全文获取类型
收费全文 | 3963篇 |
免费 | 91篇 |
国内免费 | 21篇 |
专业分类
化学 | 2757篇 |
晶体学 | 42篇 |
力学 | 50篇 |
数学 | 182篇 |
物理学 | 1044篇 |
出版年
2022年 | 16篇 |
2021年 | 33篇 |
2020年 | 44篇 |
2019年 | 56篇 |
2018年 | 38篇 |
2017年 | 22篇 |
2016年 | 56篇 |
2015年 | 68篇 |
2014年 | 65篇 |
2013年 | 162篇 |
2012年 | 171篇 |
2011年 | 229篇 |
2010年 | 104篇 |
2009年 | 141篇 |
2008年 | 207篇 |
2007年 | 216篇 |
2006年 | 219篇 |
2005年 | 177篇 |
2004年 | 170篇 |
2003年 | 157篇 |
2002年 | 169篇 |
2001年 | 131篇 |
2000年 | 106篇 |
1999年 | 69篇 |
1998年 | 52篇 |
1997年 | 57篇 |
1996年 | 53篇 |
1995年 | 41篇 |
1994年 | 54篇 |
1993年 | 62篇 |
1992年 | 75篇 |
1991年 | 60篇 |
1990年 | 50篇 |
1989年 | 57篇 |
1988年 | 43篇 |
1987年 | 56篇 |
1986年 | 48篇 |
1985年 | 55篇 |
1984年 | 51篇 |
1983年 | 39篇 |
1982年 | 28篇 |
1981年 | 41篇 |
1980年 | 30篇 |
1979年 | 48篇 |
1978年 | 40篇 |
1977年 | 25篇 |
1976年 | 31篇 |
1975年 | 26篇 |
1974年 | 28篇 |
1973年 | 21篇 |
排序方式: 共有4075条查询结果,搜索用时 15 毫秒
991.
The Lanczos homogeneous filter diagonalization method has been employed to compute the HOCl ro-vibrational states for a range of total angular momenta (J = 0, 1, 5, 10, 11, 20, 30) on a newly developed ab initio potential energy surface by Nanbu et al. (J. Theor. Comput. Chem. 2002, 1, 263). For such computationally challenging calculations, a parallel computing strategy has been incorporated into our method to perform the matrix-vector multiplications. For the computed low bound states, a spectroscopic assignment has been made and the widely used approximate adiabatic rotation method has been tested for the broad range of total angular momenta for this deep-well system. Comparison of experimental results with exact quantum mechanical calculations for the selected far-infrared transitions involving the range of total angular momenta has been made possible for the first time. 相似文献
992.
Liu B Qian DJ Chen M Wakayama T Nakamura C Miyake J 《Chemical communications (Cambridge, England)》2006,(30):3175-3177
Coordination polymer nanotubes have been prepared by using the Hg2+-mediated co-assembly of two ligands, tetrapyridylporphine (TPyP) and tris(4-pyridyl)-1,3,5-triazine (TPyTa), at the water-chloroform interface. 相似文献
993.
Yongzhu J Hirose K Nakamura T Nishioka R Ueshige T Tobe Y 《Journal of chromatography. A》2006,1129(2):201-207
In order to develop a chiral stationary phase (CSP), which has even higher separation ability than the corresponding commercially available crown ether based CSP (OA-8000 having a pseudo-18-crown-6 ether with an OMe group as a selector), chemically bonded type CSP having a phenolic OH group on a crown ring was developed. Normal mobile phases with or without acid additive can be used with this OH type CSP in contrast to the conventional OMe type CSP which has a neutral chiral selector. Enantiomers of 25 out of 27 amino compounds, including 20 amino acids, 5 amino alcohols, and 2 lipophilic amines, were efficiently separated on a column with this CSP. Nine amino compounds out of 27 were separated with better separation factors than the corresponding OMe type CSP. It is noteworthy that the chromatography on this CSP exhibited excellent enantiomer-separations for amines and amino alcohols when triethyl amine was used as an additive in the mobile phase. Comparison of enantiomer separation ability on this OH type of CSP and on the OMe type of CSP and correlation between the enantioselectivity in chiral chromatography and that of the corresponding model compounds in solution imply that the chiral separation arose from chiral recognition in host guest interactions. 相似文献
994.
The rheological behavior and microstructure of shear-thinning suspensions of core-shell structured carboxylated latex particles were examined. The steady shear viscosity of the suspension increased with increasing dissociation of the carboxyl groups or increasing particle concentration, however the critical shear stress sigma(c) and inter-particle distance xi of the microstructure did not change. With increasing particle diameter, sigma(c) increased and xi decreased. These results were consistent with a Brownian hard sphere model, in which competition exists between the bulk mass transfer due to the applied field and diffusion of the particles. We confirmed that sigma(c) depends on xi, as expressed by sigma(c) = 3kT/4pi xi3. This relationship is consistent with the dynamics of a Brownian hard sphere model with particle diameter xi. Thus the dynamics of shear-thinning suspensions of core-shell particles can be explained by a Brownian thermodynamic model. 相似文献
995.
Orito K Miyazawa M Nakamura T Horibata A Ushito H Nagasaki H Yuguchi M Yamashita S Yamazaki T Tokuda M 《The Journal of organic chemistry》2006,71(16):5951-5958
A phosphine-free catalytic system [Pd(OAc)2-Cu(OAc)2-air] induced a substrate-specific carbonylation of amines in boiling toluene under CO gas (1 atm). Symmetrical N,N'-dialkylureas were obtained by the carbonylation of primary amines. N,N,N'-Trialkylureas were selectively formed by addition of a secondary amine to the above reaction vessel. Secondary amines did not give tetraalkylureas. However, dialkylamines with a phenyl group on their alkyl chains, such as N-monoalkylated benzylic amine or phenethylamine derivatives, underwent a direct aromatic carbonylation to afford five- or six-membered benzolactams. In the carbonylation, the chelation effect or steric repulsion between Pd(II) and the meta-substituent in the ortho-palladation and the ring sizes of cyclopalladation products that were formed prior to carbonylation were found to generate good site selectivity and increase the reaction rate. In contrast, carbonylation of omega-arylalkylamines with a hydroxyl group gave neither ureas nor benzolactams but instead produced 1,3-oxazolidinones smoothly. Hydrochlorides of amines also underwent carbonylation to afford the corresponding amides under the conditions used. This procedure made it possible to prepare ureas of amino acid esters and N-alkylcarbamates in practical yields. 相似文献
996.
Isocyanide-bound model hemes always adopt the (dxz, dyz)4(dxy)1 ground state, however, we have found that the replacement of porphyrin by diazaporphyrin leads to the formation of an unprecedented low-spin bis(tert-butylisocyanide) complex with the (dxy)2(dxz, dyz)3 ground state. 相似文献
997.
Shimoyama Y Ukai M Nakamura H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(4):888-890
We revealed free radicals in wheat flour before and after gamma-ray irradiation and their thermal behavior during heat-treatment using electron spin resonance (ESR) spectroscopy. The ESR spectrum of wheat flour before irradiation consists of a sextet centered at g = 2.0 and a singlet signal at the same g-value position. The first one is attributable to a signal with hyperfine (hf) interactions of Mn2+ ion (hf constant: 7.4 mT). The second is originated from carbon-centered radical. Upon gamma-ray irradiation, however, a new signal with two triplet lines at the low and high field ends was detected in wheat flour on top of the Mn2+ sextet lines. We analyzed the triplet ESR lines as powder spectra (rhombic g-tensor symmetry) with nitrogen (14N) hyperfine interactions. This indicates that a new organic radical was induced in the conjugated protein portion of wheat flour by the gamma-ray irradiation. Intensity of the organic free radical at g = 2.0 detected in irradiated wheat flour increased monotonically by the thermal treatment. The analysis of the time-dependent evolution and decay process based on the theory of transient phenomena as well as the nonlinear least-squares numerical method provided a unique time constant for the radical evolution and decay in wheat flour during the heat-treatment. 相似文献
998.
Ukai M Nakamura H Shimoyama Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(4):879-882
We found various free radicals in a commercially available pepper in Japan before and after irradiation using electron spin resonance (ESR) spectroscopy. The typical ESR spectrum of the pepper consists of a sextet centered at g = 2.0, a singlet at the same g-value and a singlet at g = 4.0. Upon gamma ray irradiation, a new pair of signals appeared in the pepper. The progressive saturation behavior (PSB) at various microwave power levels indicated quite different relaxation behaviors of those radicals. Namely, the peak intensity of the organic free radical component decreases in a monotonic fashion, whereas the Mn2+ and Fe3+ ESR signals substantially keep constant. This reflects the evidence of three independent radicals in the pepper before irradiation. The PSB of the pair peaks as induced by irradiation possessed quite different PSB from that of the free radical located at g = 2.0. We proposed a new protocol for the ESR detection of irradiated foods by the PSB method at different microwave power levels. This would call for a major modification of the CEN protocol in European Union. 相似文献
999.
1000.