全文获取类型
收费全文 | 1226篇 |
免费 | 68篇 |
专业分类
化学 | 1015篇 |
晶体学 | 17篇 |
力学 | 15篇 |
数学 | 31篇 |
物理学 | 216篇 |
出版年
2023年 | 14篇 |
2022年 | 17篇 |
2021年 | 19篇 |
2020年 | 29篇 |
2019年 | 41篇 |
2018年 | 27篇 |
2017年 | 13篇 |
2016年 | 44篇 |
2015年 | 34篇 |
2014年 | 35篇 |
2013年 | 67篇 |
2012年 | 109篇 |
2011年 | 103篇 |
2010年 | 44篇 |
2009年 | 51篇 |
2008年 | 68篇 |
2007年 | 57篇 |
2006年 | 83篇 |
2005年 | 53篇 |
2004年 | 51篇 |
2003年 | 53篇 |
2002年 | 49篇 |
2001年 | 15篇 |
2000年 | 17篇 |
1999年 | 12篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 11篇 |
1995年 | 5篇 |
1994年 | 13篇 |
1993年 | 9篇 |
1992年 | 6篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1986年 | 6篇 |
1985年 | 8篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1980年 | 6篇 |
1979年 | 11篇 |
1978年 | 9篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1973年 | 7篇 |
1969年 | 4篇 |
1967年 | 3篇 |
排序方式: 共有1294条查询结果,搜索用时 15 毫秒
11.
12.
Uesato S Taniuchi K Kumagai A Nagaoka Y Seto R Hara Y Tokuda H Nishino H 《Chemical & pharmaceutical bulletin》2003,51(12):1448-1450
In the course of an exploratory investigation of antitumor-promoting catechins, 3-O-acyl-(+)-catechins of varying carbon lengths from C(4) to C(18) were assessed for inhibitory effects on the activation of the Epstein-Barr virus early antigen. Like 3-O-acyl-(-)-epigallocatechins, the (+)-catechin derivatives showed promising effects with the C-3 acyl chain of C(8)-C(11) carbon atoms. 相似文献
13.
Direct compression is able to produce tablets at a lower cost than wet granulation and tableting method, due to a fewer items of process validation. In this study, acetaminophen was used as a medicine with various granular diameters to formulate tablets by direct compression, thus evaluating their physical properties. Consequently, direct compression was found effective in formulating tablets with excellent physical properties, with the granular diameter taken into account. It was confirmed that tablets produced by direct compression were similar in physical properties in tablets produced by wet granulation and tableting method. Further, it was suggested that use of a dry-type binder would make it possible to provide a tablet having higher content of the medicine with excellent physical properties. 相似文献
14.
Exciton charge separation in photosynthetic reaction centers from purple bacteria (PbRC) and photosystem II (PSII) occurs exclusively along one of the two pseudo-symmetric branches (active branch) of pigment–protein complexes. The microscopic origin of unidirectional charge separation in photosynthesis remains controversial. Here we elucidate the essential factors leading to unidirectional charge separation in PbRC and PSII, using nonadiabatic quantum dynamics calculations in conjunction with time-dependent density functional theory (TDDFT) with the quantum mechanics/molecular mechanics/polarizable continuum model (QM/MM/PCM) method. This approach accounts for energetics, electronic coupling, and vibronic coupling of the pigment excited states under electrostatic interactions and polarization of whole protein environments. The calculated time constants of charge separation along the active branches of PbRC and PSII are similar to those observed in time-resolved spectroscopic experiments. In PbRC, Tyr-M210 near the accessary bacteriochlorophyll reduces the energy of the intermediate state and drastically accelerates charge separation overcoming the electron–hole interaction. Remarkably, even though both the active and inactive branches in PSII can accept excitons from light-harvesting complexes, charge separation in the inactive branch is prevented by a weak electronic coupling due to symmetry-breaking of the chlorophyll configurations. The exciton in the inactive branch in PSII can be transferred to the active branch via direct and indirect pathways. Subsequently, the ultrafast electron transfer to pheophytin in the active branch prevents exciton back transfer to the inactive branch, thereby achieving unidirectional charge separation.Essential factors leading to unidirectional charge separation in photosynthetic reaction centers are clarified via nonadiabatic quantum dynamics calculations. 相似文献
15.
Ikedou K Yamamoto H Nagashima H Nemoto N Tashiro K 《The journal of physical chemistry. B》2005,109(21):10668-10675
We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches. 相似文献
16.
Chiaki Azuma Takao Mitsuboshi Kohei Sanui Naoya Ogata 《Journal of polymer science. Part A, Polymer chemistry》1980,18(3):781-797
cis-1,4-Polybutadiene and polypentenamer having pendant functional groups such as formyl, aldoxime, hydroxymethyl, or cinnamoyloxymethyl groups have been prepared, and some of their properties were investigated in terms of structural effect on physical properties of these polymers. cis-1, 4-Polybutadiene and polypentenamer having a different content of formyl group were prepared by the hydroformylation reaction with rhodium catalyst under mild conditions. The pendant formyl group was reduced to a hydroxymethyl group by using various reducing agents such as sodium borohydride or sodium trimethoxyborohydride which were effective to avoid a crosslinking reaction among the formyl groups. Glass transition temperature of polypentenamer having hydroxymethyl groups increased with increasing the content of the hydroxymethyl groups in the polymer. Cinnamoyl group was introduced into the polypentenamer having hydroxymethyl groups by reacting with cinnamoyl chloride so as to prepare a photosensitive rubber. The relationships between the photosensitivity of the cinnamoylated polypentenamer and the mobility of polymer main chains have been elucidated. A linear relationship between the photodimerization rate constant and the difference between ultraviolet (UV) irradiation temperature and the glass transition temperature of the polymer was found. It has become apparent that the photosensitivity of cinnamoylated polypentenamer can be estimated by the glass transition temperature of the original polymer, UV irradiation temperature, activation energy of the dimerization, and γ, which is a coefficient of the relationship between the photosensitive group concentration and the glass transition temperature of the polymer. 相似文献
17.
Rijssenbeek JT Saito T Malo S Azuma M Takano M Poeppelmeier KR 《Journal of the American Chemical Society》2005,127(2):675-681
The related parameters of cation size and valence that control the crystallization of Sr(3)CaRu(2)O(9) into a 1:2 B-site-ordered perovskite structure were explored by cationic substitution at the strontium and calcium sites and by the application of high pressure. At ambient pressures, Sr(3)MRu(2)O(9) stoichiometries yield multiphasic mixtures for M = Ni(2+), Mg(2+), and Y(3+), whereas pseudocubic perovskites result for M = Cu(2+) and Zn(2+). For A-site substitutions, an ordered perovskite structure results for Sr(3-x)Ca(x)CaRu(2)O(9), with 0 = x = 1.5. In contrast, Ba(2+) substitution for Sr(2+) is accompanied by a phase change to a hexagonal BaTiO(3) structure type. At high pressures and temperatures, a 1:2 B-site-ordered perovskite structure is stabilized for Sr(3-x)Ba(x)CaRu(2)O(9), with 0 = x = 3. The scarcity of B-site-ordered perovskite ruthenates at ambient pressure and the metastable nature of the high-pressure phases underscore the strict size and valence requirements that must be met by the constituent cations to achieve these uncommon ordered structures. 相似文献
18.
Jun-ichi Azuma Nam-Hun Kim Laurent Heux Roger Vuong Henri Chanzy 《Cellulose (London, England)》2000,7(1):3-19
The cellulose system of the viscous fibrous cellulosic polysaccharide (viscan) in the viscin tissue of the European mistletoe, Viscum album L., was analyzed by chemical and physicochemical techniques including sugar analysis, optical and transmission electron microscopy, X-ray and electron diffraction together with solid state CP/MAS 13C-NMR spectroscopy. The results confirmed that in the elongated thin viscin cells, the cellulose microfibrils (having a diameter of around 3 nm) were tightly coiled with their axes perpendicular to the long axis of the cell. Upon stretching these cells became deformed by more than a hundred fold. In such a deformation, the cellulose microfibrils became unwound to be perfectly aligned along the stretching direction. Based on solid-state CP/MAS 13C-NMR spectroscopic analysis of the viscin tissue, it was found that its cellulose consisted of I and I polymorphs in the ratio 1:1. 相似文献
19.
[reaction: see text] Base-promoted cyclocondensation of C-chloro oximes with cyclic 1,3-diketones affords functionalized isoxazoles in good yield and under convenient reaction conditions. This process enables the synthesis of highly substituted products with notable functional group tolerance. The products obtained are directly converted to a variety of polyketide-derived polycyclic structures including xanthenes, anthracenes, and benzophenones. 相似文献
20.
E Makino N Iwasaki N Yagi T Ohashi H Kato Y Ito H Azuma 《Chemical & pharmaceutical bulletin》1990,38(1):201-207
Various pyrazine derivatives were synthesized and their antiallergic activity was examined. The inhibitory activity on allergic histamine release of the compounds bearing a 5-tetrazolyl group was more potent than that of the corresponding carboxyl derivatives. The introduction of -CONH- or -NHCO- between the pyrazine ring and the 5-tetrazolyl group as a spacer greatly enhanced the activity. N-(1H-Tetrazol-5-yl)-2-pyrazinecarboxamide (I-3) was estimated to exhibit nearly the same potency as disodium cromoglycate (DSCG). The structure-activity relationship among various derivatives modified by introducing some substituents onto the 3-, 5- or 6-position of the pyrazine ring of I-3 was investigated. The activity remained unchanged or was reduced when such substituents as methyl, chloro, methoxy, methylamino and dimethylamino were introduced at the 3- or 5-position. In contrast, 6-substitution with various alkylamino groups more or less increased the activity. Among them, the 6-dimethylamino (I-17c) and 6-(1-pyrrolidinyl) (I-34) derivative were proved to be most potent. The IC50 values (concentration which produces 50% inhibition of the allergic histamine release) of I-17c and I-34 were determined to be 4.7 x 10(-10) and 4.6 x 10(-10) M, respectively. These two compounds produced a potent inhibitory activity on passive cutaneous anaphylaxis (PCA) in rat, not only by the intravenous route (ED50 = 0.0096 mg/kg for both compounds) but also by the oral route (ED50 = 0.19 and 0.18 mg/kg, respectively). On the other hand, when the pyrazine ring of some representative compounds was replaced with a pyridine ring, the inhibitory activity on histamine release was significantly reduced. 相似文献