全文获取类型
收费全文 | 170594篇 |
免费 | 16945篇 |
国内免费 | 13518篇 |
专业分类
化学 | 91425篇 |
晶体学 | 2181篇 |
力学 | 12329篇 |
综合类 | 916篇 |
数学 | 42425篇 |
物理学 | 51781篇 |
出版年
2024年 | 289篇 |
2023年 | 1798篇 |
2022年 | 3505篇 |
2021年 | 3616篇 |
2020年 | 3847篇 |
2019年 | 3846篇 |
2018年 | 13052篇 |
2017年 | 12953篇 |
2016年 | 10323篇 |
2015年 | 5703篇 |
2014年 | 6125篇 |
2013年 | 7728篇 |
2012年 | 12470篇 |
2011年 | 18918篇 |
2010年 | 11801篇 |
2009年 | 12079篇 |
2008年 | 13157篇 |
2007年 | 14394篇 |
2006年 | 5760篇 |
2005年 | 5831篇 |
2004年 | 5069篇 |
2003年 | 4842篇 |
2002年 | 3919篇 |
2001年 | 2659篇 |
2000年 | 2260篇 |
1999年 | 2068篇 |
1998年 | 1640篇 |
1997年 | 1436篇 |
1996年 | 1442篇 |
1995年 | 1208篇 |
1994年 | 1041篇 |
1993年 | 896篇 |
1992年 | 691篇 |
1991年 | 621篇 |
1990年 | 545篇 |
1989年 | 418篇 |
1988年 | 336篇 |
1987年 | 297篇 |
1986年 | 297篇 |
1985年 | 245篇 |
1984年 | 158篇 |
1983年 | 161篇 |
1982年 | 111篇 |
1981年 | 94篇 |
1980年 | 87篇 |
1979年 | 82篇 |
1978年 | 49篇 |
1977年 | 47篇 |
1973年 | 46篇 |
1914年 | 46篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
21.
Bingjie Chen Dr. Lianhai Zu Dr. Yao Liu Dr. Ruijing Meng Yutong Feng Prof. Chengxin Peng Feng Zhu Tianzi Hao Jiajia Ru Prof. Yonggang Wang Prof. Jinhu Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(8):3161-3166
Incorporating nanoscale Si into a carbon matrix with high dispersity is desirable for the preparation of lithium-ion batteries (LIBs) but remains challenging. A space-confined catalytic strategy is proposed for direct superassembly of Si nanodots within a carbon (Si NDs⊂C) framework by copyrolysis of triphenyltin hydride (TPT) and diphenylsilane (DPS), where Sn atomic clusters created from TPT pyrolysis serve as the catalyst for DPS pyrolysis and Si catalytic growth. The use of Sn atomic cluster catalysts alters the reaction pathway to avoid SiC generation and enable formation of Si NDs with reduced dimensions. A typical Si NDs⊂C framework demonstrates a remarkable comprehensive performance comparable to other Si-based high-performance half LIBs, and higher energy densities compared to commercial full LIBs, as a consequence of the high dispersity of Si NDs with low lithiation stress. Supported by mechanic simulations, this study paves the way for construction of Si/C composites suitable for applications in future energy technologies. 相似文献
22.
Rongrong Li Hongjie Peng Qingping Wu Xuejun Zhou Jiang He Hangjia Shen Minghui Yang Chilin Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):12227-12236
Herein, we propose the construction of a sandwich-structured host filled with continuous 2D catalysis–conduction interfaces. This MoN-C-MoN trilayer architecture causes the strong conformal adsorption of S/Li2Sx and its high-efficiency conversion on the two-sided nitride polar surfaces, which are supplied with high-flux electron transfer from the buried carbon interlayer. The 3D self-assembly of these 2D sandwich structures further reinforces the interconnection of conductive and catalytic networks. The maximized exposure of adsorptive/catalytic planes endows the MoN-C@S electrode with excellent cycling stability and high rate performance even under high S loading and low host surface area. The high conductivity of this trilayer texture does not compromise the capacity retention after the S content is increased. Such a job-synergistic mode between catalytic and conductive functions guarantees the homogeneous deposition of S/Li2Sx, and avoids thick and devitalized accumulation (electrode passivation) even after high-rate and long-term cycling. 相似文献
23.
Dr. Yong-Sheng Wei Dr. Liming Sun Miao Wang Dr. Jinhua Hong Dr. Lianli Zou Hongwen Liu Dr. Yu Wang Dr. Mei Zhang Dr. Zheng Liu Prof. Yinwei Li Prof. Satoshi Horike Prof. Kazu Suenaga Prof. Qiang Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16147-16156
Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear FeIII2FeII complex (denoted as Fe3) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of FeII by other metal(II) ions (e.g., ZnII/CoII) via synthesizing isostructural trinuclear-complex precursors (Fe2Zn/Fe2Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities. 相似文献
24.
Lei Chen Hui-Qing Yang Cheng-Yu Jin Zhao-Xu Chen 《International journal of quantum chemistry》2020,120(22):e26366
We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH− group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH− group and the Fukui function condensed on the OH− group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts. 相似文献
25.
Xinghua Li Yuqin Yang Junjie Miao Zhendong Yin Yijing Zhai Hongmei Shi Zengning Li 《Electrophoresis》2020,41(18-19):1584-1591
In the present research, field-amplified sample injection–CZE (FASI–CZE) coupled with a diode array detector was established to determine trace level sulfa antibiotic. Sulfathiazole, sulfadiazine, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfisoxazole were selected as analytes for the experiments. The background electrolyte solution consisted of 70.0 mmol/L borax and 60.0 mmol/L boric acid (including 10% methanol, pH 9.1). The plug was 2.5 mmol/L borax, which was injected into the capillary at a pressure of 0.5 psi for 5 s. Then the sample was injected into the capillary at an injection voltage of –10 kV for 20 s. The electrophoretic separation was carried out under a voltage of +19 kV. The capillary temperature was maintained at 20˚C throughout the analysis, and six sulfonamides were completely separated within 35 min. Compared with pressure injection-CZE, the sensitivity of FASI-CZE was increased by 6.25–10.0 times, and the LODs were reduced from 0.2–0.5 to 0.02–0.05 μg/mL. The method was applied to the determination of sulfonamides in river water and particulate matter samples. The recoveries were 78.59–106.59%. The intraday and interday precisions were 2.89–7.35% and 2.77–7.09%, respectively. This provides a simpler and faster method for the analysis of sulfa antibiotic residues in environmental samples. 相似文献
26.
Simultaneous determination of cinnamaldehyde and its metabolite in rat tissues by gas chromatography–mass spectrometry
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hang Zhao Qian Yang Yanhua Xie Jiyuan Sun Honghai Tu Wei Cao Siwang Wang 《Biomedical chromatography : BMC》2015,29(2):182-187
Cinnamaldehyde (CA), an active ingredient isolated from the traditional Chinese medicine Cortex Cinnamomi, has a wide range of bioactivities. To clarify the distribution characteristics of CA, a selective and sensitive method utilizing gas chromatography–mass spetrometry was initially developed for simultaneously determining the concentration of CA and its metabolite cinnamyl alcohol in rat tissues. Selected ion masses of m/z 131, 105 and 92 were chosen, and separation of the analytes was performed on a DB‐5 ms (30 m × 0.25 mm, 0.25 µm, thickness) capillary column by gas chromatography–mass spectrometry. The calibration curves demonstrated good linearity and reproducibility over the range of 20–2000 and 20–4000 ng/mL for various tissue samples. Recoveries ranged from 86.8 to 107.5%, while intra‐ and interday relative standard deviations were all <11.3%. The analysis method was successfully applied in tissue distribution studies for CA and cinnamyl alcohol. As CA and cinnamyl alcohol may inter‐convert to one another, simultaneous determination of both analytes provides a comparative and accurate data for tissue study. The concentrations of CA and cinnamyl alcohol remaining in spleen were the highest among the main organs, including heart, liver, spleen, lung, kidney and brain. In addition, there was no long‐term accumulation of CA in rat tissues. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
27.
Analysis and pharmacokinetic study of polyphyllin H in beagle dog plasma after oral administration of Rhizoma Paridis Extracts by LC‐MS/MS
下载免费PDF全文
![点击此处可从《Biomedical chromatography : BMC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
28.
Jing Zhihong Ling Baoping Yu Yang Qi Wei Zhang Shufang 《Journal of Sol-Gel Science and Technology》2015,73(1):112-117
Journal of Sol-Gel Science and Technology - A novel gas sensing material, La–Y co-doped TiO2 nanoparticles, was synthesized by sol–gel method and applied to detect organic pollutants... 相似文献
29.
Mesoscopic modeling at the pore scale offers great promise in exploring the underlying structure transport performance of flow through porous media. The present work studies the fluid flow subjected to capillarity-induced resonance in porous media characterized by different porous structure and wettability. The effects of porosity and wettability on the displacement behavior of the fluid flow through porous media are discussed. The results are presented in the form of temporal evolution of percentage saturation and displacement of the fluid front through porous media. The present study reveals that the vibration in the form of acoustic excitation could be significant in the mobilization of fluid through the porous media. The dependence of displacement of the fluid on physicochemical parameters like wettability of the surface, frequency along with the porosity is analyzed. It was observed that the mean displacement of the fluid is more in the case of invading fluid with wetting phase where the driving force strength is not so dominant. 相似文献
30.