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641.
Perry JL Goldsmith MR Williams TR Radack KP Christensen T Gorham J Pasquinelli MA Toone EJ Beratan DN Simon JD 《Photochemistry and photobiology》2006,82(5):1365-1369
Sudlow Site I of human serum albumin (HSA) is located in subdomain IIA of the protein and serves as a binding cavity for a variety of ligands. In this study, the binding of warfarin (W) is examined using computational techniques and isothermal titration calorimetry (ITC). The structure of the docked warfarin anion (W-) to Site I is similar to that revealed by X-ray crystallography, with a calculated binding constant of 5.8 x 10(5) M(-1). ITC experiments (pH 7.13 and I = 0.1) carried out in three different buffers (MOPs, phosphate and Tris) reveal binding of W- is accompanied by uptake of 0.30+/-0.02 protons from the solvent. This measurement suggests that the binding of W- is stabilized by an ion-pair interaction between protonated H242 and the phenoxide group of W-. 相似文献
642.
Here we report a modular design of self-assembly of DNA nanostructures in a combinatorial approach; a square with approximately 25 nm cavity dimension, a chair with approximately 80 nm in height and a line with approximately 100 nm in length are formed through combinations of four cross-shaped DNA tiles which are kept constant and six variable linker tiles. 相似文献
643.
The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu(3)Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated. 相似文献
644.
A microwave gas chromatography (GC) column oven is engineered to generate a uniform microwave field around an open tubular column with the elimination of cold spots, which are common in a domestic microwave oven. Short cool-down time in microwave heating makes it possible to employ negative temperature programming for the enhanced separation of compounds during the process. The feasibility of negative temperature programming in microwave GC is investigated for the analysis and quantitation of four different pairs of nonvolatile and volatile compounds. The influence of intermediate column cooling rate, holding time in the cooling ramp, and reheating rate after the cooling ramp for enhanced resolution are investigated. The results obtained from negative temperature programming are compared with those from positive temperature programming. Negative temperature programming affords greater resolution of some critical pairs of analytes. 相似文献
645.
Kyle Siegrist 《Journal of Theoretical Probability》2006,19(1):204-220
Let (S,·) be a positive semigroup and T a sub-semigroup of S. In many natural cases, an element can be factored uniquely as x=yz, where and where z is in an associated “quotient space” S/T. If X has an exponential distribution on S, we show that Y and Z are independent and that Y has an exponential distribution on T. We prove a converse when the sub-semigroup is for . Specifically, we show that if Y
t
and Z
t
are independent and Y
t
has an exponential distribution on S
t
for each , then X has an exponential distribution on S. When applied to ([0,∞), +) and , these results unify and extend known results on the quotient and remainder when X is divided by t. 相似文献
646.
Substituted 1,4-dimagnesium reagents were synthesized by the zirconocene-catalyzed reaction of alkenes with ethylmagnesium
reagents in the presence of a methylmagnesium containing additive. Improved selectivity for formation of dimagnesium reagents
over monomagnesium reagents was obtained in the presence of the methylmagnesium containing additive. The ratio of mono- to
dimagnesiated products was extrapolated from the ratio of alkene to diene in the products formed when the reaction was quenched
with allyl bromide. The extent of the increase in the alkene/diene ratio was dependent on the type of organomagnesium halide,
with greatest increases (59%) for the alkylmagnesium chlorides. A mechanism for improved selectivity by suppression of β-hydrogen
abstraction in the catalytic cycle is presented. Quenching the 1,4-dimagnesium reagents with allyl bromide yielded decadienes. 相似文献
647.
648.
We demonstrate a new class of passively temperature stabilized resonant silicon electro-optic modulators. The modulators consist of a ring resonator coupled to a Mach-Zehnder interferometer with tailored thermal properties. We demonstrate 2 GHz continuous modulation over a temperature range of 35 °C and describe the scalability and design rules for such a device. 相似文献
649.
Dr. Kazuto Suzuki Dr. Joshua Kyle Stanfield Dr. Keita Omura Dr. Yuma Shisaka Dr. Shinya Ariyasu Chie Kasai Dr. Yuichiro Aiba Dr. Hiroshi Sugimoto Prof. Dr. Osami Shoji 《Angewandte Chemie (International ed. in English)》2023,62(13):e202215706
Catching the structure of cytochrome P450 enzymes in flagrante is crucial for the development of P450 biocatalysts, as most structures collected are found trapped in a precatalytic conformation. At the heart of P450 catalysis lies Cpd I, a short-lived, highly reactive intermediate, whose recalcitrant nature has thwarted most attempts at capturing catalytically relevant poses of P450s. We report the crystal structure of P450BM3 mimicking the state in the precise moment preceding epoxidation, which is in perfect agreement with the experimentally observed stereoselectivity. This structure was attained by incorporation of the stable Cpd I mimic oxomolybdenum mesoporphyrin IX into P450BM3 in the presence of styrene. The orientation of styrene to the Mo-oxo species in the crystal structures sheds light onto the dynamics involved in the rotation of styrene to present its vinyl group to Cpd I. This method serves as a powerful tool for predicting and modelling the stereoselectivity of P450 reactions. 相似文献
650.
Kyoung Chul Park Prof. Dr. Preecha Kittikhunnatham Dr. Jaewoong Lim Grace C. Thaggard Yuan Liu Dr. Corey R. Martin Dr. Gabrielle A. Leith Donald J. Toler Dr. An T. Ta Dr. Nancy Birkner Dr. Ingrid Lehman-Andino Dr. Alejandra Hernandez-Jimenez Dr. Gregory Morrison Dr. Jake W. Amoroso Prof. Dr. Hans-Conrad zur Loye Dr. Dave P. DiPrete Dr. Mark D. Smith Prof. Dr. Kyle S. Brinkman Prof. Dr. Simon R. Phillpot Prof. Dr. Natalia B. Shustova 《Angewandte Chemie (International ed. in English)》2023,62(5):e202216349
A novel series of heterometallic f-block-frameworks including the first examples of transuranic heterometallic 238U/239Pu-metal–organic frameworks (MOFs) and a novel monometallic 239Pu-analog are reported. In combination with theoretical calculations, we probed the kinetics and thermodynamics of heterometallic actinide(An)-MOF formation and reported the first value of a U-to-Th transmetallation rate. We concluded that formation of uranyl species could be a driving force for solid-state metathesis. Density of states near the Fermi edge, enthalpy of formation, band gap, proton affinity, and thermal/chemical stability were probed as a function of metal ratios. Furthermore, we achieved 97 % of the theoretical maximum capacity for An-integration. These studies shed light on fundamental aspects of actinide chemistry and also foreshadow avenues for the development of emerging classes of An-containing materials, including radioisotope thermoelectric generators or metalloradiopharmaceuticals. 相似文献