全文获取类型
收费全文 | 66051篇 |
免费 | 6665篇 |
国内免费 | 9237篇 |
专业分类
化学 | 40269篇 |
晶体学 | 1346篇 |
力学 | 9764篇 |
综合类 | 799篇 |
数学 | 14752篇 |
物理学 | 15023篇 |
出版年
2024年 | 96篇 |
2023年 | 675篇 |
2022年 | 1057篇 |
2021年 | 1689篇 |
2020年 | 1984篇 |
2019年 | 1803篇 |
2018年 | 1736篇 |
2017年 | 2251篇 |
2016年 | 2658篇 |
2015年 | 2222篇 |
2014年 | 3177篇 |
2013年 | 5301篇 |
2012年 | 4321篇 |
2011年 | 4308篇 |
2010年 | 3691篇 |
2009年 | 4191篇 |
2008年 | 4200篇 |
2007年 | 4338篇 |
2006年 | 4010篇 |
2005年 | 3726篇 |
2004年 | 3296篇 |
2003年 | 2870篇 |
2002年 | 2531篇 |
2001年 | 2009篇 |
2000年 | 1901篇 |
1999年 | 1638篇 |
1998年 | 1471篇 |
1997年 | 1348篇 |
1996年 | 1136篇 |
1995年 | 1001篇 |
1994年 | 906篇 |
1993年 | 740篇 |
1992年 | 734篇 |
1991年 | 559篇 |
1990年 | 433篇 |
1989年 | 388篇 |
1988年 | 303篇 |
1987年 | 212篇 |
1986年 | 150篇 |
1985年 | 164篇 |
1984年 | 162篇 |
1983年 | 83篇 |
1982年 | 113篇 |
1981年 | 78篇 |
1980年 | 48篇 |
1979年 | 63篇 |
1978年 | 53篇 |
1977年 | 41篇 |
1976年 | 18篇 |
1957年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 359 毫秒
11.
The indentation technique is widely used in measuring the mechanical properties of soft matter at the microscale or nanoscale,but still faces challenges by these unique properties as well as the consequent strong surface adhesion, including the strong nonlinear effect, unclear judgment of the contact point, difficulties in estimating the contact area, and the risk of the indenter piercing the sample. Here we propose a two-step method to solve these problems: lay a hard film on a soft matter, and obtain the viscoelastic properties of this soft matter through the indentation response of this composite structure. We first establish a theoretical indentation model of the hard film-soft substrate system based on the theory of plates, elastic-viscoelastic correspondence principle and Boltzmann superposition principle. To verify the correctness of this method, we measure the mechanical properties of the methyl vinyl silicone rubber(MVSR) covered by a Cu nanofilm. Finally, we test the effectiveness and error sensitivity of this method with the finite element method(FEM). The results show that our method can accurately measure the mechanical properties of soft matter, while effectively circumventing the problems of the traditional indentation technique. 相似文献
12.
13.
The biodegradability of phtalic acid esters in marine and freshwater environments was characterized by their binding free energy with corresponding degrading enzymes. According to comprehensive biodegradation effects weights, the binding free energy values were converted into dimensionless efficacy coefficient using ratio normalization method. Then, considering comprehensive dual biodegradation effects value and the structural parameters of PAEs in both marine and freshwater environments, a 3D-QSAR pharmacophore model was constructed, five PAE derivatives (DBP−COOH, DBP−CHO, DBP−OH, DINP−NH2, and DINP−NO2) were screened out based on their environmental friendliness, functionality and stability. The prediction of biodegradation effects on five PAE derivatives by biodegradation models in marine and freshwater environment increased by 15.90 %, 15.84 %, 27.21 %, 12.33 %, and 8.32 %, and 21.57 %, 15.21 %, 20.99 %, 15.10 %, and 9.74 %, respectively. By simulating the photodegradation path of the PAE derivative molecular, it was found that DBP−OH can generate .OH and provides free radicals for the photodegradation of microplastics in the environment. 相似文献
14.
Erosion and sediments transport processes have a great impact on industrial structures and on water quality. Despite its limitations, the Saint‐Venant‐Exner system is still (and for sure for some years) widely used in industrial codes to model the bedload sediment transport. In practice, its numerical resolution is mostly handled by a splitting technique that allows a weak coupling between hydraulic and morphodynamic distinct softwares but may suffer from important stability issues. In recent works, many authors proposed alternative methods based on a strong coupling that cure this problem but are not so trivial to implement in an industrial context. In this work, we then pursue 2 objectives. First, we propose a very simple scheme based on an approximate Riemann solver, respecting the strong coupling framework, and we demonstrate its stability and accuracy through a number of numerical test cases. However, second, we reinterpret our scheme as a splitting technique and we extend the purpose to propose what should be the minimal coupling that ensures the stability of the global numerical process in industrial codes, at least, when dealing with collocated finite volume method. The resulting splitting method is, up to our knowledge, the only one for which stability properties are fully demonstrated. 相似文献
15.
Recyclable and reusable Pd(OAc)2/PPh3/PEG‐2000 system for homocoupling reaction of arylboronic acids under air without base 下载免费PDF全文
A stable and efficient Pd(OAc)2/PPh3/PEG‐2000 catalytic system for homocoupling of arylboronic acids has been developed. In the presence of Pd(OAc)2 and PPh3, the homocoupling reaction of arylboronic acids was carried out smoothly in PEG‐2000 at 70 °C under air without base to afford a variety of symmetric biaryls in good to excellent yields. The isolation of the products was readily performed by extraction with diethyl ether, and the Pd(OAc)2/PPh3/PEG‐2000 system could be easily recycled and reused six times without significant loss of catalytic activity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
16.
Identification of metabolites of rupestonic acid in rat urine by liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry 下载免费PDF全文
Dongyu Gu Yi Yang Qibin Chen Madina Habasi Jiangyu Zhao Haji Akber Aisa 《Biomedical chromatography : BMC》2015,29(4):595-603
Rupestonic acid, a potential anti‐influenza agent, is an important and characteristic compound in Artemisia rupestris L., a well‐known traditional Uighur medicine for the treatment of colds. In the present study, high‐performance liquid chromatography combined with electrospray ionization quadrupole time‐of‐flight tandem mass spectrometry was used to detect and identify the metabolites in rat urine after oral administration of rupestonic acid. A total of 10 metabolites were identified or partially characterized. The structure elucidations of the metabolites were performed by comparing the changes in accurate molecular masses and fragment ions with those of the parent compound. The results showed that the main metabolites of rupestonic acid in rat urine were formed by oxidation, hydrogenation and glucuronidation. A metabolism pathway was proposed for the first time based on the characterized structures. This metabolism study can provide essential information for drug discovery, design and clinical application of rupestonic acid. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
17.
《Arabian Journal of Chemistry》2021,14(11):103421
Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS+) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC50: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS+ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain. 相似文献
18.
采用量子统计系综理论,研究了基态NO分子宏观气体摩尔熵、摩尔内能、摩尔热容等热力学性质.首先应用课题组前期建立的变分代数法(variational algebraic method, VAM)计算获得了基态NO分子的完全振动能级,得到的VAM振动能级作为振动部分,结合欧拉-麦克劳林渐进展开公式的转动贡献,应用于经典的热力学与统计物理公式中,从而计算得到了1000-5000 K温度范围内NO宏观气体的摩尔内能、摩尔熵和摩尔热容.将不同方法计算得到的摩尔热容结果分别与实验值进行比较,结果表明基于VAM完全振动能级获得的结果优于其他方法获得的理论结果.振动部分采用谐振子模型对无限能级求和计算热力学性质的方法有一定的局限性,应当使用有限的完全振动能级进行统计求和. 相似文献
19.
Molecularly imprinted polymer (MIP) computational design is expected to become a routine technique prior to synthesis to produce polymers with high affinity and selectivity towards target molecules. Furthermore, using these simulations reduces the cost of optimizing polymerization composition. There are several computational methods used in MIP fabrication and each requires a comprehensive study in order to select a process with results that are most similar to properties exhibited by polymers synthesized through laboratory experiments. Until now, no review has linked computational strategies with experimental results, which are needed to determine the method that is most appropriate for use in designing MIP with high molecular recognition. This review will present an update of the computational approaches started from 2016 until now on quantum mechanics, molecular mechanics and molecular dynamics that have been widely used. It will also discuss the linear correlation between computational results and the polymer performance tests through laboratory experiments to examine to what extent these methods can be relied upon to obtain polymers with high molecular recognition. Based on the literature search, density functional theory (DFT) with various hybrid functions and basis sets is most often used as a theoretical method to provide a shorter MIP manufacturing process as well as good analytical performance as recognition material. 相似文献
20.