catena‐Poly[[tetra­aqua­manganese(II)]‐μ‐4‐(carboxyl­ato­methyl­sulfanyl)­phenoxy­acetato]

The title compound, [Mn(C₁₀H₈O₅S)(H₂O)₄]_n, a one‐dimensional manganese(II) complex comprising helical chains bridged by 4‐(carboxylatomethylsulfanyl)phenoxyacetate ligands has been characterized by single‐crystal X‐ray diffraction analysis. Hydrogen‐bonding inter­actions between adjacent chains extend the complex into a three‐dimensional supra­molecular architecture.     

Die Tieftemperatur-Synthese von Oxidhalogeniden,YOX (X = Cl,Br, I), als Quelle der Verunreinigung von Yttriumtrihalogeniden,YX3, bei der Gewinnung nach der Ammoniumhalogenid-Methode. Die Analogie von YOCl und YSCl

Low-Temperature Synthesis of Oxyhalides, YOX (X = Cl, Br, I), as the Source of Impurity in the Preparation of Trihalides, YX₃, via the Ammonium Halide Route. Analogy of YOCl and YSCl Ammonium halides, NH₄X (X = Cl, Br, I), react with Y₂O₃ and Y₂S₃, respectively, at temperatures as low as 230=C (X = Cl), 280=C (Br), and 360=C (I) (molar ratio 12:1) to yield (NH₄)₃YX₆, NH₃, and H₂O (H₂S). The choice of smaller ratios than 12:1 (for example 2:1) results in the formation of oxyhalides, YOX, via the reaction of (NH₄)₃YX₆ with surplus Y₂O₃. This reaction is therefore the actual source of impurity of rare-earth trihalides in their preparation via the ammonium halide routes.     

Radical ions : XXVI. Radical anions of perphenylcyclopolysilanes

Perphenylcyclopolysilanes [Si(C₆H₅)₂]_n (n = 4, 5) are reduced by potassium to radical anions. Their simple ESR spectra demonstrate, that the extra electron is confined to the inner Si_nC_2n skeleton of the uncleaved and presumably planarized cyclopolysilanes.     

Xanthine Sensors Based on Anodic and Cathodic Detection of Enzymatically Generated Hydrogen Peroxide

A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s^?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10^?6?1.0×10^?4 M and 5.0×10^?7 to 1.0×10^?4 M, respectively. The detection limits were determined to be of 1.0×10^?6 M and 9.0×10^?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples.     

catena‐Poly[[[pyridinecopper(II)]bis[μ3‐4‐(2‐oxidobenzylideneamino)benzoato]] dimethylformamide disolvate], a polymer composed of dimeric dicopper building units

The title compound, {[Cu(C₁₄H₉NO₃)(C₅H₅N)]·C₃H₇NO}_n or {[Cu₂L₂(py)₂]·2DMF}_n [py is pyridine, L is 4‐(salicylideneamino)benzoate and DMF is dimethylformamide], is composed of dimeric dicopper [CuL(py)]₂ building units, which are interlinked into a one‐dimensional chain through the formation of Cu—O_COO bonds. The dimeric unit is centrosymmetric, containing two Cu^II atoms linked by bridging phenolate O atoms into a Cu₂O₂ plane with a chelating Cu—O bond length of 1.927 (2) Å and a bridging Cu—O bond length of 2.440 (2) Å. Interchain C—H...O and π–π stacking interactions are responsible for an extensive three‐dimensional structure in which the resulting channels are filled by DMF solvent molecules.     

Poly(ethyleneimine) as reducing and stabilizing agent for the formation of gold nanoparticles in w/o microemulsions

This paper is focused on the use of branched poly(ethyleneimine) (PEI) as reducing as well as stabilizing agent for the formation of gold nanoparticles in different media. The process of nanoparticle formation was investigated, in the absence of any other reducing agents, in microemulsion template phase in comparison to the nucleation process in aqueous polymer solution.

On the one hand, it was shown that the polyelectrolyte can be used for the controlled single-step synthesis and stabilization of gold nanoparticles via a nucleation reaction and particles with an average diameter of 7.1 nm can be produced.

On the other hand, it was demonstrated that the polymer can also act as reducing and stabilizing agent in much more complex systems, i.e. in water-in-oil (w/o) microemulsion droplets. The reverse microemulsion droplets of the quaternary system sodium dodecylsulfate (SDS)/toluene–pentanol (1:1)/water were successfully used for the synthesis of gold nanoparticles. The polymer, incorporated in the droplets, exhibits reducing properties, adsorbs on the surface of the nanoparticles and prevents their aggregation. Consequently, nanoparticles of 8.6 nm can be redispersed after solvent evaporation without a change of their size.

Nevertheless, the polymer acts already as a “template” during the formation of the nanoparticles in water and in microemulsion, so that an additional template effect of the microemulsion is not observed.

The particle formation for both methods is checked by means of UV–vis spectroscopy and the particle size and size distribution are investigated via dynamic light scattering and transmission electron microscopy (TEM).     

Thermotropic Liquid Crystals Based on Extended 2,5‐Disubstituted‐1,3,4‐Oxadiazoles: Structure–Property Relationships,Variable‐Temperature Powder X‐ray Diffraction,and Small‐Angle X‐ray Scattering Studies

A class of extended 2,5‐disubstituted‐1,3,4‐oxadiazoles R¹‐C₆H₄‐{OC₂N₂}‐C₆H₄‐R² (R¹=R²=C₁₀H₂₁O 1 a , p‐C₁₀H₂₁O‐C₆H₄‐C?C 3 a , p‐CH₃O‐C₆H₄‐C?C 3 b ; R¹=C₁₀H₂₁O, R²=CH₃O 1 b , (CH₃)₂N 1 c ; F 1 d ; R¹=C₁₀H₂₁O‐C₆H₄‐C?C, R²=C₁₀H₂₁O 2 a , CH₃O 2 b , (CH₃)₂N 2 c , F 2 d ) were prepared, and their liquid‐crystalline properties were examined. In CH₂Cl₂ solution, these compounds displayed a room‐temperature emission with λ_max at 340–471 nm and quantum yields of 0.73–0.97. Compounds 1 d , 2 a – 2 d , and 3 a exhibited various thermotropic mesophases (monotropic, enantiotropic nematic/smectic), which were examined by polarized‐light optical microscopy and differential scanning calorimetry. Structure determination by a direct‐space approach using simulated annealing or parallel tempering of the powder X‐ray diffraction data revealed distinctive crystal‐packing arrangements for mesogenic molecules 2 b and 3 a , leading to different nematic mesophase behavior, with 2 b being monotropic and 3 a enantiotropic in the narrow temperature range of 200–210 °C. The structural transitions associated with these crystalline solids and their mesophases were studied by variable‐temperature X‐ray diffractometry. Nondestructive phase transitions (crystal‐to‐crystal, crystal‐to‐mesophase, mesophase‐to‐liquid) were observed in the diffractograms of 1 b, 1 d , 2 b, 2 d , and 3 a measured at 25–200 °C. Powder X‐ray diffraction and small‐angle X‐ray scattering data revealed that the structure of the annealed solid residue 2 b reverted to its original crystal/molecular packing when the isotropic liquid was cooled to room temperature. Structure–property relationships within these mesomorphic solids are discussed in the context of their molecular structures and intermolecular interactions.     

A Selective Cholesterol Biosensor Based on Composite Film Modified Electrode for Amperometric Detection

An amperometric cholesterol biosensor based on immobilization of cholesterol oxidase in a Prussian blue (PB)/polypyrrole (PPy) composite film on the surface of a glassy carbon electrode was fabricated. Hydrogen peroxide produced by the enzymatic reaction was catalytically reduced on the PB film electrode at 0 V with a sensitivity of 39 μA (mol/L)^?1. Cholesterol in the concentration range of 10^?5 ? 10^?4 mol/L was determined with a detection limit of 6 × 10^?7 mol/L by amperometric method. Normal coexisting compounds in the bio‐samples such as ascorbic acid and uric acid do not interfere with the determination. The excellent properties of the sensor in sensitivity and selectivity are attributed to the PB/PPy layer modified on the sensor.     

A novel three‐dimensional cadmium(II) coordination polymer incorporating 1,4‐bis­(1,2,4‐triazol‐1‐ylmethyl)­benzene and thio­cyanate

In the title complex, poly[cadmium(II)‐μ₂‐1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene‐di‐μ₂‐thio­cyanato], [Cd(NCS)₂(C₁₂H₁₂N₆)]_n, the Cd^II atom lies on an inversion centre in a distorted octa­hedral environment. Four N atoms from the thio­cyanate and 1,4‐bis­(1,2,4‐triazol‐1‐ylmeth­yl)benzene (bbtz) ligands occupy the equatorial positions, and two S atoms from symmetry‐related thio­cyanate ligands occupy the axial positions. The benzene ring of the bbtz ligand lies about an inversion centre. Single thio­cyanate bridges link the Cd^II atoms into two‐dimensional sheets containing novel 16‐membered [Cd₄(μ‐NCS‐N:S)₄] rings. The bbtz ligands further link these two‐dimensional sheets into an unprecedented covalent three‐dimensional network for the cadmium–thio­cyanate system.     

Probing the Helical Secondary Structure of Short-Chain β-Peptides

Structural prerequisites for the stability of the 3₁ helix of β-peptides can be defined from inspection of models (Figs. 1 and 2): lateral non-H-substituents in 2- and 3-position on the 3-amino-acid residues of the helix are allowed, axial ones are forbidden. To be able to test this prediction, we synthesized a series of heptapeptide derivatives Boc-(β-HVal-β-HAla-β-HLeu-Xaa-β-HVal-β-HAla-β-HLeu)-OMe 13–22 (Xaa = α- or β-amino-acid residue) and a β-depsipeptide 25 with a central (S)-3-hydroxybutanoic-acid residue (Xaa = –OCH(Me)CH₂C(O)–) (Schemes 1 3). Detailed NMR analysis (DQF-COSY, HSQC, HMBC, ROESY, and TOCSY experiments) in methanol solution of the β-hexapeptide H(-β-HVal-β-HAla-β-HLeu)₂-OH ( 1 ) and of the β-heptapeptide H-β-HVal-β-HAla-β-HLeu-(S,S)-β-HAla(αMe)-β-HVal-β-HAla- β-HLeu-OH ( 22 ), with a central (2S,3S)-3-amino-2-methylbutanoic-acid residue, confirm the helical structure of such β-peptides (previously discovered in pyridine solution) (Fig.3 and Tables 1–5). The CD spectra of helical β-peptides, the residues of which were prepared by (retentive) Arndt-Eistert homologation of the (S)- or L -α-amino acids, show a trough at 215 nm. Thus, this characteristic pattern of the CD spectra was taken as an indicator for the presence of a helix in methanol solutions of compounds 13–22 and 25 (including partially and fully deprotected forms) (Figs.4–6). The results fully confirm predicted structural effects: incorporation of a single ‘wrong’ residue ((R)-β-HAla, β-HAib, (R,S)-β-HAla(α Me), or N-Me-β-HAla) in the central position of the β-heptapeptide derivatives A (see 17, 18, 20 , or 21 , resp.) causes the CD minimum to disappear. Also, the β-heptadepsipetide 25 (missing H-bond) and the β-heptapeptide analogs with a single α-amino-acid moiety in the middle ( 13 and 14 ) are not helical, according to this analysis. An interesting case is the heptapeptide 15 with the central achiral, unsubstituted 3-aminopropanoic-acid moiety: helical conformation appears to depend upon the presence or absence of terminal protection and upon the solvent (MeOH vs. MeOH/H₂O).