全文获取类型
收费全文 | 2947篇 |
免费 | 1336篇 |
国内免费 | 234篇 |
专业分类
化学 | 1126篇 |
晶体学 | 9篇 |
力学 | 140篇 |
综合类 | 36篇 |
数学 | 83篇 |
物理学 | 3123篇 |
出版年
2024年 | 4篇 |
2023年 | 24篇 |
2022年 | 53篇 |
2021年 | 60篇 |
2020年 | 74篇 |
2019年 | 62篇 |
2018年 | 52篇 |
2017年 | 104篇 |
2016年 | 108篇 |
2015年 | 107篇 |
2014年 | 274篇 |
2013年 | 225篇 |
2012年 | 298篇 |
2011年 | 294篇 |
2010年 | 233篇 |
2009年 | 261篇 |
2008年 | 254篇 |
2007年 | 255篇 |
2006年 | 227篇 |
2005年 | 203篇 |
2004年 | 192篇 |
2003年 | 168篇 |
2002年 | 139篇 |
2001年 | 116篇 |
2000年 | 108篇 |
1999年 | 107篇 |
1998年 | 88篇 |
1997年 | 77篇 |
1996年 | 70篇 |
1995年 | 47篇 |
1994年 | 45篇 |
1993年 | 35篇 |
1992年 | 32篇 |
1991年 | 38篇 |
1990年 | 14篇 |
1989年 | 20篇 |
1988年 | 11篇 |
1987年 | 15篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有4517条查询结果,搜索用时 31 毫秒
121.
The electrocatalytic oxidation of cephalexin and cefazolin has been studied at a carbon paste electrode modified with cobalt salophen (CoSal) by cyclic voltammetry. The selectivity of the carbon paste modified with CoSal in detecting cephalexin and cefazolin was examined. To suggest the electrocatalytic mechanism for electro-oxidation of cefazolin, the electrochemical behavior of ceftriaxone was investigated which has a thiol group out of the beta lactam ring. The electrocatalytic oxidation of these antibiotics is shown to be irreversible at the CoSal modified electrode. Scan rate dependence of cefazolin, which is a sulfur-containing compound, has been examined. The results indicated that the electrocatalytic oxidation of the compounds is diffusion controlled. The responses of the modified electrode were compared with those of unmodified electrode and it has shown that the modified electrode has better sensitivity than unmodified electrode to the detection of cefazolin. The overall number of electrons contributed to the oxidation of cefazolin is obtained 1 by chronoamperometry; the number of electron involved in the rate-determining step was 1. The results of differential pulse voltammetry (DPV) using the modified electrode with high sensitivity were applied for the determination of cefazolin in human synthetic serum samples. The linear range was obtained from 1 × 10−5 to 1 × 10−3 M for DPV determination of cefazolin in buffered solutions (pH 3.0). 相似文献
122.
《Electroanalysis》2003,15(4):254-262
The new electrochemical double pulse technique, known as additive differential normal pulse voltammetry (ADNPV) when there is no restriction on the duration of both pulses, and additive differential pulse voltammetry (ADPV) when t2?t1, has been applied to a pseudo‐first‐order catalytic mechanism. The expressions obtained here are applicable to planar and spherical electrodes, of any radius. This is of great interest since the size of the electrode plays an important role in the preponderating of diffusive and kinetics processes. The signal obtained with this technique presents the same morphological characteristics as the triple pulse technique, double differential pulse voltammetry (DDPV) and is more advantageous than DDPV and than the double pulse one, differential pulse voltammetry (DPV). 相似文献
123.
在镉离子浓度为5.00×10-5~2.00×10-4mol.L-1、甘氨酸与镉离子浓度比为100~400条件下,应用示差脉冲极谱技术测定不同溶液pH值时镉(Ⅱ)-甘氨酸体系的极谱峰电位和峰电流,依据极谱峰电位随溶液pH和自由金属离子浓度的变化关系曲线,建立合适的金属配合物体系模型。通过求解体系的质量平衡方程及拟合试验配合物形成曲线,用计算机分析程序优化得到MHL、ML、ML2、ML3和ML2(OH)五种金属配合物的稳定常数(lgβ)分别为9.67±0.15,4.35±0.02,7.83±0.03,10.04±0.04和11.48±0.13。 相似文献
124.
二茂铁化学修饰电极测定丙二醛的研究 总被引:4,自引:0,他引:4
报道了在玻碳电极上共价键合二茂铁的新型化学修饰电极。研究了该电极对丙二醛的电催化作用。以微分脉冲伏安法测定丙二醛,方法具有较好的灵敏度和选择性。丙二醛的峰电流与其浓度在20×10-6~20×10-3mol/L呈良好的线性关系。 相似文献
125.
Pezzatini G Midili I Toti G Loglio F Innocenti M 《Analytical and bioanalytical chemistry》2004,380(4):650-657
The chlorite ion is an unavoidable by-product of the disinfection of drinking water by means of chlorine dioxide. The maximum concentration values of chlorite accepted in many countries regulations range from 0.2 to 1.0 mg L–1. A simple, inexpensive and quickly set up voltammetric procedure for the on-site determination of chlorite in drinking water networks is described. This procedure is suitable for the whole range of applications in drinking water plants. A useful cell for on-field analysis has been developed. Surface morphology and behaviour of carbon-based working electrodes have been investigated by voltammetry and atomic force microscopy (AFM). Actual samples of different types of water networks have been analysed for chlorite concentration. 相似文献
126.
O. M. Shabanov F. O. Ismailova D. G. Maksumova S. M. Gadzhiev A. O. Magomedova 《Russian Journal of Electrochemistry》2006,42(9):986-989
Effects of high-voltage pulses on electrochemical properties of a molten magnesium electrolyte is studied experimentally. It is established that the electroconductivity of the melt subjected to the pulses and the electrolysis current at a constant voltage increase by up to 25%. The relaxation time of nonequilibrium melt reaches a few tens of minutes and under certain conditions its dynamics is oscillatory. 相似文献
127.
《Electroanalysis》2002,14(24):1699-1706
An application of a partial least squares calibration method for the simultaneous voltammetric determination of indomethacin, acemethacin, piroxicam and tenoxicam is suggested. It was shown that it is possible to resolve complex mixtures of analytes even when they have strongly overlapped signals. In order to check the proposed method, statistical analysis of the results was performed by mean of hypothesis tests. The method developed was applied to the electrochemical reduction region of four anti‐inflammatory drugs and allowed the drugs to be quantified at concentrations between 0.52 and 4.09 μg mL?1 for acemethacin, 0.44 and 3.50 μg mL?1 for indomethacin, 0.43 and 3.40 μg mL?1 for piroxicam, and 0.42 and 3.30 μg mL?1 for tenoxicam with good results. The average absolute value of relative errors was 2.25%, 4.31%, 1.68% and 2.49%, respectively. 相似文献
128.
The behaviour of oxazepam in adsorptive stripping voltammetry was studied taking into account those conditions which have an influence on the accumulation step (electrolyte, pH, time, potential, drop size and stirring rate), rest time and stripping step (pulse amplitude and scan rate). Oxazepam can be determined at a hanging mercury drop electrode by differential-pulse voltammetry in 0.008 M Britton-Robinson buffer at pH 2.0 with a ?0.50 V accumulation potential. Its detection limit was found to be 3.6 × 10?10 M (30-s accumulation) and the relative standard deviation for oxazepam concentrations in the range 2.8 × 10?8?4.0 × 10?7 M is lower than 2.8% (80-s accumulation). In addition, a procedure using adsorptive stripping voltammetry was developed to study the interactions occurring between human albumin and the camazepam metabolic series (camazepam, temazepam and oxazepam). The interactions decreased in the order temazepam ? oxazepam ? camazepam and the groups and structural modifications favouring interaction were determined. 相似文献
129.
Dazhang Zhu Shilong Wang Xiaoyu Sun Yaming Ni Side Yao 《Frontiers of Chemistry in China》2007,2(4):354-358
The reaction mechanism between isoquinoline and ·OH radical in aqueous dilute solutions under different conditions was studied
by pulse radiolysis. The main characteristic peaks in these transient absorption spectra were attributed and the growth-decay
trends of several transient species were investigated. Under neutral or alkaline conditions, the reaction of ·OH radical and
isoquinoline produces OH-adducts with respective rate constants of 3.4 × 109 and 6.6 × 109 mol−1 · dm3 · s−1 while under acidic conditions, the isoquinoline was firstly protonated and then ·OH added to the benzene ring and produced
protonated isoquinoline OH-adducts with a rate constant of 3.9 × 109 mol−1 · dm3 · s−1. With a better understanding on radiolysis of isoquinoline, this study is of help for its degradation and for environmental
protection.
__________
Translated from Journal of Fudan University (Natural Science), 2006, 45(6): 774–778 [8BD1;81EA: 590D;65E6;5B66;62A5;(自然科学版)] 相似文献
130.
采用时域有限差分方法,对水平极化电磁脉冲模拟器所产生的电磁场进行数值模拟,在时域中计算了电磁场的时间 空间分布。讨论了电磁脉冲模拟器产生的电磁脉冲波形和场的空间变化、均匀性等重要因素。结果表明,模拟器产生的电磁脉冲前沿为10ns,接近脉冲电压前沿,波形与脉冲电压波形(双指数波)相差较大;峰值场强在对称轴上并非与距离成反比,而是随距离增大而迅速减弱;该模拟器的双锥 笼形天线能在大范围内(大于等于50m,水平方向)产生均匀分布、高峰值场强、快前沿的电磁脉冲。 相似文献