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101.
de Oliveira PR Rittner R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):30-37
The conformational equilibria of 3-X-cyclohexanol [X=F (1), Cl (2), Br (3), I (4), Me (5), NMe(2) (6) and MeO (7)] and of 3-X-methoxycyclohexane [X=F (8), Cl (9), Br (10), I (11), Me (12), NMe(2) (13) and MeO (14)] cis isomers were determined from low temperature NMR spectra and PCMODEL calculated coupling constants. The energy differences between aa and ee conformers were obtained from these data (DeltaG(J)(av) and DeltaG(PC)(av), respectively) and also by the additivity principle from data for the monosubstituted cyclohexanes (DeltaG(Ad)). H-1 and H-3 hydrogen vicinal coupling constants and DeltaG(J)(av) values showed that the diequatorial conformer is predominant in the conformational equilibrium of the compounds studied at low temperature. However, DeltaG(PC)(av) data show that compounds 6 and 7 constitute an exception, since they are almost equally populated by ee and aa at room temperature, due to stabilization of their aa conformer by an intramolecular hydrogen bond. DeltaG(Ad) values, obtained according to the additivity principle, show a better agreement for compounds 2 and 3, since the 1,3-diaxial steric effect is counterbalanced by the formation of an intramolecular hydrogen bond (IAHB). For the remaining compounds, DeltaG(Ad) values underestimate the energy differences, since the 1,3-diaxial steric effect, between X and OH or OCH(3), is absent in the monosubstituted compounds used as references. Moreover, the DeltaG(PC)(av), calculated from the coupling constants, obtained through the PCMODEL program, are rather smaller than the DeltaG(J)(av) values, since the program does not have parameters for the effect, observed in this report, of a substituent at gamma position on coupling constants values for the hydrogen under consideration. 相似文献
102.
Paul N Nashine VC Hoops G Zhang P Zhou J Bergstrom DE Davisson VJ 《Chemistry & biology》2003,10(9):815-825
The development of novel artificial nucleobases and detailed X-ray crystal structures for primer/template/DNA polymerase complexes provide opportunities to assess DNA-protein interactions that dictate specificity. Recent results have shown that base pair shape recognition in the context of DNA polymerase must be considered a significant component. The isosteric azole carboxamide nucleobases (compounds 1-5; ) differ only in the number and placement of nitrogen atoms within a common shape and therefore present unique electronic distributions that are shown to dictate the selectivity of template-directed nucleotide incorporation by DNA polymerases. The results demonstrate how nucleoside triphosphate substrate selection by DNA polymerase is a complex phenomenon involving electrostatic interactions in addition to hydrogen bonding and shape recognition. These azole nucleobase analogs offer unique molecular tools for probing nonbonded interactions dictating substrate selection and fidelity of DNA polymerases. 相似文献
103.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献
104.
The morphology of poly(methyl methacrylate), poly(ethylene oxide) blend and the grafted copolymer poly(methyl methacrylate-g-ethylene oxide) was observed by scanning electron microscopy. The contrast was obtained by an etching technique, removing the PEO phase out of the blend. The PEO phase of the copolymer was stained with OsO4 and better contrast was observed using a back-scattering image. The PEO phase was shown to be distributed as spherical domains in the PMMA matrix for both the copolymer and the blend. 相似文献
105.
E. M. Araújo Renata Barbosa Amanda D. Oliveira Crislene R. S. Morais T. J. A. deMélo A. G. Souza 《Journal of Thermal Analysis and Calorimetry》2007,87(3):811-814
Polyethylene/montmorillonite clay nanocomposites were obtained via direct
melt intercalation. The clay was organically modified with four different
types of quaternary ammonium salts. The objective of this work is to study
the use of montmorillonite clay in the production of nanocomposites by means
on rheological, mechanical and crystallization properties of nanocomposites
and to compare to the properties of the matrix and PE/unmodified clay nanocomposites.
In general, the tensile test showed that the yield strength and modulus of
the nanocomposites are close to the pure PE. Apparently, the mixture with
Dodigen salt seems to be more stable than the pure PE and PE/unmodified clay. 相似文献
106.
Non-coherent visible and infrared radiation increase survival to UV (254 nm) in Escherichia coli K12
Lage C Teixeira PC Leitão AC 《Journal of photochemistry and photobiology. B, Biology》2000,54(2-3):155-161
Interactions between visible or infrared (IR) and ultraviolet (UV, 254 nm) radiation have been studied in E. coli. Pre-illumination with non-coherent monochromatic 446, 466, 570 and 685 nm radiation, as well as with polychromatic red and IR radiation at room temperature, leads to increased cell survival after a subsequent irradiation with UV light. In the thermic range of the spectrum (red and IR), IR but not red light pre-treatment is able to increase cell survival to a subsequent lethal heat (51 degrees C) challenge, suggesting that increased UV survival may be due to IR-induced heat-shock response. On the other hand, visible-light-induced resistance may be due to a different mechanism, possibly involved with unknown bacterial light receptors. 相似文献
107.
The total synthesis of 1-(Z)-atractylodinol, a natural polyacetylenic alcohol with several biological activities, has been achieved using a newly developed telluride synthon and a novel use for the Negishi type coupling reaction employing vinyl tellurides. 相似文献
108.
Fernando J. S. Oliveira Francisca P. de França 《Applied biochemistry and biotechnology》2005,122(1-3):581-591
Hexane is a toxic volatile organic compound that is quite abundant in gas emissions from chemical industries and printing
press and painting centers, and it is necessary to treat these airstreams before they discharge into the atmosphere. This
article presents a treatment for hexane-contaminated air in steady-state conditions using an internal-loop airlift bioreactor
inoculated with a Pseudomonas aeruginosa strain. Bioprocesses were conducted at 20-mL/min, a load of 1.26 g/m3 of C6H14, and a temperature of 28°C. The results of hexane removal efficiencies were presented as a function of the inoculum size
(approx 0.07 and 0.2 g/L) and cell reuse. Bioprocess monitoring comprises quantification of the biomass, the surface tension
of the medium, and the hexane concentration in the fermentation medium as well as in the inlet and outlet airstreams. The
steady-state results suggest that the variation in inoculum size from 0.07 to 0.2 g/L promotes hexane abatement from the influent
from 65 to 85%, respectively. Total hydrocarbon removal from the waste gas was achieved during experiments conducted using
reused cells at an initial microbial concentration of 0.2 g/L. 相似文献
109.
Yiyi Weng Xingxing Ding Joo C. A. Oliveira Xiaobin Xu Nikolaos Kaplaneris Meijie Zhu Hantao Chen Zhuo Chen Lutz Ackermann 《Chemical science》2020,11(34):9290
There is a strong demand for novel native peptide motifs for post-synthetic modifications of peptides without pre-installation and subsequent removal of directing groups. Herein, we report an efficient method for peptide late-stage C(sp3)–H arylations assisted by the unmodified side chain of asparagine (Asn) without any exogenous directing group. Thereby, site-selective arylations of C(sp3)–H bonds at the N-terminus of di-, tri-, and tetrapeptides have been achieved. Likewise, we have constructed a key building block for accessing agouti-related protein (AGRP) active loop analogues in a concise manner.An efficient method for peptide late-stage C(sp3)-H arylations assisted by unmodified side chain of asparagine (Asn) without any exogenous directing group has been reported. 相似文献
110.
Laura Marcu Javier A. Jo Pramod V. Butte William H. Yong Brian K. Pikul Keith L. Black Reid C. Thompson 《Photochemistry and photobiology》2004,80(1):98-103
Fluorescence spectroscopy of the endogenous emission of brain tumors has been researched as a potentially important method for the intraoperative localization of brain tumor margins. We investigated the use of time‐resolved, laser‐induced fluorescence spectroscopy for demarcation of primary brain tumors by studying the time‐resolved spectra of gliomas. The fluorescence of human brain samples (glioblastoma multiforme, cortex and white matter: six patients, 23 sites) was induced ex vivo with a pulsed nitrogen laser (337 nm, 3 ns). The time‐resolved spectra were detected in a 360–550 nm wavelength range using a fast digitizer and gated detection. Parameters derived from both the spectral‐ (intensities from narrow spectral bands) and the time domain (average lifetime) measured at 390 and 460 nm were used for tissue characterization. We determined that high‐grade gliomas are characterized by fluorescence lifetimes that varied with the emission wavelength (>3 ns at 390 nm, <1 ns at 460 nm) and their emission is overall longer than that of normal brain tissue. Our study demonstrates that the use of fluorescence lifetime not only improves the specificity of fluorescence measurements but also allows a more robust evaluation of data collected from brain tissue. Combined information from both the spectraland the time domain can enhance the ability of fluorescencebased techniques to diagnose and detect brain tumor margins intraoperatively. 相似文献