-1). The potential dependence of IR bands observed during oxidation of the polymers was compared to that of the ESR intensity and the absorption data and points to the diamagnetic species like π-dimers formed at higher oxidation level of PANI. This charged state is shown to be fixed at the link of the phenazine-like units with the linear segments of PANI.