Rhodium Carbenoid Mediated C-H Activation of a Tertiary Methyl Group: An Enantiospecific Approach to the Angular Triquinanes Norsilphiperfolane and Norcameroonanes

An enantiospecific synthesis of the angular triquinane system present in the sesquiterpenes cameroonanes and silphiperfolanes has been accomplished, starting from 5-isopropenyl-2-methylcyclopent-1-ene-1-methanol [readily available in three steps from (R)-limonene] employing an intramolecular rhodium carbenoid insertion into the C-H bond of a tertiary methyl group for the construction of the triquinane system.

Electrocatalysis and redox behavior of Pt(2+) ion in CeO(2) and Ce(0.85)Ti(0.15)O(2): XPS evidence of participation of lattice oxygen for high activity

Electronic states of CeO(2), Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) , and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) is active toward these reactions compared with CeO(2) alone. Higher electrocatalytic activity of Pt(2+) ions in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) compared with the same amount of Pt(0) in Pt/C is attributed to Pt(2+) ion interaction with CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) does not suffer from CO poisoning effect unlike Pt(0) in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO(2). Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.

A new semi-empirical model for correlating the solubilities of solids in supercritical carbon dioxide with cosolvents

The equilibrium solubilities of the solids in supercritical carbon dioxide (SCCO(2)) are considerably enhanced in the presence of cosolvents. The solubilities of m-dinitrobenzene at 308 and 318 K over a pressure range of 9.5-14.5 MPa in the presence of 1.13-2.17 mol% methanol as cosolvent were determined. The average increase in the solubilities in the presence of methanol compared to that obtained in the absence of methanol was around 35%. A new semi-empirical equation in terms of temperature, pressure, density of SCCO(2) and cosolvent composition comprising of 7 adjustable parameters was developed. The proposed model was used to correlate the solubility of the solids in SCCO(2) for the 44 systems available in the literature along with current data. The average absolute relative deviation of the experimental data from the model equation was 3.58%, which is better than the existing models. (C) 2011 Elsevier B.V. All rights reserved.

An eight-connected metal organic framework based on Cu(5) clusters: Synthesis, structure, magnetic and catalytic properties

A reaction of copper acetate, 5-nitroisophthalic acid in a water-methanol mixture under solvothermal condition results in a new metal-organic framework compound, [Cu(5)(mu(3)-OH)(2)(H(2)O)(6){(NO(2))-C(6)H(3)-(COO)(2)}(4)]center dot 5H(2)O, (1). The compound contains Cu5 pentameric cluster units connected by 5-nitro isophthalate (NIPA) moieties forming a CdCl(2)-like layer, which are further connected by another NIPA moiety forming the three-dimensional structure. The water molecules in (1) can be reversibly adsorbed. The removal of water accompanies a change in the colour as well as a structural re-organization. Magnetic studies suggest strong antiferromagnetie correlations between the Cu5 cluster units. The compound (1) exhibits heterogeneous Lewis acid catalysis for the cyanosilylation of imines with more than 95 % selectivity. Compound (1) has been characterized by IR, UV-vis, TGA, powder XRD studies.

Catabolite repression of phosphoenolpyruvate carboxykinase by a zinc finger protein under biotin- and pyruvate carboxylase-deficient conditions in Pichia pastoris

We have identified a methanol- and biotin-starvation-inducible zinc finger protein named ROP [repressor of phosphoenolpyruvate carboxykinase (PEPCK)] in the methylotrophic yeast Pichia pastoris. When P. pastoris strain GS115 (wild-type, WT) is cultured in biotin-deficient, glucose-ammonium (Bio(-)) medium, growth is suppressed due to the inhibition of anaplerotic synthesis of oxaloacetate, catalysed by the biotin-dependent enzyme pyruvate carboxylase (PC). Deletion of ROP results in a strain (Delta ROP) that can grow under biotin-deficient conditions due to derepression of a biotin- and PC-independent pathway of anaplerotic synthesis of oxaloacetate. Northern analysis as well as microarray expression profiling of RNA isolated from WT and Delta ROP strains cultured in Bio(-) medium indicate that expression of the phosphoenolpyruvate carboxykinase gene (PEPCK) is induced in Delta ROP during biotin- or PC-deficiency even under glucose-abundant conditions. There is an excellent correlation between PEPCK expression and growth of Delta ROP in Bio(-) medium, suggesting that ROP-mediated regulation of PEPCK may have a crucial role in the biotin- and PC-independent growth of the Delta ROP strain. To our knowledge, ROP is the first example of a zinc finger transcription factor involved in the catabolite repression of PEPCK in yeast cells cultured under biotin- or PC-deficient and glucose-abundant conditions.

Two new 1D chains of Ni(2)Na(2) heterometallic double half-cubane building units: Synthesis, structures and variable temperature magnetic study

An equimolar mixture of Ni(NO(3))(2)center dot 6H(2)O and pyridine-2-aldehyde with two equivalents of NaN(3) in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide (DMF) yielded light green single crystals [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(2)(MeOH)}center dot MeOH center dot 3H(2)O](n) (1) and [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(4)}center dot 2DMF center dot H(2)O](n) (2) (pic = pyridine-2-carboxylate) at room temperature and high temperature (100 degrees C), respectively. Variable temperature magnetic studies revealed the existence of overall ferromagnetic behaviour with J approximate to + 10 cm(-1) and D approximate to -2 to -7 cm(-1) for 1 and 2, respectively. Negative D values as well as variation of D upon slight distortion of structure by varying reaction temperature were observed. The X-band Electron Paramagnetic Resonance (EPR) spectra of both 2 and 3 were recorded below 50 K. The structural distortion was also implicated from the EPR spectra. Density Functional Theory (DFT) calculations on both complexes were performed in two different ways to corroborate the magnetic results. Considering only Ni(2)(II) dimeric unit, results were J = + 20.65 cm(-1) and D = -3.16 cm(-1) for 1, and J = +24.56 cm(-1) and D = -4.67 cm(-1) for 2. However, considering Ni(2)(II)Na(2)(I) cubane as magnetic core the results were J = +16.35 cm(-1) (1), +19.54 cm(-1) (2); D = -3.05 cm(-1) (1), -4.25 cm(-1) (2).

DNA-binding and nuclease activity of1,10-phenanthroline-based thiocyanato, acetato, azido and benzoato bridged dinuclear copper(II) complexes

The mononuclear Cu(II) complex [Cu(phen)(H2O)(NO3)(2)] (1), obtained by the reaction of 1,10-phenanthroline with Cu(NO3)(2)center dot 3H(2)O in methanol solution, reacts with anionic ligands SCN-, AcO-, N-3(-) and PhCO2- in MeOH solution to form the stable binuclear complexes [Cu-2(H2O)(2)(phen)(2)(mu-X)(2)](2) (NO3)(2), where X = SCN- (2), AcO- (3), N-3(-) (4) or PhCO2- (5). The molecular structure of complex 3 was determined by single-crystal X-ray diffraction studies. These complexes were characterized by electronic, IR, ESR, magnetic moments and conductivity measurements. The electrochemical behaviour of the complexes was investigated by cyclic voltammetry. The interactions of these complexes with calf thymus DNA have been investigated using absorption spectrophotometry. Their DNA cleavage activity was studied on double-stranded pBR322 plasmid DNA using gel electrophoresis experiments in the absence and presence of H2O2 as oxidant.

Towards sustainability: a new, solid-state synthetic route for supported metal nanocatalysts

Noble metal ions like Pt(IV) and Pd(II) were impregnated on gamma-alumina and aerosol 300 silica surfaces. Reduction of these ions using ammonia borane in the solid state resulted in the formation of the respective metal nanoparticles embedded in BNHx polymer which is dispersed on the oxide support. Removal of the BNH polymer was accomplished by washing the samples repeatedly with methanol. In this process the polymer undergoes solvolysis to release H-2 accompanied by the formation of ammonium methoxy borate salt, which has been removed by repeated methanol washings. As a result, metal nanoparticles well dispersed on gamma-alumina and aerosol 300 silica were obtained. These samples have been characterized by a combination of techniques, including electron microscopy, powder X-ray diffraction, NMR spectroscopy and surface area analyser.

NMR Structure Implications of Enhanced Efficacy of Obestatin Fragment Analogs

Obestatin is a more recently discovered hormone that is encoded by the ghrelin gene and produced in the stomach and gut. We report NMR analysis on synthetic Obestatin (OB23), a 23 residue peptide, along with three overlapping fragments of the same in methanol solvent as a first step towards structure activity relationship. Selective substitutions on the promising N-terminal and middle fragments of obestatin have been carried out in order to improve the efficacy and potency. In the N-terminal fragment two peptides were obtained by the replacement of Gly (8) with a-aminoisobutyric acid (Aib, U) and Phe (F5) with Cyclohexylalanine (Cha). In case of the middle fragment both Gly (3) and Gly (8) were replaced with Aib residues. The rationale being, these unusual amino acids could provide protection from immediate degradation and aid structure stabilization. Our previous studies showed that the N-terminal and the middle fragment were unstructured and hence this substitution would directly evaluate the effect of structure on the activity of these fragment analogs. Detailed NMR analysis clearly demonstrates formation of helical secondary structure in all the peptide analogues and provides justification for relative activities reported by our group previously (Nagaraj et al. 2009).

DNA-binding and nuclease activity of 1,10-phenanthroline-based thiocyanato, acetato, azido and benzoato bridged dinuclear copper(II) complexes

The mononuclear Cu(II) complex [Cu(phen)(H2O)(NO3)(2)] (1), obtained by the reaction of 1,10-phenanthroline with Cu(NO3)(2)center dot 3H(2)O in methanol solution, reacts with anionic ligands SCN-, AcO-, N-3(-) and PhCO2- in MeOH solution to form the stable binuclear complexes [Cu-2(H2O)(2)(phen)(2)(mu-X)(2)](2) (NO3)(2), where X = SCN- (2), AcO- (3), N-3(-) (4) or PhCO2- (5). The molecular structure of complex 3 was determined by single-crystal X-ray diffraction studies. These complexes were characterized by electronic, IR, ESR, magnetic moments and conductivity measurements. The electrochemical behaviour of the complexes was investigated by cyclic voltammetry. The interactions of these complexes with calf thymus DNA have been investigated using absorption spectrophotometry. Their DNA cleavage activity was studied on double-stranded pBR322 plasmid DNA using gel electrophoresis experiments in the absence and presence of H2O2 as oxidant.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.

Non-Thermal Plasma Applications at Very Low Temperature

Application of non-thermal plasma for gas cleaning is gaining prominence in the recent years. Normally, the gas treatment was carried out at or above room temperature, by the dry type plasma reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the flue gas mixture. We propose the non-thermal plasma process at very low temperature, and report here some interesting results of treatment of NO or N2O with pulsed plasma below — 100°C ambient temperature. Direct methanol synthesis from CH4 and CO2 at very low temperature is also reported. A comparative analysis of the various tests are presented together with a note on the energy consideration

Non-thermal plasma applications at Very Low Temperature

Application of non-thermal plasma for gas cleaning is gaining prominence in the recent years. Normally, the gas treatment was carried out at or above room temperature, by the dry type plasma reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the flue gas mixture. We propose the non-thermal plasma process at very low temperature, and report here some interesting results of treatment of NO or N2O with pulsed plasma below — 100°C ambient temperature. Direct methanol synthesis from CH4 and CO2 at very low temperature is also reported. A comparative analysis of the various tests are presented together with a note on the energy consideration

Chain Length Effects on Helix-Hairpin Distribution in Short Peptides with Aib-(D)Ala and Aib-Aib Segments

The Aib-(D)Ala dipeptide segment has a tendency to form both type-I'/III' and type-I/III beta-turns. The occurrence of prime turns facilitates the formation of beta-hairpin conformations, while type-I/III turns can nucleate helix formation. The octapeptide Boc-Leu-Phe-Val-Aib-(D)Ala-Leu-Phe-Val-OMe (1) has been previously shown to form a beta-hairpin in the crystalline state and in solution. The effects of sequence truncation have been examined using the model peptides Boc-Phe-Val-Aib-Xxx-Leu-Phe-NHMe (2, 6), Boc-Val-Aib-Xxx-Leu-NHMe (3, 7), and Boc-Aib-Xxx-NHMe (4, 8), where Xxx = (D)Ala, Aib. For peptides with central Aib-Aib segments, Boc-Phe-Val-Aib-Aib-Leu-Phe-NHMe (6), Boc-Val-Aib-Aib-Leu-NHMe (7), and Boc-Aib-Aib-NHMe (8) helical conformations have been established by NMR studies in both hydrogen bonding (CD(3)OH) and non-hydrogen bonding (CDCl(3)) solvents. In contrast, the corresponding hexapeptide Boc-Phe-Val-Aib-(D)Ala-Leu-Phe-Val-NHMe (2) favors helical conformations in CDCl(3) and beta-hairpin conformations in CD(3)OH. The beta-turn conformations (type-I'/III) stabilized by intramolecular 4 -> 1 hydrogen bonds are observed for the peptide Boc-Aib-(D)Ala-NHMe (4) and Boc-Aib-Aib-NIiMe (8) in crystals. The tetrapeptide Boc-Val-Aib-Aib-Leu-NHMe (7) adopts an incipient 3(10)-helical conformation stabilized by three 4 -> 1 hydrogen bonds. The peptide Boc-Val-Aib-(D)Ala-Leu-NHMe (3) adopts a novel et-turn conformation, stabilized by three intramolecular hydrogen bonds (two 4 -> 1 and one 5 -> 1). The Aib-L(D)Ala segment adopts a type-I' beta-turn conformation. The observation of an NOE between Val (1) NH <-> HNCH(3) (5) in CD(3)OH suggests, that the solid state conformation is maintained in methanol solutions. (C) 2011 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 96: 744-756, 2011.

Helix and hairpin nucleation in short peptides using centrally positioned conformationally constrained dipeptide segments

The effect of incorporation of a centrally positioned Ac(6)c-Xxx segment where Xxx = (L)Val/(D)Val into a host oligopeptide composed of L-amino acid residues has been investigated. Studies of four designed octapeptides Boc-Leu-Phe-Val-Ac(6)c-Xxx-Leu-Phe-Val-OMe (Xxx = (D)Val 1, (L)Val 2) Boc-Leu-Val-Val-Ac(6)c-Xxx-Leu-Val-Val-OMe (Xxx = (D)Val 3, (L)Val 4) are reported. Diagnostic nuclear Overhouse effects characteristic of hairpin conformations are observed for Xxx = (D)Val peptides (1 and 3) while continuous helical conformation characterized by sequential NiH <-> Ni+1H NOEs are favored for Xxx = (L)Val peptides (2 and 4) in methanol solutions. Temperature co-efficient of NH chemical shifts are in agreement with distinctly different conformational preferences upon changing the configuration of the residue at position 5. Crystal structures of peptides 2 and 4 (Xxx = (L)Val) establish helical conformations in the solid state, in agreement with the structures deduced from NMR data. The results support the design principle that centrally positioned type I beta-turns may be used to nucleate helices in short peptides, while type I' beta-turns can facilitate folding into beta-hairpins.