A highly stable short alpha-helix constrained by a main-chain hydrogen-bond surrogate

Herein we describe a strategy for the preparation of artificial alpha-helices involving replacement of one of the main-chain hydrogen bonds with a covalent linkage. To mimic the C=O...H-N hydrogen bond as closely as possible, we envisioned a covalent bond of the type C=X-Y-N, where X and Y are two carbon atoms connected through an olefin metathesis reaction. Our results demonstrate that the replacement of a hydrogen bond between the i and i + 4 residues at the N-terminus of a short peptide with a carbon-carbon bond results in a highly stable constrained alpha-helix at physiological conditions as indicated by CD and NMR spectroscopies. The advantage of this strategy is that it allows access to short alpha-helices with strict preservation of molecular recognition surfaces required for biomolecular interactions.     

Copper(II), nickel(II), cobalt(II) and zinc(II) complexes of 2-[2-(6-methylbenzothiazolyl)azo]-5-dimethylaminobenzoic acid: synthesis,spectral, thermal and molecular modelling studies

Complexes of copper(II), nickel(II), cobalt(II), and zinc(II) with 2-[2-(6-methylbenzothiazolyl)azo]-5-dimethylaminobenzoic acid have been prepared and characterized by elemental analysis, vibrational spectra, magnetic susceptibility measurements, conductance measurements and e.p.r. spectra. Stability constants have been evaluated potentiometrically. Electronic spectra, magnetic susceptibility measurements and molecular modeling studies support a distorted square planar geometry around the metal ions. Vibrational spectra indicate the coordination of the azo group, nitrogen of benzothiazole, the carboxylate anion and the acetate ion on complexation with the metal ion. All complexes are found to be monomers. The stability of the complexes follow the order: copper(II) > nickel(II) > cobalt(II) > zinc(II).     

Thiocarboxylato Complexes of Biscyclopentadienyl and Bisindenyl Titanium (IV)

Reactions of biscyclopentadienyl (and bisindenyl) titanium (IV) dichlorides with sodium salts of various thiocarboxylic acids in tetrahydrofuran medium, yield the complexes of the general formula (D) ²Ti(SCOR) ² where D is cyclopentadienyl or indenyl group and R? H, CH₃, C₂H₅, C⁴H⁵ or p-C⁴H⁴CH³ group. The foul smelling complexes are monomeric in nature. The IR spectra, thermal stabilities and Some physical characteristics of these complexes have been studied.     

Study of EPR, optical properties and electrical conductivity of vanadyl doped Bi2O3.PbO.B2O3 glasses

Heavy metal based oxide glasses having composition xBi(2)O(3).(0.30 - x)PbO.0.70B(2)O(3) have been prepared (0.00 < or = x < or = 0.15, mol%) containing 2.0mol% of V(2)O(5) by normal melt-quenching technique. Electron paramagnetic resonance (EPR), optical spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHP) of VO(2+) ions, dipolar hyperfine parameter, P and Fermi contact interaction parameter, K, molecular orbital coefficients (alpha(2) and gamma(2)) and optical band gap have been calculated. It is observed that in these glasses, the tetragonal nature of V(4+)O(6) complex increases with Bi(2)O(3) content. Increase in Bi(2)O(3):PbO ratio results in the contraction of 3d(xy) orbit of the unpaired electron in the vanadium ion, and the SHP are dependent on the theoretical optical basicity, Lambda(th). In present glasses, the conductivity (activation energy) first decreases (increases) with increase in mol% of Bi(2)O(3) content upto x = 0.08 and then shows a maxima (minima) at x = 0.10 and then starts decreasing (increasing) upto x < or = 0.15 with mol% of Bi(2)O(3) content.     

Mechanism and kinetics of thermal decomposition of precipitates of the zinc oxide-aluminium oxide system from non-isothermal tg curves

Kinetics of decomposition of the precipitates of the ZnO&2sbndAl₂O₃ system, prepared by coprecipitation and mechanical mixing of the individual precipitates, have been studied. The decomposition of zinc basic carbonate is a first order rate process with an activation energy of 34.5 kcal/mole (Coats and Redfern equation). The decomposition of aluminium hydroxide is also best described as a first order rate process with one break in the Coats and Redfern plot corresponding to activation energies of 29.4 and 8.3 kcal/mole respectively. The entire course of decomposition of coprecipitated as well as mechanically mixed samples cannot be described by any one of the many rate equations available. Consequently, the Coats and Redfern equation has been employed. The plots indicate one or two breaks and thus two to three values of activation energy are reported. From the results it is to be concluded that decomposition of these precipitates is a heterogeneous process. The first step is definitely the decomposition of zinc basic carbonate followed by decomposition of aluminium hydroxide and/or interaction of the two precipitates resulting in the formation of “precursor” to spinel. The results of our earlier investigation on the same system (especially the formation of precursors) are well supported by the results reported in this investigation. p]A new equation (a modified form of the Elovich equation) has been proposed for such heterogeneous decomposition processes. The proposed equation also appears to be the general form of the equations where diffusion is the rate controlling process.     

Interaction of chloroform with aniline, o-toluidine and N,N-dimethyl aniline

Heats of mixing aniline, o-toluidine, and N,N-dimethyl aniline with chloroform have been determined by an adiabatic calorimeter. The results have been examined for molecular interactions between them, and they indicate that aniline and o-toluidine are associated through hydrogen bonds. Enthalpy of bond formation in a 1:1 complex has also been determined.     

Carbazole substituted N-acylated linear polyethylenimines (PEI). synthesis and characterization of poly[N-(9-carbazolyl)acetylethylenimine] and poly[N-(2-(9-carbazolyl))propanoylethylenimine]

The synthesis of carbazola substituted N-acylated polyethylenimines, namely, poly[N-(9-carbazolyl)acetylethylenimine] 20 and poly[N-(2-(9-carbazolyl))propanoylethylenimine] 21 by a grafting reaction onto PEI and isomerization polymerization of the carbazole substituted 2-oxazolines is reported. A complete acylation of amino groups in PEI by the 9-carbazolylacetyl groups was achieved by the p-nitrophenyl active ester method but PEI was only partially N-acylated by the 2-(9-carbazolyl)propanoyl groups under similar reaction conditions. The carbazole substituted 2-oxazolines, namely, 2-(9-carbazolyl)methyl-2-oxazoline 18 and (R,S)-2-[1-(9-carbazolyl)]ethyl-2-oxazoline 19 , were prepared by a base induced cyclization of ß-chloroamides. The ring-opening isomerization polymerization of 18 and 19 in the molten state with a cationic initiator (dimethyl sulfate, methyl triflate, or ethylene glycol ditosylate) gave 20 and 21. Gel permeation chromatography of 20 and 21 obtained with different monomerto-initiator ratios gave evidence of a chain transfer reaction with the monomer. The polymers were characterized by elemental analyses, IR, and ¹H-NMR spectroscopy.     

Interconnectivity between Surface Reactivity and Self-Assembly of Kemp Elimination Catalyzing Nanorods

Understanding the fundamental facts behind dynamicity of catalytic processes has been a longstanding quest across disciplines. Herein, we report self-assembly of catalytically active gold nanorods that can be regulated by tuning its reactivity towards a proton transfer reaction at different pH. Unlike substrate-induced templating and co-operativity, the enhanced aggregation rate is due to alteration of catalytic surface charge only during reactivity as negatively charged transition state of reactant (5-nitrobenzisoxazole) is formed on positively charged nanorod while undergoing a concerted E2-pathway. Herein, enhanced diffusivity during catalytic processes might also act as an additional contributing factor. Furthermore, we have also shown that nanosized hydrophobic cavities of clustered nanorods can also efficiently accelerate the rate of an aromatic nucleophilic substitution reaction, which also demonstrates a catalytic phenomenon that can lead to cascading of other reactions where substrates and products of the starting reactions are not directly involved.     

Greener approach toward the generation of dimedone derivatives

The use of dimedone in green chemistry has been described for the synthesis of selective heterocyclic motifs which are both pharmacologically and industrially important. The objective of this review is to summarize some of the selected recent advances of dimedone in the synthesis of organic compounds utilizing green chemistry procedures.     

Fabrication of dissolved O2 metric uric acid biosensor using uricase epoxy resin biocomposite membrane

Uricase purified from 20-day-old leaves of cowpea was immobilized on to epoxy resin membrane with 80% retention of initial activity of free enzyme and a conjugation yield of 0.056 mg/cm². The uricase epoxy resin bioconjugate membrane was mounted over the sensing part of the combined electrode of ‘Aqualytic’ dissolved O₂ (DO) meter to construct a uric acid biosensor. The biosensor measures the depletion of dissolved O₂ during the oxidation of uric acid by immobilized uricase, which is directly proportional to uric acid concentration. The biosensor showed optimum response within 10-12 s at a pH 8.5 and 35 °C. A linear relationship was found between uric acid concentration from 0.025 to 0.1 mM and O₂ (mg/l) consumed. The biosensor was employed for measurement of uric acid in serum. The mean value of uric acid in serum was 4.92 mg/dl in apparently healthy males and 3.11 mg/dl in apparently healthy females. The mean analytic recoveries of added uric acid in reaction mixture (8.9 and 9.8 mg/dl) were 93.6 ± 2.34 and 87.18 ± 3.17% respectively. The within and between batch CVs were <6.5 and <5.0%, respectively. The serum uric acid values obtained by present method and standard enzymic colorimetric method, showed a good correlation (r = 0.996) and regression equation being y = 0.984x + 0.0674. Among the various metabolites tested only, glucose (11%), urea (38%), NaCl (25%) and cholesterol (13%) and ascorbic acid (56%) caused decrease, while, MgSO₄ and CaCl₂ had no effect on immobilized enzyme. The enzyme electrode showed only 32% decrease during its use for 100 times over a period of 60 days at 4 °C.