全文获取类型
收费全文 | 17899篇 |
免费 | 3344篇 |
国内免费 | 2935篇 |
专业分类
化学 | 11627篇 |
晶体学 | 186篇 |
力学 | 1452篇 |
综合类 | 164篇 |
数学 | 1388篇 |
物理学 | 9361篇 |
出版年
2024年 | 54篇 |
2023年 | 226篇 |
2022年 | 374篇 |
2021年 | 633篇 |
2020年 | 822篇 |
2019年 | 632篇 |
2018年 | 615篇 |
2017年 | 688篇 |
2016年 | 796篇 |
2015年 | 722篇 |
2014年 | 1004篇 |
2013年 | 1572篇 |
2012年 | 1147篇 |
2011年 | 1183篇 |
2010年 | 1000篇 |
2009年 | 1239篇 |
2008年 | 1231篇 |
2007年 | 1270篇 |
2006年 | 1225篇 |
2005年 | 976篇 |
2004年 | 885篇 |
2003年 | 828篇 |
2002年 | 680篇 |
2001年 | 583篇 |
2000年 | 544篇 |
1999年 | 499篇 |
1998年 | 432篇 |
1997年 | 349篇 |
1996年 | 284篇 |
1995年 | 243篇 |
1994年 | 225篇 |
1993年 | 168篇 |
1992年 | 138篇 |
1991年 | 137篇 |
1990年 | 101篇 |
1989年 | 94篇 |
1988年 | 87篇 |
1987年 | 71篇 |
1986年 | 68篇 |
1985年 | 62篇 |
1984年 | 48篇 |
1983年 | 22篇 |
1982年 | 36篇 |
1981年 | 36篇 |
1980年 | 29篇 |
1979年 | 32篇 |
1978年 | 13篇 |
1977年 | 22篇 |
1976年 | 12篇 |
1974年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
《Arabian Journal of Chemistry》2022,15(1):103492
Matrix metalloproteinases (MMPs) are a large family of zinc-dependent endoproteases known to exert multiple regulatory roles in tumor progression. A variety of chemical classes have been explored for targeting individual MMP isoforms. In the present study, we further developed our isatin based scaffold BB0223107 capable of binding to and inactivating MMP-2 in a zinc-independent manner (Agamennone et al., 2016). Forty four new compounds were synthesized based on the modified BB0223107. All compounds were tested in enzyme inhibition assays against MMP-2, ?8 and ?13. SAR studies demonstrated that 5-het(aryl)-3-aminoindolin-2-ones (37–39) were active toward MMP-2 and MMP-13. The most potent compounds 33 and 37 displayed an IC50 of 3 µM against MMP-13 and showed a negligible activity toward MMP-8; almost all new compounds were inactive toward MMP-8. Replacement of the isatin ring with a biaryl system (compound 33) did not decrease the potency against MMP-13 but reduced the selectivity. Structure-based computational studies were carried out to rationalize the inhibitory activity data. The analysis of binding geometries confirmed that all fragments occupied the S1′ site in the three enzymes while no ligand was able to bind the catalytic zinc ion. To the best of our knowledge, this is the first example of 3-aminoindolin-2-one-based MMP inhibitors that, based on the computer modeling study, do not coordinate the zinc ion. Thus, the het(aryl)-3-aminoindolin-2-one derivatives emerge as a drug-like and promising chemotype that, along with the hetaryl variations, represents an alternative and thrifty tool for chemical space exploration aimed at MMP inhibitor design. 相似文献
2.
This paper is concerned with the Cauchy problem on the Boltzmann equation without angular cutoff assumption for hard potential in the whole space. When the initial data is a small perturbation of a global Maxwellian, the global existence of solution to this problem is proved in unweighted Sobolev spaces with . But if we want to obtain the optimal temporal decay estimates, we need to add the velocity weight function, in this case the global existence and the optimal temporal decay estimate of the Boltzmann equation are all established. Meanwhile, we further gain a more accurate energy estimate, which can guarantee the validity of the assumption in Chen et al. (0000). 相似文献
3.
We investigate the possibility of phantom crossing in the dark energy sector and the solution for the Hubble tension between early and late universe observations. We use robust combinations of different cosmological observations, namely the Cosmic Microwave Background (CMB), local measurement of Hubble constant (), Baryon Acoustic Oscillation (BAO) and SnIa for this purpose. For a combination of CMB+BAO data that is related to early universe physics, phantom crossing in the dark energy sector was confirmed at a 95% confidence level and we obtained the constraint km/s/Mpc at a 68% confidence level, which is in perfect agreement with the local measurement by Riess et al. We show that constraints from different combinations of data are consistent with each other and all of them are consistent with phantom crossing in the dark energy sector. For the combination of all data considered, we obtained the constraint km/s/Mpc at a 68% confidence level and the phantom crossing happening at the scale factor at a 68% confidence level. 相似文献
4.
本文合成了配合物[Cu(pcba)2·(phen)(H2O)] (pcba =对氯苯甲酸,phen = 1,10-邻菲罗啉),该配合物属于三斜晶系,P1空间群,晶胞参数为a=0.790 98(2) nm,b=1.072 40(4) nm,c=1.487 19(6) nm,α=100.613(3)°,β=95.239(3)°,γ=108.334(3)°,Z=2,Dc=1.638 g·cm-3,F(000)=582,最终结构残差因子R1=0.035 9,wR2=0.089 1。采用紫外及荧光研究了配合物和人血清蛋白(HSA)的相互作用方式。结果表明,配合物静态猝灭HSA荧光,可求得配合物与HSA的猝灭常数Ksv=2.35×105 L·mol-1,猝灭速率常数Kq=2.35×1013 L·mol-1·s-1,结合常数为Ka=2.14×1013 L·mol-1,结合位点n=2.37。同时,研究了配合物对胃癌细胞A549、宫颈癌细胞Hela和肝癌细胞HepG2的抗增殖能力。 相似文献
5.
Dr. Joaquim Torra Dr. Felipe Viela Dr. Diego Megías Dr. Begoña Sot Prof. Cristina Flors 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200026
CRANAD-2 is a fluorogenic curcumin derivative used for near-infrared detection and imaging in vivo of amyloid aggregates, which are involved in neurodegenerative diseases. We explore the performance of CRANAD-2 in two super-resolution imaging techniques, namely stimulated emission depletion (STED) and single-molecule localization microscopy (SMLM), with markedly different fluorophore requirements. By conveniently adapting the concentration of CRANAD-2, which transiently binds to amyloid fibrils, we show that it performs well in both techniques, achieving a resolution in the range of 45–55 nm. Correlation of SMLM with atomic force microscopy (AFM) validates the resolution of fine features in the reconstructed super-resolved image. The good performance and versatility of CRANAD-2 provides a powerful tool for near-infrared nanoscopic imaging of amyloids in vitro and in vivo. 相似文献
6.
Hongjin Wang Tengfei Long Hao Zhang Meng Li Qi Sun Xin Zhai Lixin Sun 《Biomedical chromatography : BMC》2022,36(4):e5301
3,4-Difluorobenzyl(1-ethyl-5-(4-((4-hydroxypiperidin-1-yl)-methyl)thiazol-2-yl)-1H-indol-3-yl)carbamate (NAI59), a small molecule with outstanding therapeutic effectiveness to anti-pulmonary fibrosis, was developed as an autotaxin inhibitor candidate compound. To evaluate the pharmacokinetics and plasma protein binding of NAI59, a UPLC–MS/MS method was developed to quantify NAI59 in plasma and phosphate-buffered saline. The calibration curve linearity ranged from 9.95 to 1990.00 ng/mL in plasma. The accuracy was −6.8 to 5.9%, and the intra- and inter-day precision was within 15%. The matrix effect and recovery, as well as dilution integrity, were within the criteria. The chromatographic and mass spectrometric conditions were also feasible to determine phosphate-buffered saline samples, and it has been proved that this method exhibits good precision and accuracy in the range of 9.95–497.50 ng/mL in phosphate-buffered saline. This study is the first to determine the pharmacokinetics, absolute bioavailability, and plasma protein binding of NAI59 in rats using this established method. Therefore, the pharmacokinetic profiles of NAI59 showed a dose-dependent relationship after oral administration, and the absolute bioavailability in rats was 6.3%. In addition, the results of protein binding showed that the combining capacity of NAI59 with plasma protein attained 90% and increased with the increase in drug concentration. 相似文献
7.
Corinne Rondeau-Mouro Mireille Cambert Laurent Blondel Yves Diascorn Léo Mbaya Nor Nadiah Binti Ahmad Nazari Sarah Helary Tiphaine Lucas 《Magnetic resonance in chemistry : MRC》2022,60(7):678-691
A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample. 相似文献
8.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
9.
We present the fabrication of core-shell-satellite Au@SiO2-Pt nanostructures and demonstrate that LSPR excitation of the core Au nanoparticle can induce plasmon coupling effect to initiate photocatalytic hydrogen generation from decomposition of formic acid. Further studies suggest that the plasmon coupling effect induces a strong local electric field between the Au core and Pt nanoparticles on the SiO2 shell, which enables creation of hot electrons on the non-plasmonic-active Pt nanoparticles to participate hydrogen evolution reaction on the Pt surface. In addition, small SiO2 shell thickness is required in order to obtain a strong plamon coupling effect and achieve efficient photocatalytic activities for hydrogen generation. 相似文献
10.
Lithium-sulfur batteries (LSBs) with high energy density and low cost have been recognized as one of the most promising next-generation energy storage systems. Although it has taken decades of development, the practical application of LSBs has been hindered by several inherent obstacles, particularly the severe shuttle effect and sluggish reaction kinetics in the sulfur cathode. Various strategies have been proposed to address these problems via rational design of electrode materials and configurations. Freestanding sulfur cathode could be a promising strategy to improve the sulfur mass loading at the cathode level and energy density of LSBs. This minireview will briefly summary the recent advances in freestanding cathodes for LSBs. The advantages and disadvantages of various freestanding cathodes are discussed and the prospects for the development of flexible cathodes are envisioned. 相似文献