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41.
Ab initio calculations employing the STO-3G basis set are used to obtain the relative energies of the benzene valence isomers and some selected monosubstituted derivatives. We find that 3,3'-bicyclopropenyl, the least stable of the five (CH)6 examined, is slightly more stable in the anti conformation than the gauche (Φ = 45°) conformation in agreement with experiment. Substituents are calculated to produce significant changes in the relative energies of the benzene valence isomers. The ground-state isomerization of 1-Dewar benzeneearbinyl cation to benzyl cation is more exothermic than the aromatization of Dewar benzene, but is, in contrast to the latter, symmetry-allowed. 相似文献
42.
Arthur de Sousa 《Microchemical Journal》1973,18(2):137-141
An indirect microdetermination of phosphate via EDTA titration is described, which can be applied to minerals, soils, fertilizers, biological samples, drugs and organo-phosphorus compounds. The method is based on the precipitation of phosphate as the very insoluble silver orthophosphate (Ksp = 1.3 × 10?20), dissolution of this precipitate in a solution of potassium cyanonickelate and titration of the nickel displaced by silver. The phosphate content is obtained indirectly by multiplying the number of ml of the titrant by a factor. The method takes about an hour after the phosphate is brought into solution. The accuracy is about 1% for samples containing 5–50 mg PO43? and about 3–5% for samples with 100 to 5000 μg PO43?. 相似文献
43.
Peter C Oostenbrink C van Dorp A van Gunsteren WF 《The Journal of chemical physics》2004,120(6):2652-2661
While the determination of free-energy differences by MD simulation has become a standard procedure for which many techniques have been developed, total entropies and entropy differences are still hardly ever computed. An overview of techniques to determine entropy differences is given, and the accuracy and convergence behavior of five methods based on thermodynamic integration and perturbation techniques was evaluated using liquid water as a test system. Reasonably accurate entropy differences are obtained through thermodynamic integration in which many copies of a solute are desolvated. When only one solute molecule is involved, only two methods seem to yield useful results, the calculation of solute-solvent entropy through thermodynamic integration, and the calculation of solvation entropy through the temperature derivative of the corresponding free-energy difference. One-step perturbation methods seem unsuitable to obtain entropy estimates. 相似文献
44.
A new class of nonstoichiometric layered ternary rare-earth tin antimonides, RESn(x)()Sb(2) (RE = La, Ce, Pr, Nd, Sm), has been synthesized through reaction of the elements at 950 degrees C. In the lanthanum series LaSn(x)()Sb(2), tin can be incorporated from a maximum content of x approximately 0.7 or 0.8 to as low as x approximately 0.10. The structure of lanthanum tin diantimonide with the maximum tin content, LaSn(0.75)Sb(2), has been determined by single-crystal X-ray diffraction methods. It crystallizes in the orthorhombic space group -Cmcm with a = 4.2425(5) ?, b = 23.121(2) ?, c = 4.5053(6) ?, and Z = 4. The isostructural rare-earth analogues were characterized by powder X-ray diffraction. The structure of LaSn(0.75)Sb(2) comprises layers of composition "LaSb(2)" in which La atoms are coordinated by Sb atoms in a square-antiprismatic geometry. Between these layers reside chains of Sn atoms distributed over three crystallographically independent sites, each partially occupied at about 20%. The structure of LaSn(0.75)Sb(2) can be regarded as resulting from the excision of RE-Sb and Sb-Sb bonds in the related structures of binary rare-earth diantimonides, RESb(2), and then intercalation of Sn atoms between layers. 相似文献
45.
Stphane Chalais Andr Cornlis Andr Gerstmans Wacaw Koodziejski Pierre Laszlo Arthur Mathy Pierre Mtra 《Helvetica chimica acta》1985,68(5):1196-1203
Multiple chlorinations and arylations at the tertiary positions of adamantane are promoted by FeCl3-doped K10 montmorillonite in CCl4 or in aromatic solvents. The process, remarkably easy to implement, can be tailored to selective formation of monosubstituted 1-adamantyl derivatives or 1,3-disubstituted adamantanes. The process achieves alkylation at the meta- and para-positions of toluene leading to a purely statistical distribution and displays no substrate specificity in competition experiments between toluene and benzene. 相似文献
46.
Francis M. Wampler Arthur T. Blades Paul Kebarle 《Journal of the American Society for Mass Spectrometry》1993,4(4):289-295
The total current and selected ion currents from the electrospray ionization (ES1) of 10?5 M solutions of cocaine hydrochloride and deoxycytidine monophosphate (dCMP) monosodium salt in methanol and water solvents were compared in positive and negative ion modes, respectively, without and with SF6, gas as a discharge suppressant. The ESI onset voltages (Von), were the same for the positive and negative ion modes. The Von, for methanol was much lower than that for water and in agreement with the equation of D. P. H. Smith, who attributes the difference to the higher surface tension of water. The onset of electric discharge (Vdis) without SF6, occurred at lower capillary voltages for the negative relative to the positive ion mode for methanol; but Vdis is much higher than Von for methanol, and discharges do not interfere with ESI operation. For water, Von ≈ Vdis in the absence of SF6, in the negative ion mode, and ESI operation is impossible without SF6, discharge suppression. The discharge problem in the positive ion mode is less severe, but SF6, is still very useful. A dynamic range of 10 ?7–10?5 M was obtained by selected ion monitoring of [dCMP - H]? at 4.5 and 20 μL/min. flows. Subpicomole detection limits for the nucleotide salt were obtained under these conditions. 相似文献
47.
The synthesis of 4-carbomethoxy-4-methyl-3-(trimethylsilyl)-2,5-cyclohexadien-1-one (1) in 60% overall yield from benzaldehyde is described. Irradiation (366 nm) of 1 in benzene solution gave products of type A photorearrangement; e.g., diastereomers of the 4-(trimethylsilyl)- and 5-(trimethylsilyl)bicyclo[3.1.0]hex-3-en-2-ones 8 and 9. Bicyclohexenones 9a and 9b could not be isolated, but underwent acid-catalyzed protiodesilylative rearrangements on attempted chromatography (silica gel) to give a 1:1 mixture of (E)- and (Z)-4-(carbomethoxymethylmethylene)cyclopent-2-en-1-ones 12 and 13. Irradiation (366 nm) of either 12 or 13 resulted in photoisomerization to a photostationary state that was also a 1:1 mixture. Irradiation of 8a or 8b gave equivalent mixtures of phenols 14 and 15 by way of the type B oxyallyl zwitterion 17. The available experimental evidence suggests that both 9a and 9b undergo regiospecific photorearrangement to phenol 16 with no trace of 3-methyl-4-carbomethoxyphenol (19), the product of ipso substitution of the Me(3)Si group at C(4). Phenol 15 was isolated in 65% yield from the photoreaction of 1 in benzene with 20 equiv of CF(3)CO(2)H. The acid-catalyzed rearrangement of 1 to 3-carbomethoxy-4-methylphenol (21) occurs in 91% yield by way of CO(2)Me group rearrangement to C(3) to give the Me(3)Si-stabilized carbocation 23. 相似文献
48.
Rondelez Y Rager MN Duprat A Reinaud O 《Journal of the American Chemical Society》2002,124(7):1334-1340
Two calixarene-based model systems (a and b) for monocopper enzymes are compared. Both present a tris(pyridine) coordination site for Cu that mimics the imidazole-rich neutral binding site in enzymes. Upon reaction with 1 equiv of copper(I), the tridentate ligands gave rise to ill-defined unsymmetrical complexes. However, in the presence of an organonitrile RCN (R = Me, Et, Ph), tetrahedral species were obtained, with the nitrilo ligand included in the calixarene hydrophobic cone. System b presents a larger cavity than system a, with a wider opening thanks to the removal of three tBu groups from the calixarene structure. As a result, the recognition pattern for MeCN vs PhCN is inverted, and the relative affinity constants differ by 3 orders of magnitude. The mechanism of the acetonitrile exchange at the cuprous centers was studied by (1)H NMR spectroscopy. Thermodynamic and kinetic data show that it follows a dissociative pathway in both cases. The main differences between systems a and b stem from the presence of a door that entraps the guest in case a. In system b indeed, the removal of three calixarene tBu groups led to a 100-fold acceleration of the MeCN exchange rate. Hence, these supramolecular systems provide a rare and interesting model for the hydrophobic substrate channel giving access to a metalloenzyme active site. 相似文献
49.
Ethan Y. H. LI Grace M. X. LI Arthur L. B. YANG Candice X. T. ZHANG 《Frontiers of Mathematics in China》2022,17(5):887
We give some sufficient conditions for the nonnegativity of immanants of square submatrices of Catalan-Stieltjes matrices and their corresponding Hankel matrices. To obtain these sufficient conditions, we construct new planar networks with a recursive nature for Catalan-Stieltjes matrices. As applications, we provide a unified way to produce inequalities for many combinatorial polynomials, such as the Eulerian polynomials, Schröder polynomials, and Narayana polynomials. 相似文献
50.