全文获取类型
收费全文 | 3378篇 |
免费 | 126篇 |
国内免费 | 177篇 |
专业分类
化学 | 3223篇 |
晶体学 | 5篇 |
力学 | 193篇 |
综合类 | 11篇 |
数学 | 25篇 |
物理学 | 224篇 |
出版年
2024年 | 1篇 |
2023年 | 56篇 |
2022年 | 62篇 |
2021年 | 57篇 |
2020年 | 90篇 |
2019年 | 80篇 |
2018年 | 58篇 |
2017年 | 100篇 |
2016年 | 59篇 |
2015年 | 77篇 |
2014年 | 65篇 |
2013年 | 112篇 |
2012年 | 148篇 |
2011年 | 142篇 |
2010年 | 124篇 |
2009年 | 142篇 |
2008年 | 109篇 |
2007年 | 156篇 |
2006年 | 199篇 |
2005年 | 233篇 |
2004年 | 167篇 |
2003年 | 144篇 |
2002年 | 115篇 |
2001年 | 88篇 |
2000年 | 93篇 |
1999年 | 117篇 |
1998年 | 125篇 |
1997年 | 100篇 |
1996年 | 79篇 |
1995年 | 58篇 |
1994年 | 61篇 |
1993年 | 34篇 |
1992年 | 30篇 |
1991年 | 31篇 |
1990年 | 32篇 |
1989年 | 25篇 |
1988年 | 40篇 |
1987年 | 26篇 |
1986年 | 37篇 |
1985年 | 63篇 |
1984年 | 35篇 |
1983年 | 22篇 |
1982年 | 31篇 |
1981年 | 20篇 |
1980年 | 15篇 |
1979年 | 18篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有3681条查询结果,搜索用时 234 毫秒
101.
The use of a low-temperature (0 degrees C) bath-assisted coupled capillary for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized dopamine and norepinephrine using the sweeping-micellar electrokinetic capillary chromatography (MEKC) mode is described. In this technique, a capillary consisting of two portions with different inside diameters is used. Therefore, the field strength inside the capillary is different. Hence, the electrophoretic migration velocities of the analytes and the electro-osmotic flow (EOF) also are different. Furthermore, when a portion of the capillary (wide portion, used for sweeping) is immersed in a low-temperature bath, the viscosity of the buffer and the retention factor of the analytes inside are increased. Thus, not only are the interactions between the SDS micelles and the analytes increased, but the SDS-analytes also move more slowly. As a result, a more complete separation can be achieved, even when the sample injection volume is large, up to approximately 2 microL. In general, when the volume of an injected sample is larger, the effects of sweeping and separation would become insufficient, especially when the retention values (k) of the analytes are quite different. However, this limitation can be improved when the low-temperature bath/coupled capillary/sweeping-MEKC mode is used. 相似文献
102.
天祝煤MRF工艺热解焦油的组成分析 总被引:5,自引:0,他引:5
本文对天祝煤MRF(MutistageRotaryFurnace)热解焦油进行了常规及元素分析,了解其基本特性;用毛细管色谱分别对焦油各馏分进行了分析,共定性定量了103种化合物,酚类化合物以低级酚(苯酚、甲酚)为主,中性化合物为多烷基芳烃衍生物、脂肪族链状烷烃和烯烃。上述分析结果为从焦油中提取酚类化工原料或将其加工成各种燃料油的可行性提供了依据。 相似文献
103.
采用温和条件下的溶胶-凝胶技术,成功制备了阴离子交换-反相混合模式硅胶基质毛细管电色谱整体柱。通过调整反应液中不同前体的比例,优化了整体柱的制备条件。通过扫瞄电镜,对柱床进行了表征和分析。实验发现,所制备的整体柱电渗流的方向和大小可随流动相pH值的改变而改变,在酸性和中性条件下,具有从阴极流向阳极的电渗流;当流动相pH值升至约7.5时,电渗流方向发生了反转(由阳极流向阴极)。在优化的实验条件下,用所制备的整体柱对所考察的酸性(中性)化合物实现了快速分离,并获得了高达160,000N/m的柱效。 相似文献
104.
K. E. Markides B. J. Tarbet C. M. Schregenberger J. S. Bradshaw M. L. Lee K. D. Bartle 《Journal of separation science》1985,8(11):741-747
A method is described for surface deactivation and modification of fused silica capillary columns with a cyanopropyl-containing reagent. The deactivation procedure involved a dehydrocondensation reaction between a bis(cyanopropyl)methylhydropolysiloxane reagent and surface silanol groups at an optimum temperature of only 250°C. Actual critical surface tension measurements were made using the capillary rise method. Excellent deactivation for acidic and basic compounds at the low ng level, and wettability for nonpolar and polar polysiloxane stationary phases were obtained. A procedure was developed to remove acidic impurities that are present in polar stationary phases. 相似文献
105.
106.
p-tert-Butylcalix[8]arene bonded capillaries for open-tubular capillary electrochromatography were prepared with γ-glycidoxypropyltrimethoxysilane as a bridge. The bonded capillary displayed low and steady electroosmotic flow (EOF) values over the pH range from 4 to 9. Detection limits for direct spectrophotometric detection at 277 nm for benzenediols (at a signal to noise ratio of 2) were 0.96 mg l−1 for the unbonded capillary and 1.48 mg l−1 for the bonded capillary, showing that the bonded layer did not show significant absorbance and hence decreased sensitivity. The bonded capillaries showed good separation selectivity for o-, m- and p-benzenediols, α- and β-naphthols, and α- and β-naphthylamines. This selectivity was attributed to significant interactions between the analytes and the bonded p-tert-butylcalix[8]arene, which contributed to the electrochromatographic separation mechanism. The bonded capillaries gave high stability and reproducibility. 相似文献
107.
L. Hernandez M. Rudolph R. Lammertink J. Kornfield C. Zurita F. A. Gomez 《Chromatographia》2007,65(5-6):299-303
Vancomycin (Van) from Streptomyces orientalis has been derivatized with polyethylene glycol [PEG; PEG-550 (1), 750 (2), 1,100 (3), 2,000 (4), 5,000 (5), and 8,000 (6) g mol−1] at the N-terminus of the glycopeptide backbone and their binding to d-Ala-d-Ala terminus peptides assessed using affinity capillary electrophoresis (ACE). Utilizing ACE, a plug of Van-PEG and non-interacting
standards are injected and electrophoresed. Analysis of the change in the relative migration time ratio of the Van-PEG species,
relative to the non-interacting standards, as a function of the concentration of peptide, yields a value for the binding constant
(K
b). Values of K
b for N-acetyl-d-Ala-d-Ala, 7 to the Van-PEG derivatives are weaker than those for N
α,N
ε-diacetyl-Lys-d-Ala-d-Ala, 8 (for example, values of K
b for 7-1 and 8-1 are 1.8 and 47.7 × 103 M−1, respectively). These results demonstrate that derivatization of Van with PEG has little effect on the affinity of d-Ala-d-Ala peptide ligands to it. The findings further prove the versatility of ACE and its ability to estimate binding parameters
of ligands to antibiotics. 相似文献
108.
V. F. Ruban 《Journal of separation science》1990,13(2):112-115
The main characteristics of a dual-electrode amperometric detector with a cell of the “cylinder-in-flow” type with a working wire electrode have been investigated. The effective cell volume is 10–40 nl in a system with 0.2–0.4 mm i.d. packed fused-silica columns. Extra-column spreading at the optimum elution rate does not exceed 0.005 μl2. The linear range is 103 at a relative standard deviation of 0.009. The low noise level (2–3 pA) facilitates determination of electro-active substances. The detection limit for catecholamines is of the order of tenths of a femtomole. 相似文献
109.
The chiral separation of simendan enantiomers using capillary electrophoresis was studied with beta-cyclodextrin (beta-CD) as chiral selector. The influences of the concentration and pH of borate buffer solution, beta-CD concentration and methanol content in the background electrolyte were investigated. These factors were compared with those in an HPLC with beta-CD as chiral mobile phase additive (CMPA-HPLC). The quantification properties of the developed CE method were examined. A baseline separation of simendan enantiomers was achieved in the background electrolyte of 20 mmol/L borate buffer (pH 11.0) containing 12 mmol/L beta-CD-methanol (50:50 in volume ratio). The CE method is comparable with CMPA-HPLC in chiral resolution, although the optimal pH in CE (11.0) is much higher than that (6.0) in CMPA-HPLC. This chiral CE method is applicable to the quantitative ananlysis and enantiomeric excess value determination of L-simendan. 相似文献
110.
A novel capillary flow device has been developed and applied to study the orientation of worm‐like micelles, among other systems. Small‐angle X‐ray scattering (SAXS) data from micelles formed by a Pluronic block copolymer in aqueous salt solution provides evidence for the formation of worm‐like micelles, which align under flow. A transition from a rod‐like form factor to a less persistent conformation is observed under flow. Flow alignment of worm‐like micelles formed by the low molar mass amphiphile system cetyl pyridinium chloride+sodium salicylate is studied for comparative purposes. Here, inhomogenous flow at the micron scale is revealed by streaks in the small‐angle light scattering pattern perpendicular to the flow direction. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献