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71.
Xin-Yi Du Prof. Dr. Quan-Song Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(56):12891-12897
N,C-chelate organoboron compounds are widely employed as photoresponsive and optoelectronic materials due to their efficient photochromic reactivity. It was found in experiments that two diphenyl-substituted organoboron compounds, namely B(ppy)Ph2 (ppy=2-phenylpyridyl) and B(iba)Ph2 (iba=N-isopropylbenzylideneamine), show distinct photochemical reactivity. B(ppy)Ph2 is inert on irradiation, whereas B(iba)Ph2 undergoes photoinduced transformations, yielding BN-cyclohepta-1,3,5-triene via a borirane intermediate. In this work, the complete active space self-consistent field and its second-order perturbation (CASPT2//CASSCF) methods were used to investigate the photoinduced reaction mechanisms of B(ppy)Ph2 and B(iba)Ph2. The calculations showed that the two compounds isomerize to borirane in the same way by passing a transition state in the S1 state and a conical intersection between the S1 and S0 states. The energy barriers in the S1 state of 0.54 and 0.26 eV for B(ppy)Ph2 and B(iba)Ph2, respectively, were explained by analyzing the charge distributions of minima in S0 and S1 states. The results provide helpful insights into the excited-state dynamics of organoboron compounds, which could assist in rational design of boron-based photoresponsive materials. 相似文献
72.
Prof. Wook Lee Prof. Spiridoula Matsika 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(62):14181-14186
Cyclobutane pyrimidine dimer (CPD) is a photoproduct formed by two stacked pyrimidine bases through a cycloaddition reaction upon irradiation. Owing to its close association with skin cancer, the mechanism of CPD formation has been studied thoroughly. Among many aspects of CPD, its formation involving 5-methylcytosine (5mC) has been of special interest because the CPD yield is known to increase with C5-methylation of cytosine. In this work, high-level quantum mechanics/molecular mechanics (QM/MM) calculations are used to examine a previously experimentally detected pathway for CPD formation in hetero (thymine-cytosine and thymine-5mC) dipyrimidines, which is facilitated through intersystem crossing in thymine and formation of a triplet biradical intermediate. A DNA duplex model system containing a core sequence TmCG or TCG is used. The stabilization of a radical center in the biradical intermediate by the methyl group of 5mC can lead to increased CPD yield in TmCG compared with its non-methylated counterpart, TCG, thereby suggesting the existence of a new pathway of CPD formation enhanced by 5mC. 相似文献
73.
Yeray Dorca Roberto Sánchez-Naya Jesús Cerdá Dr. Joaquín Calbo Dr. Juan Aragó Dr. Rafael Gómez Prof. Dr. Enrique Ortí Prof. Dr. Luis Sánchez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(64):14700-14707
A comparative investigation of the chiral amplification features of a series of three families of C3-symmetric tricarboxamides, 1,3,5-triphenylbenzenetricarboxamides (TPBAs), benzenetricarboxamides (BTAs) and oligo(phenylene ethynylene) tricarboxamides (OPE-TAs), is here reported. As previously observed for BTAs and OPE-TAs, a similar dichroic response is obtained for TPBAs decorated with one, two or three chiral side chains bearing stereogenic centers, thus confirming the efficient transfer of point chirality to the supramolecular helical aggregates. Unlike BTAs and OPE-TAs, the chiral amplification ability of TPBAs in majority rules experiments shows a negligible dependence on the number of chiral centers per monomeric unit, and stands the largest among the series of tricarboxamides. Detailed experimental and theoretical studies demonstrate that the rotation angle between the TPBA units in the helical stack is intermediate to that observed for BTAs and OPE-TAs. This feature strongly conditions the steric interactions between vicinal molecules in the stack and the final chiral amplification outcome. Furthermore, theoretical calculations show that achiral side chains favor the interdigitation of the helical aggregates and thereby the formation of bundle superstructures. 相似文献
74.
Prof. Allan J. Canty Prof. Alireza Ariafard Prof. Gerard van Koten 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15629-15635
Density Functional Theory studies of square-planar PtII pincer structures, (4-Z-NCN)PtCl ([4-Z-NCN]−=[4-Z-2,6-(Me2NCH2)2C6H2-N,C,N]−, Z=H, NO2, CF3, CO2H, CHO, Cl, Br, I, F, SMe, SiMe3, tBu, OH, NH2, NMe2), enable characterisation of mesomerism for the pincer-Pt interaction. Relationships between Hammett σp substituent parameters of Z and DFT data obtained from NBO6 and AOMix computation are used to probe the interaction of the 5dyz orbital of platinum with π-orbitals of the arene ring. Analogous computation for 2,6-(Me2CH2)2C6H3Z (Z=H, CF3, CHO, Cl, Br, I, F, SMe, SiMe3, tBu, OH, NH2) and (4-H-NCN)PtZ allows an estimation of the relative substituent effects of “(CH2NMe2)2PtZ” on π-delocalisation in the pincer system. 相似文献
75.
Dr. Imma Escofet Helena Armengol-Relats Dr. Hanna Bruss Dr. Maria Besora Prof. Dr. Antonio M. Echavarren 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(67):15738-15745
The nature of cyclopropyl gold(I) carbene-type intermediates has been reexamined as part of a mechanistic study on the formation of cis- or trans-fused bicyclo[5.1.0]octanes in a gold(I)-catalyzed cascade reaction. Benchmark of DFT methods together with QTAIM theory and NBO analysis confirms the formation of distinct intermediates with carbenic or carbocationic structures in the cycloisomerizations of enynes. 相似文献
76.
77.
Erix W. Hernández-Rodríguez Andrés M. Escorcia Marc W. van der Kamp Ana L. Montero-Alejo Julio Caballero 《Journal of computational chemistry》2020,41(26):2278-2295
Evaluating the availability of molecular oxygen (O2) and energy of excited states in the retinal binding site of rhodopsin is a crucial challenging first step to understand photosensitizing reactions in wild-type (WT) and mutant rhodopsins by absorbing visible light. In the present work, energies of the ground and excited states related to 11-cis-retinal and the O2 accessibility to the β-ionone ring are evaluated inside WT and human M207R mutant rhodopsins. Putative O2 pathways within rhodopsins are identified by using molecular dynamics simulations, Voronoi-diagram analysis, and implicit ligand sampling while retinal energetic properties are investigated through density functional theory, and quantum mechanical/molecular mechanical methods. Here, the predictions reveal that an amino acid substitution can lead to enough energy and O2 accessibility in the core hosting retinal of mutant rhodopsins to favor the photosensitized singlet oxygen generation, which can be useful in understanding retinal degeneration mechanisms and in designing blue-lighting-absorbing proteic photosensitizers. 相似文献
78.
Ming-Tsz Chen Yu-Yang Chen Guan-Lin Li Kai-Wen Chou Ching-Han Hu Guo-Cyuan Huang Chi-Tien Chen 《应用有机金属化学》2020,34(4):e5464
This paper describes the effect of solvent-induced synthetic routes of aluminium pendant oxazoline-amido-phenolate complexes. Treatment of ligand precursor L with AlMe3 in a 1:1 ratio in diethyl ether yielded the four-coordinated complex (LAlMe)2. Reaction of ligand precursor L with AlMe3 in a 1:2 ratio in hexane generated the four-coordinated complex L(AlMe2)2. A novel transformation mode occurred from L(AlMe2)2 to (LAlMe)2 when using diethyl ether or tetrahydrofuran as solvent. A density functional theory computational study also supports a plausible mechanism. All results were supported by spectroscopic data and in agreement with single-crystal X-ray diffraction structural analysis. 相似文献
79.
A new series of transition-metal complexes of Schiff base ligand containing the amino mercapto triazole moiety ( HL ) was prepared. The Schiff base and its metal complexes were elucidated by different spectroscopic techniques (infrared [IR], 1H nuclear magnetic resonance, UV–Visible, mass, and electron spin resonance [ESR]), and magnetic moment and thermal studies. Quantum chemical calculations have been carried out to study the structure of the ligand and some of its complexes. The IR spectra showed that the ligand is chelated with the metal ion in a neutral, tridentate, and bidentate manner using NOS and NO donors in complexes 1 – 6 , 10–12 , and 7 and 8 , respectively, whereas it behaves in a monobasic tridentate fashion using NOS donor sites in copper(II) nitrate complex ( 9 ). The magnetic moment and electronic spectra data revealed octahedral and square pyramidal geometries for complexes 2 , 11 , 12 , and 5 – 8 and 10 , respectively. However, the other complexes were found to have tetrahedral ( 4 ), trigonal bipyramidal ( 1 and 3 ), and square planar ( 9 ) structures. Thermal studies revealed that the chelates with different crystallized solvents undergo different types of interactions and the decomposition pathway ended with the formation of metal oxygen (MO) and metal sulfur (MS) as final products. The ESR spectrum of copper(II) complex 10 is axial in nature with hyperfine splitting with 2B1g as a ground state. By contrast, complexes 7 and 8 undergo distortion around the Cu(II) center, affording rhombic ESR spectra. The HL ligand and some of its complexes were screened against two bacterial species. Data showed that complex 12 demonstrated a better antibacterial activity than HL ligand and other chelates. 相似文献
80.
Dr. Sébastien Lemouzy Florian Cuminet Dimitri Berne Dr. Sylvain Caillol Dr. Vincent Ladmiral Prof. Rinaldo Poli Dr. Eric Leclerc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202201135
Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate. 相似文献