The skeletal rearrangement of gold- and platinum-catalyzed cycloisomerization of cis-4,6-dien-1-yn-3-ols: pinacol rearrangement and formation of bicyclo[4.1.0]heptenone and reorganized styrene derivatives

With gold and platinum catalysts, cis-4,6-dien-1-yn-3-ols undergo cycloisomerizations that enable structural reorganization of cyclized products chemoselectively. The AuCl3-catalyzed cyclizations of 6-substituted cis-4,6-dien-1-yn-3-ols proceeded via a 6-exo-dig pathway to give allyl cations, which subsequently undergo a pinacol rearrangement to produce reorganized cyclopentenyl aldehyde products. Using chiral alcohol substrates, such cyclizations proceed with reasonable chirality transfer. In the PtCl2-catalyzed cyclization of 7,7-disubstituted cis-4,6-dien-1-yn-3-ols, we obtained exclusively either bicyclo[4.1.0]heptenones or reorganized styrene products with varied substrate structures. On the basis of the chemoselectivity/structure relationship, we propose that bicyclo[4.1.0]heptenone products result from 6-endo-dig cyclization, whereas reorganized styrene products are derived from the 5-exo-dig pathway. This proposed mechanism is supported by theoretic calculations.     

Concomitant synthesis of highly crystalline Zn-Al layered double hydroxide and ZnO: phase interconversion and enhanced photocatalytic activity

Metal oxide/hydroxide with hierarchical nanostructures has emerged as one of the most promising materials for their unique, attractive properties and feasibility of applications in various fields. In this report, a concomitant synthesis of crystalline zinc aluminum layered double hydroxide (ZnAl-LDH) nanostructure and ZnO is presented using Al substrate as template. Studies on interconversion of ZnO to LDH phase in bulk solution under hydrothermal conditions produced Al-doped ZnO (AZO) in one case, and in other, it improves the crystallinity of LDH film templated on Al substrate. In presence of Al salt, the self-limiting growth nature of plate LDH turned to non-self-limiting. Materials obtained during phase transition, AZO in bulk solution and crystalline porous ZnAl-LDH on substrate, have been demonstrated as effective photocatalysts for decomposition of congo red in aqueous medium.     

Biosynthesis of Indigo Dye by Newly Isolated Naphthalene-Degrading Strain <Emphasis Type="Italic">Pseudomonas s</Emphasis>p. HOB1 and its Application in Dyeing Cotton Fabric

Indigo is one of the oldest dyes manufactured chemically and is mostly used in textile, food, and pharmaceutical industries. However, owing to the environmental hazards posed by the chemical production, the present scenario in the field stipulates a biosynthesis alternative for indigo production. The present study describes an indigenously isolated naphthalene-degrading strain Pseudomonas sp. HOB1 producing a blue pigment when indole was added in the growth medium. This blue pigment was analyzed by high-pressure thin-layer chromatography and other spectroscopic techniques which revealed it to be the indigo dye. Pseudomonas sp. HOB1 showed ability to produce 246 mg indigo liter⁻¹ of the medium. The K _m for the enzyme naphthalene dioxygenase which is involved in indigo formation is 0.3 mM, and V _max was as high as 50 nmol min⁻¹ mg dry biomass⁻¹. The bacterial indigo dye was further successfully applied for dyeing cotton fabrics. The high indigo productivity of Pseudomonas sp. HOB1 using naphthalene as growth substrate and its applicability on cotton fabrics, therefore, stems the probability of using this culture for commercial indigo production.     

Structures and electronic properties of silicene clusters: a promising material for FET and hydrogen storage

Structures and electronic properties of clusters of an all-Si analogue of graphene, silicene, have been studied through quantum chemical calculations. The structures of the six-membered rings show interesting chair like puckering, which for large sheet-like clusters form ordered ripples. Binding energies, HOMO-LUMO gaps and polarizabilities for the silicene clusters show interesting monotonic trends analogous to polyacenes. Stacking of two silicene layers leads to the formation of closed 3D clusters with high symmetry and strong Si-Si bonds. The heat of hydrogenation of silicene to form silicanes is overwhelmingly exothermic and leads to the opening up of the HOMO-LUMO gaps. Thus, analogous to graphanes, silicanes are predicted to be interesting materials for hydrogen storage and for their band engineering properties.     

The racemization of an optically active sulfilimine and optically active aminosulfonium salts

The racemization of an optically active sulfilimine and optically active aminosulfonium salts was kinetically measured. The mechanism of the racemization of optically active sulfilimine (?)-1 has been established. The activation parameters for the racemization of (?)-1 and (?)-7 were calculated. A plausible pathway for the decomposition of (?)-6, (?)-7 and (?)-8 with tetra-n-butylammonium bromide in the presence of methyl ethyl ketone to provide 3-p-tolylthio-2-butanone 22 is proposed.     

Theoretical investigation of the rates of electron transfer processes Q−I + QII → QI + Q−II and Q−I + Q−II → QI + Q2−II in photosynthesis

A theoretical investigation on the rates of electron-transfer processes Q⁻_I + Q_II → Q⁻_I + Q⁻_II and Q⁻_I + Q⁻_II → Q_I + Q²⁻_II was carried out by using the Marcus theory of long-range electron transfer in solution. The molecular reorganizational parameter λ, the free-energy change ΔG⁰ for the overall reaction, and the electronic matrix element H_DA for these two processes were calculated from the INDO-optimized geometries of molecules Q_I, Q_II, and histidine. Q_I and Q_II are plastoquinones (PQ) which are hydrogen-bonded to a histidine each, and the two histidines may or may not be coordinated to a Fe²⁺ ion. The plastoquinone representing Q_I is additionally flanked by two peptide fragments. Each of the species (Pep)₂Q_I · His and His · Q_II has been considered to be immersed in a dielectric continuum that represents the surrounding molecules and protein folds. INDO calculations confirm the standard reduction potential for the first process (calculated 0.127 V; observed 0.13 V) and predict a midpoint potential of 0.174 V for the second process at 300 K at pH 7 (experimental value remains uncertain but is known to be close to 0.13 V). The plastoquinone fragment carries almost all the net charge (about 95.7%) in [PQ · His]⁻ and the net charge in [PQH · His]⁻. The electron is transferred effectively from the plastoquinone part of [(Pep)₂Q_I · His]⁻ to the plastoquinone moiety of Q_II · His in the first step and to the plastoquinone fragment of HisH⁺ · Q⁻_II in the second step. Therefore, we made use of the formula for the rate of through-space electron transfer from Q_I to Q_II (and to Q⁻_II). The plastoquinones are, of course, electronically coupled to histidines, and the transfer is, in reality, through the molecular bridge consisting of histidines and also Fe²⁺. The through-bridge effect is inherent in our calculation of ΔG⁰, H_DA, and the reorganization parameter λ. We investigated the correlation between half-times for the transfer and (D⁻¹_op− D⁻¹_s), where D_op and D_s are, respectively, optical and static dielectric constants of the condensed phase in the vicinity of the plastoquinones. We found that with reasonable values of D_op (2.6) and D_s (8.5) the experimental rates are adequately explained in terms of transfers from the plastoquinone moiety of Q_I to that of Q_II. The t_1/2 values calculated for the two processes are 247 and 472 μs in the absence of Fe²⁺ and 134 and 181 μs in the presence of Fe²⁺. These are in good agreement with the observed values which are ≈ 100 and ≈ 200 μs when Fe²⁺ is present in the matrix and which are known to be almost twice as large when the Fe²⁺ is evicted from the matrix. The present work also shows that the Marcus-Hush theory of long-range electron transfers can be successfully applied to the investigation of processes occurring in a semirigid condensed phase like the thylakoid membrane region. © 1997 John Wiley & Sons, Inc.     

Hybridization of PNA to structured DNA targets: quadruplex invasion and the overhang effect

Peptide nucleic acid (PNA) probes have been synthesized and targeted to quadruplex DNA. UV-vis and CD spectroscopy reveal that the quadruplex structure of the thrombin binding aptamer (TBA) is disrupted at 37 degrees C by a short PNA probe. The corresponding DNA probe fails to bind to the stable secondary structure at this temperature. Thermal denaturation experiments indicate surprisingly high thermal and thermodynamic stabilities for the PNA-TBA hybrid. Our results point to the nonbonded nucleobase overhangs on the DNA as being responsible for this stability. This "overhang effect" is found for two different PNA-DNA sequences and a variety of different overhang lengths and sequences. The stabilization offered by the overhangs assists the PNA in overcoming the stable secondary structure of the DNA target, an effect which may be significant in the targeting of biological nucleic acids, which will always be much longer than the PNA probe. The ability of PNA to invade a structured DNA target expands its potential utility as an antigene agent or hybridization probe.