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31.
金属配合物中的水簇研究为研究宏观意义上的水以及与蛋白质分子有关的水分子提供了有效途径。本文合成了一个含有阴离子水簇的带状超分子配合物[Co(2,2-bipy)2(N3)2](N3)0.5Cl0.5·2H2O(1,2, 2-bipy=2, 2-联吡啶)。单晶结构解析表明,配合物属于三斜晶系,P-1空间群,晶胞参数为:a=0.822 54(7) nm,b=1.175 58(9) nm,c=1.237 06(10) nm,α=91.379 0(10)°,β=92.151 0(10)°,γ=108.119 0(10)°,V=1.135 27(16) nm3,由一个单核[Co(2,2-bipy)2(N3)2]+配合物阳离子、两个非配位水分子、0.5个游离的叠氮离子和0.5个氯离子组成,叠氮离子和氯离子位置无序,占有率各为50%。两个客体水分子通过强烈的分子间氢键作用形成了环状水四聚体,且与无序的N-3和Cl-通过氢键作用形成了一个[(H2O)4(N3)Cl]2- 阴离子水簇。此外,本文基于密度泛函理论(DFT)对配合物[Co(2,2-bipy)2(N3)2]+阳离子进行了量子化学计算,分析了其单点能和原子电荷,并计算了中心金属离子的氧化态,计算结果与实验相吻合。 相似文献
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Dionysios Raptis Charalampos Livas George Stavroglou Rafaela Maria Giappa Emmanuel Tylianakis Taxiarchis Stergiannakos George E. Froudakis 《Molecules (Basel, Switzerland)》2022,27(11)
The interaction strength of nitrogen dioxide (NO2) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal–organic frameworks (MOFs) in order to enhance their uptake of NO2 molecules. Among the functional groups considered, the highest interaction energy with NO2 (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSO3H) at the RI-DSD-BLYP/def2-TZVPP level of theory—an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO2 interactions (-OSO3H, -PO3H2, -OPO3H2) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO2 uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO2 uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO2 uptake performance not only in MOFs but also in various other porous materials. 相似文献
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Rui Li Xin Gou Xinyan Li Hainuo Wang Haibo Ruan Yuting Xiong Xianlun Tang Yuanyuan Li Ping-an Yang 《Molecules (Basel, Switzerland)》2022,27(15)
Flexible strain sensors, when considering high sensitivity and a large strain range, have become a key requirement for current robotic applications. However, it is still a thorny issue to take both factors into consideration at the same time. Here, we report a sandwich-structured strain sensor based on Fe nanowires (Fe NWs) that has a high GF (37–53) while taking into account a large strain range (15–57.5%), low hysteresis (2.45%), stability, and low cost with an areal density of Fe NWs of 4.4 mg/cm2. Additionally, the relationship between the contact point of the conductive network, the output resistance, and the areal density of the sensing unit is analyzed. Microscopically, the contact points of the conductive network directly affect the sensor output resistance distribution, thereby affecting the gauge factor (GF) of the sensor. Macroscopically, the areal density and the output resistivity of the strain sensor have the opposite percolation theory, which affects its linearity performance. At the same time, there is a positive correlation between the areal density and the contact point: when the stretching amount is constant, it theoretically shows that the areal density affects the GF. When the areal density reaches this percolation threshold range, the sensing performance is the best. This will lay the foundation for rapid applications in wearable robots. 相似文献
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Yue Jia Tingji Yao Guangcai Ma Qi Xu Xianglong Zhao Hui Ding Xiaoxuan Wei Haiying Yu Zhiguo Wang 《Molecules (Basel, Switzerland)》2022,27(9)
Biotransformation of organophosphorus flame retardants (OPFRs) mediated by cytochrome P450 enzymes (CYPs) has a potential correlation with their toxicological effects on humans. In this work, we employed five typical OPFRs including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), and 2-ethylhexyl diphenyl phosphate (EHDPHP), and performed density functional theory (DFT) calculations to clarify the CYP-catalyzed biotransformation of five OPFRs to their diester metabolites. The DFT results show that the reaction mechanism consists of Cα-hydroxylation and O-dealkylation steps, and the biotransformation activities of five OPFRs may follow the order of TCEP ≈ TEP ≈ EHDPHP > TCIPP > TDCIPP. We further performed molecular dynamics (MD) simulations to unravel the binding interactions of five OPFRs in the CYP3A4 isoform. Binding mode analyses demonstrate that CYP3A4-mediated metabolism of TDCIPP, TCIPP, TCEP, and TEP can produce the diester metabolites, while EHDPHP metabolism may generate para-hydroxyEHDPHP as the primary metabolite. Moreover, the EHDPHP and TDCIPP have higher binding potential to CYP3A4 than TCIPP, TCEP, and TEP. This work reports the biotransformation profiles and binding features of five OPFRs in CYP, which can provide meaningful clues for the further studies of the metabolic fates of OPFRs and toxicological effects associated with the relevant metabolites. 相似文献
38.
Deformed Hartree-Fock calculations are performed for some light nuclei in a large configuration space consisting of first
four major shells. The interaction employed is the modified Skyrme interaction in which the deformed density is replaced by
the band averaged scalar density that makes the Hamiltonian rotationally invariant rendering the spectroscopic calculations
feasible. It is shown that the introduction of density dependence spreads out the energy spectra and that the Skyrme variant
SIV which has a weak density dependence gives best overall agreement for energy spectra and the available data for the electromagnetic
properties of the nuclei studied. It is found that the maximum contribution to the energy of any state in the low lying spectrum
comes from thes-state attractive ands-state repulsive parts of the Skyrme interaction. It is also shown that when two-body density dependent version of Skyrme
interaction is used, the Koopmans theorem no longer holds. 相似文献
39.
Effects of Organic Acids on the Release of Fruity Esters in Water: An Insight at the Molecular Level
It is well known that organic acids (OAs) could affect the flavour of fruit juices and beverages. However, the molecular mechanism of aroma release is still unclear. In this study, the effects of citric acid (CA), L-(-)-malic acid (MA) and L-lactic acid (LA) on the release of six selected esters and their sensory perception were investigated by means of HS-GC-MS analyses and odour detection threshold determination, respectively. Meanwhile, the density functional theory (DFT) calculation was employed to explore the interaction modes between esters and OAs. HS-GC-MS analyses showed that the concentration and the type of OAs regulated the release of esters. The results were basically consistent with the detection threshold change of those esters. The DFT calculation suggested that the main intermolecular interaction was hydrogen bonds, and several esters could form a ternary ring structure with OAs through hydrogen bonds. The interactions can induce the different release behaviours of esters in OAs water solution. The number of carboxyl functional groups in OAs and the spatial conformation of esters appeared to influence the magnitude of the interaction. The above results demonstrated the mechanism of OAs affecting the release of esters and indicated a possible flavour control way by using different OAs and OA concentrations. 相似文献
40.