全文获取类型
收费全文 | 57864篇 |
免费 | 8177篇 |
国内免费 | 5055篇 |
专业分类
化学 | 30891篇 |
晶体学 | 1024篇 |
力学 | 9750篇 |
综合类 | 598篇 |
数学 | 14815篇 |
物理学 | 14018篇 |
出版年
2024年 | 110篇 |
2023年 | 671篇 |
2022年 | 1340篇 |
2021年 | 1593篇 |
2020年 | 2430篇 |
2019年 | 1963篇 |
2018年 | 1794篇 |
2017年 | 2051篇 |
2016年 | 2894篇 |
2015年 | 2338篇 |
2014年 | 3157篇 |
2013年 | 4204篇 |
2012年 | 3488篇 |
2011年 | 3900篇 |
2010年 | 3321篇 |
2009年 | 3606篇 |
2008年 | 3485篇 |
2007年 | 3394篇 |
2006年 | 3110篇 |
2005年 | 2887篇 |
2004年 | 2579篇 |
2003年 | 2270篇 |
2002年 | 2739篇 |
2001年 | 1543篇 |
2000年 | 1369篇 |
1999年 | 1303篇 |
1998年 | 1236篇 |
1997年 | 1022篇 |
1996年 | 808篇 |
1995年 | 714篇 |
1994年 | 612篇 |
1993年 | 487篇 |
1992年 | 493篇 |
1991年 | 387篇 |
1990年 | 313篇 |
1989年 | 237篇 |
1988年 | 205篇 |
1987年 | 149篇 |
1986年 | 154篇 |
1985年 | 132篇 |
1984年 | 116篇 |
1983年 | 63篇 |
1982年 | 72篇 |
1981年 | 57篇 |
1980年 | 37篇 |
1979年 | 55篇 |
1978年 | 43篇 |
1977年 | 43篇 |
1976年 | 20篇 |
1974年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
1.
Dan Chen Kaixin Du Xiaochen Niu Hongwei Zhang Xue Zhang Yu Tang Jianchun Zhao 《Biomedical chromatography : BMC》2022,36(3):e5288
Amlexanox, an anti-inflammatory and anti-allergic agent, has been widely used clinically for the treatment of canker sores, asthma, and allergic rhinitis. Recently, amlexanox has received considerable attention in curing nonalcoholic fatty liver diseases and hepatitis virus infection. Herein, we first established a sensitive high-performance liquid chromatography-tandem mass spectrum (LC–MS/MS) method for the determination of amlexanox in rat plasma. Propranolol was used as the internal standard (IS). Using a simple protein precipitation method, the amlexanox and IS were separated with Capcell Pak C18 column (2.0 × 50 mm, 5 μm) and eluted with water and acetonitrile each containing 0.1% formic acid using gradient elution condition at a flow rate of 0.4 mL·min−1. Amlexanox and IS were detected by a triple quadrupole mass in multiple reactive monitoring (MRM) under the transitions of m/z 299.2 → 281.2 and m/z 259.9 → 116.1 with positive electrospray ionization, respectively. The calibration curves of amlexanox were established with the range of 50 to 2000 ng·mL−1 (r2 > 0.99). The validation method consisted of selectivity, accuracy, precision, carryover effect, matrix effect, recovery, dilution effect, and stability. The fully validated method was successfully applied to the pharmacokinetic study of amlexanox in Wistar rats. 相似文献
2.
Giang Truong Nguyen Prof. Dr. Liviu Ungur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202200227
Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs. 相似文献
3.
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
4.
深挖高职院校公选课“生活中的化学”的育人元素,精心设计教学内容,运用课堂主题辩论、趣味生活实验的设计与展示、探秘生活中的化学等理论知识传授与课内外实践相结合的教学方式,实现全过程育人,充分展现了公选课在立德树人方面的价值。 相似文献
5.
《Mendeleev Communications》2022,32(4):507-509
We report on the synthesis of new Ru(bpy)2(phen) catalyst for the oscillatory Belousov–Zhabotinsky chemical reaction and on the preparation of novel Ru(bpy)2(phen)-based self-oscillating gels. The synthesized gels exhibit high-amplitude autonomous mechanical oscillations when the Belousov–Zhabotinsky reaction proceeds inside these gels 相似文献
6.
7.
Sol-gel method has been used for the synthesis of biocompatible superparamagnetic nanoferrites of AFeO2 (A = Li, Na, K, Ca). Structural study of the nanoferrites reveals that LiFeO2 exhibits cubic phase on the other hand NaFeO2, KFeO2, CaFeO2 nanoparticles possess orthorhombic phase. Transmission electron microscopy (TEM) suggests that synthesized nanoferrites are nano-sized with spherical morphology. Optical properties confirm that nanoferrites emit and absorb light in a visible range of the electromagnetic spectrum. International Commission on Illumination (CIE) study discloses that the nanoparticles can be used to produce light of various colors. Magnetic study reveals that the nanoferrites exhibit superparamagnetic nature with high values of saturation magnetization 40.26 emu/g, 41.69 emu/g, 57.16 emu/g, and 43.66 emu/g, respectively for LiFeO2, NaFeO2, KFeO2, and CaFeO2. Biocompatibility study of the nanoferrites has been performed using Sulforhodamine B (SRB) and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The reason behind the observed properties and behavior has been discussed. 相似文献
8.
9.
Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Marta E. Alberto Gaspar Pinto Prof. Nino Russo Dr. Marirosa Toscano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3736-3745
The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐CoII derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear CoII center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered. 相似文献
10.
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