全文获取类型
收费全文 | 84905篇 |
免费 | 6386篇 |
国内免费 | 6558篇 |
专业分类
化学 | 41334篇 |
晶体学 | 569篇 |
力学 | 5714篇 |
综合类 | 1184篇 |
数学 | 17734篇 |
物理学 | 31314篇 |
出版年
2023年 | 874篇 |
2022年 | 1271篇 |
2021年 | 2368篇 |
2020年 | 2139篇 |
2019年 | 1983篇 |
2018年 | 1796篇 |
2017年 | 2106篇 |
2016年 | 2462篇 |
2015年 | 2196篇 |
2014年 | 3276篇 |
2013年 | 5905篇 |
2012年 | 3840篇 |
2011年 | 4404篇 |
2010年 | 3763篇 |
2009年 | 5117篇 |
2008年 | 5319篇 |
2007年 | 5730篇 |
2006年 | 4684篇 |
2005年 | 3713篇 |
2004年 | 3251篇 |
2003年 | 3252篇 |
2002年 | 3015篇 |
2001年 | 2691篇 |
2000年 | 2512篇 |
1999年 | 2089篇 |
1998年 | 2076篇 |
1997年 | 1329篇 |
1996年 | 1331篇 |
1995年 | 1278篇 |
1994年 | 1280篇 |
1993年 | 1084篇 |
1992年 | 1110篇 |
1991年 | 790篇 |
1990年 | 709篇 |
1989年 | 561篇 |
1988年 | 543篇 |
1987年 | 482篇 |
1986年 | 449篇 |
1985年 | 503篇 |
1984年 | 448篇 |
1983年 | 267篇 |
1982年 | 454篇 |
1981年 | 633篇 |
1980年 | 518篇 |
1979年 | 560篇 |
1978年 | 451篇 |
1977年 | 357篇 |
1976年 | 278篇 |
1974年 | 108篇 |
1973年 | 193篇 |
排序方式: 共有10000条查询结果,搜索用时 250 毫秒
81.
Vera Deneva 《Molecular physics》2019,117(13):1613-1620
ABSTRACTThe tautomeric optical sensors based on 4-(phenyldiazenyl)naphthalen-1-ol exist in their pure enol tautomeric form as free ligands, while the addition of metal ion fully shifts the equilibrium towards the keto tautomer allowing a red shift in the measured absorbance. This effect is achieved when a side ionophore group is connected to a tautomeric backbone by a spacer in a way that stabilizes the enol form via hydrogen boding. When the ionophore captures the metal ion the keto form is stabilized due to C─O tautomeric group participation in the complex. In the current study, we model theoretically the effect of symmetric tweezer like ionophores (RCOXCOR, where X, being CH or N, is the linker to the tautomeric backbone) on the tautomeric state and complexation ability of 4-(phenyldiazenyl)naphthalen-1-ol containing ligands. It was found that enol form stabilisation is achieved when R?=?NMe2, independing on the linker. Both ligands are unsuitable for capturing alkali metal ions. The calculations predict that the complexation with alkali earth metal ions could lead to a full shift of the tautomeric equilibrium towards keto tautomer. 相似文献
82.
Chikashi Shinagawa Yusuke Morikawa Shin-ichi Nishimura Hiroshi Ushiyama Atsuo Yamada Koichi Yamashita 《Journal of computational chemistry》2019,40(1):237-246
Na2FePO4F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na2FePO4F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na1.5FePO4F has the P21/b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P21/b11 Na1.5FePO4F and Pbcn Na2FePO4F or Na1FePO4F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na2FePO4F has diffusion paths in the a- and c-axis directions, Na2FePO4F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc. 相似文献
83.
Chunlai Wu Chuanyun Peng 《International journal of environmental analytical chemistry》2019,99(7):670-682
To develop an accurate and precise method for separation and pre-concentration of Hg(II), a novel thionin functionalised core shell structure magnetic material has been prepared and characterised. The extraction ability of the material was evaluated by magnetic solid-phase extraction coupled with inductively coupled plasma mass spectrometry determination of Hg(II) in food and water samples. Combining the advantages of magnetic separation with selective extraction of thionin towards Hg(II), the material exhibits enhanced enrich selectivity and efficiency for Hg(II). The experimental parameters influencing Hg(II) extraction efficiency, including pH of the aqueous solution, the dosage of the adsorbent, extraction time and sample volume, were systematically investigated. Under the optimised conditions, concentration of Hg(II) at 1.0 μg L?1 can be successfully enriched by the material without the interference of the common co-existing ions. The enrichment factor and adsorption capacity were 250 and 75.2 mg g?1, and precise of the method was confirmed by analysing the spiked food, water samples and standard water reference samples with the recoveries of 92.5–101.8%. 相似文献
84.
Xuan Thinh Duong Irina Holmes Ji Li Brett D. Wick Dongyong Yang 《Journal of Functional Analysis》2019,276(4):1007-1060
In this paper we establish the characterization of the weighted BMO via two weight commutators in the settings of the Neumann Laplacian on the upper half space and the reflection Neumann Laplacian on with respect to the weights associated to and respectively. This in turn yields a weak factorization for the corresponding weighted Hardy spaces, where in particular, the weighted class associated to is strictly larger than the Muckenhoupt weighted class and contains non-doubling weights. In our study, we also make contributions to the classical Muckenhoupt–Wheeden weighted Hardy space (BMO space respectively) by showing that it can be characterized via the area function (Carleson measure respectively) involving the semigroup generated by the Laplacian on and that the duality of these weighted Hardy and BMO spaces holds for Muckenhoupt weights with while the previously known related results cover only . We also point out that this two weight commutator theorem might not be true in the setting of general operators L, and in particular we show that it is not true when L is the Dirichlet Laplacian on . 相似文献
85.
86.
A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH2–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO2 adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g−1 for CO2, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO2 adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R2) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO2/N2 adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO2 molecules. 相似文献
87.
We describe matrices with extremal generalized centralizers over algebraically closed fields. 相似文献
88.
Consider an elastic thin three-dimensional body made of a periodic distribution of elastic inclusions. When both the thickness of the beam and the size of the heterogeneities tend simultaneously to zero the authors obtain three different one-dimensional models of beam depending upon the limit of the ratio of these two small parameters. 相似文献
89.
Poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) receives increasing attention in membrane separation field based on its advantages such as high mechanical strength, thermal and chemical stability. However, controlling the microporous structure is still challenging.In this work, we attempted to tailor the morphology of PVDF-HFP membrane via a one-step reactive vapor induced phase separation method.Namely, PVDF-HFP was dissolved in a volatile solvent and then was cast in an ammonia water vapor atmosphere. After complete evaporation of solvent, membranes with adjustable porous structure were prepared, and the microstructures of the membranes were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction characterizations. Based on the results, a mechanism of dehydrofluorination induced cross-linking of PVDF-HFP has been suggested to understand the morphology tailoring.To our knowledge, this is the first report of one-step reactive vapor induced phase separation strategy to tailor morphology of PVDF-HFP membrane. In addition, the membranes prepared in the ammonia water vapor exhibited enhanced mechanical strength and achieved satisfactory separation efficiency for water-in-oil emulsions, suggesting promising potential. 相似文献
90.
This paper is our attempt, on the basis of physical theory, to bring more clarification on the question “What is life?” formulated in the well-known book of Schrödinger in 1944. According to Schrödinger, the main distinguishing feature of a biosystem’s functioning is the ability to preserve its order structure or, in mathematical terms, to prevent increasing of entropy. However, Schrödinger’s analysis shows that the classical theory is not able to adequately describe the order-stability in a biosystem. Schrödinger also appealed to the ambiguous notion of negative entropy. We apply quantum theory. As is well-known, behaviour of the quantum von Neumann entropy crucially differs from behaviour of classical entropy. We consider a complex biosystem S composed of many subsystems, say proteins, cells, or neural networks in the brain, that is, We study the following problem: whether the compound system S can maintain “global order” in the situation of an increase of local disorder and if S can preserve the low entropy while other increase their entropies (may be essentially). We show that the entropy of a system as a whole can be constant, while the entropies of its parts rising. For classical systems, this is impossible, because the entropy of S cannot be less than the entropy of its subsystem . And if a subsystems’s entropy increases, then a system’s entropy should also increase, by at least the same amount. However, within the quantum information theory, the answer is positive. The significant role is played by the entanglement of a subsystems’ states. In the absence of entanglement, the increasing of local disorder implies an increasing disorder in the compound system S (as in the classical regime). In this note, we proceed within a quantum-like approach to mathematical modeling of information processing by biosystems—respecting the quantum laws need not be based on genuine quantum physical processes in biosystems. Recently, such modeling found numerous applications in molecular biology, genetics, evolution theory, cognition, psychology and decision making. The quantum-like model of order stability can be applied not only in biology, but also in social science and artificial intelligence. 相似文献