全文获取类型
收费全文 | 7032篇 |
免费 | 655篇 |
国内免费 | 416篇 |
专业分类
化学 | 5231篇 |
晶体学 | 64篇 |
力学 | 216篇 |
综合类 | 45篇 |
数学 | 893篇 |
物理学 | 1654篇 |
出版年
2024年 | 15篇 |
2023年 | 94篇 |
2022年 | 171篇 |
2021年 | 178篇 |
2020年 | 215篇 |
2019年 | 223篇 |
2018年 | 197篇 |
2017年 | 159篇 |
2016年 | 272篇 |
2015年 | 254篇 |
2014年 | 342篇 |
2013年 | 412篇 |
2012年 | 586篇 |
2011年 | 628篇 |
2010年 | 355篇 |
2009年 | 320篇 |
2008年 | 482篇 |
2007年 | 461篇 |
2006年 | 427篇 |
2005年 | 399篇 |
2004年 | 344篇 |
2003年 | 283篇 |
2002年 | 310篇 |
2001年 | 162篇 |
2000年 | 105篇 |
1999年 | 83篇 |
1998年 | 78篇 |
1997年 | 58篇 |
1996年 | 63篇 |
1995年 | 51篇 |
1994年 | 56篇 |
1993年 | 45篇 |
1992年 | 36篇 |
1991年 | 44篇 |
1990年 | 32篇 |
1989年 | 17篇 |
1988年 | 15篇 |
1987年 | 15篇 |
1986年 | 10篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1971年 | 5篇 |
1962年 | 3篇 |
排序方式: 共有8103条查询结果,搜索用时 0 毫秒
111.
Synthesis of the rearranged drimane sesquiterpenoids (+)-avarol and (+)-avarone from Wieland-Miescher ketone is described. This synthetic sequence provides convenient access to the natural enantiomers and, based on comparison of the optical rotation of synthetic avarol dimethyl ether with literature data, affords material of significantly higher optical rotation than a natural source. Similar synthetic strategies have been used to obtain several related compounds, including a decalin bearing an exocyclic olefin and a highly substituted cyclohexane, that can be viewed as hybrids of the trans-fused avarol and cis-fused arenarol skeletons. 相似文献
112.
The design, synthesis and evaluation of a pentacyclic scaffold, CWO-324 to mimic saframycin A is described. CWO-324 is readily synthesized in five steps from 1,4-diacetyl-piperazine-2,5-dione and 2,5-dimethoxybenzaldehyde. CWO-324 was found to scission DNA, binds to bases 69-83(5′-GCAGTCAGG CACCGT-3′) of Hind III/Rsa I from plasmid pBR322 DNA in a foot-printing study and possesses anti-tumor activity. 相似文献
113.
Despite the popularity of boron and silicon allylation reagents in stereocontrolled synthesis, they suffer from a number of inherent limitations that have slowed down their development as synthetic tools for nucleophilic additions to carbonyl compounds and imine derivatives. These limitations are the low reactivity and diastereoselectivity of allyl trialkylsilane reagents, and the lack of catalytic systems for the activation and substoichiometric control of enantioselectivity in the additions of allyl boron reagents. To develop more efficient and general methods for the control of absolute stereochemistry in the resulting homoallylic alcohols, new approaches aimed at solving the problem of activation of allylic boron and silicon reagents are needed. This Minireview describes a number of recent approaches that have been devised to address this problem. 相似文献
114.
By means of a large-scale molecular dynamics simulation, we show that the Tolman length, although positive, is much smaller in magnitude than previously reported. We found that the range of interparticle interaction can significantly affect the magnitude of the Tolman length. When the range of interaction is longer than five molecular diameters, the Tolman length is on the order of a few hundredths of the molecular diameter, rather than a few tenths known previously. 相似文献
115.
Seasonal fluctuation of DNA photodamage in marine plankton assemblages at Palmer Station, Antarctica
Meador J Jeffrey WH Kase JP Pakulski JD Chiarello S Mitchell DL 《Photochemistry and photobiology》2002,75(3):266-271
Ultraviolet radiation-induced DNA damage frequencies were measured in DNA dosimeters and natural plankton communities during the austral spring at Palmer Station, Antarctica, during the 1999-2000 field season. We found that the fluence of solar ultraviolet-B radiation (UV-B) at the earth's surface correlated with stratospheric ozone concentrations, with significant ozone depletion observed because of "ozone hole" conditions. To verify the interdependence of ozone depletion and DNA damage in natural microbial communities, seawater was collected daily or weekly from Arthur Harbor at Palmer Station, Antarctica, throughout "ozone season," exposed to ambient sunlight between 0600 and 1800 h and fractionated using membrane filtration to separate phytoplankton and bacterioplankton populations. DNA from these fractions was isolated and DNA damage measured using radioimmunoassay. Under low-ozone conditions cyclobutane dimer concentrations in bacterioplankton and phytoplankton communities were maximal. DNA damage measured in dosimeters correlated closely with ozone concentrations and UV-B fluence. Our studies offer further support to the theory that stratospheric deozonation is detrimental to marine planktonic organisms in the Southern Ocean. 相似文献
116.
Chemosensors for the marine toxin saxitoxin 总被引:1,自引:0,他引:1
Gawley RE Pinet S Cardona CM Datta PK Ren T Guida WC Nydick J Leblanc RM 《Journal of the American Chemical Society》2002,124(45):13448-13453
Eleven anthracylmethyl crown ethers have been synthesized and evaluated as fluorescence sensors for the marine toxin saxitoxin. Fluorescence enhancement data are consistent with a 1:1 binding complex for all crowns. The binding constants are in the range of 10(4) M(-)(1) in ammonium phosphate buffer (pH 7.1) in 80% ethanol solvent. Selectivity for sensing saxitoxin versus several organic analytes has been demonstrated for the first time. Possible modes of binding are presented, and relevance to saxitoxin monitoring programs are discussed. 相似文献
117.
Hill RT Lyon JL Allen R Stevenson KJ Shear JB 《Journal of the American Chemical Society》2005,127(30):10707-10711
The functionality and structural diversity of biological macromolecules has motivated efforts to exploit proteins and DNA as templates for synthesis of electronic architectures. Although such materials offer promise for numerous applications in the fabrication of cellular interfaces, biosensors, and nanoelectronics, identification of techniques for positioning and ordering bioelectronic components into useful patterns capable of sophisticated function has presented a major challenge. Here, we describe the fabrication of electronic materials using biomolecular scaffolds that can be constructed with precisely defined topographies. In this approach, a tightly focused pulsed laser beam capable of promoting protein photo-cross-linking in specified femtoliter volume elements is scanned within a protein solution, creating biomolecular matrices that either remain in integral contact with a support surface or extend as free-standing structures through solution, tethered at their ends. Once fabricated, specific protein scaffolds can be selectively metallized via targeted deposition and growth of metal nanoparticles, yielding high-conductivity bioelectronic materials. This aqueous fabrication strategy opens new opportunities for creating electronic materials in chemically sensitive environments and may offer a general approach for creating microscopically defined inorganic landscapes. 相似文献
118.
The creation and use of unnatural molecules to control cellular function is a long standing goal of the chemical community, but in general, these efforts have been directed at finding molecules to inhibit or activate a particular molecular target or function, or to elicit a particular phenotype. Here we show that multiple unnatural molecules (orthogonal ribosomes) can be used combinatorially, in a single cell, to program Boolean logic functions. These experiments show how attention to the molecular specificity of noncovalent interactions between unnatural macromolecules allows the synthesis of complex function from the "bottom-up" in living matter. 相似文献
119.
M. F. Shostakovskii G. G. Skvortsova V. V. An Yu. A. Mansurov 《Chemistry of Heterocyclic Compounds》1969,5(1):6-7
Vinyl-furancarboxylate has been synthesized by the reaction of-furancarboxylic acid with acetylene and with vinyl acetate in the presence of various catalysts. The structure of the vinyl ester has been confirmed by IR spectra and by catalytic hydrogenation. The acid and alkaline hydrolyses of vinyl-furancarboxylate have been studied. 相似文献
120.
[structure: see text] Thiophene dendrons and dendrimers were designed and synthesized using a convergent approach. Metal-mediated coupling reactions were used in the synthesis. A rational approach allowed the formation of alphaalpha, betabeta, and alphabeta linkages between the dendrons and thiophene units. 相似文献