全文获取类型
收费全文 | 1254篇 |
免费 | 64篇 |
国内免费 | 4篇 |
专业分类
化学 | 999篇 |
晶体学 | 11篇 |
力学 | 15篇 |
数学 | 61篇 |
物理学 | 236篇 |
出版年
2023年 | 8篇 |
2022年 | 9篇 |
2021年 | 17篇 |
2020年 | 22篇 |
2019年 | 30篇 |
2018年 | 23篇 |
2017年 | 15篇 |
2016年 | 34篇 |
2015年 | 35篇 |
2014年 | 38篇 |
2013年 | 47篇 |
2012年 | 91篇 |
2011年 | 109篇 |
2010年 | 61篇 |
2009年 | 50篇 |
2008年 | 56篇 |
2007年 | 87篇 |
2006年 | 88篇 |
2005年 | 77篇 |
2004年 | 56篇 |
2003年 | 67篇 |
2002年 | 68篇 |
2001年 | 20篇 |
2000年 | 27篇 |
1999年 | 18篇 |
1998年 | 8篇 |
1997年 | 12篇 |
1996年 | 11篇 |
1995年 | 13篇 |
1994年 | 15篇 |
1993年 | 9篇 |
1992年 | 12篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 6篇 |
1980年 | 5篇 |
1978年 | 6篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1968年 | 4篇 |
排序方式: 共有1322条查询结果,搜索用时 15 毫秒
71.
Hydrothermal formation of tobermorite studied by in situ X‐ray diffraction under autoclave condition
Jun Kikuma Masamichi Tsunashima Tetsuji Ishikawa Shin‐ya Matsuno Akihiro Ogawa Kunio Matsui Masugu Sato 《Journal of synchrotron radiation》2009,16(5):683-686
Hydrothermal formation of tobermorite from a pre‐cured cake has been investigated by transmission X‐ray diffraction (XRD) using high‐energy X‐rays from a synchrotron radiation source in combination with a newly designed autoclave cell. The autoclave cell has a large and thin beryllium window for wide‐angle X‐ray diffraction; nevertheless, it withstands a steam pressure of more than 1.2 MPa, which enables in situ XRD measurements in a temperature range of 373 to 463 K under a saturated steam pressure. Formation and/or decomposition of several components has been successfully observed during 7.5 h of reaction time. From the intensity changes of the intermediate materials, namely non‐crystalline C–S–H and hydroxylellestadite, two pathways for tobermorite formation have been confirmed. Thus, the newly developed autoclave cell can be used for the analyses of reaction mechanisms under specific atmospheres and temperatures. 相似文献
72.
9,10‐Diaminoanthracenes Revisited: The Influence of N‐Substituents on Their Electronic States
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Masashi Uebe Prof. Dr. Tatsuhisa Kato Prof. Dr. Kazuyoshi Tanaka Dr. Akihiro Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18923-18931
The electronic and molecular structures of 9,10‐diamino‐substituted anthracenes with different N‐substituents have been re‐examined. In particular, different N‐substituents influence both the electronic and molecular structures of the oxidized species of 9,10‐diaminoanthracenes. The anthrylene moiety of 9,10‐bis(N,N‐di(p‐anisyl)amino)anthracene retains its planarity during the course of two successive one‐electron oxidations, whereas 9,10‐bis(N,N‐dimethylamino)anthracene and 9,10‐bis(N‐p‐anisyl‐N‐methylamino)anthracene undergo a substantial structural change to a butterfly‐like structure through a two‐electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above‐mentioned three kinds of 9,10‐diaminoanthracenes due to different extents of mixing between the amine‐localized and anthrylene‐localized orbitals. 相似文献
73.
Porphyrin accumulation onto a self-assembled monolayer (SAM) of imidazole-substituted porphyrins by a supramolecular method to form a chain structure leads to significant increase of light absorption in the visible light region and therefore photocurrents. 相似文献
74.
In view of recent developments in the investigation on cuprate high- T(c) superconductors and the spin-Peierls compound CuGeO3, we study the effect of dilute impurity doping on the spin-Peierls state in quasi-one-dimensional systems. We identify a common origin for the emergence of antiferromagnetic order upon the introduction of static vacancies and superconductivity for mobile holes. 相似文献
75.
Hiroshi Tanaka Takeo Yoshioka Yasutaka Shimauchi Akihiro Yoshimoto Tomoyuki Ishikura Hiroshi Naganawa Tomio Takeuchi Hamao Umezawa 《Tetrahedron letters》1984,25(31):3351-3354
The tricyclic quinone 8 was successfully synthesized from naphthazalin, and the total synthesis of (±)-2-hydroxyaklavinone via 8 was accomplished in an overall yield of about 18% through the regio-controlled route. 相似文献
76.
77.
78.
Mayumi Tsutsui Tokuhiro Watanabe Akihiro Ohta Kayoko Takizawa 《Journal of heterocyclic chemistry》1980,17(4):809-812
1 H-Nmr spectra of cis and trans isomers of 2,3-, 2,5-, and 2,6-dimethylpiperazines were taken at various temperatures. The spectra of geometrical isomers bearing the ae or ea dimethyl groups showed broadening at lower temperatures. It was clarified that the measurement of the spectra at lower temperatures is useful for the discrimination of the geometrical isomers of dimethylpiperazines. 相似文献
79.
Akihiro Abe J. W. Kennedy P. J. Flory 《Journal of Polymer Science.Polymer Physics》1976,14(7):1337-1349
Statistical mechanical averages of vectors and tensors characterizing the spatial configurations of polyoxymethylene (POM) and polyoxyethylene (POE) chains, i.e., the chain vector r connecting the ends of the chain and the tensors formed from this vector, are evaluated in internal reference frames attached to the first two bonds of each chain as functions of its length. Convergences of the persistence vectors a ≡ 〈 r 〉 with chain length to their limits a ∞ are delineated. For POE, the orientation of a ∞ with respect to the X1 axes (the direction of the first bond) depends markedly on the choice of the initial bond and hence also on the internal frame of reference. Cartesian tensors up to fourth rank formed from the displacement vector ρ = r ? a are evaluated for n = 4–1922 bonds for POM and n = 3–300 bonds for POE. The second moment tensor 〈ρρT〉 calculated for POM is nearly cylindrically symmetric about the axis perpendicular to the plane of the first two bonds. Corresponding symmetry is absent in POE. Correlation with the freely jointed chain is investigated for the components of the tensors of fourth rank formed from the reduced vector \documentclass{article}\pagestyle{empty}\begin{document} $\tilde \rho = \left\langle {\rho \rho ^{\rm T} } \right\rangle ^{ - 1/2} \rho $\end{document}. Use of the equivalent chain model for this purpose is validated for POE but not for POM, even at n = 2000 bonds. At the limit 1/n = 0, the parameter m, representing the number of bonds of the real chain equivalent to one of the model, is estimated to be ca. 31 for POM. For POE a value of m = 10.3 ± 1.3 holds for n > 20 for all components. Results are compared with those calculated previously for polymethylene, poly(dimethylsiloxane) and polypeptides. The fact that values of m derived by analysis of moments are larger than those obtained in the usual manner by fitting the model chain to 〈r2〉0 and rmax for the real chain demonstrates the inadequacy of artificial models for the representation of the real chain. 相似文献
80.
Nishioka H Kimura A Yamato T Kawatsu T Kakitani T 《The journal of physical chemistry. B》2005,109(32):15621-15635
Developing the quantum transition rate theory of Prezhdo and Rossky (J. Chem. Phys. 1997, 107, 5863), we produced a new non-Condon theory of the rate of electron transfer (ET) which happens through a protein medium with conformational fluctuation. The new theory is expressed by a convolution form of the power spectrum for the autocorrelation function of the electronic tunneling matrix element T(DA)(t) with quantum correction and the ordinary Franck-Condon factor. The new theory satisfies the detailed balance condition for the forward and backward ET rates. The ET rate formula is divided into two terms of elastic and inelastic tunneling mechanisms on the mathematical basis. The present theory is applied to the ET from Bph(-) to Q(A) in the reaction center of Rhodobacter sphaeroides. Numerical calculations of T(DA)(t) were made by a combined method of molecular dynamics simulations and quantum chemistry calculations. We showed that the normalized autocorrelation function of T(DA)(t) is almost expressed by exponential forms. The calculated energy gap law of the ET rate is nearly Marcus' parabola in most of the normal region and around the maximum region, but it does not decay substantially in the inverted region, which is called the anomalous inverted region. We also showed that the energy gap law at the high uphill energy gap in the normal region is elevated considerably from the Marcus' parabola, which is called the anomalous normal region. Those anomalous energy gap laws are due to the inelastic tunneling mechanism which works actively at the energy gap far from zero. We presented an empirical formula for easily calculating the non-Condon ET rate, which is usable by many researchers. We provided experimental evidence for the anomalous inverted region which was basically reproduced by the present theory. The present theory was extensively compared with the previous non-Condon theories. 相似文献