全文获取类型
收费全文 | 35564篇 |
免费 | 6173篇 |
国内免费 | 5378篇 |
专业分类
化学 | 19007篇 |
晶体学 | 119篇 |
力学 | 2943篇 |
综合类 | 689篇 |
数学 | 12436篇 |
物理学 | 11921篇 |
出版年
2024年 | 78篇 |
2023年 | 450篇 |
2022年 | 693篇 |
2021年 | 1069篇 |
2020年 | 1261篇 |
2019年 | 1192篇 |
2018年 | 1034篇 |
2017年 | 1376篇 |
2016年 | 1825篇 |
2015年 | 1642篇 |
2014年 | 2213篇 |
2013年 | 2934篇 |
2012年 | 2323篇 |
2011年 | 2510篇 |
2010年 | 2177篇 |
2009年 | 2497篇 |
2008年 | 2608篇 |
2007年 | 2738篇 |
2006年 | 2308篇 |
2005年 | 2010篇 |
2004年 | 1806篇 |
2003年 | 1602篇 |
2002年 | 1308篇 |
2001年 | 1087篇 |
2000年 | 969篇 |
1999年 | 847篇 |
1998年 | 720篇 |
1997年 | 655篇 |
1996年 | 502篇 |
1995年 | 499篇 |
1994年 | 364篇 |
1993年 | 293篇 |
1992年 | 219篇 |
1991年 | 240篇 |
1990年 | 171篇 |
1989年 | 117篇 |
1988年 | 141篇 |
1987年 | 97篇 |
1986年 | 78篇 |
1985年 | 88篇 |
1984年 | 63篇 |
1983年 | 39篇 |
1982年 | 47篇 |
1981年 | 50篇 |
1980年 | 38篇 |
1979年 | 34篇 |
1978年 | 28篇 |
1977年 | 19篇 |
1976年 | 14篇 |
1973年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 32 毫秒
1.
2.
3.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
4.
为提高煤与瓦斯突出矿井瓦斯抽放效果,建立了3个一级指标、14个二级指标的突出矿井瓦斯抽放限制影响因素评价指标体系,利用AHP和熵权法分别确定指标因子主、客观权重.通过实地调研分析和反馈验证了AHP-熵权法的可行性和正确性,利用加权平均法确定评价模型的综合权重.研究表明:封孔方式、钻孔半径、抽放时间、煤体裂隙发育程度和抽放负压是目前影响煤矿瓦斯抽放效果的主控因素. 相似文献
5.
6.
Dynamical analysis,circuit realization,and application in pseudorandom number generators of a fractional-order laser chaotic system 下载免费PDF全文
Chenguang Ma 《中国物理 B》2021,30(12):120504-120504
A new five-dimensional fractional-order laser chaotic system (FOLCS) is constructed by incorporating complex variables and fractional calculus into a Lorentz-Haken-type laser system. Dynamical behavior of the system, circuit realization and application in pseudorandom number generators are studied. Many types of multi-stable states are discovered in the system. Interestingly, there are two types of state transition phenomena in the system, one is the chaotic state degenerates to a periodical state, and the other is the intermittent chaotic oscillation. In addition, the complexity of the system when two parameters change simultaneously is measured by the spectral entropy algorithm. Moreover, a digital circuit is design and the chaotic oscillation behaviors of the system are verified on this circuit. Finally, a pseudo-random sequence generator is designed using the FOLCS, and the statistical characteristics of the generated pseudo-random sequence are tested with the NIST-800-22. This study enriches the research on the dynamics and applications of FOLCS. 相似文献
7.
8.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
9.
Atopic dermatitis is characterized by leukocyte migration into the skin dermis and typically driven by excessive chemokine production at the site of inflammation. Conventional topical formulations such as gels, creams, and ointments are insufficient for this treatment because of low penetration of drug molecules into the targeted skin tissues. Herein, using a simple, green, sustainable strategy, we have developed novel primary zein nanoparticles embedded in curcumin (Cur) and coated with silk sericin (ZHSCs) for the topical delivery of Cur to penetrate into the dermis and exercise anti-dermatitis effects on the lesion with minimal side-effects. Transdermal delivery experiments and porcine skin fluorescence imaging indicated that ZHSCs facilitate the penetration of Cur across the epidermis layer of skin to reach deep-seated sites. Notably, ZHSCs = 1:0.25 (zein-to-silk sericin mass ratios of 1:0.25) markedly elevated the skin permeability and cumulative turnover of Cur transferred, which were provided a greater than a 3.8-fold increase relative to free Cur. The special nanoparticles of ZHS = 1:0.25 possessed the deepest localization depth and experience a transition of the particle structure and core-shell separation after penetrating into the dermis of skin. In a cell model of dermatitis induced by tumor necrosis factor α/interferon γ co-stimulation, compared with free Cur, Cur-loaded ZHS nanoparticles down-regulated the generation of inflammatory cytokines and chemokines in keratinocytes through suppression of the nuclear translocation of NF-κBp65 and hence exerted an anti-dermatitis effect. This strategy may provide new avenues and direction for the demanding issues of valid topical delivery systems. 相似文献
10.