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81.
A theoretical study is made of the states of nonrigid molecules, extending earlier work to apply Longuet–Higgins' symmetry group of feasible permutation/inversions in two previously untreated cases. The first involves nonrigid molecule processes between different stereoisomers, that is between molecular equilibrium configurations of different geometrical shapes. The second takes into account nonrigid molecule processes in linear molecules. The theory is applied to the specific case of nonrigid molecule effects in the butyl ion C4H (case i), and the form of the nonrigid molecule energy levels and spectra are determined. The theory is also applied to determine the nonrigid molecule energy levels in linear H2F2 (case ii). 相似文献
82.
Oxygen plasma-treatment is commonly used to increase the hydrophilicity of poly(dimethylsiloxane) (PDMS) stamps used for microcontact printing (muCP) aqueous-based inks. Review of the literature reveals that a wide range of plasma parameters are currently employed to modify stamp surfaces. However, little is known about the effect of these parameters (e.g., power, chamber pressure, duration) on the undesirable transfer of low-molecular-weight silicon-containing fragments from the stamps that commonly occurs during muCP. To study the effect of oxygen plasma-treatment on Si transfer, unpatterned PDMS stamps were treated with oxygen plasma under various conditions and used to stamp deionized water on plasma-activated poly(methyl methacrylate) (PMMA) substrates. Once stamped, the PMMA substrates were analyzed with X-ray photoelectron spectroscopy (XPS) to quantify and characterize silicon present on the substrate surface. In addition, used PDMS stamps were analyzed with scanning electron microscopy (SEM) to observe topographical changes that occur during oxygen plasma-treatment. XPS results show that all plasma treatments studied significantly reduced the amount of Si transfer from the treated stamps during muCP as compared to untreated PDMS stamps and that the source of transfer is residual PDMS fragments not removed by oxygen plasma. SEM results show that, although the treated stamps undergo a variety of topographical changes, no correlation exists between stamp topography and extent of Si transfer from the stamps. 相似文献
83.
We investigate the dynamics and mechanism of the IR-driven cis-trans isomerization of nitrous acid (HONO) in a low-temperature krypton matrix applying ultrafast time resolved IR spectroscopy. After excitation of the OH-stretching mode the trans HONO state decays biexponentially on a 8 and 260 ps time scale. The initially excited cis HONO state decays on a 20 ps time scale. Cis HONO isomerizes with 10% quantum yield on a 20 ps time scale to trans HONO. The quantum yield we observe is significantly smaller than the previously reported 100%, which could imply that additional, much slower reaction channels exist. We furthermore developed a four-dimensional model of the system, which includes the three proton intramolecular degrees of freedom of HONO fully quantum mechanically and one intermolecular translational degree of freedom of the molecule in the crystal cage. We find that cis-trans isomerization necessarily is accompanied by a translation of the molecule as a whole in the crystal cage. The translational degree of freedom tunes the intramolecular proton states of HONO with respect to each other. When resonances occur, the proton states might couple and transfer population. We suggest a possible reaction pathway, where the cis OH-stretch excited state first couples to a high cis torsional mode, which then may transfer almost instantaneously to the trans side. The model qualitatively explains all experimental observations. 相似文献
84.
The chiral phosphine‐oxazoline ligands 3 and 4 bearing 4‐alkoxymethyl substituents on the oxazoline ring with (R)‐configuration were prepared from L‐serine methyl ester in 66% and 33% yields, respectively. Along this synthetic pathway, the β‐hydroxylamides derived from L‐serine methyl ester and 2‐halobenzoyl chlorides were expediently converted to the corresponding oxazolines by using diethylaminosulfur trifluoride as the activation agent. Potassium diphenylphosphide was the reagent of choice for replacing the bromine atom on the phenyl ring, giving the desired oxazoline‐phosphine ligands 3 and 4 . Together with [Pd(η3‐allyl)Cl]2, ligands 3 and 4 induced an enantioselective allylic substitution reaction of 1,3‐diphenyl‐2‐pro‐penyl acetate by dimethyl malonate. Although ligands 3 and 4 exhibit the (R)‐configuration, differing from the (S)‐configuration of Pfaltz‐Helmchen‐Williams phosphine‐oxazoline ligands, all these ligands led to the same enantiotopic preference in the allylic substitution reaction. To facilitate the recovery and reuse of the phosphine‐oxazoline ligand, immobilization on Merrifield resin was attempted, albeit in low loading. 相似文献
85.
J. Kučera J. Kučera A. R. Byrne A. R. Byrne J. Mizera J. Mizera M. Lučaníková M. Lučaníková Z. Řanda Z. Řanda 《Journal of Radioanalytical and Nuclear Chemistry》2006,269(2):251-257
Summary Radiochemical neutron activation procedures using liquid-liquid extraction with tetraphenylarsonium chloride in chloroform
from 1M HCl and solid extraction with ALIQUAT 336 incorporated in a polyacrylonitrile binding matrix from 0.1M HCl were developed
for accurate determination of rhenium in biological and environmental samples at the sub-ng . g-1 level. Concentrations of Re in the range of 0.1 to 2.4 ng . g-1 were determined in several botanical reference materials (RM), while in a RM of road dust a value of ~10 ng . g-1 was found. Significantly elevated values of Re, up to 90 ng . g-1 were found in seaweed (brown algae). Results for Re in the brown algae Fucus vesiculosus in which elevated 99Tc values had previously been determined suggested possible competition between Re and Tc in the accumulation process. 相似文献
86.
Mikkelsen LM Hernáiz MJ Martín-Pastor M Skrydstrup T Jiménez-Barbero J 《Journal of the American Chemical Society》2002,124(50):14940-14951
The conformational properties of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man in solution have been carefully analyzed by a combination of NMR spectroscopy and time-averaged restrained molecular dynamics. It has been found that both the alpha-1,3- and the alpha-1,6-glycosidic linkages show a major conformational averaging. Unusual Phi ca. 60 degrees orientations for both Phi torsion angles are found. Moreover, a major conformational distinction between the natural compound and the glycomimetic affects to the behavior of the omega(16) torsion angle around the alpha-1 --> 6-linkage. Despite this increased flexibility, the C-glycosyl analogue is recognized by three mannose binding lectins, as shown by NMR (line broadening, TR-NOE, and STD) and surface plasmon resonance (SPR) methods. Moreover, a process of conformational selection takes place, so that these lectins probably bind the glycomimetic similarly to the way they recognize the natural analogue. Depending upon the architecture and extension of the binding site of the lectin, loss or gain of binding affinity with respect to the natural analogue is found. 相似文献
87.
Smith BD Soellner MB Raines RT 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):187-190
Intact RNA and DNA are of central importance to biochemical research and biotechnology. The preservation of these nucleic acids requires the absence of nuclease activity. Here, radical-mediated polymerization of vinylsulfonate on resin and glass surfaces is shown to produce a high-density poly(vinylsulfonate) coating that sequesters ribonucleases from aqueous solutions quickly and completely. The adsorptive efficacy of this coating exceeds that of other known coatings by > or =10(7)-fold. Surfaces coated with poly(vinylsulfonate) could be used to maintain the integrity of ribonucleic acids in a variety of contexts. 相似文献
88.
Determination of rotenone residues in raw honey by solid-phase extraction and high-performance liquid chromatography 总被引:8,自引:0,他引:8
Jiménez JJ Bernal JL del Nozal MJ Novo M Higes M Llorente J 《Journal of chromatography. A》2000,871(1-2):67-73
A method for determining residues of the insecticide rotenone in raw-honey by high-performance liquid chromatography (HPLC) is described. To extract the residues, organic solvents such as ethyl acetate, n-hexane/dichloromethane and solid-phase extraction with octadecylsilane cartridges or Florisil packed columns were tested. Determination was carried out by reversed-phase HPLC using acetonitrile-buffer phosphate (pH 7) (60:40, v/v) as mobile phase and detection at 210 nm. Although the data showed that the two extraction methods were able to isolate the pesticide residues, the extraction on octadecylsilane cartridges was preferred due to its simplicity and higher recovery. Recoveries depended strongly on the fortification level for the two extraction procedures. Practical determination limits of 0.015 mg/kg were obtained. In the analysis of honeys, from beehives treated with rotenone at therapeutical doses for 1 month, residual amounts below 0.2 mg/kg were found. 相似文献
89.
Two families of mixed finite elements for second order elliptic problems 总被引:32,自引:2,他引:30
Summary Two families of mixed finite elements, one based on triangles and the other on rectangles, are introduced as alternatives to the usual Raviart-Thomas-Nedelec spaces. Error estimates inL
2
() andH
–5
() are derived for these elements. A hybrid version of the mixed method is also considered, and some superconvergence phenomena are discussed. 相似文献
90.
Verdejo B Aguilar J Doménech A Miranda C Navarro P Jiménez HR Soriano C García-España E 《Chemical communications (Cambridge, England)》2005,(24):3086-3088
L-glutamate and L-aspartate selectivity is achieved by the action of two Cu2+ metal ions rightly disposed in a cyclophane-type macrocyclic framework; electrochemical sensing of glutamate has been achieved by adsorption of the copper complexes on graphite electrodes. 相似文献