Uptake of HNO3 on hexane and aviation kerosene soots

The uptake of HNO(3) on aviation kerosene (TC-1) soot was measured as a function of temperature (253-295 K) and the partial pressure of HNO(3), and the uptake of HNO(3) on hexane soot was studied at 295 K and over a limited partial pressure of HNO(3). The HNO(3) uptake was mostly reversible and did not release measurable amounts of gas-phase products such as HONO, NO(3), NO(2) or N(2)O(5). The heat of adsorption of HNO(3) on soot was dependent on the surface coverage. The isosteric heats of adsorption, Delta(0)H(isosteric), were determined as a function of coverage. Delta(0)H(isosteric) values were in the range -16 to -13 kcal mol(-1). The heats of adsorption decrease with increasing coverage. The adsorption data were fit to Freundlich and to Langmuir-Freundlich isotherms. The heterogeneity parameter values were close to 0.5, which suggested that a HNO(3) molecule can occupy two sites on the surface with or without being dissociated and that the soot surface could be nonuniform. Surface FTIR studies on the interaction of soot with HNO(3) did not reveal formation of any minor product such as organic nitrate or nitro compound on the soot surface. Using our measured coverage, we calculate that the partitioning of gas-phase nitric acid to black carbon aerosol is not a significant loss process of HNO(3) in the atmosphere.     

KI‐VO(acac)2‐H2O2‐AcOH,A New Iodinating System for Selective Iodination at C‐5 Position of Activated Pyrimidinediones: A Combined Experimental and Density Functional Study

KI‐VO(acac)₂‐H₂O₂ in aqueous ethanolic medium with acetic acid as additive has been found to iodinate pyrimidinediones and aromatic amines. The methodology is mild, efficient, and environmentally benign. Density functional theory‐based reactivity parameters support the experimentally observed reactivity of pyrimidinedione derivatives.     

Rate coefficients for the reactions of OH with n‐propanol and iso‐propanol between 237 and 376 K

The rate coefficients for the reaction OH + CH₃CH₂CH₂OH → products (k₁) and OH + CH₃CH(OH)CH₃ → products (k₂) were measured by the pulsed‐laser photolysis–laser‐induced fluorescence technique between 237 and 376 K. Arrhenius expressions for k₁ and k₂ are as follows: k₁ = (6.2 ± 0.8) × 10^?12 exp[?(10 ± 30)/T] cm³ molecule^?1 s^?1, with k₁(298 K) = (5.90 ± 0.56) × 10^?12 cm³ molecule^?1 s^?1, and k₂ = (3.2 ± 0.3) × 10^?12 exp[(150 ± 20)/T] cm³ molecule^?1 s^?1, with k₂(298) = (5.22 ± 0.46) × 10^?12 cm³ molecule^?1 s^?1. The quoted uncertainties are at the 95% confidence level and include estimated systematic errors. The results are compared with those from previous measurements and rate coefficient expressions for atmospheric modeling are recommended. The absorption cross sections for n‐propanol and iso‐propanol at 184.9 nm were measured to be (8.89 ± 0.44) × 10^?19 and (1.90 ± 0.10) × 10^?18 cm² molecule^?1, respectively. The atmospheric implications of the degradation of n‐propanol and iso‐propanol are discussed. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 10–24, 2010     

On the Bi-Hamiltonian Structure of the KdV Hierarchy

A construction procedure is derived to obtain expressions for Hamiltonian densities which characterize the bi-Hamiltonian structure of the equations in the KdV hierarchy. All results are obtained by Hamiltonizing the appropriate Lagrangian densities recently found by us. The method is seento work for both real and complex fields.     

Synthesis and structure-activity relationship study of isoglobotrihexosylceramide analogues

Invariant natural killer T (iNKT) cells are innate T lymphocytes that express T cell receptors binding to exogenous and endogenous glycosphingolpid antigens presented by a nonpolymorphic, non-MHC antigen presenting molecule, CD1d. The endogenous glycosphingolipid metabolite, isoglobotrihexosylceramide (iGb3), is the first known natural ligand for both human and mouse iNKT cells, whose activity has been confirmed in a variety of iNKT cell clones generated by different investigators, representing the majority of the iNKT cell population. The signaling pathway mediated by T cell receptor is largely influenced by the structural variation of glycosphingolpid antigens, leading to multiple and varied biological functions of iNKT cells. In order to investigate the structural requirements behind iGb3 triggered iNKT cell activation, the structure-activity relationship (SAR) of iGb3 needs to be characterized. In this study, iGb3 analogues containing 2' ', 3' ', 4' ' and 6' ' deoxy terminal galactose were synthesized for probing the SAR between iGb3 and TCR. The biological assays on the synthetic iGb3 analogues were performed with use of the murine iNKT cell hybridoma DN32.D3. The results showed that the 2' ' and 3' ' hydroxyl groups of terminal galactose play more important roles for the recognition of iGb3 by TCR; while 4' ' and 6' ' hydroxyl groups were not as crucial for this recognition. These studies might help to understand the general structural requirements for natural endogenous ligands recognized by iNKT cells.     

Identification of Potential Vaccine Candidates Against Streptococcus pneumoniae by Reverse Vaccinology Approach

In the past few decades, genome-based approaches have contributed significantly to vaccine development. Our aim was to identify the most conserved and immunogenic antigens of Streptococcus pneumoniae, which can be potential vaccine candidates in the future. BLASTn was done to identify the most conserved antigens. PSORTb 3.0.2 was run to predict the subcellular localization of the proteins. B cell epitope prediction was done for the immunogenicity testing. Finally, BLASTp was done for verifying the extent of similarity to human proteome to exclude the possibility of autoimmunity. Proteins failing to comply with the set parameters were filtered at each step. Based on the above criteria, out of the initial 22 pneumococcal proteins selected for screening, pavB and pullulanase were the most promising candidate proteins.     

BODIPY based ‘click on’ fluorogenic dyes: application in live cell imaging

The design, synthesis, and photophysical properties of new BODIPY-based fluorogenic ‘click on’ dyes are reported. CuAAC reaction of non-fluorescent BODIPY azide with a series of non-fluorescent alkyne molecules resulted in fluorescent triazoles which displayed up to 532-fold enhancement of fluorescence in the red region. Imaging studies confirmed the general trend of cell permeability and a cholesterol linked derivative exhibited selective localization into intracellular membranes.     

Discrete transfer method with the concept of blocked-off region for irregular geometries

The discrete transfer method (DTM) is applied to irregular geometries with a concept of blocked-off region previously applied in the problems of computational fluid dynamics. This gives a new alternative to the DTM for its implementation to irregular structures. The Cartesian coordinate-based ray-tracing algorithm can be applied to the geometries with inclined or curved boundaries. Some test problems are considered and results are validated with the available results in the literature. Both radiative and non-radiative equilibrium situations are considered. The medium is assumed to be both participating and non-participating. Results are found to be accurate for all kinds of situations.     

Application of variational calculus to propagation of coupled pulses in optical fibers

Two nonlinear Schrödinger equations, linked by cross-modulation terms, are used to study the nature of coupled pulse propagation in an optical fiber. The problem is formulated within the framework of variational calculus. Using Gaussian trial functions for the propagating pulses, an expression is constructed for the effective Lagrangian of the system. It is shown that this Lagrangian, via the Ritz optimization procedure, provides a basis to construct approximate solutions of the problem. Some judicious approximations are invoked to investigate how the cross modulation affects the behavior of pulse propagation. Conditions are derived under which both pulses can propagate without distortion.