Mechanistic studies on the pyrolysis and combustion of polystyrene/ammonium perchlorate propellants in the presence of transition metal oxides

The effect of transition metal oxides (Fe₂O₃, MnO₂, Ni₂O₃ and Co₂O₃) on polystyrene/ammonium perchlorate propellant systems has been examined. The mechanism of action of the oxides in increasing the burning rate was examined by studying the effect of the oxides on the thermal decomposition and combustion of the oxidizer and the propellant. It has been concluded that one of the mechanisms by which the oxides act is by promoting the charge-transfer process, which is indicated by the enhancement of the electron-transfer process in ammonium perchlorate and by the correlation between the redox potential of the metal ions and the corresponding burning rates of the propellant.     

Contiguous relations, continued fractions and orthogonality

We examine a special linear combination of balanced very-well-poised basic hypergeometric series that is known to satisfy a transformation. We call this and show that it satisfies certain three-term contiguous relations. From two of these contiguous relations for we obtain fifty-six pairwise linearly independent solutions to a three-term recurrence that generalizes the recurrence for Askey-Wilson polynomials. The associated continued fraction is evaluated using Pincherle's theorem. From this continued fraction we are able to derive a discrete system of biorthogonal rational functions. This ties together Wilson's results for rational biorthogonality, Watson's -analogue of Ramanujan's Entry 40 continued fraction, and a conjecture of Askey concerning the latter. Some new -series identities are also obtained. One is an important three-term transformation for 's which generalizes all the known two- and three-term transformations. Others are new and unexpected quadratic identities for these very-well-poised 's.

     

Synthesis and conformational studies of peptides from new C-linked carbo-beta-amino acids (beta-Caas) with anomeric methylamino- and difluorophenyl moieties

New C-linked carbo-beta-amino acids (beta-Caas), Cbz-(S)-beta-Caa-(NHBoc)-OMe (1) and Cbz-(R)-beta-Caa-(NHBoc)-OMe (2), with an additional amine group (methylamino group of NHBoc) at the C-1 position of the lyxofuranoside side chain and Boc-(S)-beta-Caa-(diFP)-OMe (3) and Boc-(R)-beta-Caa-(diFP)-OMe (4), with a C-difluorophenyl (diFP) moiety at the anomeric position of the lyxofuranoside side chain were prepared from D-mannose. Beta-peptides [tetra- and hexapeptides] were synthesized from these beta-Caas, 'epimeric' [at the amine stereocentre (C(beta))], using the concept of 'alternating chirality' to carry out their conformational studies [NMR (CDCl(3)), CD and MD]. In the monomer design, it was envisaged that the presence of an additional amine group in 1 or 2 would help in solubilizing the peptides in water, while, the C-difluorophenyl (diFP) moiety of 3 and 4 is expected to enhance the biological activity. The peptides having 1 and 2, though could not retain their 12-10-mixed helices in water, have shown moderate activity against gram positive and gram negative bacterial strains. The peptides prepared from 3 and 4, much against our expectations, did not display any biological activity.     

Isothermal titration calorimetric and spectroscopic studies on (alcohol + salt) induced partially folded state of α-lactalbumin and its binding with 8-anilino-1-naphthalenesulfonic acid

Interaction of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and isopropanol in the presence of equimolar quantities of guanidine thiocyanate (GndSCN) with bovine α-lactalbumin (α-LA) has been investigated by using a combination of isothermal titration calorimetry, circular dichroism, fluorescence, and ultra-violet spectroscopies at in 20 · 10^?3 mol · dm^?3 phosphate buffer pH 7.0. All the thermal unfolding transitions, in the presence of both the (alcohol + salt) mixtures were found to be reversible as judged by the same values of absorbance observed at different temperatures during cooling after the completion of thermal unfolding. In the presence of the 0.25 mol · dm^?3 (HFIP + GndSCN) equimolar mixture and 0.85 mol · dm^?3 (isopropanol + GndSCN) equimolar mixture, α-lactalbumin was observed to be in the partially folded state with significant loss of native tertiary structure. Intrinsic fluorescence results, acrylamide and potassium iodide quenching, 8-anilino-1-naphthalenesulfonic acid (ANS) binding, and energy transfer results also corroborate the presence of partially folded states of α-lactalbumin. Apart from the generation of the partially folded states, it was also observed that destabilizing action of GndSCN is reduced in the presence of isopropanol compared to that in HFIP. Isothermal titration calorimetry has been used to characterize the energetics of ANS binding to the partially folded states of the protein. ITC results indicate that ANS binds to these partially folded states at pH 7.0 due to the presence of two sequentially binding sites on the protein under the solvent conditions employed. For example, ANS binds to the 0.25 mol · dm^?3 (HFIP + GndSCN) induced partially folded state with affinity constants K₁ = (858 ± 220), K₂ = (1.12 ± 0.25) · 10³; enthalpies of binding ΔH₁ = (4.4 ± 1.0) kJ · mol^?1, ΔH₂ = (2.1 ± 0.2) kJ · mol^?1; and entropies of binding ΔS₁ = 70 J · K^?1 · mol^?1 and ΔS₂ = 65 J · K^?1 · mol^?1, respectively at these two sequential binding sites. In light of the fluorescence results, possible binding sites where ANS can bind to the protein have also been suggested.     

Thermodynamical equilibrium of binary supramolecular networks at the liquid-solid interface

Coadsorption of two different carboxylic acids, benzenetribenzoic acid and trimesic acid, was studied at the liquid-solid interface in two different solvents (heptanoic and nonanoic acid). Independent alteration of both concentrations in binary solutions resulted in six nondensely packed monolayer phases with different structures and stoichiometries, as revealed by means of scanning tunneling microscopy (STM). All of these structures are stabilized by intermolecular hydrogen bonding between the carboxylic acid functional groups. Moreover, phase transitions of the monolayer structures, accompanied by an alteration of the size and shape of cavity voids in the 2D molecular assembly, could be achieved by in situ dilution. The emergence of the various phases could be described by a simple thermodynamic model.     

A review on recent developments for biomolecule separation at analytical scale using microfluidic devices

Microfluidic devices with their inherent advantages like the ability to handle 10⁻⁹ to 10⁻¹⁸ L volume, multiplexing of microchannels, rapid analysis and on-chip detection are proving to be efficient systems in various fields of life sciences. This review highlights articles published since 2010 that reports the use of microfluidic devices to separate biomolecules (DNA, RNA and proteins) using chromatography principles (size, charge, hydrophobicity and affinity) along with microchip capillary electrophoresis, isotachophoresis etc. A detailed overview of stationary phase materials and the approaches to incorporate them within the microchannels of microchips is provided as well as a brief overview of chemical methods to immobilize ligand(s). Furthermore, we review research articles that deal with microfluidic devices as analytical tools for biomolecule (DNA, RNA and protein) separation.     

Hyperbranched polyesters: synthesis, characterization, and molecular simulations

New types of hyperbranched polyesters were synthesized by the reaction of 2,2-bis(hydroxymethyl) propionic acid as an AB2-type monomer with pentaerythritol, trimethylol propane, or glycerol as the core moiety. The obtained globular networks were characterized by NMR and MALDI-TOF spectroscopic techniques. Molecular weights determined by MALDI-TOF were confirmed by gel permeation chromatography. Fourier transform infrared (FTIR) spectroscopy was used for the quantitative evaluation of hydrogen bonding as well as to study the structure-property relationship. To investigate the changes and types of intermolecular H-bonding interactions in hyperbranched polyesters with a variation in molecular structure, the deconvolution of FTIR spectra was carried out using Origin 6.0 software through the Gaussian curve-fitting method. Molecular simulations were performed through molecular mechanics and molecular dynamics (MD) calculations using the DISCOVER module. Cohesive energy density, solubility parameters, and surface properties of the hyperbranched polyesters were calculated. Further, vibrational analysis was computed using MD simulations for all the hyperbranched polyesters developed in this work.     

Unambiguous Stereochemical Assignment of Cyclo(Phe-Pro), Cyclo(Leu-Pro), and Cyclo(Val-Pro) by Electronic Circular Dichroic Spectroscopy

2,5-diketopiperazines (DKPs) are cyclic dipeptides ubiquitously found in nature. In particular, cyclo(Phe-Pro), cyclo(Leu-Pro), and cyclo(Val-Pro) are frequently detected in many microbial cultures. Each of these DKPs has four possible stereoisomers due to the presence of two chirality centers. However, absolute configurations of natural DKPs are often ambiguous due to the lack of a simple, sensitive, and reproducible method for stereochemical assignment. This is an important problem because stereochemistry is a key determinant of biological activity. Here, we report a synthetic DKP library containing all stereoisomers of cyclo(Phe-Pro), cyclo(Leu-Pro), and cyclo(Val-Pro). The library was subjected to spectroscopic characterization using mass spectrometry, NMR, and electronic circular dichroism (ECD). It turned out that ECD can clearly differentiate DKP stereoisomers. Thus, our ECD dataset can serve as a reference for unambiguous stereochemical assignment of cyclo(Phe-Pro), cyclo(Leu-Pro), and cyclo(Val-Pro) samples from natural sources. The DKP library was also subjected to a biological screening using assays for E. coli growth and biofilm formation, which revealed distinct biological effects of cyclo(D-Phe-L-Pro).     

Palladium‐Catalyzed Carbonylations of Aryl Bromides using Paraformaldehyde: Synthesis of Aldehydes and Esters

Carbonylation reactions represent useful tools for organic synthesis. However, the necessity to use gaseous carbon monoxide is a disadvantage for most organic chemists. To solve this problem, novel protocols have been developed for conducting palladium‐catalyzed reductive carbonylations of aryl bromides and alkoxycarbonylations using paraformaldehyde as an external CO source (CO gas free). Hence, aromatic aldehydes and esters were synthesized in moderate to good yields.