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221.
Alberto Hernandez Gainza 《国际化学动力学杂志》2004,36(9):500-509
Halogenated hydrocarbon solvents, SolvCl, (dichloromethane, chloroform, and 1,2‐dichloroethane) react with various types of tertiary amines, A, such as tri‐n‐buthylamine, tropane derivatives (tropine and atropine) and quinine generating a quaternary ammonium salt, N‐halogenalkylammonium chloride (SolvA+Cl?). Some tertiary amines, as well as secondary and primary amines, cannot react with these solvents. This reaction has been detected and studied by both conductivity and visible spectrophotometry measures—the latter after adding a small quantity of a dye, such as bromocresol green (BCGH2), bromophenol blue (BPBH2), or tetrabromophenolphthaleinethyl ester (TBPEH). Both study methods permit the determination of the kinetic parameters, and they are in good agreement. The monoprotic TBPEH is the dye of the simplest mechanism, useful to study kinetics of amines of uncertain behavior as quinine, while BPBH2 is the best dye for quantitative determinations. Kinetics for this reaction are of first order for both amine, A, and solvent, SolvCl; activation energy, Ea, and frequency factor are also determined. Rate constants increase with the amine basicity and with a reduction in the number of the halogen atoms present in the solvent. This reaction is slow but not negligible and must be considered a side reaction of these universally used solvents. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:500–509, 2004 相似文献
222.
Lei Gao Koji Narita Taro Ozaki Naoyoshi Kumakura Pamela Gan Atsushi Minami Chengwei Liu Xiaoguang Lei Ken Shirasu Hideaki Oikawa 《Tetrahedron letters》2018,59(12):1136-1139
Two homologous gene clusters for the biosynthesis of sesterterpenes betaestacins were identified from two phytopathogens, Phoma betae and Colletotrichum orbiculare. Heterologous expression of identified oxidation enzymes with previously-characterized PbTS1 (BtcAPb) resulted in the production of seven novel sesterterpenes. Although both strains possessed homologous enzymes, oxidation state of corresponding products were different from each other, suggesting that structural diversification of sesterterpene skeletons might be achieved by these homologous enzymes with different functions. 相似文献
223.
M. Tariq Riaz Ivanna Pohorilets Jackson J. Hernandez Jeovanna Rios Nancy I. Totah 《Tetrahedron letters》2018,59(29):2809-2812
A practical, operationally simple preparation of 2-(trimethylsilyl)methyl-2-propen-1-ol derivatives is described. The cobalt catalyzed coupling of a protected vinyl halide with trimethylsilylmethylmagnesium chloride shows excellent functional group tolerance and provides these synthetically useful allyl silanes in good overall yield. By this method, the use of highly concentrated organolithium reagents, complex reaction protocols, and expensive starting materials is avoided. 相似文献
224.
Dr. Haibin Gu Dr. Roberto Ciganda Dr. Patricia Castel Sergio Moya Ricardo Hernandez Dr. Jaime Ruiz Prof. Didier Astruc 《Angewandte Chemie (International ed. in English)》2018,57(8):2204-2208
Multi‐block polymers are highly desirable for their addressable functions that are both unique and complementary among the blocks. With metal‐containing polymers, the goal is even more challenging insofar as the metal properties may considerably extend the materials functions to sensing, catalysis, interaction with metal nanoparticles, and electro‐ or photochrome switching. Ring‐opening metathesis polymerization (ROMP) has become available for the formation of living polymers using highly efficient initiators such as the 3rd generation Grubbs catalyst [RuCl2(NHC)(=CHPh)(3‐Br‐C5H4N)2], 1 . Among the 24 possibilities to introduce 4 blocks of metallopolymers into a tetrablock metallocopolymer by ROMP using the catalyst 1 , two viable pathways are disclosed. The synthesis, characterization, electrochemistry, electron‐transfer chemistry, and remarkable electrochromic properties of these new nanomaterials are presented. 相似文献
225.
226.
A quantitative attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopic method is developed for the analysis of total carboxylate concentration, [COO−], in aqueous solution. The short (12–13 μm) and highly reproducible pathlength of the ATR cell permits quantitative subtraction of the water peak at 1640 cm−1. Carboxylate quantitation is based on the area of the asymmetric stretching peak, which is nearly independent of compound structure. The molar absorptivity of alkyl carboxylates in water is 438 ± 58 l mol−1 cm−1, and the integrated molar absorptivity is 2.95 ± 0.08 × 104 l mol−1 cm−2 (n = 15 compounds, 0.1 M ≤ [COO−] ≤ 1.5 M). The [COO−] in solutions of mixed carboxylates is measured with a root mean square error of 2.4% and a small (+1.5) positive bias. The accuracy of the method is limited by the assumption that integrated absorbance is constant for all COO− groups. 相似文献
227.
Antunez-de-Mayolo G Antunez-de-Mayolo A Antunez-de-Mayolo P Papiha SS Hammer M Yunis JJ Yunis EJ Damodaran C Martinez de Pancorbo M Caeiro JL Puzyrev VP Herrera RJ 《Electrophoresis》2002,23(19):3346-3356
Alu elements, the largest family of interspersed repeats, mobilize throughout the genomes of primates by retroposition. Alu are present in humans in an excess of 500 000 copies per haploid genome. Since some of the insertion alleles have not reached fixation, they remain polymorphic and can be used as biallelic DNA marker systems in investigations of human evolution. In this study, six polymorphic Alu insertional (PAI) loci were used as genetic markers. These markers are thought to be selectively neutral. The presence of these six PAIs was determined by a polymerase chain reaction (PCR)-based assay in 1646 individuals from 47 populations from around the world. Examination of the populations by plotting the first and second principal components, shows the expected segregation of populations according to geographical vicinity and established ethnic affinities. Centroid analysis demonstrated that sub-Sahara populations have experienced higher than average gene flow and/or represent larger populations as compared to groups in other parts of the globe and especially to known inbreed populations. This is consistent with greater heterogeneity and diversity expected of source groups. In addition, maximum likelihood (ML) analyses were performed with these 47 populations and a hypothetical ancestral group lacking the insertion in all six loci. Analysis of our data supports the Out of Africa hypothesis. African populations and admixed groups of African descent formed a single monophyletic group with a basal placement on the tree, which grouped closest to the hypothetical ancestor. 相似文献
228.
Gao R Ho DG Hernandez B Selke M Murphy D Djurovich PI Thompson ME 《Journal of the American Chemical Society》2002,124(50):14828-14829
We report the singlet oxygen sensitization properties of a series of bis-cyclometalated Ir(III) complexes (i.e., (bt)2Ir(acac), (bsn)2Ir(acac), and (pq)2Ir(acac); bt = 2-phenylbenzothiazole, bsn = 2-(1-naphthyl)benzothiazole, pq = 2-phenylquinoline, and acac = acetylacetonate). Complexes with acetylacetonate ancillary ligands give singlet oxygen quantum yields near unity (PhiDelta = (0.7-1.0) +/- 0.1), whether exciting the ligand-based state or the lowest energy excited state (MLCT + 3LC). The singlet oxygen quenching rates for these beta-diketonate complexes were found to be small [(5 +/- 2) x 105 to (6 +/- 0.2) x 106 M-1 s-1], roughly 3 orders of magnitude slower than the corresponding phosphorescence quenching rate. Similar complexes were prepared with glycine or pyridine tethered to the Ir(III) center (i.e., (bsn)2Ir(gly) and (bt)2Ir(py)Cl; gly = glycine and py = pyridine). The glycine and pyridine derivatives give high singlet oxygen yields (PhiDelta = (0.7-1.0) +/- 0.1). 相似文献
229.
Ortí E Viruela PM Viruela R Effenberger F Hernandez V López Navarrete JT 《The journal of physical chemistry. A》2005,109(39):8724-8731
In this paper, we analyze the degree of intramolecular charge transfer in a push-pull pi-conjugated system, 5-(dimethylamino)-5'-nitro-2,2'-bithiophene, from changes in frequencies and relative intensities of its strongest Raman scatterings in a bunch of solvents with different polarities. Density functional theory (DFT) was used as a support of the experimental study. Solvent effects on the molecular and electronic structures and on the vibrational properties were estimated by performing B3LYP/6-31G calculations within the framework of the polarized continuum model (PCM) developed by Tomasi. Calculations reveal that the molecule is highly polarized in the ground state and behaves as a very efficient photoinduced push-pull system. The polarization of the molecule strongly increases with solvent polarity and determines that the profile of the Raman spectra greatly changes from one solvent to another and in going to the solid. The strongest Raman scattering associated with the nu(sym)(NO(2)) stretching undergoes a downshift of 48 cm(-1) in passing from CCl(4) to the solid. DFT calculations provide a comprehensive interpretation of the evolution of the Raman spectra with solvent polarity. 相似文献
230.
Grotjahn DB Van S Combs D Lev DA Schneider C Rideout M Meyer C Hernandez G Mejorado L 《The Journal of organic chemistry》2002,67(26):9200-9209
Syntheses of pyrazoles featuring a functionalized side chain attached to carbon 3 and varying alkyl and aryl substituents attached to carbon 5 are presented. Installation of R = methyl, isopropyl, tert-butyl, adamantyl, or phenyl groups at C5 is reported here, starting by coupling protected alkynols with acid chlorides RCOCl, forming alkynyl ketones, which are reacted with hydrazine to form the pyrazole nucleus. Alcohol deprotection and conversion to a chloride gave 5-substituted 3-(chloromethyl)- or 3-(2-chloroethyl)pyrazoles. This sequence can be done within 2 d on a 30 g scale in excellent overall yield. Through nucleophilic substitution reactions, the chlorides are useful precursors to other polyfunctional pyrazoles. In the work here, derivatives with side chains LCH(2)- and LCH(2)CH(2)- at C3 (L = thioether or phosphine) were made as ligands. The significance of the ligands made here is that by placing a ligating side chain on a ring carbon (C3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton will be available for hydrogen bonding, depending on the steric environment created by R at C5. 相似文献