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1.
Journal of Thermal Analysis and Calorimetry - The aim of the present work is to characterize the phosphate sludge from two different countries: Morocco and Tunisia, and to study the difference...  相似文献   
2.
The emergence of untreatable drug-resistant strains of Mycobacterium tuberculosis is a major public health problem worldwide, and the identification of new efficient treatments is urgently needed. Mycobacterium tuberculosis cytochrome P450 CYP121A1 is a promising drug target for the treatment of tuberculosis owing to its essential role in mycobacterial growth. Using a rational approach, which includes molecular modelling studies, three series of azole pyrazole derivatives were designed through two synthetic pathways. The synthesized compounds were biologically evaluated for their inhibitory activity towards M. tuberculosis and their protein binding affinity (KD). Series 3 biarylpyrazole imidazole derivatives were the most effective with the isobutyl ( 10 f ) and tert-butyl ( 10 g ) compounds displaying optimal activity (MIC 1.562 μg/mL, KD 0.22 μM ( 10 f ) and 4.81 μM ( 10 g )). The spectroscopic data showed that all the synthesised compounds produced a type II red shift of the heme Soret band indicating either direct binding to heme iron or (where less extensive Soret shifts are observed) putative indirect binding via an interstitial water molecule. Evaluation of biological and physicochemical properties identified the following as requirements for activity: LogP >4, H-bond acceptors/H-bond donors 4/0, number of rotatable bonds 5–6, molecular volume >340 Å3, topological polar surface area <40 Å2.  相似文献   
3.
The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.  相似文献   
4.
We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.  相似文献   
5.
The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to one of the intermediates, but we now highlight the interplay and competition between them.

The combination of potassium tert-butoxide and triethylsilane provides simultaneous access to multiple reactive intermediates, radicals, H-atom donors, hydride donors and electron donors, giving scope for unprecedented reaction outcomes.  相似文献   
6.
Model studies of prebiotic chemistry have revealed compelling routes for the formation of the building blocks of proteins and RNA, but not DNA. Today, deoxynucleotides required for the construction of DNA are produced by reduction of nucleotides catalysed by ribonucleotide reductases, which are radical enzymes. This study considers potential non‐enzymatic routes via intermediate radicals for the ancient formation of deoxynucleotides. In this context, several mechanisms for ribonucleotide reduction, in a putative H2S/HS. environment, are characterized using computational chemistry. A bio‐inspired mechanistic cycle involving a keto intermediate and HSSH production is found to be potentially viable. An alternative pathway, proceeding through an enol intermediate is found to exhibit similar energetic requirements. Non‐cyclical pathways, in which HSS. is generated in the final step instead of HS., show a markedly increased thermodynamic driving force (ca. 70 kJ mol?1) and thus warrant serious consideration in the context of the prebiotic ribonucleotide reduction.  相似文献   
7.
Catalytically active MnOx species have been reported to form in situ from various Mn‐complexes during electrocatalytic and solution‐based water oxidation when employing cerium(IV) ammonium ammonium nitrate (CAN) oxidant as a sacrificial reagent. The full structural characterization of these oxides may be complicated by the presence of support material and lack of a pure bulk phase. For the first time, we show that highly active MnOx catalysts form without supports in situ under photocatalytic conditions. Our most active 4MnOx catalyst (~0.84 mmol O2 mol Mn?1 s?1) forms from a Mn4O4 bearing a metal–organic framework. 4MnOx is characterized by pair distribution function analysis (PDF), Raman spectroscopy, and HR‐TEM as a disordered, layered Mn‐oxide with high surface area (216 m2g?1) and small regions of crystallinity and layer flexibility. In contrast, the SMnOx formed from Mn2+ salt gives an amorphous species of lower surface area (80 m2g?1) and lower activity (~0.15 mmol O2 mol Mn?1 s?1). We compare these catalysts to crystalline hexagonal birnessite, which activates under the same conditions. Full deconvolution of the XPS Mn2p3/2 core levels detects enriched Mn3+ and Mn2+ content on the surfaces, which indicates possible disproportionation/comproportionation surface equilibria.  相似文献   
8.
9.
Using Reaction Mechanism Generator (RMG), we have automatically constructed a detailed mechanism for acetylene pyrolysis, which predicts formation of polycyclic aromatic hydrocarbons (PAHs) up to pyrene. To improve the data available for formation pathways from naphthalene to pyrene, new high‐pressure limit reaction rate coefficients and species thermochemistry were calculated using a combination of electronic structure data from the literature and new quantum calculations. Pressure‐dependent kinetics for the CH potential energy surface calculated by Zádor et al. were incorporated to ensure accurate pathways for acetylene initiation reactions. After adding these new data into the RMG database, a pressure‐dependent mechanism was generated in a single RMG simulation which captures chemistry from C to C. In general, the RMG‐generated model accurately predicts major species profiles in comparison to plug‐flow reactor data from the literature. The primary shortcoming of the model is that formation of anthracene, phenanthrene, and pyrene are underpredicted, and PAHs beyond pyrene are not captured. Reaction path analysis was performed for the RMG model to identify key pathways. Notable conclusions include the importance of accounting for the acetone impurity in acetylene in accurately predicting formation of odd‐carbon species, the remarkably low contribution of acetylene dimerization to vinylacetylene or diacetylene, and the dominance of the hydrogen abstraction CH addition (HACA) mechanism in the formation pathways to all PAH species in the model. This work demonstrates the improved ability of RMG to model PAH formation, while highlighting the need for more kinetics data for elementary reaction pathways to larger PAHs.  相似文献   
10.
This quasi‐experimental study investigated how explicit instruction about multiple modes of representation (MMR) impacted grades 7 (n = 61) and 8 (n = 141) students’ learning and multimodal use on end‐of‐unit assessments. Half of each teacher's (n = 3) students received an intervention consisting of explicit instruction on MMR in science discourse, in addition to regular science instruction enhanced by a focus on MMR; comparison groups of students received regular science instruction. Three ordinary least squares regression models used student demographic variables and whether or not students received the intervention to predict students’ (a) gain scores on end‐of‐unit tests, (b) voluntary use of embedded MMR on unit tests, and (c) retention of science knowledge as measured by a state end‐of‐level criterion‐referenced assessment. Analyses showed that explicit instruction on MMR did not make a significant impact on student gain scores, the amount of embeddedness on unit tests, or end‐of‐level scores. However, Models 2 and 3 showed Hispanics and females used MMR more on end‐of‐unit tests than Whites or males, respectively, whether or not they received the intervention. Hispanics and females scored lower than Whites or males, respectively, on end‐of‐level, multiple‐choice assessments. Implications for classroom teachers and educational researchers in relation to these underserved populations are discussed.  相似文献   
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