全文获取类型
收费全文 | 4877篇 |
免费 | 287篇 |
国内免费 | 656篇 |
专业分类
化学 | 5491篇 |
晶体学 | 21篇 |
力学 | 7篇 |
综合类 | 42篇 |
数学 | 5篇 |
物理学 | 254篇 |
出版年
2023年 | 75篇 |
2022年 | 62篇 |
2021年 | 128篇 |
2020年 | 102篇 |
2019年 | 119篇 |
2018年 | 75篇 |
2017年 | 115篇 |
2016年 | 138篇 |
2015年 | 140篇 |
2014年 | 158篇 |
2013年 | 244篇 |
2012年 | 474篇 |
2011年 | 267篇 |
2010年 | 257篇 |
2009年 | 307篇 |
2008年 | 335篇 |
2007年 | 392篇 |
2006年 | 339篇 |
2005年 | 324篇 |
2004年 | 310篇 |
2003年 | 238篇 |
2002年 | 168篇 |
2001年 | 117篇 |
2000年 | 103篇 |
1999年 | 97篇 |
1998年 | 101篇 |
1997年 | 104篇 |
1996年 | 73篇 |
1995年 | 96篇 |
1994年 | 62篇 |
1993年 | 58篇 |
1992年 | 57篇 |
1991年 | 66篇 |
1990年 | 38篇 |
1989年 | 30篇 |
1988年 | 20篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有5820条查询结果,搜索用时 837 毫秒
1.
《Electroanalysis》2006,18(6):595-604
The following two numerical models have been applied to zinc cations electroreduction in 1 M NaClO4 water solution: a classical EE model describing the concentration of involved species in solution (semi infinitive diffusion region), an extended EE model describing both: the concentration of involved species in solution and the concentration of metallic zinc inside mercury drop (in limited area of diffusion). In the latter model the inner part of mercury drop and surrounding solution were treated as dynamic interrelated system. Both models were applied to experimental cyclic voltammetric CV data in 1 M NaClO4, the results compared and discussed. The concentration profiles of all species including metallic zinc inside mercury drop were performed. The presented integrated model is essential for theoretical and analytical aspects of the electrochemistry of mercury soluble metal cations and amalgams. 相似文献
2.
Teresa uczak Radosaw Pankiewicz Bogusawa ska Grzegorz Schroeder Maria Betowska-Brzezinska Bogumil Brzezinski 《Journal of Molecular Structure》2006,800(1-3):140-145
Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li+ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods. 相似文献
3.
甲基对硫磷的快速测定及电化学性质 总被引:3,自引:2,他引:1
研究了杀虫剂甲基对硫磷的电化学性质。在pH10.38的Bdtton—Robinson缓冲溶液中,采用微分脉冲溶出伏安法在悬汞电极上得到一个还原峰,峰电位为-0.5V(vs.Ag/AgCl),本工作对实验条件进行了深入的研究,结合线性扫描伏安法等手段。研究了体系的电化学行为。实验表明,甲基对硫磷在汞电极上具有吸附性,电极反应具有不可逆性。该法用于水果及水样中甲基对硫磷残余量的测定,结果满意。 相似文献
4.
Christophe Roussel Loc Dayon Henrik Jensen Hubert H. Girault 《Journal of Electroanalytical Chemistry》2004,570(2):187-199
A series of electrogenerated selective electrophiles based on substituted benzoquinones has been characterized as tags for l-cysteine and cysteine residues in proteins. The electrophiles are generated electrochemically from the corresponding hydroquinones. It is shown from mass spectrometry analysis that the electrogenerated benzoquinone can tag the biomolecules. The rate constants pertaining to the addition of l-cysteine onto the electrogenerated benzoquinones have been determined using electrochemical techniques. The substitution patterns have been unraveled leading to the assessment of site-specific rate constants. It is shown that the rate constants are primarily dependent on the electronic nature of the substituents as expressed by the Hammett substitution constant. The apparent tagging yields observed for l-cysteine in nanospray mass spectrometry experiments do not correspond to the yields expected from the electrochemical study, as the ionisation efficiencies are highly dependent on the tag. Finally, the on-line tagging has been tested using β-lactoglobulin A and myoglobin. Based on these results, it is concluded that the tagging reaction is selective towards cysteine when it takes place in the nanospray interface. The results show that the methodology presented can be used for a rapid characterization and identification of reactive sites in biomolecules. 相似文献
5.
《Electroanalysis》2004,16(9):748-756
A strategy for constructing a global multivariate calibration model that includes calibration samples measured over time on different days is developed and applied in electroanalysis. Both synthetic and real samples (tap, extracted and river water) are analyzed by differential‐pulse anodic stripping voltammetry, showing the suitability of the global model constructed that provides successful results similar to those of the usual multivariate calibration. In addition the capability of discrimination of this model is evaluated in prediction for the mean of three replicates with estimation of probability of false noncompliance, α, and false compliance, β, being found 3.1, 11.2, 6.7 and 64.7 nM for nominal concentrations of zinc, cadmium, lead and copper of 96.0, 40.4, 37.3 and 328.0 nM respectively when α=β=0.05. It has been proven that the use of the global calibration does not imply a loss of multivariate analytical sensitivity, using this parameter as quality index of the analytical procedure. The viability of using calibration maintenance strategies with electroanalytical techniques is shown, providing a way to save time and experimental effort when these techniques are used in routine analysis. 相似文献
6.
用微分脉冲溶出伏安法研究了镍(11)与酸性铬兰K(ACBK)所生成的络合物在悬汞电极上的电化学特性及电化学反应机理,发现电极反应为镍与酸性铬兰K所生成的络合物吸附在电极表面后发生的不可逆还原。在HCl-硼砂介质中(pH8.67),络合物在-316mV处有一吸附还原峰,其峰电流与镍浓度在0.001~0.010μ/mL范围内呈现良好的线性关系,其最低检出浓度为0.0005μg/mL。 相似文献
7.
本文报道了用吸附溶出伏安法测定毗喳酮.以悬汞电极为工作电极,在Na}B,O,-NaOH介质(pH=10)中,毗喳酮产生一尖锐的吸附还原峰,E,二一1. 29V (vs. SCE ),峰电流与毗喳酮浓度在2. 0 X 10-'-8. 0 X 10-smol " L-’范围内呈良好的线性关系.检测限为2. 0 X 10-0mol " L-'(富集90s).本文对毗喳酮在悬汞电极上的电化学行为进行了探讨,对测定毗喳酮的最佳条件进行了详细的选择,利用本法测定了片剂中毗喳酮含量,结果满意. 相似文献
8.
Dailly A. Schneider R. Billaud D. Fort Y. Ghanbaja J. 《Journal of nanoparticle research》2003,5(3-4):389-393
A novel chemical reduction method using an activated alkaline hydride (LiH or NaH-t-BuONa) in tetrahydrofuran solvent has been applied to antimony salt reduction. X-ray diffraction and transmission electron microscopy studies have been carried out to characterize the morphology and structure of the materials. Alkali hydride nature influence has been proved. In both cases the process allows to prepare antimony particles in nanometer range from few nanometers to about 20nm which could be used as anodic materials for lithium–ion batteries. With lithium hydride well-crystallized particles inclined to agglomeration were observed whereas finely dispersed amorphous particles were pointing out after activated sodium hydride reduction. 相似文献
9.
Highly ordered composite nanowires with multilayer Ni/Cu and NiFe/Cu have been fabricated by pulsed electrodeposition into
nanoporous alumina membrane. The diameter of wires can be easily varied by pore size of alumina, ranging from 30 to 100 nm.
The applied potential and the duration of each potential square pulse determine the thickness of the metal layers. The nanowires
have been characterized by transmission electron microscopy (TEM), magnetic force microscopy (MFM), and vibrating sample magnetometer
(VSM) measurements. The MFM images indicate that every ferromagnetic layer separated by Cu layer was present as single isolated
domain-like magnet. This technique has potential use in the measurement and application of magnetic nanodevices. 相似文献
10.
提出了线性扫描溶出伏安法测定福美双的电分析化学方法.在 pH 5.0 HAc-NaAc缓冲溶液中福美双在汞电极上出现一还原峰,峰电位为-610 mV(vs.Ag/AgCl).采用各种电化学技术如循环伏安法和线性扫描溶出伏安法等对本体系进行研究,发现采用线性扫描溶出伏安法能得到较灵敏的还原峰,呈现不可逆电极反应现象,并具有一定的吸附性,在210 s时能达到吸附平衡.选择吸附时间为180 s时,线性范围为0.02~0.14 μg·mL-1,最低检测限为9.5 ng·mL-1.将本方法用于实际样品的测定,得到满意的结果. 相似文献