全文获取类型
收费全文 | 1927篇 |
免费 | 224篇 |
国内免费 | 130篇 |
专业分类
化学 | 1933篇 |
晶体学 | 9篇 |
力学 | 16篇 |
综合类 | 23篇 |
数学 | 14篇 |
物理学 | 286篇 |
出版年
2024年 | 5篇 |
2023年 | 26篇 |
2022年 | 32篇 |
2021年 | 50篇 |
2020年 | 51篇 |
2019年 | 68篇 |
2018年 | 44篇 |
2017年 | 68篇 |
2016年 | 76篇 |
2015年 | 89篇 |
2014年 | 85篇 |
2013年 | 131篇 |
2012年 | 158篇 |
2011年 | 86篇 |
2010年 | 91篇 |
2009年 | 120篇 |
2008年 | 107篇 |
2007年 | 134篇 |
2006年 | 120篇 |
2005年 | 115篇 |
2004年 | 113篇 |
2003年 | 66篇 |
2002年 | 53篇 |
2001年 | 51篇 |
2000年 | 36篇 |
1999年 | 27篇 |
1998年 | 44篇 |
1997年 | 30篇 |
1996年 | 24篇 |
1995年 | 31篇 |
1994年 | 18篇 |
1993年 | 13篇 |
1992年 | 13篇 |
1991年 | 43篇 |
1990年 | 29篇 |
1989年 | 4篇 |
1988年 | 9篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有2281条查询结果,搜索用时 15 毫秒
131.
Jaeyoung Ko Janggyoo Choi Soo Kyung Bae Jinwoong Kim Kee Dong Yoon 《Journal of separation science》2013,36(24):3860-3865
A rapid and efficient high‐performance counter‐current chromatography (HPCCC) method was developed to separate five oligostilbenes from the roots of Vitis amurensis. An n‐hexane/ethyl acetate/methanol/water system (4:8:4:10, v/v/v/v) was selected as an optimal two‐phase solvent system of which the upper phase was used as the stationary phase and the lower phase was used as the mobile one. Partition coefficient values for the target compounds under these optimized conditions were 0.28 ( 1 , ampleosin A), 7.12 ( 2 , (+)‐g‐viniferin), 2.26 ( 3 , vitisin A), 5.38 ( 4 , wilsonol C), and 11.23 ( 5 , vitisin B). Flow‐rate gradient HPCCC (4 mL/min in 0–70 min, 8 mL/min in 70–250 min) was applied to isolate the target compounds in as high purity as possible within the shortest possible run time. Under these conditions, ampelopsin A (12.1 mg), (+)‐g‐viniferin (10.4 mg), vitisin A (2.8 mg), wilsonol C (3.2 mg), and vitisin B (37 mg) were isolated with >95% purity from 150 mg of enriched oligostilbene extract. Although the KD of the last eluted compound, vitisin B (KD = 11.23), was relatively large, it was eluted in 115–145 min using the two‐phase solvent system. This study shows that HPCCC is an efficient tool for the isolation and purification of natural products. 相似文献
132.
Abbas Afkhami Farzaneh Soltani-Felehgari Tayyebeh Madrakian Hamed Ghaedi Majid Rezaeivala 《Analytica chimica acta》2013
A new chemically modified carbon paste electrode was constructed and used for rapid, simple, accurate, selective and highly sensitive simultaneous determination of cadmium, copper and mercury using square wave anodic stripping voltammetry (SWASV). The carbon paste electrode was modified by N,N′-bis(3-(2-thenylidenimino)propyl)piperazine coated silica nanoparticles. Compared with carbon paste electrode, the stripping peak currents had a significant increase at the modified electrode. Under the optimized conditions (deposition potential, −1.100 V vs. Ag/AgCl; deposition time, 60 s; resting time, 10 s; SW frequency, 25 Hz; pulse amplitude, 0.15 V; dc voltage step height, 4.4 mV), the detection limit was 0.3, 0.1 and 0.05 ng mL−1 for the determination of Cd2+, Cu2+ and Hg2+, respectively. The complexation reaction of the ligand with several metal cations in methanol was studied and the stability constants of the complexes were obtained. The effects of different cations and anions on the simultaneous determination of metal ions were studied and it was found that the electrode is highly selective for the simultaneous determination of Cd2+, Cu2+ and Hg2+. Furthermore, the present method was applied to the determination of Cd2+, Cu2+ and Hg2+ in water and some foodstuff samples. 相似文献
133.
Robert Piech Bogusław Baś 《International journal of environmental analytical chemistry》2013,93(5):410-420
Simple cyclic renewable silver amalgam film electrode (Hg(Ag)FE), applied for the determination of gallium(III) using differential pulse anodic stripping voltammetry (DP ASV), is presented. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimised. The calibration graph is linear from 5?nM (0.35?µg?L?1) to 80?nM (5.6?µg?L?1) for a preconcentration time of 60?s, with correlation coefficient of 0.995. For a Hg(Ag)FE with a surface area of 9.9?mm2 the detection limit for a preconcentration time of 120?s is as low as 0.1?µg?L?1. The repeatability of the method at a concentration level of the analyte as low as 3.5?µg?L?1, expressed as RSD is 3.2% (n?=?5). The proposed method was successfully applied by studying the synthetic samples and simultaneously recovery of Ga(III) from spiked aluminium samples. 相似文献
134.
Yunhua Wu 《International journal of environmental analytical chemistry》2013,93(13):1244-1255
A multi-walled carbon nanotubes (MWNTs) modified glassy carbon electrode (MWNT-GCE) was used to study the electrochemical behaviour of1-hydroxypyrene (1-OHP) and applied to its determination. The results showed that the modified electrode had a strong adsorptive ability to 1-OHP and enhances its electrochemical signal. By square wave voltammetry, the linear relationship of 1-OHP was 6?×?10?9???8?×?10?7?mol?L?1 with a linear correlation coefficient of 0.996, and the detection limit was 1?×?10?10?mol?L?1. Compared with other published methods, this newly proposed method possesses many advantages such as very low detection limit, fast response, low cost and simplicity. And this method was applied successfully in the determination of 1‐OHP in real human urine samples. 相似文献
135.
Emmanuel Urandu Mapesa Ludwig Popp Wycliffe Kiprop Kipnusu Martin Tress Friedrich Kremer 《Soft Materials》2014,12(4):S22-S30
Broadband Dielectric Spectroscopy (BDS) is used to probe the molecular dynamics of Type A polymer, poly(cis-1,4-isoprene), when confined in the 1-dimensional (1D) exploring space of thin layers and the 2-dimensional (2D) constraining geometry of unidirectional anodic aluminum oxide (AAO) nanopores. For both cases, it was observed that the structural relaxation remains bulk-like in its mean relaxation rate, although the distribution of its relaxation times is broadened in 2D confinement. Furthermore, the fluctuation of the end-to-end vector is interrupted, with the 1D case being relatively less pronounced. By this clear-cut comparison, it is demonstrated that the effects of confinement on molecular dynamics depend, inter alia, on the dimensionality of the restricting space. 相似文献
136.
Determination of sulfonamides in milk samples by HPLC with amperometric detection using a glassy carbon electrode modified with multiwalled carbon nanotubes
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
A sensitive and accurate method for determining five sulfonamides based on HPLC with amperometric detection and using a glassy carbon electrode modified with multiwalled carbon nanotubes is proposed. Optimal conditions for the quantitative separation of selected sulfonamides were studied, and glassy carbon electrodes with and without modification with carbon nanotubes were systematically investigated as electrodic materials. Statistical analysis of the obtained results demonstrated that these modified electrodes achieved considerably better stability and sensitivity than the conventional unmodified ones. Detection limits were in the 1.2–6.0 ng/mL range. The usefulness of the method was demonstrated by the analysis of milk samples, taking into account the European legislation on residues in food products, following both a screening method to classify the samples and a confirmation method to provide more detailed information in the case of positive samples. 相似文献
137.
Carbon‐Coated LiTi2(PO4)3: An Ideal Insertion Host for Lithium‐Ion and Sodium‐Ion Batteries
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Vanchiappan Aravindan Dr. Wong Chui Ling Steffen Hartung Nicolas Bucher Prof. Srinivasan Madhavi 《化学:亚洲杂志》2014,9(3):878-882
We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi2(PO4)3 as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi2(PO4)3 hosts attractive for the development of next‐generation batteries. 相似文献
138.
Taking advantage of large conjugated structure and reductivity of boron-doped graphenethe palladium nanoparticles/boron-doped graphene catalyst was prepared by electroless deposition method using boron-doped graphene as reductant and stabilizer. The average size of palladium nanoparticles highly dispersed on the surface of boron-doped graphene was about 6.5 nm. The electrochemical sensor was prepared by modifying the as-formed catalyst on the surface of glassy carbon electrode. The obtained electrochemical sensor exhibited an excellent electrochemical catalytic activity for H2 O2 . It exhibited high sensitivity with the detection limit as low as 830 nmol/L and good linearity in the range of 2.5-300 μµmol/L for detection of H2 O2 . It could be utilized for the determination of H2 O2 in milk samples. © 2022, Youke Publishing Co.,Ltd. All rights reserved. 相似文献
139.
Enhanced Crystal Quality of Perovskite via Protonated Graphitic Carbon Nitride Added in Carbon-Based Perovskite Solar Cells
下载免费PDF全文
![点击此处可从《化学物理学报(中文版)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Mingxing Guo Wenchao Liu Junyan Huang Jiaqi Liu Shuhui Yin Jing Leng 《化学物理学报(中文版)》2022,35(2):390-398
The quality of perovskite layers has a great impact on the performance of perovskite solar cells (PSCs). However, defects and related trap sites are generated inevitably in the solution-processed polycrystalline perovskite films. It is meaningful to reduce and passivate the defect states by incorporating additive into the perovskite layer to improve perovskite crystallization. Here an environmental friendly 2D nanomaterial protonated graphitic carbon nitride (p-g-C\begin{document}$_3$\end{document} N\begin{document}$_4$\end{document} ) was successfully synthesized and doped into perovskite layer of carbon-based PSCs. The addition of p-g-C\begin{document}$_3$\end{document} N\begin{document}$_4$\end{document} into perovskite precursor solution not only adjusts nucleation and growth rate of methylammonium lead tri-iodide (MAPbI\begin{document}$_3$\end{document} ) crystal for obtaining flat perovskite surface with larger grain size, but also reduces intrinsic defects of perovskite layer. It is found that the p-g-C\begin{document}$_3$\end{document} N\begin{document}$_4$\end{document} locates at the perovskite core, and the active groups -NH\begin{document}$_2$\end{document} /NH\begin{document}$_3$\end{document} and NH have a hydrogen bond strengthening, which effectively passivates electron traps and enhances the crystal quality of perovskite. As a result, a higher power conversion efficiency of 6.61% is achieved, compared with that doped with g-C\begin{document}$_3$\end{document} N\begin{document}$_4$\end{document} (5.93%) and undoped one (4.48%). This work demonstrates a simple method to modify the perovskite film by doping new modified additives and develops a low-cost preparation for carbon-based PSCs. 相似文献
140.
The rapidly growing existence of a number of contaminants (i.e. heavy metals, dye compounds, explosives and pesticides etc.) in environment is an alarming concern not only due to their harmful impacts for the environment bur also due to their potential high risk for human health. Thus, the careful and sensitive detection of these environmental contaminants is ver crucial. Electrochemical sensors combined with molecularly imprinted polymers (MIPs) become an attractive area for environmental monitoring. Benefiting from their great features such as high chemical and physical stability, cheap preparation process, excellent selectivity, sensitivity and fast response towards the target compound/s.This review paper aims to present and highlight the latest progresses in the design and development of novel electrochemical sensor systems composed of MIPs and carbon paste electrodes (CPEs) for the sensitive detection of pollutants in environmental samples. 相似文献