全文获取类型
收费全文 | 3173篇 |
免费 | 392篇 |
国内免费 | 181篇 |
专业分类
化学 | 895篇 |
晶体学 | 55篇 |
力学 | 564篇 |
综合类 | 44篇 |
数学 | 1192篇 |
物理学 | 996篇 |
出版年
2024年 | 3篇 |
2023年 | 39篇 |
2022年 | 90篇 |
2021年 | 87篇 |
2020年 | 81篇 |
2019年 | 74篇 |
2018年 | 80篇 |
2017年 | 107篇 |
2016年 | 137篇 |
2015年 | 111篇 |
2014年 | 150篇 |
2013年 | 228篇 |
2012年 | 174篇 |
2011年 | 177篇 |
2010年 | 170篇 |
2009年 | 202篇 |
2008年 | 170篇 |
2007年 | 191篇 |
2006年 | 157篇 |
2005年 | 144篇 |
2004年 | 133篇 |
2003年 | 127篇 |
2002年 | 168篇 |
2001年 | 97篇 |
2000年 | 87篇 |
1999年 | 62篇 |
1998年 | 69篇 |
1997年 | 60篇 |
1996年 | 52篇 |
1995年 | 36篇 |
1994年 | 38篇 |
1993年 | 27篇 |
1992年 | 36篇 |
1991年 | 27篇 |
1990年 | 25篇 |
1989年 | 10篇 |
1988年 | 16篇 |
1987年 | 20篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 15篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 10篇 |
1977年 | 5篇 |
1976年 | 6篇 |
1974年 | 2篇 |
排序方式: 共有3746条查询结果,搜索用时 15 毫秒
51.
A simple and fast method was developed to determine non-UV active compounds directly without derivatization. The usefulness of the method was demonstrated by detecting the major components in aminoglycoside antibiotic mixtures using capillary zone electrophoresis with potential gradient detection. Under optimized separation conditions (0.2 mM cetyltrimethylammonium bromide (CTAB), 1 mM ammonium citrate, pH 3.5), gentamicin was separated into three major peaks (C1, C1a, and C2+C2a) within 15 min. This method showed better sensitivity than other capillary electrophoresis (CE) methods for determining underivatized gentamicin. The linear range was from 10 to 500 ppm. Because of its good repeatability and simplicity, this new method could be a good alternative for the current assays given by US Pharmacopoeia and European Pharmacopoeia. 相似文献
52.
One of the major techniques used for the method development of ternary and quaternary high performance liquid chromatography (HPLC) systems has been to use mixture designs, often referred to as "Glajch's Triangle". This technique does not allow for the systematic and simultaneous optimization of other factors such as gradient time, pH and temperature that affect the quality of separations. An alternative approach is to use experimental designs. The condition, however, that the composition of all components of the mobile phase must total 100% presents a problem when trying to mathematically represent ranges of each mobile phase constituent of a ternary or quaternary system. A method is described here, based on spherical coordinate representations, that adheres to the constraints of the mobile phase composition and allows experimental designs, such as central composite and factorial designs, to be applied to the simultaneous optimization of the mobile phase composition. Other factors, in particular temperature and gradient time, can then be included in the design. As a result of applying these designs to the HPLC separation of phenols and corticosteroids, it was found necessary to include three-way interactions between experimental factors in the model. The significance of these interactions shows that they need to be considered in HPLC method development. 相似文献
53.
《Journal of separation science》2003,26(17):1541-1546
A novel approach is proposed for the simultaneous optimization of mobile phase pH and gradient steepness in RP‐HPLC using artificial neural networks. By presetting the initial and final concentration of the organic solvent, a limited number of experiments with different gradient time and pH value of mobile phase are arranged in the two‐dimensional space of mobile phase parameters. The retention behavior of each solute is modeled using an individual artificial neural network. An “early stopping” strategy is adopted to ensure the predicting capability of neural networks. The trained neural networks can be used to predict the retention time of solutes under arbitrary mobile phase conditions in the optimization region. Finally, the optimal separation conditions can be found according to a global resolution function. The effectiveness of this method is validated by optimization of separation conditions for amino acids derivatised by a new fluorescent reagent. 相似文献
54.
Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer 总被引:1,自引:0,他引:1
Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents. 相似文献
55.
一种基于流动注射梯度技术识别异常峰及校正的方法 总被引:1,自引:0,他引:1
基于流动注射梯度信息提出了一种利用梯度比均值进行定量的校正方法。方法具有在线自动判别和修复异常峰并自行校正的功能,和通用的标准系列定量方法相比,两者测定精度相当。但本文提出的方法抗干扰能力明显优于后者,可适用于在线过程监测。 相似文献
56.
Summary The separation of two families of plastics additives (phenolic antioxidants and UV absorbers) has been achieved by high performance liquid chromatography with a quaternary gradient. A methodology of separation based on a sequential optimization is described. After a preliminary study of the effects of solvents on retention of compounds, the mobile phase is first chosen for each class of additives (Irganox and Tinuvin), then for the mixture of all the compounds and the separation is finally optimized. The importance of the column phase ratio is also reported. The use of two detectors, UV absorbance and light-scattering, enables all the compounds to be detected. The performance of the detectors has been compared and the effects of the nebulization temperature on the detection of low molecular mass compounds is reported. 相似文献
57.
Wandrey C 《Chemical record (New York, N.Y.)》2004,4(4):254-265
Redox reactions are still a challenge for biochemical engineers. A personal view for the development of this field is given. Cofactor regeneration was an obstacle for quite some time. The first technical breakthrough was achieved with the system formate/formate dehydrogenase for the regeneration of NADH2. In cases where the same enzyme could be used for chiral reduction as well as for cofactor regeneration, isopropanol as a hydrogen source proved to be beneficial. The coproduct (acetone) can be removed by pervaporation. Whole-cell reductions (often yeast reductions) can also be used. By proper biochemical reaction engineering, it is possible to apply these systems in a continuous way. By cloning a formate dehydrogenase and an oxidoreductase "designer bug" can be obtained where formate is used instead of glucose as the hydrogen source. Complex sequences of redox reactions can be established by pathway engineering with a focus on gene overexpression or with a focus on establishing non-natural pathways. The success of pathway engineering can be controlled by measuring cytosolic metabolite concentrations. The optimal exploitation of such systems calls for the integrated cooperation of classical and molecular biochemical engineering. 相似文献
58.
59.
Geometries and stabilization energies of various simple H-bonded complexes (water dimer, hydrogen fluoride dimer, formamide
dimer, formic acid dimer) have been determined by a gradient optimization that eliminates the basis set superposition error
(BSSE) by the counterpoise (CP) method in each gradient cycle as well as by the standard gradient optimization. Both optimization
methods lead to different potential energy surfaces (PES). The difference depends on the theoretical level used and is larger
if correlation energy is considered. Intermolecular distances from the CP-corrected PES are consistently longer, and this
difference might be significant (∼0.1 ?); also angular characteristics determined from both surfaces differ significantly.
Different geometries were obtained even when passing to larger basis sets (aug-cc-pVDZ). The standard optimization procedure
can result in a completely wrong structure. For example, the “quasi-linear” structure of the (HF)2 (global minimum) does not exist at the standard MP2/ 6-31G** PES (where only cyclic structure was detected) and is found
only at the CP-corrected PES. Stabilization energies obtained from the CP-corrected PES are always larger than these from
the standard PES where the BSSE is added only a posteriori for the final optimized structure; both energies converge only
when passing to a larger basis set (aug-cc-pVDZ).
Received: 11 March 1998 / Accepted: 19 June 1998 / Published online: 4 September 1998
RID="
ID=" <E6>Acknowledgements.</E6> The project was supported by the Grant Agency of the Czech Republic (Grant No. 203/98/1166).
RID="
ID=" <E5>Correspondence to</E5>: P. Hobza 相似文献
60.
Extrapolated Smoothing Descent Algorithm for Constrained Nonconvex and Nonsmooth Composite Problems*
In this paper, the authors propose a novel smoothing descent type algorithm with extrapolation for solving a class of constrained nonsmooth and nonconvex problems,where the nonconvex term is possibly nonsmooth. Their algorithm adopts the proximal gradient algorithm with extrapolation and a safe-guarding policy to minimize the smoothed objective function for better practical and theoretical performance. Moreover, the algorithm uses a easily checking rule to update the smoothing parameter to ensure that any accumulation point of the generated sequence is an (affine-scaled) Clarke stationary point of the original nonsmooth and nonconvex problem. Their experimental results indicate the effectiveness of the proposed algorithm. 相似文献