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991.
The ligninolytic system from the fungi Trametes villosa and Panus crinitus can efficiently degrade all fractions of different molecular mass contained in E1-bleaching effluent, but with different degradation rates. The lower-molecular-mass (MM) materials were better characterized when the elution in the size-exclusion high-performance liquid chromatography were monitored at 210 than at 280 nm, which indicates that these compounds may be ring cleavage byproducts from depolymerized chlorolignin. The biodegradation of E1 effluent by both fungi was a multistage process, involving an initial chemical modification of the higher-MM compounds and concomitant oxidation of the lower-MM materials. A subsequent depolymerization of chemically modified polymeric lignin-like compounds also took place. Each stage may require one or several different enzymes. The results suggested that laccase was involved in the initial stage. 相似文献
992.
B. S. Razbirin E. F. Sheka A. N. Starukhin D. K. Nelson P. A. Troshin R. N. Lyubovskaya 《JETP Letters》2008,87(3):133-139
Two new nonlinear optic effects are observed in crystalline solutions of fullerenes in toluene and carbon tetrachloride. Both
are provided by a self-clustering of the solute molecules and are referred to fullerene-enhanced Raman scattering and solvent-enhanced
luminescence. The effects are induced by the excitation of charge-transfer states of the fullerene nanoclusters, which makes
the latter act as amplifiers of local electric fields.
The text was submitted by the authors in English. 相似文献
993.
The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found (p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength. 相似文献
994.
Rapid analytical method for the simultaneous separation and determination of amines and organic acids is a vital interest for quality control of citrus and their products. In the present study, a simultaneous high performance liquid chromatography (HPLC) method for the rapid separation of three amines and two organic acids was developed. Chromatographic separation of compounds was achieved using Xbridge C18 column at ambient temperature, with an isocratic mobile phase of 3 mM phosphoric acid at a flow rate of 1.0 mL min−1. A photodiode array (PDA) detector was used to monitor the eluent at 223 nm and 254 nm with a total analysis time of 10 min. Extraction of amines and organic acids from citrus juice was optimized. The method was validated by tests of linearity, recovery, precision and ruggedness. The limit of detection (LOD) and limit of quantification (LOQ) for amines and ascorbic acid were determined to be 5 ng and 9.8 ng, respectively. All calibration curves showed good linearity (R2 ≥ 0.9999) within the test ranges. The recoveries of the amines and organic acids ranged between 84% and 117%. The identity of each peak was confirmed by mass spectral (MS) analysis. The developed method was successfully applied to analyze the content of amines and organic acids in six different species and two varieties of citrus. Results indicate that mandarin and Marrs sweet orange contain high level of amines, while pummelo and Rio Red grapefruit had high content of ascorbic acid (137-251 μg mL−1) and citric acid (5-22 mg mL−1). Synephrine was the major amine present in Clementine (114 μg mL−1) and Marrs sweet orange (85 μg mL−1). To the best of our knowledge, this is the first report on simultaneous separation and quantification of amines and organic acids in Marrs sweet orange, Meyer lemon, Nova tangerine, Clementine, Ugli tangelo and Wekiwa tangelo. 相似文献
995.
Nelson T Fernandez-Alberti S Chernyak V Roitberg AE Tretiak S 《The Journal of chemical physics》2012,136(5):054108
Nonadiabatic molecular dynamics simulations, involving multiple Born-Oppenheimer potential energy surfaces, often require a large number of independent trajectories in order to achieve the desired convergence of the results, and simulation relies on different parameters that should be tested and compared. In addition to influencing the speed of the simulation, the chosen parameters combined with the frequently reduced number of trajectories can sometimes lead to unanticipated changes in the accuracy of the simulated dynamics. We have previously developed a nonadiabatic excited state molecular dynamics methodology employing Tully's fewest switches surface hopping algorithm. In this study, we seek to investigate the impact of the number of trajectories and the various parameters on the simulation of the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene) within our developed framework. Various user-defined parameters are analyzed: classical and quantum integration time steps, the value of the friction coefficient for Langevin dynamics, and the initial seed used for stochastic thermostat and hopping algorithms. Common approximations such as reduced number of nonadiabatic coupling terms and the classical path approximation are also investigated. Our analysis shows that, at least for the considered molecular system, a minimum of ~400 independent trajectories should be calculated in order to achieve statistical averaging necessary for convergence of the calculated relaxation timescales. 相似文献
996.
We have performed depolarized impulsive stimulated scattering experiments to observe shear acoustic phonons in supercooled triphenylphosphite (TPP) from ~10-500 MHz. These measurements, in tandem with previously performed longitudinal and shear measurements, permit further analyses of the relaxation dynamics of TPP within the framework of the mode coupling theory. Our results provide evidence of α coupling between the shear and longitudinal degrees of freedom up to a decoupling temperature T(c) = 231 K. A lower bound length scale of shear wave propagation in liquids verified the exponent predicted by theory in the vicinity of the decoupling temperature. 相似文献
997.
S Fernandez-Alberti AE Roitberg T Nelson S Tretiak 《The Journal of chemical physics》2012,137(1):014512
Radiationless transitions between electronic excited states in polyatomic molecules take place through unavoided crossings of the potential energy surfaces with substantial non-adiabatic coupling between the respective adiabatic states. While the extent in time of these couplings are large enough, these transitions can be reasonably well simulated through quantum transitions using trajectory surface hopping-like methods. In addition, complex molecular systems may have multiple "trivial" unavoided crossings between noninteracting states. In these cases, the non-adiabatic couplings are described as sharp peaks strongly localized in time. Therefore, their modeling is commonly subjected to the identification of regions close to the particular instantaneous nuclear configurations for which the energy surfaces actually cross each other. Here, we present a novel procedure to identify and treat these regions of unavoided crossings between non-interacting states using the so-called Min-Cost algorithm. The method differentiates between unavoided crossings between interacting states (simulated by quantum hops), and trivial unavoided crossings between non-interacting states (detected by tracking the states in time with Min-Cost procedure). We discuss its implementation within our recently developed non-adiabatic excited state molecular dynamics framework. Fragments of two- and four-ring linear polyphenylene ethynylene chromophore units at various separations have been used as a representative molecular system to test the algorithm. Our results enable us to distinguish and analyze the main features of these different types of radiationless transitions the molecular system undertakes during internal conversion. 相似文献
998.
The synthesis of β-hydroxy-γ-amino acids via SmI(2)-mediated Reformatsky reactions of α-chloroacetyloxazolidinones with aminoaldehydes is reported. Diastereoselective coupling is demonstrated to depend on the absolute configuration of the Evans chiral auxiliary employed in the reaction, allowing erythro or threo products to be obtained selectively. The potential utility of the methodology is exemplified by the facile synthesis of biologically relevant N-Boc-isostatine (2b) and N-Boc-dolaisoleucine (3c). 相似文献
999.
Angela Kinnell Thomas Harman Matilda Bingham Alan Berry Adam Nelson 《Tetrahedron》2012,68(37):7719-7722
A one-pot, three-component process is described which involves both organo- and enzyme-catalysed carbon–carbon bond-forming steps. In the first step, an organocatalyst catalyses the aldol reaction between acetaldehyde and a glyoxylamide. After dilution with additional aqueous buffer, and addition of pyruvate and an aldolase enzyme variant, a second aldol reaction occurs to yield a final product. Crucially, it was possible to develop a reaction in which both the organo- and enzyme-catalysed reactions could be performed in the same aqueous buffer system. The reaction described is the first example of a one-pot, three-component reaction in which the two carbon–carbon bond-forming processes are catalysed using the combination of an organocatalyst and an enzyme. 相似文献
1000.
Zhang S Nelson A Beales PA 《Langmuir : the ACS journal of surfaces and colloids》2012,28(35):12831-12837
Understanding the interactions between nanoparticles (NPs) and biological matter is a high-priority research area because of the importance of elucidating the physical mechanisms underlying the interactions leading to NP potential toxicity as well as NP viability as therapeutic vectors in nanomedicine. Here, we use two model membrane systems, giant unilamellar vesicles (GUVs) and supported monolayers, to demonstrate the competition between adhesion and elastic energy at the nanobio interface, leading to different mechanisms of NP-membrane interaction relating to NP size. Small NPs (18 nm) cause a "freeze effect" of otherwise fluid phospholipids, significantly decreasing the phospholipid lateral mobility. The release of tension through stress-induced fracture mechanics results in a single microsize hole in the GUVs after interaction. Large particles (>78 nm) promote membrane wrapping, which leads to increased lipid lateral mobility and the eventual collapse of the vesicles. Electrochemical impedance spectroscopy on the supported monolayer model confirms that differently sized NPs interact differently with the phospholipids in close proximity to the electrode during the lipid desorption process. The time scale of these processes is in accordance with the proposed NP/GUV interaction mechanism. 相似文献