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121.
122.
Mutagenic primary polycyclic aromatic amines present in shale oil and synthetic crudes may be readily detected by a simple derivatization and Chromatographic procedure. Nitrogenous bases and amines are extracted from the sample with dilute mineral acid and derivatized with trifluoroacetic anhydride. The derivatized amines are separated by gas chromatography and specifically detected using a glow-discharge detector tuned to an emission wavelength of fluorine. Under these conditions, the aromatic nitrogenous bases, such as acridine, are not detected even though they are present in the sample. As little as 14 ng of fluorine, arising from the derivative of 33 ng of 2,4,6-trimethylaniline, can be detected. The selectivity of the glow-discharge detector for derivatized amines vs. nonderivatized aromatic nitrogenous bases was estimated to be a minimum of 200:1. 相似文献
123.
Ruiz V Nicholson PG Jollands S Thomas PA Macpherson JV Unwin PR 《The journal of physical chemistry. B》2005,109(41):19335-19344
This paper reports the first comparison of the structure and electrical conductivity properties of spin cast (SC) and Langmuir-Schaeffer (LS) films of regioregular poly(3-hexylthiophene) (P3HT). In addition, the effect of incorporating highly monodisperse Au nanoparticles (NPs), with a core diameter of approximately 5 nm, into SC and LS P3HT films is described. A detailed picture of molecular organization in the films has been obtained using ultraviolet-visible absorption spectroscopy, atomic force microscopy, field-emission scanning electron microscopy, X-ray diffraction, and X-ray reflectivity. Film morphology was correlated with pseudo-two-dimensional conductivity measured using scanning electrochemical microscopy, with P3HT in the semiconducting regime. It was found that SC films, which were slightly thicker than those formed with the LS technique, exhibited greater organization. This resulted in an order of magnitude higher lateral conductivity for the SC films. Inclusion of Au NPs (50 wt %) into both SC and LS films resulted in the formation of uniform and relatively flat (rms roughness approximately 1 nm) composite films. Surprisingly, the addition of NPs did not disrupt the characteristic crystal structure found for the native P3HT films. The effect of Au NPs on film lateral conductivity was found to be determined by the distribution of Au NPs within the polymer, which varied significantly between SC and LS films. Whereas Au NPs aggregated into hexagonally packed clusters in SC films, NPs in LS films were predominantly uniformly distributed between the lamella bilayer. It was found that, while the inclusion of Au NPs caused the lateral conductivity to decrease in SC films, in LS films, the lateral conductivity increased by a factor of 2. 相似文献
124.
Rios R Jimeno C Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(35):10272-10273
We have demonstrated the feasibility of the kinetic resolution of atropisomeric amides using the commercially avaliable AD-mix. To our knowledge, this methodology represents the first catalytic kinetic resolution of such compounds. Relative rates of up to 32 have been found for the kinetic resolution processes. We have also determined the barriers to rotation and half-lives of some of these amides. The half-lives range from 7 to 135 h at room temperature. 相似文献
125.
John Fielden Patrick T. Gunning De-Liang Long Margaret Nutley Arkady Ellern Paul Kgerler Leroy Cronin 《Polyhedron》2006,25(18):3474-3480
The coordination chemistry of the tetradentate pyridyl N-donor ligand cis-3,5-bis-[2-pyridinyleneamin]-trans-hydroxycyclohexane (DDOP) has been investigated with zinc(II) nitrate and triflate. The resulting complexes, [Zn(DDOP)(H2O)(NO3)](NO3) (1), and [Zn(DDOP)(H2O)(OTf)](OTf) (2) differ not only in their counterions, but also the arrangement of the axial ligands and their solid state hydrogen bonded networks. Isothermal titration calorimetry was used to assess the difference in binding properties exhibited by the two zinc complexes at physiological pH in an aqueous environment. A series of coordinating amino acids were found to preferentially bind to the mononuclear zinc triflate (1) complex over the corresponding nitrate (2) assembly, with histidine exhibiting a two centre binding mode. 相似文献
126.
Patrick DL Flanagan JF Kohl P Lynden-Bell RM 《Journal of the American Chemical Society》2003,125(22):6762-6773
Chemical force microscopy and related force measurement techniques have emerged as powerful tools for studying fundamental interactions central to understanding adhesion and tribology at the molecular scale. However, detailed interpretation of these interactions requires knowledge of chemical and physical processes occurring in the region of the tip-sample junction that experiments cannot provide, such as atomic-scale motions and distribution of forces. In an effort to address some of these open issues, atomistic molecular dynamics simulations were performed modeling a chemical force microscope stylus covered with a planar C12 alkylthiolate self-assembled monolayer (SAM) interacting with a solid wall. A complete loading-unloading sequence was simulated under conditions of near-constant equilibrium, approximating the case of infinitely slow tip motion. In the absence of the solid wall, the stylus film existed in a fluid state with structural and dynamic properties similar to those of the analogous planar SAM at an elevated temperature. When the wall was brought into contact with the stylus and pressed against it, a series of reversible changes occurred culminating with solidification of the SAM film at the largest compressive force. During loading, the chemical composition of the contact changed, as much of the film's interior was exposed to the wall. At all tip heights, the distribution of forces within the contact zone was uneven and subject to large local fluctuations. Analysis using the Johnson-Kendall-Roberts, Derjaguin-Muller-Toporov, and Hertz contacts mechanics models revealed significant deviations from the simulation results, with the JKR model providing best overall agreement. Some of the discrepancies found would be overlooked in an actual experiment, where, unlike the simulations, contact area is not separately known, possibly producing a misleading or incorrect interpretation of experimental results. These shortcomings may be improved upon by using a model that correctly accounts for the finite thickness of the compliant components and nonlinear elastic effects. 相似文献
127.
A novel pyridinium salt photoelectrocyclization-nucleophilic bicyclic aziridine ring opening reaction sequence has been investigated in order to determine its preparative potential. N-Alkylpyridinium perchlorates were found to undergo photoinduced electrocyclization upon irradiation in nucleophilic solvents, such as H(2)O and MeOH, to efficiently produce 6-alkyl-6-azabicyclo[3.1.0]hex-2-en-4-yl alcohols and ethers. The bicyclic aziridine photoproducts react with a number of different nucleophiles (e.g., H(2)O, MeOH, AcOH, AcSH) under acid-catalyzed conditions to produce 5-(nucleophile-substituted)-4-(alkylamino)cyclopenten-3-yl alcohols and ethers. The aziridine ring opening processes are both regioselective and stereoselective, yielding trans,trans-trisubstituted cyclopentenes exclusively, apparently as a consequence of the operation of an SN(2) mechanism. The effects of C-alkyl substitution on the regiochemistry of the pyridinium cation photocyclization reaction were briefly probed, and a method was developed to produce trans,cis-trisubstituted cyclopentenes by use of this tandem preparative sequence. 相似文献
128.
The effect of the chemical structure of styrene-based epoxides, namely, styrene epoxide (SE), α-methylstyrene epoxide (MSE), p-methylstyrene epoxide (pM-SE) and α-methyl-p-methylstyrene epoxide (pM-MSE), in conjunction with TiCl4, on the initiation efficiency (Ieff) in the carbocationic polymerization of isobutylene (IB) was investigated. SE yielded living polymerization, but the initiation efficiency was low when compared to MSE (Ieff=8% and 35%, respectively). pM-SE led to non-living IB polymerization, while pM-MSE revealed linear Mn-conversion plot and narrow MWD with a non-linear first order rate plot. Among the epoxides investigated, MSE was the best initiator to scale up the one-step synthesis of polyisobutylenes (PIBs) carrying one primary hydroxyl head group and one tertiary chloride end group. The hydroxyl functionality of these PIBs determined by 1H-NMR was Fn=1.09±0.16 from 24 experiments. 相似文献
129.
Mousumi Sannigrahi Patrick Pinto T.M. Chan Neng-Yang Shih F. George Njoroge 《Tetrahedron letters》2006,47(28):4877-4880
An efficient and practical synthesis of sterically hindered N-substituted lactams has been developed starting from simple starting materials. The stereochemistry of the synthetically useful N,N acetal intermediate has been established. 相似文献
130.
Volumetric heat capacities of the six binary mixtures formed from cyclopentane, cyclohexane, cycloheptane and cyclooctane were determined at 298.15 K in a Picker flow microcalorimeter. Excess heat capacities obtained from the results are compred with the temperature variation of excess enthalpies from the literature. 相似文献