(Tl[Au(C(6)Cl(5))(2)])(n): A vapochromic complex

The X-ray structure of (Tl[Au(C(6)Cl(5))(2)])(n), 1, consists of 1-D linear polymer chains parallel to the crystallographic z axis. The crystal structure of 1 has channels that run parallel to these chains with interatom distances in the range 3.231-4.076 A. There are holes in these channels with diameters as large as 10.471 A, which can accommodate a variety of solvents. Complex 1 displays reversible vapochromic emission and absorption spectral behavior when the solid is exposed to a variety of organic vapors such as acetone, acetonitrile, triethylamine, acetylacetone, tetrahydrothiophene, 2-fluoropyridine, tetrahydrofuran, and pyridine. Complex 1 is luminescent at room temperature and at 77 K in the solid state. UV excitation at 495 nm leads to an emission at 531 nm.     

Analysis of short-pulse laser photon transport through tissues for optical tomography

We describe a method for analyzing short-pulse laser propagation through tissues for the detection of tumors and inhomogeneities in tissues with the goal of developing a time-resolved optical tomography system. Traditional methods for analyzing photon transport in tissues usually involve the parabolic or diffusion approximation, which implies infinite speed of propagation of the optical signal. To overcome such limitations we calculate the transmitted and reflected intensity distributions, using the damped-wave hyperbolic P(1) and the discrete-ordinates methods, for a wide range of laser, tissue, and tumor parameters. The results are compared with the parabolic diffusion P(1) approximation.     

Influence of attenuation on the behavior of refracted elastic waves at the interface between anisotropic media

During the ultrasonic non-destructive evaluation of complex materials, like multilayer or composite materials, the behavior of the ultrasonic waves at the interface of samples is strongly dependent upon the anisotropy as well as the attenuation characteristics of the propagation media. In the generally arbitrary case, the incident wave is assumed to be inhomogeneous. Therefore the application of the Snell-Descartes laws requires to consider the real as well as the imaginary parts of all the quantities encountered during the study. In that aim, we use a representation of the complex slowness curves so-called slowness interface curves which point out the evolution of the interaction of the waves at the interface with the inhomogeneity factors, i.e. the imaginary part of the slowness vectors. The continuous distortion of the curves with the inhomogeneity factor increasing is an interesting approach of these complicated phenomena.     

Ab initio Computational Modeling of Glyphosate Analogs: Conformational Perspective

A historical perspective on the application of conformational analysis to structure-based ligand design approach is presented. The application of isodensity molecular electrostatic potential surfaces with the conformational energy surfaces (CES) have allowed us to reach pertinent conclusions for aiding synthetic and biochemical studies. Here we illustrate such an application on the modeling of the potent analogs of an important, environmentally stringent herbicidal compound glyphosate by constructing conformational energy surfaces. The systems were modeled by substituting F, Cl, and NH— OH moiety to the position of pharmacophoric nitrogen center in glyphosate structure. All the calculations were thoroughly performed with ab initio MO theory at Hartree–Fock method using 3-21G(d) basis functions. On the basis of the results, we identified the bioactive conformations for N-fluoro-glyphosate, N-chloro-glyphosate, and N-hydroxyamino-glyphosate as (−38^∘, 77^∘), (−61^∘, 111^∘), and (−167^∘, −169^∘), respectively. Geometry optimization of certain selected conformations of these compounds using hybrid DFT method with 6–31+G(d) basis functions provides nearly equal values of φ and ψ. Moreover, the results indicate that the global minimum structures of N-fluoro and N-chloro analogs of glyphosate show cyclic conformation whereas the N-hydroxyamino-glyphosate global minimum structure shows spyrocyclic and zig-zag conformation. Also, the predicted bioactive conformation of N-hydroxyamino analog optimally overlaps with glyphosate backbone in EPSPS complex with 0.1 Å RMSD value. However, the other two compounds slightly deviate from the backbone of glyphosate with RMSD of 0.92 Å for N-fluoro-glyphosate and 0.83 Å for N-chloro-glyphosate. The linear N-hydroxyamino-glyphosate exhibits relatively more number of intermolecular hydrogen bond interactions as compared to the other two analogs. Further, comparison of CES of previously studied glyphosate analogs such as N-hydroxy-glyphosate (2.2 μM) and N-amino-glyphosate (0.61 μM) with the present systems reveals the order of activity as: N-hydroxyamino-glyphosate > N-fluoro-glyphosate > N-chloro-glyphosate based on CES flexibility. Also, the calculated heats of formation of N-fluoro-glyphosate, N-chloro-glyphosate, and N-hydroxyamino-glyphosate are −288, −209, and −288 kcal/mol, respectively, which clearly indicate that the N-hydroxyamino and N-fluoro analogs of glyphosate are thermodynamically more stable than N-amino-glyphosate (−278 kcal/mol).     

Linking chemistry and genetics in the growing cyanobactin natural products family

Ribosomal peptide natural products are ubiquitous, yet relatively few tools exist to predict structures and clone new pathways. Cyanobactin ribosomal peptides are found in ~30% of all cyanobacteria, but the connection between gene sequence and structure was not defined, limiting the rapid identification of new compounds and pathways. Here, we report discovery of four orphan cyanobactin gene clusters by genome mining and an additional pathway by targeted cloning, which represented a tyrosine O-prenylating biosynthetic pathway. Genome mining enabled discovery of five cyanobactins, including peptide natural products from Spirulina supplements. A phylogenetic model defined four cyanobactin genotypes, which explain the synthesis of multiple cyanobactin structural classes and help direct pathway cloning and structure prediction efforts. These strategies were applied to DNA isolated from a mixed cyanobacterial bloom containing cyanobactins.     

Microwave assisted synthesis and unusual coupling of some novel pyrido[3,2-f][1,4]thiazepines

3-Amino-3-thioxopropanamide (1) reacted with ethyl acetoacetate to form 6-hydroxy-4-methyl-2-thioxo-2,3-dihydropyridine-3-carboxamide (2), which reacted with α-haloketones 3 to produce 2,3-disubstituted-8-hydroxy-6-methyl-2H,5H-pyrido[3,2-f]-[1,4]thiazepin-5-ones 4a-c. Benzoylation of 4c led to the formation of the dibenzoate derivative 9. Compounds 4a-c could be prepared stepwise through the formation of S-alkylated derivatives 10a-c. Compounds 2, 4a-c, 9 and 10a-c were prepared using microwave as a source of heat, and gave better yields in shorter times than those achieved by traditional methods. Coupling of 4a-c with arenediazonium chlorides proceeded unusually to give the 6-hydroxy-4-methyl-2-(arylazo)thieno[2,3-b]pyridin-3(2H)-one ring contraction products 14. Structures of the newly synthesized compounds were proven by spectral and chemical methods.     

Studies with 2‐arylhydrazononitriles: Further investigations on reactivity of 2‐arylhydrazononitriles towards hydroxylamine

The utilization of arylhydrazononitriles ( 6‐9 ) for synthesis of azoles is demonstrated. Thus, arylazomalononitriles ( 6 ) reacted with hydroxylamine hydrochloride to afford isoxazol‐5‐imine ( 10 ), amidoxime ( 12 ) and bis‐amidoxime ( 13 ) derivatives depending upon both the reaction conditions and molar ratio employed. 2‐Thiazolyl‐2‐arylhydrazononitriles ( 7 ) and cyanoformazans ( 8 ) gave 1,2,3‐triazole derivatives ( 15 ) and ( 17 ) respectively upon treatment with hydroxylamine hydrochloride and concomitant loss of water molecule. Formation of novel 1,2,4‐triazin‐5(4H)‐one derivatives ( 21 ) has efficiently been carried out by treatment of amidoximes ( 18 ) with acetic anhydride in acetic acid.     

Ion-selective electrode for gallium determination in nickel alloy, fly-ash and biological samples

A poly(vinyl chloride)-based membrane of 2,9-dimethyl-4,11-diphenyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene (DDTCT) with sodium tetraphenyl borate (STB) as an anion excluder and dibutyl phthalate (DBP), dibutyl butylphosphonate (DBBP), tris(2-ethylhexyl) phosphate (TEP) and tributyl phosphate (TBP) as plasticizing solvent mediators was prepared and investigated as a Ga(III)-selective electrode. The best performance was observed with the membrane having the ligand-PVC-DBP-STB composition 1:4:1:1, which worked well over a wide concentration range (1.45 × 10⁻⁶ to 0.1 mol L⁻¹) with a Nernstian slope of 28.7 mV per decade of activity between pH 4.0 and 10.0. This electrode showed a fast response time of 12 s and was used over a period of 100 days with good reproducibility (s = 0.3 mV). The selectivity coefficients for monovalent, divalent and trivalent cations indicate excellent selectivity for Ga(III) ions over a large number of cations. Anions such as Cl⁻ and SO₄²⁻ do not interfere and the electrode also works satisfactorily in partially water-alcohol medium. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergents, i.e., cetyltrimethylammonium bromide and sodium dodecyl sulfate and used for the determination of gallium in nickel alloy, fly-ash and biological samples.     

The role of intermolecular interactions in the assemblies of Fe and Co tetrakis-isothiocyanatometalates with tris(1,10-phenanthroline)-Ru: Crystal structures of two dual-metal assemblies featuring octahedral cationic and tetrahedral anionic modules

Two new dual-metal assemblies: 2[Ru(phen)₃]²⁺·[Fe(SCN)₄]²⁻·2SCN⁻·4H₂O 1 and [Ru(phen)₃]²⁺·[Co(SCN)₄]²⁻2, (phen:1,10-phenanthroline), have been prepared and their structures were characterized by X-ray diffraction. In 1, the cationic octahedral enantiomers are arranged with a ΛΔΛΔΛ sequence supported by π-π stacking and the anionic inorganic tetrahedral units are oriented between these stacks by interacting with the nearby water molecules through strong O-H?O and O-H?S hydrogen bonds. In 2, homochiral double helices in the b-direction are revealed, with tetrakis-isothiocyanate Co^II anions arranged in the crystal to furnish one-dimensional (1D)-helical chains with S?S intermolecular interactions at 3.512(2) and 3.966(2) Å supporting [Ru(phen)₃]²⁺Λ- and Δ-helices with Ru?Ru shortest distance of 8.676(7) Å. In both 1 and 2, the supramolecular assembly is maintained by C-H?S hydrogen bonds extending between the phenanthroline aromatic carbons in the cationic nodes and the sulphur atoms of the isothiocyanates anions. Analysis of S?S interactions in isothiocyanate containing compounds using Cambridge structural database (CSD) showed an angle dependence categorizing these interactions into “type-I” and “type-II”.     

Vibrational spectra, DFT calculations, unusual structure, anomalous CH2 wagging and twisting modes, and phase-dependent conformation of 1,3-disilacyclobutane

Our previously published infrared and Raman spectra of 1,3-disilacyclobutane (13DSCB) and its 1,1,3,3-d4 isotopomer have been reexamined and partially reassigned on the basis of DFT and ab initio calculations. The calculations confirm previous microwave work that the CSiC angles in the ring are unexpectedly larger than the SiCSi angles. This may arise from the partial charges on the ring atoms. The calculations are in excellent agreement with the observed spectra in both frequency and intensity. They also demonstrate that this molecule has CH2 wagging and twisting vibrations with frequencies below 1000 cm-1, about 200 cm-1 lower than expected. These unprecedented low values can be explained by the decreased slope in the potential energy curves for these vibrations as the sideways motions of the CH2 groups result in attractive forces between the positively charged hydrogens on the carbon atoms and the negatively charged hydrogens on the silicon atoms. The theoretical calculations also confirm the previous conclusions that the individual molecules (vapor) have C2v symmetry whereas in the solid the molecules become planar with D2h symmetry. The vibrational coupling between the ring-angle bending mode and the SiH2 in-phase rocking, which is present for the C2v structure, is forbidden for D2h and hence disappears.