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41.
Evert A. Dijksman 《Meccanica》1996,31(4):407-420
New inversors are proposed which are generalizations of the well-known inversor of Peaucellier. It appears that a kite in the Peaucellier cell is replaceable by an arbitrary 4-bar linkage (abhk) whereas the direction and length of the straight line, produced by the inversor, can be manipulated through the particular choice of the relative polar coordinates
of a vertex A of the triangular input link. Formulas are derived for practical inversors with a revolving input link. The ones selected are basically governed by the choice of two transmission angles, 1 and 3, by the length L of the acquired line, as well as by its direction represented by the angle /2- comprised between the line L and the frame.
Sommario Vengono proposti nuovi inversori quali generalizzazioni del ben noto inversore di Peaucellier. Si mostra che un quadrilatero isoscele nella cella di Peaucellier è sostituibile da un'arbitraria connessione a quattro barre, mentre la direzione e la lunghezza della retta, prodotta dall'inversore, possono essere manipolate con la particolare scelta delle relative coordinate polari di un vertice A del collegamento triangolare di input. Vengono derivate formule per inversori funzionali con un collegamento di input rotante. Quelli solezionati sono principalmente governati dalla scelta di due angoli di trasmissione, 1 e 3, dalla lunghezza L della linea ottenuta, così come dalla sua direzione rappresentata dall' angolo /2- compreso tra la linea L ed il riferimento.相似文献
42.
43.
In this paper we apply the methods of supercompactifications and normal subbases to characterize subspaces of compact treelike spaces. This characterization is related to the subbase characterizations of ordered spaces, of trees and of normally supercompact spaces described in [5, 1, 9, 10, 14]. 相似文献
44.
Harmer J Finazzo C Piskorski R Ebner S Duin EC Goenrich M Thauer RK Reiher M Schweiger A Hinderberger D Jaun B 《Journal of the American Chemical Society》2008,130(33):10907-10920
Methanogenic archaea utilize a specific pathway in their metabolism, converting C1 substrates (i.e., CO2) or acetate to methane and thereby providing energy for the cell. Methyl-coenzyme M reductase (MCR) catalyzes the key step in the process, namely methyl-coenzyme M (CH3-S-CoM) plus coenzyme B (HS-CoB) to methane and CoM-S-S-CoB. The active site of MCR contains the nickel porphinoid F430. We report here on the coordinated ligands of the two paramagnetic MCR red2 states, induced when HS-CoM (a reversible competitive inhibitor) and the second substrate HS-CoB or its analogue CH3-S-CoB are added to the enzyme in the active MCR red1 state (Ni(I)F430). Continuous wave and pulse EPR spectroscopy are used to show that the MCR red2a state exhibits a very large proton hyperfine interaction with principal values A((1)H) = [-43,-42,-5] MHz and thus represents formally a Ni(III)F430 hydride complex formed by oxidative addition to Ni(I). In view of the known ability of nickel hydrides to activate methane, and the growing body of evidence for the involvement of MCR in "reverse" methanogenesis (anaerobic oxidation of methane), we believe that the nickel hydride complex reported here could play a key role in helping to understand both the mechanism of "reverse" and "forward" methanogenesis. 相似文献
45.
The determination of absolute configurations of chiral compounds using VCD is performed by comparing measured vibrational circular dichroism (VCD) spectra with calculated spectra. The process is based on two facts: the two enantiomers have rotational strengths of opposite sign, and the absolute configuration of the molecule used in the calculation is known. However, calculations on isolated molecules very often predict VCD intensities of very different magnitude or even different signs compared to the spectra measured in solution. Therefore, we have carefully analyzed what type of changes are induced by complexation of a solvent molecule to a solute. In the theoretical example of benzoyl-benzoic acid (in a particular chiral conformation) hydrogen bonded to the achiral NH3, we distinguish six cases, ranging from no or very small changes in the rotational strengths of solute modes (case A) to changes of sign of rotational strengths (case B), changes in magnitude (case C), nonzero rotational strengths for modes of the achiral solvent ("transfer of chirality", case D), large frequency shifts accompanied by giant enhancements of the IR and VCD intensities of modes involved in hydrogen bonding (case E), and emergence of new peaks (case F). In this work, all of these situations will be discussed and their origin will be elucidated. On the basis of our analysis, we advocate that codes for VCD rotational strength calculation should output for each mode i the angle xi(i) between the electric and magnetic transition dipole moments because only "robust modes" with xi far from 90 degrees should be used for the determination of the absolute configuration. 相似文献
46.
47.
Leenders EJ Guidoni L Röthlisberger U Vreede J Bolhuis PG Meijer EJ 《The journal of physical chemistry. B》2007,111(14):3765-3773
The photoactive yellow protein (PYP) acts as a light sensor to its bacterial host: it responds to light by changing shape. After excitation by blue light, PYP undergoes several transformations, to partially unfold into its signaling state. One of the crucial steps in this photocycle is the protonation of p-coumaric acid after excitation and isomerization of this chromophore. Experimentalists still debate on the nature of the proton donor and on whether it donates the hydrogen directly or indirectly. To obtain better knowledge of the mechanism, we studied this proton transfer using Car-Parrinello molecular dynamics, classical molecular dynamics, and computer simulations combining these two methods (quantum mechanics/molecular mechanics, QMMM). The simulations reproduce the chromophore structure and hydrogen-bond network of the protein measured by X-ray crystallography and NMR. When the chromophore is protonated, it leaves the assumed proton donor, glutamic acid 46, with a negative charge in a hydrophobic environment. We show that the stabilization of this charge is a very important factor in the mechanism of protonation. Protonation frequently occurs in simplified ab initio simulations of the chromophore binding pocket in vacuum, where amino acids can easily hydrogen bond to Glu46. When the complete protein environment is incorporated in a QMMM simulation on the complete protein, no proton transfer is observed within 14 ps. The hydrogen-bond rearrangements in this time span are not sufficient to stabilize the new protonation state. Force field molecular dynamics simulations on a much longer time scale have shown which internal rearrangements of the protein are needed. Combining these simulations with more QMMM calculations enabled us to check the stability of protonation states and clarify the initial requirements for the proton transfer in PYP. 相似文献
48.
Dhage P Samokhvalov A Repala D Duin EC Tatarchuk BJ 《Physical chemistry chemical physics : PCCP》2011,13(6):2179-2187
Fe- and Mn-promoted H(2)S sorbents Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) (x, y = 0, 0.025) for desulfurization of model fuel reformates at room temperature were prepared, tested and characterized. Sulfur uptake capacity at 25 °C significantly exceeds that of both commercial unsupported ZnO sorbents and un-promoted supported ZnO/SiO(2) sorbents. Sulfur capacity and breakthrough characteristics remain satisfactory after multiple (~10) cycles of adsorption/regeneration, with regeneration performed by a simple and robust heating in air. XRD shows that both "calcined" and "spent" sorbents contain nano-dispersed ZnO, and XPS confirms conversion of ZnO to ZnS. "Calcined" sorbent contains Fe(3+) and Mn(3+) that are reduced to Mn(2+) upon reaction with H(2)S, but not with H(2). Operando ESR is used for the first time to study dynamics of reduction of Mn(3+) promoter sites simultaneously with measuring sulfidation dynamics of the Fe(x)-Mn(y)-Zn(1-x-y)O/SiO(2) sorbent. Fe cations are believed to occupy the surface of supported ZnO nanocrystallites, while Mn cations are distributed within ZnO. 相似文献
49.
The concept of robustness of rotational strengths of vibrational modes in a VCD spectrum has been introduced as an aid in assignment of the absolute configuration with the help of the VCD spectrum. The criteria for robustness have been based on the distribution around 90° of the angles ξ(i) between electric and magnetic transition dipoles of all the modes i of a molecule. The angles ξ(i) (not, of course, the rotational strengths) are, however, dependent on the choice of origin. The derived criteria are for the center of mass chosen as the origin of the coordinate system. We stress in this note that application of the derived criteria assumes that excessive translation of the coordinate origin is not applied. Although the ξ(i) angles are not very sensitive to the position of the origin, very small displacements (a few ?) are not a problem, excessive translation of the origin does have considerable effect on the ξ(i) angles. In this note we quantify this effect and demonstrate how the distribution of ξ(i) angles is affected. Although it is possible to recalibrate the robustness criteria for the angles for a specific (large) displacement, we recommend that such displacement simply be avoided. It is to be noted that some modeling software does yield output with excessively displaced coordinate origin; this should be checked and corrected. 相似文献
50.
Hoek-van den Hil EF Beekmann K Keijer J Hollman PC Rietjens IM van Schothorst EM 《Analytical and bioanalytical chemistry》2012,402(3):1389-1392
Flavonoids are bioactive food compounds with potential lipid-lowering effects. Commercially available enzymatic assays are
widely used to determine free fatty acid (FFA) and triglyceride (TG) levels both in vivo in plasma or serum and in vitro in
cell culture medium or cell lysate. However, we have observed that various flavonoids interfere with peroxidases used in these
enzymatic assays, resulting in incorrect lower FFA and TG levels than actually present. Furthermore, addition of isorhamnetin
or the major metabolite of the flavonoid quercetin in human and rat plasma, quercetin-3-O-glucuronide, to murine serum also resulted in a significant reduction of the detected TG levels, while a trend was seen for
FFA levels. It is concluded that when applying these assays, vigilance is needed and alternative analytical methods, directly
assessing FFA or TG levels, should be used for studying the biological effects of flavonoids on FFA and TG levels. 相似文献