The linearized buckling response of uniform steel beam-columns resting on a Pasternak foundation type is dealt with in this work. The corresponding two-point boundary value problem depends on the two parameters associated with the foundation model, that is, shear layer constant and Winkler spring coefficient, as well as on the axial loading. The fourth-order differential equation of buckling and the consequent characteristic one yield exact values of the buckling loads, which may lead to shape functions, being either one sinusoidal waveform or the sum of two different waveforms. The former case is associated with a single-mode response, while the latter with mode coupling. The conditions for which each of these cases characterizes the beam-column behavior are fully assessed and the dependence on the combination of the aforementioned parameters on the response is discussed in detail. It is found that regardless of the order of coupling, the corresponding mode is not related to rational values of buckling loads and hence this unfavorable phenomenon is excluded in structural design. 相似文献
A central question in biological water splitting concerns the oxidation states of the manganese ions that comprise the oxygen-evolving complex of photosystem II. Understanding the nature and order of oxidation events that occur during the catalytic cycle of five Si states (i = 0–4) is of fundamental importance both for the natural system and for artificial water oxidation catalysts. Despite the widespread adoption of the so-called “high-valent scheme”—where, for example, the Mn oxidation states in the S2 state are assigned as III, IV, IV, IV—the competing “low-valent scheme” that differs by a total of two metal unpaired electrons (i.e. III, III, III, IV in the S2 state) is favored by several recent studies for the biological catalyst. The question of the correct oxidation state assignment is addressed here by a detailed computational comparison of the two schemes using a common structural platform and theoretical approach. Models based on crystallographic constraints were constructed for all conceivable oxidation state assignments in the four (semi)stable S states of the oxygen evolving complex, sampling various protonation levels and patterns to ensure comprehensive coverage. The models are evaluated with respect to their geometric, energetic, electronic, and spectroscopic properties against available experimental EXAFS, XFEL-XRD, EPR, ENDOR and Mn K pre-edge XANES data. New 2.5 K 55Mn ENDOR data of the S2 state are also reported. Our results conclusively show that the entire S state phenomenology can only be accommodated within the high-valent scheme by adopting a single motif and protonation pattern that progresses smoothly from S0 (III, III, III, IV) to S3 (IV, IV, IV, IV), satisfying all experimental constraints and reproducing all observables. By contrast, it was impossible to construct a consistent cycle based on the low-valent scheme for all S states. Instead, the low-valent models developed here may provide new insight into the over-reduced S states and the states involved in the assembly of the catalytically active water oxidizing cluster. 相似文献
Since Arabinoxylans are natural polysaccharides that seem promising candidates as cryostabilizers, the state diagram (i.e. the representation in the temperature-composition plan of the macroscopic phases) of their aqueous solutions seemed worth determining.
Two lots of purified water extractable arabinoxylans (WEA) of different molecular mass (56 and 410 kDa labeled as LMW-AX and HMW-AX, respectively) were used to prepare aqueous solutions of various composition. These were cooled below their freezing point and annealed for 2 h at a suitable temperature before a DSC 5°C min−1 heating run aimed at determining their primary glass transition temperature, Tg′, and the onset of ice fusion. Once the corresponding composition, Cg′, was assessed, the main curves of the corresponding state diagram were drawn.
As expected, the Tg′ value drawn for HMW-AX was higher (−17°C) than for LMW-AX (−35°C). The Cg′ was instead found close to 75% w/w for both HMW-AX and LMW-AX. The fictitiousness of this coincidence could be easily recognized by expressing the solute concentration in molar fraction, X: it was then possible to verify that, as expected, Xg′ for LMW-AX was one order of magnitude larger than for HLW-AX. 相似文献
Summary An ion-exchange high-performance liquid chromatographic method is described for the quantitative assay of glutathione (GSH) conjugates derived from endogenous electrophilic substances as well as xenobiotics. GSH (reduced and oxidized forms) and GSH conjugates were condensated with o-phthaldialdehyde to highly fluorescent derivatives and monitored at 338 nm excitation and 450 nm emission wavelengths after separation by ion-exchange HPLC on a 60-5NH2 Polygosil analytical column. The detection limit was 2 pmol for the GSH conjugate of cholesterol epoxide and 6 pmol for the GSH conjugate of oleic acid epoxide. This method allows sensitive determination of all GSH conjugates independent of the chromatographic and spectrophotometric properties of the electrophilic substrates. Using this method we could show for the first time that the endogenous compound oleic acid epoxide is a specific substrate for the cytosolic rat liver GSH S-transferase. The method is applied to the determination of GSH S-transferase activity towards oleic acid epoxide and cholesterol epoxide. 相似文献
Designing natural gas pipelines to safely and efficiently handle unsteady flows, requires knowledge of pressure drop, flowrate and temperature distribution throughout the system. The accurate prediction of these parameters is essential in order to achieve optimum cumulative deliverability, and safe and reliable operation. An Adaptive Method of Lines algorithm is formulated for the solution of Euler system of equations, which fully simulates slow and fast transients. Two test cases present the improvement of the numerical solution from grid adaptation. Good results are obtained both for slow and fast transients simulations proving that the suggested numerical procedure is appropriate for such predictions. To cite this article: E. Tentis et al., C. R. Mecanique 331 (2003).相似文献
New calixarene‐based dendrimers, containing calix[4]arene as the core and different generations of Fréchet‐type poly(benzyl ether) dendrons as building blocks, which possess either Br‐atoms or COOtBu groups at their surface were synthesized and presented herein for the first time. The new calix[4]arene‐cored dendritic macromolecules were fully characterized and found to prefer strictly the cone conformation. 相似文献