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101.
Chen Zhou Matthew R. Hermes Dihua Wu Jie J. Bao Riddhish Pandharkar Daniel S. King Dayou Zhang Thais R. Scott Aleksandr O. Lykhin Laura Gagliardi Donald G. Truhlar 《Chemical science》2022,13(26):7685
Strong electron correlation plays an important role in transition-metal and heavy-metal chemistry, magnetic molecules, bond breaking, biradicals, excited states, and many functional materials, but it provides a significant challenge for modern electronic structure theory. The treatment of strongly correlated systems usually requires a multireference method to adequately describe spin densities and near-degeneracy correlation. However, quantitative computation of dynamic correlation with multireference wave functions is often difficult or impractical. Multiconfiguration pair-density functional theory (MC-PDFT) provides a way to blend multiconfiguration wave function theory and density functional theory to quantitatively treat both near-degeneracy correlation and dynamic correlation in strongly correlated systems; it is more affordable than multireference perturbation theory, multireference configuration interaction, or multireference coupled cluster theory and more accurate for many properties than Kohn–Sham density functional theory. This perspective article provides a brief introduction to strongly correlated systems and previously reviewed progress on MC-PDFT followed by a discussion of several recent developments and applications of MC-PDFT and related methods, including localized-active-space MC-PDFT, generalized active-space MC-PDFT, density-matrix-renormalization-group MC-PDFT, hybrid MC-PDFT, multistate MC-PDFT, spin–orbit coupling, analytic gradients, and dipole moments. We also review the more recently introduced multiconfiguration nonclassical-energy functional theory (MC-NEFT), which is like MC-PDFT but allows for other ingredients in the nonclassical-energy functional. We discuss two new kinds of MC-NEFT methods, namely multiconfiguration density coherence functional theory and machine-learned functionals.This feature article overviews recent work on active spaces, matrix product reference states, treatment of quasidegeneracy, hybrid theory, density-coherence functionals, machine-learned functionals, spin–orbit coupling, gradients, and dipole moments. 相似文献
102.
Vieira Renata Leia Demario Gaglieri Caroline de Oliveira Cristina Soltovski Ferreira Laura Teófilo Schnitzler Egon Bannach Gilbert 《Journal of Thermal Analysis and Calorimetry》2021,144(3):689-697
Journal of Thermal Analysis and Calorimetry - Buckwheat starch is an alternative source to supply the high global demand for starch. The properties of starch can be modified through chemical and... 相似文献
103.
Claudia Curcio Silvia Brugiapaglia Sara Bulfamante Laura Follia Paola Cappello Francesco Novelli 《Molecules (Basel, Switzerland)》2021,26(6)
Pancreatic ductal adenocarcinoma (PDA) is one of the most lethal forms of human cancer, characterized by unrestrained progression, invasiveness and treatment resistance. To date, there are limited curative options, with surgical resection as the only effective strategy, hence the urgent need to discover novel therapies. A platform of onco-immunology targets is represented by molecules that play a role in the reprogrammed cellular metabolism as one hallmark of cancer. Due to the hypoxic tumor microenvironment (TME), PDA cells display an altered glucose metabolism—resulting in its increased uptake—and a higher glycolytic rate, which leads to lactate accumulation and them acting as fuel for cancer cells. The consequent acidification of the TME results in immunosuppression, which impairs the antitumor immunity. This review analyzes the genetic background and the emerging glycolytic enzymes that are involved in tumor progression, development and metastasis, and how this represents feasible therapeutic targets to counteract PDA. In particular, as the overexpressed or mutated glycolytic enzymes stimulate both humoral and cellular immune responses, we will discuss their possible exploitation as immunological targets in anti-PDA therapeutic strategies. 相似文献
104.
Prof. María Laura Uhrig Erwin W. Mora Flores Prof. Al Postigo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(29):7813-7825
Fluoroalkyl-substituted carbohydrates play relevant roles in diverse areas such as supramolecular chemistry, glycoconjugation, liquid crystals, and surfactants, with direct applications as wetting, antifreeze, and coating agents. In light of these promising applications, new methodologies for the late-stage incorporation of fluoroalkyl RF groups into carbohydrates and derivatives are herein presented as they are relevant to the synthetic carbohydrate community. Previously reviewed protocols for the installation of RF groups onto carbohydrates and derivatives will be succinctly summarized in the light of the new achievements. Fluoroalkyl-substituted iminosugars, on the other hand, are also interesting glycomimetic derivatives with prominent roles as glycosidases and glycosyltransferases inhibitors, as has recently been demonstrated. Also, they positively contribute to the study of sugar–protein interactions and enzyme mechanisms. New advances in the syntheses of fluoroalkyl-substituted iminosugars will also be presented here. 相似文献
105.
Laura Parejo Dr. Mahdi Chaari Sara Santiago Dr. Gonzalo Guirado Prof. Francesc Teixidor Dr. Rosario Núñez Dr. Jordi Hernando 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):270-280
Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C2B9H11)2]−, whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C2B9H11)2]− very appealing to participate in electron-transfer processes. In this work, [Co(C2B9H11)2]− is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C2B9H11)2]− with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state. 相似文献
106.
Dr. Maria Laura Tummino Dr. Roberto Nisticò Dr. Chiara Riedo Prof. Debora Fabbri Prof. Marta Cerruti Prof. Giuliana Magnacca 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):660-668
Biowaste-derived substances isolated from green compost (BBS-GC) are environmentally friendly reactants similar to humic substances, which contain multiple functionalities, that are suitable for adsorbing different kinds of pollutants in wastewater. Herein, sodium alginate (derived from brown algae) cross-linked with both Ca2+ ions and BBS-GC in the form of hydrogels and dried films are proposed as green, easy-to-form, and handleable materials for tertiary water treatments. The results show that both hydrogels and films are mechanically stable and can effectively remove differently charged dyes through an adsorption mechanism that can be described by the Freundlich model. BBS-GC-containing gels always performed better than samples prepared without BBS-GC, revealing that such unconventional materials can integrate waste valorization and water decontamination, potentially providing social and environmental benefits. 相似文献
107.
Saidbakhrom Saidjalolov Dr. Zainab Edoo Dr. Matthieu Fonvielle Louis Mayer Dr. Laura Iannazzo Dr. Michel Arthur Prof. Dr. Mélanie Etheve-Quelquejeu Dr. Emmanuelle Braud 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(10):3542-3551
The carbapenem class of β-lactams has been optimized against Gram-negative bacteria producing extended-spectrum β-lactamases by introducing substituents at position C2. Carbapenems are currently investigated for the treatment of tuberculosis as these drugs are potent covalent inhibitors of l,d -transpeptidases involved in mycobacterial cell wall assembly. The optimization of carbapenems for inactivation of these unusual targets is sought herein by exploiting the nucleophilicity of the C8 hydroxyl group to introduce chemical diversity. As β-lactams are structure analogs of peptidoglycan precursors, the substituents were chosen to increase similarity between the drug and the substrate. Fourteen peptido-carbapenems were efficiently synthesized. They were more effective than the reference drug, meropenem, owing to the positive impact of a phenethylthio substituent introduced at position C2 but the peptidomimetics added at position C8 did not further improve the activity. Thus, position C8 can be modified to modulate the pharmacokinetic properties of highly efficient carbapenems. 相似文献
108.
Laura Pop Pierrik Lassalas László Csaba Bencze Monica Ioana Toşa Botond Nagy Florin Dan Irimie Christophe Hoarau 《Tetrahedron: Asymmetry》2012,23(6-7):474-481
Stereoselective preparative enzymatic acylation and hydrolysis/methanolysis of various C-substituted rac-thiazol-2-yl-methanols were achieved for the preparation of enantiopure or enantiomerically enriched, naturally occurring 2-hydroxymethylthiazoles. The absolute configurations of the resulting secondary alcohols were determined by a detailed 1H NMR study of Mosher’s derivatives. 相似文献
109.
Maria G. Bettoli Lorenzo Cantelli Damiano Quarin Marzia Ravanelli Laura Tositti Ottavio Tubertini 《International journal of environmental analytical chemistry》2013,93(3-4):321-330
Abstract 210Pb is widely used to determine accumulation rates in order to obtain a time scale in environmental samples. The most accurate method uses the determination of 210Pb via its grand-daughter 210Po by alpha spectrometry. Unfortunately this method requires a complex wet-chemistry procedure to achieve the separation of 210Po from its matrix. In this work a simplified procedure for the chemical separation of 210Po is proposed and applied to three marine sediment cores and a 10 m snow core collected in Antarctica. The calculated sedimentation rates for marine sediments range from 0.053 to 0.071 cm y?1. The mean annual accumulation rate for the snow is 16.6 cm y?1 w.e. A comparison with literature data in the same region is given. 相似文献
110.
Nicolás D. Gómez Violeta D'Accurso V. Mariana Freytes Francisco A. Manzano Jorge Codnia M. Laura Azcárate 《国际化学动力学杂志》2013,45(5):306-313
An experimental setup that coupled IR multiple‐photon dissociation (IRMPD) and laser‐induced fluorescence (LIF) techniques was implemented to study the kinetics of the recombination reaction of dichlorocarbene radicals, CCl2, in an Ar bath. The CCl2 radicals were generated by IRMPD of CDCl3. The time dependence of the CCl2 radicals’ concentration in the presence of Ar was determined by LIF. The experimental conditions achieved allowed us to associate the decrease in the concentration of radicals to the self‐recombination reaction to form C2Cl4. The rate constant for this reaction was determined in both the falloff and the high‐pressure regimes at room temperature. The values obtained were k0 = (2.23 ± 0.89) × 10?29 cm6 molecules?2 s?1 and k∞ = (6.73 ± 0.23) × 10?13 cm3 molecules?1 s?1, respectively. 相似文献