Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss).     

Azomacrocyclic derivatives of imidazole: synthesis, structure, and metal ion complexation properties

New azocrown ethers comprising imidazoles in the macrocycle have been synthesized. Imidazole, 2-methyl-, 4-methyl-, and 4-phenylimidazole were incorporated to form macrocyclic units by coupling with the appropriate bis-diazonium salts. The syntheses were performed under high dilution conditions. The X-ray structure of a water adduct of the 21-membered crown ether derivative of 4-methylimidazole 8 has been solved. Metal cation binding was investigated with the use of UV-vis spectroscopy in acetonitrile, methanol, and methanol-water mixtures. The obtained chromoionophores were tested as ion-carriers in ion-selective membrane electrodes.     

2-(4-Phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic Acid and Its DMSO Solvate: Synthesis, Crystal Structure and Biological Activity

Abstract  

A new 1,2,4-triazole derivative, 2-(4-phenyl-5-pyridin-2-yl-4H-1,2,4-triazol-3-yl)cyclohexanecarboxylic acid, C₂₀H₂₀N₄O₂ (I), and its dimethyl sulfoxide solvate 1:1 (II) have been synthesized and their crystal structure was established. Compound (I) was screened for its antiproliferative and antiinflammatory activity. Structural analysis indicated the substantial difference between two symmetry independent molecules in (I) and this in (II), it manifests in the relative orientation of pyridine/phenyl and triazole rings, as well as in the orientation of carboxyl group with respect to cyclohexane ring. The molecules A and B in the crystal (I) form two hydrogen-bonded chains through O–H_carboxyl and N_triazole atoms, giving separate catemers of symmetry independent molecules. The catemer of (IA) running along the 2₁ axis is homochiral, while the catemer (IB) is racemic—formed about the c glide plane. In the crystalline solvate (II) complexation of (I) with DMSO induced enantiomeric self-resolution. Obtained crystals are racemic twins, in which each part is built of one enantiomer of (I) having the relative configuration 11S,12R or 11R,12S. A pair of host–guest molecules is linked by the O–H_carboxyl⋯O_DMSO hydrogen bond.     

Sorption of platinum on immobilized microorganisms for its on-line preconcentration and chemiluminescent determination in water samples

Fungi of the type Aspergillus sp. were immobilized on a cellulosic resin and used as a biosorbent for the on-line preconcentration and separation of Pt(IV) ions prior to their chemiluminescent determination via flow injection analysis. Biosorption and elution conditions were optimized, and the results compared to biosorbents based on the use of Chlorella vulgaris algae and Saccharomyces cerevisiae yeast in terms of preconcentration and selective retention of Pt(IV). The immobilized fungi presented here have a high potential for use in platinum biosorption. The procedure exhibits the currently lowest limit of detection (0.02 ng mL^?1 of Pt) and very high selectivity. The procedure was applied to the determination of Pt(IV) in river water, road run-off, and wastewater samples.

Sensitive electrospray mass spectrometry analysis of one-bead-one-compound peptide libraries labeled by quaternary ammonium salts

A rapid and straightforward method for high-throughput analysis of single resin beads from one-bead-one-compound combinatorial libraries with high resolution electrospray ionization tandem mass spectrometry (HR ESI-MS/MS) is presented. The application of an efficient method of peptide derivatization by quaternary ammonium salts (QAS) formation increases ionization efficiency and reduces the detection limit, allowing analysis of trace amounts of compounds by ESI-MS. Peptides, synthesized on solid support, contain a new cleavable linker composed of a Peg spacer (9-aza-3,6,12,15-tetraoxa-10-on-heptadecanoic acid), lysine with ?-amino group marked by the N,N,N-triethylglycine salt, and methionine, which makes possible the selective cleavage by cyanogen bromide. Even a small portion of peptides derivatized by QAS cleaved from a single resin bead is sufficient for sequencing by HR ESI-MS/MS experiments. The developed strategy was applied to a small training library of α chymotrypsin substrates. The obtained results confirm the applicability of the proposed method in combinatorial chemistry.     

New Strategies for the Simple and Sensitive Voltammetric Direct Quantification of Se(IV) in Environmental Waters Employing Bismuth Film Modified Glassy Carbon Electrode and Amberlite Resin

An analytical procedure regarding the determination of selenium(IV) by anodic stripping voltammetry exploiting the in situ plated bismuth film electrode is described. Since organics are commonly present in untreated natural water samples, the use of Amberlite XAD-7 resin turns out to be quite important to avoid problems such as the adsorption of these compounds on the working electrode. The optimum circumstances for the detection of selenium in water using differential pulse voltammetry techniques were found to be as follows: 0.1 mol L⁻¹ acetic acid, 1.9 × 10⁻⁵ mol L⁻¹ Bi(III), 0.1 g Amberlite XAD-7 resin, and successive potentials of −1.6 V for 5 s and −0.4 V for 60 s, during which the in situ formation of the bismuth film on glassy carbon and the accumulation of selenium took place. The current of the anodic peak varies linearly with the selenium concentration ranging from 3 × 10⁻⁹ mol L⁻¹ to 3 × 10⁻⁶ mol L⁻¹ (r = 0.9995), with a detection limit of 8 × 10⁻¹⁰ mol L⁻¹. The proposed procedure was used for Se(IV) determination in certified reference materials and natural water samples, and acceptable results and recoveries were obtained.     

Synthesis of a new class of ribose functionalized dinucleotide cap analogues for biophysical studies on interaction of cap-binding proteins with the 5' end of mRNA

mRNAs of primitive eukaryotes such as Caenorhabditis elegans and Ascaris summ possess two different caps at their 5' terminus. They have either a typical cap which consists of 7-methylguanosine linked via a 5',5'-triphosphate bridge to the first transcribed nucleotide (MMG cap) or an atypical hypermethylated form with two additional methyl groups at the N2 position (TMG cap). Studies on interaction between the 5' end of mRNA and proteins that specifically recognize its structure have been carried out for several years and they often require chemically modified cap analogues. Here, we present the synthesis of five novel dinucleotide MMG and TMG cap analogues designed for binding studies using biophysical methods such as electron spin resonance (ESR) and surface plasmon resonance (SPR). New analogues were prepared by derivatization of the 2',3'-cis diol of the second nucleotide in the cap structure with levulinic acid, and coupling of the obtained acetal through its carboxylic group with 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino TEMPO), ethylenediamine (EDA) or (+)-biotinyl-3,6,9-trioxaundecanediamine (amine-PEO(3)-biotin).     

Vertically π‐Expanded Imidazo[1,2‐a]pyridine: The Missing Link of the Puzzle

The dehydrogenative coupling of imidazo[1,2‐a]pyridine derivative has been achieved for the first time. In cases in which the most‐electron‐rich position of the electron‐excessive heterocycle was blocked by a naphthalen‐1‐yl substituent, neither oxidative aromatic coupling nor reaction under Scholl conditions enabled the fusion of the rings. The only method that converted the substrate into the corresponding imidazo[5,1,2‐de]naphtho[1,8‐ab]quinolizine was coupling in the presence of potassium in anhydrous toluene. Moreover, we discovered new, excellent conditions for this anion‐radical coupling reaction, which employed dry O₂ from the start in the reaction mixture. This method afforded vertically fused imidazo[1,2‐a]pyridine in 63 % yield. Interestingly, whereas the fluorescence quantum yield (Φ_fl) of compound 3 , despite the freedom of rotation, was close to 50 %, the Φ_fl value of flat naphthalene‐imidazo[1,2‐a]pyridine was only 5 %. Detailed analysis of this compound by using DFT calculations and a low‐temperature Shpol′skii matrix revealed phosphorescence emission, thus indicating that efficient intersystem‐crossing from the lowest‐excited S₁ level to the triplet manifold was the competing process with fluorescence.     

Process Induced Micro Structure Evolution in Polyester Polyurethane and Mechanical Properties Relationship

Summary: MDI-HQEE-Capa based thermoplastic polyurethane (TPU) with Shore hardness of 94 A was injection molded. In order to study the influence of melt conditions on the material structure evolution and resulting mechanical properties a systematical variation in processing temperatures in the range between 195 °C and 250 °C was applied. The mold temperature was kept constant at 60 °C. Process induced samples morphologies were investigated by means of light microscope (LM), scanning electron microscope (SEM) and differential scanning calorimeter (DSC). Mechanical visco-elastic properties were determined by means of cyclic tensile experiment and were correlated with results of structural investigations. The evaluation of morphology micrographs of raw TPU material and specimens molded at different temperatures shows a reduction in visual crystalline fraction. This gains a distinct change in the deformation behavior of injection molded TPU with increasing melt processing temperature.