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81.
Lars Lauterbach Hongxin Wang Marius Horch Leland B. Gee Yoshitaka Yoda Yoshihito Tanaka Ingo Zebger Oliver Lenz Stephen P. Cramer 《Chemical science》2015,6(2):1055-1060
Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD+-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H2 conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by 57Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD+-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective 13C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors. 相似文献
82.
Vera Krewald Marius Retegan Nicholas Cox Johannes Messinger Wolfgang Lubitz Serena DeBeer Frank Neese Dimitrios A. Pantazis 《Chemical science》2015,6(3):1676-1695
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
83.
84.
Marius Măntoiu 《偏微分方程通讯》2017,42(11):1659-1681
By using commutator methods, we show uniform resolvent estimates and obtain globally smooth operators for self-adjoint injective homogeneous operators H on graded groups, including Rockland operators, sublaplacians, and many others. Left or right invariance is not required. Typically the globally smooth operator has the form T = V|H|1∕2, where V only depends on the homogeneous structure of the group through Sobolev spaces, the homogeneous dimension and the minimal and maximal dilation weights. For stratified groups improvements are obtained, by using a Hardy-type inequality. Some of the results involve refined estimates in terms of real interpolation spaces and are valid in an abstract setting. Even for the commutative group ?N some new classes of partial differential operators are treated. 相似文献
85.
In this paper we use a double penalization procedure in order to reduce a set-valued optimization problem with functional constraints to an unconstrained one. The penalization results are given in several cases: for weak and strong solutions, in global and local settings, and considering two kinds of epigraphical mappings of the set-valued map that defines the constraints. Then necessary and sufficient conditions are obtained separately in terms of Bouligand derivatives of the objective and constraint mappings. 相似文献
86.
Marius Durea Radu Strugariu Christiane Tammer 《Journal of Optimization Theory and Applications》2017,175(3):738-763
The aim of this paper is to address new approaches, in separate ways, to necessary and, respectively, sufficient optimality conditions in constrained vector optimization. In this respect, for the necessary optimality conditions that we derive, we use a kind of vectorial penalization technique, while for the sufficient optimality conditions we make use of an appropriate scalarization method. In both cases, the approaches couple a basic technique (of penalization or scalarization, respectively) with several results in variational analysis and optimization obtained by the authors in the last years. These combinations allow us to arrive to optimality conditions which are, in terms of assumptions made, new. 相似文献
87.
Marius Buliga 《Journal of Elasticity》1998,52(3):201-238
88.
Marius Widerøe Truls Norby Rolf Willestofte Berg 《Journal of solid state chemistry》2011,184(7):1890-1894
A new metal oxyhydride; neodymium oxyhydride, NdHO, has been synthesized from a reactant mixture of metal hydride (CaH2 or NdH3) and neodymium oxide (Nd2O3). The unit cell dimensions decrease smoothly in the series from LaHO, CeHO, PrHO to NdHO, in line with the lanthanide contraction. The crystal structure of NdHO is described on the basis of Rietveld refinement on neutron powder diffraction data:
- Space group: P4/nmm (no. 129, D4h7).
- Axis lengths: a=7.8480(5) Å, c=5.5601(8) Å.
- Volume: V=342.46(6) Å3.
89.
Mewald M Fröhlich R Oestreich M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(34):9406-9414
An axially chiral dihydroborepine with a binaphthyl backbone and a C(6)F(5) substituent at the boron atom was prepared by transmetalation from the corresponding tin precursor. This novel motif was structurally characterized by X-ray diffraction analysis as its THF and its PhCN Lewis acid/base complex. (1)H NMR measurements at variable temperatures of the former adduct revealed a remarkable dynamic behavior in solution. Several more Lewis pairs with oxygen, nitrogen, carbon, and phosphorus σ-donors were synthesized and analyzed by multinuclear NMR spectroscopy. The determination of the borane's Lewis acidity with the Gutmann-Beckett method attests its substantial Lewis acidity [85% with Et(3) PO as well as 74% with Ph(3) PO relative to the parent B(C(6)F(5))(3)]. Representative examples of Si-H bond activation (carbonyl reduction and dehydrogenative Si-O coupling) are included, demonstrating the chemical stability and the synthetic potential of the new chiral boron-based Lewis acid. 相似文献
90.
New historical aspects of the classification, by Cayley and Cremona, of ruled quartic surfaces and the relation to string
models and plaster models are presented. In a ‘modern’ treatment of the classification of ruled quartic surfaces the classical
one is corrected and completed. The string models of Series XIII of some ruled quartic surfaces (manufactured by L. Brill
and by M. Schilling) are based on a result of Rohn concerning curves in
\mathbbP1×\mathbbP1{\mathbb{P}^1\times \mathbb{P}^1} of bi-degree (2, 2). This is given here a conceptional proof. 相似文献