Growth Mechanism of Large Monodispersed Silica Particles Prepared from Tetraethoxysilane in the Presence of Sodium Dodecyl Sulfate

Monodispersed silica particles up to ca. 1.2 μm in diameter were prepared by hydrolysis of tetraethoxysilane in the presence of sodium dodecyl sulfate (SDS). The particle size was increased with an increase of SDS added. The geometrical standard deviation of the particles was decreased with an increase of SDS. In the earlier reaction stage, double spherical particles by the coalescence of the particles were frequently observed when large amounts of SDS were added. Particle size was gradually increased after the coalescence occurred and spherical particles were finally obtained. The results of Nielsen’s chronomal analysis suggest that the polynuclear layer growth took place after the coalescence of the particles in the presence of larger amount of SDS.     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).     

New alcohol resistant strains ofSaccharomyces cerevisiae species for potable alcohol production using molasse

Two alcohol resistant strains of Saccharomyces cerevisiae species were isolated from a Greek vineyard plantation. The strain AXAZ-1 gave a concentration of 17.6% v/v alcohol and AXAZ-2 16.5%, when musts from raisin and sultana grapes, respectively, were employed in alcoholic fermentations. They were found to be more alcohol tolerant and fermentative in the fermentation of molasse than the traditional baker's yeast. Specifically, using an initial [symbol: see text] Be density of 16 [symbol: see text] Be at the repeated batch fermentation process, in the first as well as fourth batch, the better AXAZ-1 gave final [symbol: see text] Be densities of 6.0 and 10.5 respectively, and the baker's yeast 11.6 and 14.5.     

Efficient routes to optically active azido-, amino-, di-azido- and di-amino-cyclitols with chiro- and allo-configuration from myo-inositol

Efficient routes to hitherto unknown 1d-2,5-di-azido-di-deoxy-allo-inositol, 1d-2,5-di-amino-di-deoxy-allo-inositol, 1l-1-azido-1-deoxy-chiro-inositol and 1l-1-amino-1-deoxy-chiro-inositol were developed by using cheaply available myo-inositol as the starting material. Preliminary investigations on the enzyme inhibitory properties were done. The methodology reported is amenable to gram scale synthesis and thus can find application in natural product synthesis.     

Effects of electrolytes on the configuration change of cobalt(II)-halide complexes in chloroform/water reverse micelle systems.

The effects of various salts and HClO4 on the configuration change of cobalt(II)-halide complexes in CHCl3/CTAC or CTAB/H2O reverse micelle systems were examined at 25 degrees C by means of spectrophotometry, where CTAC and CTAB represent cetyltrimethylammonium chloride and bromide, respectively. The formation of the [CoCl4]> or [CoBr4]2- species of the tetrahedral configuration from [Co(H2O)6]2+ of the octahedral configuration in the reverse micelles was greatly promoted not only by a decrease in the W value (W = [H2O]/[surfactant]), but also, at a constant W value (e.g., W = 2.0), by the addition of relatively low concentrations of salts or the acid (e.g., 4.0 mol dm(-3) in the aqueous phase or 4.0 x 10(-2) mol dm(-3) in the whole reverse micelle system). The effects of perchlorate salts increased as Na+ < or = Li+ approximately H+ < Sr2+ < Ca2+ < Mg2+. Non-metallic salts, various tetraalkylammonium (R4N+) salts at lower concentrations, gave minor effects. The enhanced effects of metal salts on the configuration change of the cobalt(II)-halide complexes were interpreted by a further distortion of the hydrogen-bonded structure of the water in a "water pool" in the presence of salts of even relatively low concentrations. A conformation change with increasing temperature was also attributed to a further distortion of the water structure. An almost completed formation of [CoBr4]2- as well as [CoCl4]2- was attained in the reverse micelles at a low W value of 0.69 containing LiClO4 or HClO4. A partial transfer of the [CoX4]2- species from a "water pool" into the CHCl3 phase by the addition of the metal salts may be suspected. An examination of cobalt(II)-bromide complexes in dichloromethane/CTAB/H2O at W = 1.3 - 5.55 justified all the arguments concerning the chloroform systems. The Raman spectra of D2O containing concentrated LiBr and LiClO4 have supplied conclusive evidence that the hydrogen-bonded structure of the bulk water is completely distorted by extremely concentrated salts.     

Polymers with advanced structural and supramolecular features synthesized through topochemical polymerization

Polymers are an integral part of our daily life. Hence, there are constant efforts towards synthesizing novel polymers with unique properties. As the composition and packing of polymer chains influence polymer''s properties, sophisticated control over the molecular and supramolecular structure of the polymer helps tailor its properties as desired. However, such precise control via conventional solution-state synthesis is challenging. Topochemical polymerization (TP), a solvent- and catalyst-free reaction that occurs under the confinement of a crystal lattice, offers profound control over the molecular structure and supramolecular architecture of a polymer and usually results in ordered polymers. In particular, single-crystal-to-single-crystal (SCSC) TP is advantageous as we can correlate the structure and packing of polymer chains with their properties. By designing molecules appended with suitable reactive moieties and utilizing the principles of supramolecular chemistry to align them in a reactive orientation, the synthesis of higher-dimensional polymers and divergent topologies has been achieved via TP. Though there are a few reviews on TP in the literature, an exclusive review showcasing the topochemical synthesis of polymers with advanced structural features is not available. In this perspective, we present selected examples of the topochemical synthesis of organic polymers with sophisticated structures like ladders, tubular polymers, alternating copolymers, polymer blends, and other interesting topologies. We also detail some strategies adopted for obtaining distinct polymers from the same monomer. Finally, we highlight the main challenges and prospects for developing advanced polymers via TP and inspire future directions in this area.

This perspective showcases the potential of topochemical polymerization as an effective tool for synthesizing polymers with advanced molecular and supramolecular structures.     

Palladium-catalyzed regio- and diastereo-selective allylic alkylation using 2-(diphenylphosphino)benzoic acid: construction of vicinal quaternary and tertiary carbon centers

The palladium-catalyzed regio- and diastereo-selective allylic alkylation of allyl acetates with carbon nucleophiles occurred. The stereochemistry was highly controlled by the palladium catalyst with 2-(diphenylphosphino)benzoic acid as the ligand, and vicinal quaternary and tertiary carbon centers were constructed.     

Synthesis of fluorinated materials catalyzed by proline or antibody 38C2 in ionic liquid

The utility of reusable ionic liquid-proline (or aldolase antibody 38C2) reaction system, proceeding the aldol reactions, is described. Further, obtained α-chloro-β-hydroxy compounds were transformed to the optically active α,β-epoxy carbonyl compounds. The aldolase antibody 38C2-ionic liquid system was able to reuse in Michael additions and the reaction of fluoromethylated imines.