全文获取类型
收费全文 | 14431篇 |
免费 | 2971篇 |
国内免费 | 2268篇 |
专业分类
化学 | 7766篇 |
晶体学 | 182篇 |
力学 | 1469篇 |
综合类 | 149篇 |
数学 | 1000篇 |
物理学 | 9104篇 |
出版年
2024年 | 19篇 |
2023年 | 137篇 |
2022年 | 403篇 |
2021年 | 498篇 |
2020年 | 556篇 |
2019年 | 466篇 |
2018年 | 464篇 |
2017年 | 599篇 |
2016年 | 683篇 |
2015年 | 528篇 |
2014年 | 818篇 |
2013年 | 1262篇 |
2012年 | 947篇 |
2011年 | 1017篇 |
2010年 | 863篇 |
2009年 | 966篇 |
2008年 | 1012篇 |
2007年 | 908篇 |
2006年 | 943篇 |
2005年 | 747篇 |
2004年 | 736篇 |
2003年 | 631篇 |
2002年 | 544篇 |
2001年 | 522篇 |
2000年 | 467篇 |
1999年 | 339篇 |
1998年 | 383篇 |
1997年 | 307篇 |
1996年 | 268篇 |
1995年 | 240篇 |
1994年 | 223篇 |
1993年 | 193篇 |
1992年 | 177篇 |
1991年 | 129篇 |
1990年 | 112篇 |
1989年 | 95篇 |
1988年 | 106篇 |
1987年 | 71篇 |
1986年 | 50篇 |
1985年 | 39篇 |
1984年 | 46篇 |
1983年 | 17篇 |
1982年 | 32篇 |
1981年 | 20篇 |
1980年 | 13篇 |
1979年 | 11篇 |
1978年 | 18篇 |
1977年 | 9篇 |
1975年 | 5篇 |
1973年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 406 毫秒
961.
Hongyun Ma Hongwu Chen Mingmao Wu Fengyao Chi Feng Liu Jiaxin Bai Huhu Cheng Chun Li Liangti Qu 《Angewandte Chemie (International ed. in English)》2020,59(34):14541-14549
Capacitive energy storage has advantages of high power density, long lifespan, and good safety, but is restricted by low energy density. Inspired by the charge storage mechanism of batteries, a spatial charge density (SCD) maximization strategy is developed to compensate this shortage by densely and neatly packing ionic charges in capacitive materials. A record high SCD (ca. 550 C cm?3) was achieved by balancing the valance and size of charge‐carrier ions and matching the ion sizes with the pore structure of electrode materials, nearly five times higher than those of conventional ones (ca. 120 C cm?3). The maximization of SCD was confirmed by Monte Carlo calculations, molecular dynamics simulations, and in situ electrochemical Raman spectroscopy. A full‐cell supercapacitor was further constructed; it delivers an ultrahigh energy density of 165 Wh L?1 at a power density of 150 WL?1 and retains 120 Wh L?1 even at 36 kW L?1, opening a pathway towards high‐energy‐density capacitive energy storage. 相似文献
962.
Shotaro Hayashi Fumitaka Ishiwari Takanori Fukushima Shohei Mikage Yutaka Imamura Motomichi Tashiro Michio Katouda 《Angewandte Chemie (International ed. in English)》2020,59(37):16195-16201
Elastic organic crystals have attracted considerable attention as next‐generation flexible smart materials. However, the detailed information on both molecular packing change and macroscopic mechanical crystal deformations upon applied stress is still insufficient. Herein, we report that fluorescent single crystals of 9,10‐dibromoanthracene are elastically bendable and stretchable, which allows a detailed investigation of the deformation behavior. We clearly observed a Poisson effect for the crystal, where the short axes (b and c‐axes) of the crystal are contracted upon elongation along the long axis (a‐axis). Moreover, we found that the Poisson's ratios along the b‐axis and c‐axis are largely different. Theoretical molecular simulation suggests that the tilting motion of the anthracene may be responsible for the large deformation along the c‐axis. Spatially resolved photoluminescence (PL) measurement of the bent elastic crystals reveals that the PL spectra at the outer (elongated), central (neutral), and inner (contracted) sides are different from each other. 相似文献
963.
Morteza Rezaei Talarposhti Tristan Asset Samuel T. Garcia Yechuan Chen Sergio Herrera Sheng Dai Eric J. Peterson Kateryna Artyushkova Iryna Zenyuk Plamen Atanassov 《Chemphyschem》2020,21(12):1331-1339
We investigated the oxygen reduction reaction (ORR) mechanism on Pt nanoparticles (NPs) dispersed on several carbon blacks with various physicochemical properties (i. e. specific surface ranging from 80 to 900 m2 g−1, different graphitization degree, etc.). Using the kinetic isotope effect (KIE) along with various electrochemical characterizations, we determined that the rate determining step (RDS) of the ORR is a proton-independent step when the density of Pt NPs on the surface of the carbon support is high. Upon decrease of the density of Pt NPs on the surface, the RDS of the ORR starts involving a proton, as denoted by an increase of the KIE >1. This underlined the critical role played by the carbon support in the oxygen reduction reaction electrocatalysis by Pt supported on high surface area carbon. 相似文献
964.
Shao-Fang Xing Man Lin Yu-Rong Wang Tuo Chang Wei-Ye Cui 《Natural product research》2020,34(5):651-658
AbstractThree novel dammarane-type saponins, 2α,3β,12β,20(S),24(S)-pentahydroxydammar-25-ene-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-glucopyranoside (1, namely gypenoside J1), 2α,3β,12β,20(S),25-pentahydroxydammar-23-ene-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-glucopyranoside (2, namely gypenoside J2) and 2α,3β,12β,20(S)-tetrahydroxydammar-25-en-24-one-3-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl-20-O-β-D-xylopyranosyl-(1→6)-β-D-glucopyranoside (3, namely gypenoside J3) along with one known gypenoside (gypenoside LVII) were isolated from the aerial parts of G. pentaphyllum using various chromatographic methods. Their structures were elucidated on the basis of IR, 1D- (1H and 13C), 2D-NMR spectroscopy (HSQC, HMBC and COSY), and mass spectrometry (ESI-MS/MS). Their activity was tested using CCK-8 assay. These four compounds showed little anti-cancer activity with IC50 values more than 100?μM against four types of human cancer lines. The effects of them against H2O2-induced oxidative stress in human neuroblastoma SH-SY5Y cells were evaluated and they all showed potential neuroprotective effects with 3.64–18.16% higher cell viability than the H2O2-induced model group. 相似文献
965.
Fernanda R. Santana Liany Luna-Dulcey Víctor U. Antunes Claudio F. Tormena Marcia R. Cominetti Marcelo C. Duarte 《Natural product research》2020,34(1):102-109
AbstractHyptis pectinata is a herb popularly used in Brazil for the treatment of inflammations, pain, bacterial infections and cancer. In the present study, inflorescences (MPIn), leaves (MPL), branches (MPB), root (MPR) extracts and three compounds isolated from MPIn were assayed against breast tumor cell lines. The structures of the three compounds (pectinolide J, hyptolide and pectinolide E) were determined by means of spectroscopic analysis. Pectinolide J was isolated for the first time. The MPIn, MPL and MPR exhibited specific antiproliferative activity on tumor cell lines when compared to normal cell lines with IC50 of 52.01?±?0.64, 45.91?±?0.02?μg/mL and 82.84?±?0.03?μg/mL, respectively. Although the isolated substances did not present good antiproliferative activity, when the three were associated, a greater biological effect was observed, suggesting a synergistic effect. Hyptolide (5.6?±?0.4?μg/mL) showed IC50 sufficiently low to be considered as a drug prototype. 相似文献
966.
Joyce Cristale Izabela Oliveira Santos Enelton Fagnani 《Journal of separation science》2020,43(4):748-755
Organophosphate esters used as flame retardants and plasticizers are ubiquitous contaminants in surface waters. Many studies indicate that these compounds are neurotoxicants, endocrine disruptors, and may affect reproduction and development of aquatic organisms. Thus, analytical methods that allow accurate quantification of these contaminants at environmentally relevant concentrations are desirable for risk assessment studies. In this study, a method based on solid phase extraction and gas chromatography coupled to mass spectrometry was developed for determination of organophosphate esters in river water extracts. Multivariate optimization was used to determine the best conditions for injection of larger volumes of sample in a Programmable Temperature Vaporization inlet. Furthermore, the matrix effect on the instrumental response was evaluated and compensated by association of extraction‐blank‐matched calibration and isotopically labeled focus standards. The method quantification limits ranged from 0.009 to 0.11 µg/L, staying below the predicted non‐effect concentration for the aquatic compartment for all analytes, which is a requisite for using in risk assessment studies. The method was applied to freshwater samples collected in rivers from the Sao Paulo State, Brazil, and eight out of the ten target organophosphate esters were quantified, being tris(2‐chloroisopropyl) phosphate and tris(phenyl) phosphate the most frequently detected compounds. 相似文献
967.
In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catalytic combination allows for exclusive fluorination of tertiary C–O bonds under mild conditions even in the presence of competing reaction sites.The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules.The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols. 相似文献
968.
969.
《Arabian Journal of Chemistry》2020,13(11):8218-8225
Vortioxetine is currently used as the first-line therapy drug for major depressive disorder (MDD). In the present study, we aimed to develop and fully validate an ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method for the simultaneous quantification of vortioxetine and its major metabolite Lu AA34443 in plasma and to investigate the effects of dronedarone and amiodarone on vortioxetine metabolism in rats. After protein precipitation with acetonitrile, the separation of vortioxetine, Lu AA34443 and duloxetine (internal standard, IS) were finished on an Acquity BEH C18 (2.1 mm × 50 mm, 1.7 μm) column and their detections were conducted by a Xevo TQ-S triple quadrupole tandem mass spectrometer in the positive ion mode. The assay displayed excellent linearity in the range of 0.5–50 ng/mL for vortioxetine, and 5–1000 ng/mL for Lu AA34443. The results of this method exhibited that the precision, accuracy, matrix effect, recovery, and stability of vortioxetine and Lu AA34443 met all requirements for the quantitation in plasma samples. The validated assay was further successfully employed to study the effects of dronedarone (80 mg/kg) and amiodarone (60 mg/kg) on vortioxetine metabolism in rats. The results showed that dronedarone and amiodarone could increase the concentration of vortioxetine and have inhibitory effect on vortioxetine metabolism. Thus, vortioxetine dose interruption or reduction may be considered. 相似文献
970.
This paper presents a nonlinear thickness-shear vibration model for onedimensional infinite piezoelectric plate with flexoelectricity and geometric nonlinearity. The constitutive equations with flexoelectricity and governing equations are derived from the Gibbs energy density function and variational principle. The displacement adopted here is assumed to be antisymmetric through the thickness due to the thickness-shear vibration mode. Only the shear strain gradient through the thickness is considered in the present model. With geometric nonlinearity, the governing equations are converted into differential equations as the function of time by the Galerkin method. The method of multiple scales is employed to obtain the solution to the nonlinear governing equation with first order approximation. Numerical results show that the nonlinear thickness-shear vibration of piezoelectric plate is size dependent, and the flexoelectric effect has significant influence on the nonlinear thickness-shear vibration frequencies of micro-size thin plates. The geometric nonlinearity also affects the thickness-shear vibration frequencies greatly. The results show that flexoelectricity and geometric nonlinearity cannot be ignored in design of accurate high-frequency piezoelectric devices. 相似文献