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131.
Glauco F. Bauerfeldt Leila M. M. de Albuquerque Graciela Arbilla Edilson C. da Silva 《Journal of Molecular Structure》2002,580(1-3):147-160
The competitive unimolecular reactions of formaldehyde, H2CO→H2+CO; H2CO→trans-HCOH and H2CO→H+HCO, were comparatively studied under the direct dynamics formalism, using Density functional and ab initio levels of theory. In addition, the geometric isomerization trans-HCOH→cis-HCOH was evaluated. Calculated reaction path properties were used in the determination of Rice–Ramsperger–Kassel–Marcus microcanonical rate coefficients. The reaction dynamics was evaluated for each individual process based on the nuclear displacements in the reaction path and normal coordinate analysis. Our results found are in very good agreement with experimental barrier heights and quantum yields trends. 相似文献
132.
A. Antony Muthu Prabhu Madi Fatiha Nouar Leila T. Anantha Raj Inmaculada Navarro-González Maria Jesús Periago Maria Josefa Yáñez-Gascón Horacio Pérez-Sánchez 《Journal of solution chemistry》2018,47(3):409-429
The interactions of the neurotransmitter dopamine (DA) with β-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) was characterized using UV–visible, 2D fluorescence, 3D fluorescence, FT–IR, PXRD and SEM techniques. PM3, PM7 and DFT methods were used to optimize the structures of the inclusion complexes in the gas phase. The absorbance and fluorescence intensities of DA increased in the presence of CDs in aqueous solution. The binding energy, HOMO–LUMO energy gap and Mulliken atomic charges were computed for the inclusion complexes. NBO analysis revealed a greater number of intermolecular hydrogen bonds in DA:HP-β-CD. Experimental and theoretical results suggested that the DA molecule is deeply embedded in the cavities of both CDs. 相似文献
133.
Leila Hammoud Francisco León Ignacio Brouard Javier Gonzalez-Platas Samir Benayache Paul Mosset Fadila Benayache 《Tetrahedron letters》2018,59(27):2668-2670
Three new sesquiterpene-humulenes, (?)- asteriscunolides I (1), J (2) and (?)-(2Z,6E,9Z)-8-oxo-1α-acetoxy-2,6,9-humulatrien-12-oic acid (3) were isolated from the leaves-flowers of the Saharan medicinal plant Asteriscus graveolens along with six known compounds. The structures of the compounds were determined on the basis of spectroscopic mono and bidimensional NMR, mass spectrometry and by single-crystal X-ray diffraction. Compounds 1–3 were evaluated for cytotoxic assay, no significant activity was detected. 相似文献
134.
135.
Leila Peraro Assoc. Prof. Joshua A. Kritzer 《Angewandte Chemie (International ed. in English)》2018,57(37):11868-11881
Biomolecules such as antibodies, proteins, and peptides are important tools for chemical biology and leads for drug development. They have been used to inhibit a variety of extracellular proteins, but accessing intracellular proteins has been much more challenging. In this review, we discuss diverse chemical approaches that have yielded cell‐penetrant peptides and identify three distinct strategies: masking backbone amides, guanidinium group patterning, and amphipathic patterning. We summarize a growing number of large data sets, which are starting to reveal more specific design guidelines for each strategy. We also discuss advantages and disadvantages of current methods for quantifying cell penetration. Finally, we provide an overview of best‐odds approaches for applying these new methods and design principles to optimize cytosolic penetration for a given bioactive peptide. 相似文献
136.
Catherine L. Arthur Katherine Pratt Safa Motlagh Janusz Pawliszyn Robert P. Belardi 《Journal of separation science》1992,15(11):741-744
Solid Phase Micro Extraction (SPME) involves exposing a fused silica fiber coated with stationary phase to a contaminated water sample. The organic analytes become partitioned between the stationary phase and the water and when equilibrium is reached the fiber is removed from the solution and the analytes are thermally desorbed in the injector of a gas chromatograph. The fiber is contained in a syringe to facilitate handling. Factors which affect linear range, limit of detection, and total analysis time are discussed with regard to the development of a method for analysis of volatile compounds in environmental water samples. The sensitivity of the method was determined by the thickness of the film of stationary phase; the equilibration time, however, increased with the film thickness, although it can be minimized by use of a cross-shaped stirrer bar. Increasing the thickness of stationary phase in the analytical column enables the cryofocusing temperature to be increased from ?40 to ?15°C. With an ion trap mass spectrometer, detection limits required by the US Environmental Protection Agency are met for all compounds except chloromethane and chloroethane. The method has been applied to environmental water samples. 相似文献
137.
Alain Valtz Leila Gicquel Christophe Coquelet Dominique Richon 《Fluid Phase Equilibria》2005,230(1-2):184-191
Isothermal vapour–liquid equilibrium data have been measured for the binary system R134a + DME at five temperatures between 293.18 and 358.15 K, and pressures between 0.4899 and 2.9442 MPa. The peculiarity of this system is the existence of an azeotrope with a minimum pressure, which disappears at 358.15 K. The experimental method used in this work is of the static-analytic type, taking advantage of two pneumatic capillary samplers (Rolsi™, Armines’ patent) developed in the CENERG/TEP Laboratory. The data were obtained with uncertainties within ±0.02 K, ±0.0001 MPa and ±1% for molar compositions.
The isothermal P, x, y data are well represented with the Redlich and Kwong equation of state using the Mathias–Copeman alpha function and the Huron–Vidal mixing rules involving the NRTL model. 相似文献
138.
Novel sulfate ion-selective polymeric membrane electrode based on a derivative of pyrilium perchlorate 总被引:1,自引:0,他引:1
Ganjali MR Naji L Poursaberi T Taghizadeh M Pirelahi H Yousefi M Yeganeh-Faal A Shamsipur M 《Talanta》2002,58(2):359-366
A sulfate ion-selective PVC membrane sensor based on 4-(4-bromophenyl)-2,6-diphenylpyrilium perchlorate (BDPP) as a novel sensing material is successfully developed. The electrode shows a good selectivity for sulfate ion with respect to common organic and inorganic anions. The sensor exhibits a good linear response with slope of -28.9+/-0.5 mV per decade over the concentration range of 1.0x10(-6)-1.0x10(-2) M, and a detection limit of 8.0x10(-7) M of SO(4)(2-) ions. The electrode response is independent of pH in the range of 4.0-9.0. The proposed sensor was applied as an indicator electrode in potentiometric titration of sulfate and barium ions, and to the determination of zinc in zinc sulfate tablets. 相似文献
139.
Reger DL Gardinier JR Gemmill WR Smith MD Shahin AM Long GJ Rebbouh L Grandjean F 《Journal of the American Chemical Society》2005,127(7):2303-2316
Sonogashira coupling reactions of terminal alkynes with Fe[(p-IC6H4)B(3-Mepz)3]2 (pz = pyrazolyl ring) yield Fe[(p-PhC2C6H4)B(3-Mepz)3]2 (2), Fe[(p-Me3SiC2C6H4)B(3-Rpz)3]2 (R = H, 3a, R = Me, 3b), and Fe[(p-HC2C6H4)B(3-Mepz)3]2 (R = H, 4a, R = Me, 4b), a series of new complexes containing "third generation" poly(pyrazolyl)borate ligands. Complex 2 undergoes a fairly gradual iron(II) electronic spin-state crossover with a 30 K hysteresis, whereas complex 3b is an unusual example of a complex with equivalent iron(II) sites in the high-spin form that shows an abrupt 50% spin crossover. For complex 4b, 50% of the iron(II) sites undergo a gradual spin-state transition between 185 and 350 K with an activation energy of 1590 +/- 30 cm(-1) and a T(1/2) = 280 K and, for the remaining iron(II) sites, an abrupt cooperative spin-state crossover between 106 and 114 K. The crystal structures of 4b obtained for each of the three distinct electronic spin states reveal two crystallographically different iron(II) sites, and analysis of the molecular/supramolecular structures indicates that the difference in the degree of pyrazolyl ring tilting in the ligands between the two sites, rather than the strength of the intermolecular forces, play a prominent role in determining the temperature of the spin-state crossover. 相似文献
140.
Christopher Brenig Leila Mosberger Katja Baumann Olivier Blacque Felix Zelder 《Helvetica chimica acta》2021,104(8):e2100067
This publication describes the straightforward and redox-neutral synthesis of 10-bromophenylethynylcobalamin and its facile conversion to 10-bromoaquacobalamin. In this approach, the phenylethynyl ligand acts as convenient light-stable protecting group that is removed in quantitative yield under acidic conditions. The proteolytic cleavage at pH 2.0 was studied under pseudo-first-order conditions and is 1.5 times slower than that of phenylethynylcobalamin with a hydrogen instead of a bromine at C(10). Preliminary electrochemical studies of organometallic ethynyl-Cbls (Cbl=cobalamin) are reported for the first time. A reduction potential of −0.94 V vs. Ag/AgCl was determined for the CoIII/CoI reduction of 10-bromophenylethynylcobalamin. The positive potential shift of 180 mV compared to phenylethynylcobalamin is in agreement with earlier electrochemical studies of related cyanocobalamins. 相似文献