全文获取类型
收费全文 | 384篇 |
免费 | 23篇 |
国内免费 | 3篇 |
专业分类
化学 | 316篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 38篇 |
物理学 | 52篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 2篇 |
2019年 | 5篇 |
2018年 | 5篇 |
2017年 | 4篇 |
2016年 | 18篇 |
2015年 | 15篇 |
2014年 | 17篇 |
2013年 | 26篇 |
2012年 | 34篇 |
2011年 | 30篇 |
2010年 | 19篇 |
2009年 | 13篇 |
2008年 | 25篇 |
2007年 | 12篇 |
2006年 | 24篇 |
2005年 | 21篇 |
2004年 | 17篇 |
2003年 | 16篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1978年 | 1篇 |
1977年 | 5篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1970年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1959年 | 1篇 |
1936年 | 2篇 |
1930年 | 2篇 |
排序方式: 共有410条查询结果,搜索用时 15 毫秒
31.
Cellulose - High hygroscopicity is an unavoidable feature of cellulose materials, and it is important for clarifying the humidity dependence of the target function toward precise utilization.... 相似文献
32.
33.
Probing the Rotational Dynamics of meso‐(2‐Substituted)aryl Substituents in A2B‐Type Subporphyrins 下载免费PDF全文
Kota Yoshida Graeme Copley Hirotaka Mori Prof. Dr. Atsuhiro Osuka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10065-10072
A2B‐type B‐methoxy subporphyrins 3 a – g and B‐phenyl subporphyrins 7 a – c , e , g bearing meso‐(2‐substituted)aryl substituents are synthesized, and their rotational dynamics are examined through variable‐temperature (VT) 1H NMR spectroscopy. In these subporphyrins, the rotation of meso‐aryl substituents is hindered by a rationally installed 2‐substituent. The rotational barriers determined are considerably smaller than those reported previously for porphyrins. Comparison of the rotation activation parameters reveals a variable contribution of ΔH≠ and ΔS≠ in ΔG≠. 2‐Methyl and 2‐ethyl groups of the meso‐aryl substituents in subporphyrins 3 e , 3 f , and 7 e induce larger rotational barriers than 2‐alkoxyl substituents. The rotational barriers of 3 g and 7 g are reduced by the presence of the 4‐dibenzylamino group owing to its ability to stabilize the coplanar rotation transition state electronically. The smaller rotational barriers found for B‐phenyl subporphyrins than for B‐methoxy subporphyrins indicate a negligible contribution of SN1‐type heterolysis in the rotation of meso‐aryl substituents. 相似文献
34.
[formula: see text] Alkyl-substituted chromium Fischer carbene complexes were found to react with various N-tosylimines to give beta-methoxy allylic amine derivatives under thermal conditions. This result is essentially distinct from the photochemical outcome in which beta-lactam derivatives are obtained. 相似文献
35.
Hirotaka Ihara Ken Shudo Chuichi Hirayama Hiroshi Hachisako Kimiho Yamada 《Liquid crystals》1996,20(6):807-809
The L-glutamic acid-derived lipids form organic gels in benzene, which show enantioselective elution of N-dansyl L-phenylalanine from organic gels to aqueous phases. Differential scanning calorimetry and circular dichroism measurements demonstrate that this enantioselectivity occurred through highly-oriented structures of aggregated lipids like those of aqueous lipid membrane systems. 相似文献
36.
37.
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
38.
Takafuji M Ishiodori A Yamada T Sakurai T Ihara H 《Chemical communications (Cambridge, England)》2004,(9):1122-1123
Enhanced CD spectra based on chirally-oriented structures of pyrene-containing L-glutamic acid-derived lipid were observed in polymerizable monomers and CD strength was maintained after photo-induced polymerization of the monomer solvents. 相似文献
39.
Morimoto Y Kohyama S Nakai K Matsuo H Karasawa F Kikuchi M 《Photochemistry and photobiology》2003,78(4):372-376
Several studies have shown that UV irradiation may be effective for preventing vascular restenosis or vasopasm. However, the long-term effects of UV light on the physiological properties of vessels such as arterial tension have not been elucidated. We therefore studied the long-term effects of UV using rat carotid arteries treated with UV-B light (wavelength = 313 nm, total energy = 14 mJ/mm2). The animals were sacrificed at 1, 7 and 14 days after UV light exposure, and the carotid arteries were studied by light microscopy and the contractile responses of isolated arterial rings were recorded under isometric tension. UV treatment had induced a substantial loss of smooth muscle cells (SMC) along the entire circumference of the media on days 7 and 14, whereas loss of SMC on day 1 was negligible. Contractile responses of arteries that had been exposed to UV light were significantly reduced on days, 1, 7 and 14. The susceptibility of UV-treated arteries to phenylephrine and prostaglandin F2 alpha was significantly decreased on days 1 and 7, but decreased susceptibility was not seen on day 14. Acetylcholine-induced relaxations were not altered by UV treatment. These results suggest that the long-term effect of UV light is an attenuation of smooth muscle contractility without impairment of endothelial function. 相似文献
40.
The solution behavior of homologously obtained crystalline surfactant molecular complexes (SMCs) that are generated between quaternary ammonium bromide and several additive materials has shed light on the recognition of fundamentals of solubilization. It has been revealed that the SMCs derived from long-alkyl-chain surfactants are sufficiently dissolved in water through the path of micellar dispersion above the cmc's of the complex surfactants, whereas the short-chain homologues cannot dissolve in water but dissociate the complexes, resulting in a heterogeneous phase made up of the liberated additives. The fact agrees perfectly with the familiar aspects of solubilization by surfactant; i.e., the longer the alkyl chain of the surfactant becomes, the more effective it is for solubilization. Based on these results, it has been deduced that the possibility for any pair of surfactant and solubilizate (additive) to realize solubilization simply depends on the relative importance of equilibrium of dissociation or association of the SMC species in aqueous medium. 相似文献