Analysis of Colubroidea snake venoms by liquid chromatography with mass spectrometry: evolutionary and toxinological implications

The evolution of the venomous function of snakes and the diversification of the toxins has been of tremendous research interest and considerable debate. It has become recently evident that the evolution of the toxins in the advanced snakes (Colubroidea) predated the evolution of the advanced, front-fanged delivery mechanisms. Historically, the venoms of snakes lacking front-fanged venom-delivery systems (conventionally grouped into the paraphyletic family Colubridae) have been largely neglected. In this study we used liquid chromatography with mass spectrometry (LC/MS) to analyze a large number of venoms from a wide array of species representing the major advanced snake clades Atractaspididae, Colubrinae, Elapidae, Homalopsinae, Natricinae, Psammophiinae, Pseudoxyrhophiinae, Xenodontinae, and Viperidae. We also present the first sequences of toxins from Azemiops feae as well as additional toxin sequences from the Colubrinae. The large body of data on molecular masses and retention times thus assembled demonstrates a hitherto unsuspected diversity of toxins in all lineages, having implications ranging from clinical management of envenomings to venom evolution to the use of isolated toxins as leads for drug design and development. Although definitive assignment of a toxin to a protein family can only be done through demonstrated structural studies such as N-terminal sequencing, the molecular mass data complemented by LC retention information, presented here, do permit formulation of reasonable hypotheses concerning snake venom evolution and potential clinical effects to a degree not possible till now, and some hypotheses of this kind are proposed here. The data will also be useful in biodiscovery.     

Spectrophotometric study of interaction of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with diaza-18-crown-6 and diaza-15-crown-5 in acetonitrile and chloroform solutions

Interactions of diaza-18-crown-6 and diaza-15-crown-5, as electron donors, with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), as an electron acceptor, have been investigated spectrophotometrically in acetonitrile and chloroform solutions. The results indicated immediate formation of an electron donor-electron acceptor complex DA: [reaction in text] which is followed by two relatively slow consecutive reactions: [reaction in text]. The pseudo-first-order rate constants for the formation of the ionic intermediate and the final product have been evaluated at various temperatures by computer fitting of the absorbance time data to appropriate equations. The formation constants of the resulting DA complexes have also been determined. The influences of both the azacrown's structure and the solvent properties on the formation of DA complexes and the rates of subsequent reactions are discussed.     

Conductance study of ammonium complexes with several crown ethers and cryptands in nitrobenzene,acetonitrile and dimethylformamide solutions

The formation of ammonium complexes with several crown ethers and cryptands in nitrobenzene, acetonitrile and dimethylformamide solutions was investigated by conductometry at 25°C. Stability constants of the resulting 1:1 complexes sere determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5>12C4, in the case of crown complexes, and in the order C222>C221>C211>C22>C21 for the ammonium cryptates. The stabilities of the complexes varied inversely with the Gutmann donicity of the solvents. Influences of the number of members in the macrocycle, nature of the substituents in the polyether ring, cavity size and dimensionality, conformations of the free and complexed ligands and number of N⁺–H bonds available for hydrogen bonding are discussed.     

Conductance study of the thermodynamics of ammonium ion complexes with several crown ethers in acetonitrile solution

A conductance study concerning the interaction between ammonium ion and several crown ethers in acetonitrile solution has been carried out at different temperatures. The stability constants of the resulting 11 complexes at various temperatures were determined from the molar conductance-mole ratio data and found to vary in the order DC18C6>18C6>DB30C10>DB21C7>DB24C8>DB18C6>15C5>B15C5. The enthalpy and entropy of complexation were determined from the temperature dependence of the formation constants. The influence on the thermodynamic data of different parameters such as cavity size and dimensionality of crown ethers, nature of substituents in the polyether ring, conformations of the free and complexed ligands, solvent-ligand interaction and number of N–H bonds available for hydrogen bonding are discussed.     

Formation of homogeneous nanocomposite films at ambient temperature via miniemulsion polymerization using graphene oxide as surfactant

A convenient and industrially scalable method for synthesis of homogeneous nanocomposite films comprising poly(styrene‐stat‐butyl acrylate) and nanodimensional graphene oxide (GO) or reduced GO (rGO) is presented. Importantly, the nanocomposite latex undergoes film formation at ambient temperature, thus alleviating any need for high temperature or high pressure methods such as compression molding. The method entails synthesis of an aqueous nanocomposite latex via miniemulsion copolymerization relying on nanodimensional GO sheets as sole surfactant, followed by ambient temperature film formation resulting in homogeneous film. For comparison, a similar latex obtained by physical mixing of a polymer latex with an aqueous GO dispersion results in severe phase separation, illustrating that the miniemulsion approach using GO as surfactant is key to obtaining homogeneous nanocomposite films. Finally, it is demonstrated that the GO sheets can be readily reduced to rGO in situ by heat treatment of the film. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2289–2297     

Thermoanalytical study of linkage isomerism in coordination compounds

The non-isothermal differential scanning calorimetry (DSC) experiments revealed that linkage isomerization of both pure trans-[Co(en)₂(ONO)₂]PF₆ (dinitrito isomer) and trans-[Co(en)₂(NO₂)₂]PF₆ (dinitro isomer) occurs in the solid state at elevated temperatures. The process was found to be exothermic for the dinitrito isomer and endothermic for dinitro isomer. The pure isomers could be considered to be in metastable states at ambient temperatures which would be converted to an equilibrium mixture of both isomers (stable state) upon heating. Since the isomerization of both isomers may be described as a two stages process, the corresponding DSC peaks have been resolved into two peaks by means of nonlinear curve fitting tools of PeakFit^® software. The resolution of the peaks helped us to determine enthalpy changes of stepwise isomerization of both isomers. A first-order initial rate and Kissinger methods have been employed to estimate kinetic parameters of the stepwise isomerization reactions. The Kissinger method provided more reliable kinetic results. The high activation energy and positive entropy changes of isomerization of both isomers are considered as indication of a dissociative mechanism in solid state.     

An efficient four-component synthesis of dithiocarbamate derivatives

An environmentally benign, one-pot, four-component synthesis of chemically and pharmaceutically interesting dithiocarbamate derivatives is reported. The one-pot reaction of various aromatic aldehydes, ketones, aliphatic amines, and carbon disulfide, in the presence of potassium hydroxide in urea-choline chloride deep eutectic solvent or ethanol, leads to the corresponding dithiocarbamates in good to excellent yields. This method provides a convenient and time-saving strategy, with a simple work-up procedure.     

A CFD analysis on the effect of tube curvature,hot flow control valve profile,and inlet swirl on the thermal performance of curved vortex tubes

Journal of Thermal Analysis and Calorimetry - The influence of tube curvature, conical valve geometry, and initial swirl on the thermal performance of vortex tubes is numerically investigated....     

One-dimensional beam ordering of protons in a storage ring

The ordering of protons has been observed at a new storage ring, S-LSR, at Kyoto University. Abrupt jumps in the momentum spread and the Schottky noise power were observed for protons for the first time at a particle number of approximately 2000, upon applying electron cooling with electron currents of 25, 50, and 100 mA. The transition temperature was 0.17 and 1 meV in the longitudinal and transverse directions, respectively. The transverse temperature of the proton beam was much below that of electrons at the transition, which played an essential role in the ordering of protons.