全文获取类型
收费全文 | 4620篇 |
免费 | 453篇 |
国内免费 | 317篇 |
专业分类
化学 | 2846篇 |
晶体学 | 31篇 |
力学 | 212篇 |
综合类 | 20篇 |
数学 | 795篇 |
物理学 | 1486篇 |
出版年
2023年 | 54篇 |
2022年 | 117篇 |
2021年 | 120篇 |
2020年 | 155篇 |
2019年 | 118篇 |
2018年 | 122篇 |
2017年 | 111篇 |
2016年 | 154篇 |
2015年 | 160篇 |
2014年 | 197篇 |
2013年 | 284篇 |
2012年 | 371篇 |
2011年 | 324篇 |
2010年 | 241篇 |
2009年 | 211篇 |
2008年 | 285篇 |
2007年 | 235篇 |
2006年 | 215篇 |
2005年 | 188篇 |
2004年 | 149篇 |
2003年 | 128篇 |
2002年 | 119篇 |
2001年 | 96篇 |
2000年 | 118篇 |
1999年 | 77篇 |
1998年 | 70篇 |
1997年 | 65篇 |
1996年 | 89篇 |
1995年 | 64篇 |
1994年 | 69篇 |
1993年 | 56篇 |
1992年 | 60篇 |
1991年 | 43篇 |
1990年 | 33篇 |
1989年 | 46篇 |
1988年 | 42篇 |
1987年 | 34篇 |
1986年 | 44篇 |
1985年 | 41篇 |
1984年 | 39篇 |
1983年 | 28篇 |
1982年 | 21篇 |
1981年 | 19篇 |
1980年 | 24篇 |
1979年 | 19篇 |
1978年 | 17篇 |
1977年 | 22篇 |
1976年 | 23篇 |
1975年 | 19篇 |
1973年 | 12篇 |
排序方式: 共有5390条查询结果,搜索用时 817 毫秒
171.
172.
173.
Laser cooling below a photon recoil with three-level atoms 总被引:1,自引:0,他引:1
174.
Leslie M. Werbel Edward F. Elslager Vera P. Chu 《Journal of heterocyclic chemistry》1973,10(4):631-635
3,4-Dichlorophenylisothioeyanate ( 10 ) was allowed to react with 2-methy1-2-thiopseudourea to give methyl 4-(3,4-dichlorophenyl)(dithioaltophanimidate ( 11 ) (41%), which upon treatment with hydrazine afforded 3-amino-5-(3,4-dichloroanilino)-s-triazole ( 12 ) (54-91%). Ring-closure with ethyl acetoacetale in acetic acid afforded 2-(3,4-dichloroanilino)-5-methyl-s-triazolo[ 1,5-α ]-pyrimidin-7-ol ( 13 ) (81%). Chlorination with phosphorus oxychloride gave 7-chloro-2-(3,4-dichloroanilino)-5-methyl-s-triazolo[1,5-α ]pyrimidine ( 14 ) (98%), which was condensed with various amines to yield the desired 2-(3,4-diehloroanilino)-7-¶[(dialkylamino)alkyl]arnino¶-5-methyl-s-triazolo[ 1,5-α]pyrimidines ( 6 a-d). The structures of the s-triazolo[ 1,5-α ]pyrimidines were based on nmr spectroscopy and ring stability considerations. Several of the amino-s-triazolo[ 1,5-α ]pyrimidines possessed antimalarial activity against P. berghei in mice. 相似文献
175.
Vijay M. Krishnamurthy Dr. Brooks R. Bohall Chu‐Young Kim Dr. Demetri T. Moustakas Dr. David W. Christianson Prof. Dr. George M. Whitesides Prof. Dr. 《化学:亚洲杂志》2007,2(1):94-105
This paper describes a calorimetric study of the association of a series of seven fluorinated benzenesulfonamide ligands (C6HnF5?nSO2NH2) with bovine carbonic anhydrase II (BCA). Quantitative structure–activity relationships between the free energy, enthalpy, and entropy of binding and pKa and log P of the ligands allowed the evaluation of the thermodynamic parameters in terms of the two independent effects of fluorination on the ligand: its electrostatic potential and its hydrophobicity. The parameters were partitioned to the three different structural interactions between the ligand and BCA: the ZnII cofactor–sulfonamide bond (≈65 % of the free energy of binding), the hydrogen bonds between the ligand and BCA (≈10 %), and the contacts between the phenyl ring of the ligand and BCA (≈25 %). Calorimetry revealed that all of the ligands studied bind in a 1:1 stoichiometry with BCA; this result was confirmed by 19F NMR spectroscopy and X‐ray crystallography (for complexes with human carbonic anhydrase II). 相似文献
176.
Chu I Liu F Soares A Kumari P Nomeir AA 《Rapid communications in mass spectrometry : RCM》2002,16(15):1501-1505
Rapid, generic gradient liquid chromatography/tandem mass spectrometry (LC/MS/MS) assays, designed to accelerate sample analyses, have been developed to keep pace with the productivity of advanced synthetic procedures. In this study, LC/MS/MS was combined with an in vitro, cell-based, blood-brain barrier (BBB) model to evaluate the potential of new chemical entities (NCEs) to cross the BBB. This in vitro assay provides the permeability of discovery compounds across a monolayer of a primary culture of bovine brain microvessel endothelial cells in a fraction of the time that is required for in vivo studies (brain/plasma concentrations), using only 2 mg of the compound. The results are consistent with in vivo brain/plasma concentration ratio data. 相似文献
177.
Hydrogen peroxide (HOOH) in ice and snow is an important chemical tracer for the oxidative capacities of past atmospheres. However, photolysis in ice and snow will destroy HOOH and form the hydroxyl radical (*OH), which can react with snowpack trace species. Reactions of *OH in snow and ice will affect the composition of both the overlying atmosphere (e.g., by the release of volatile species such as formaldehyde to the boundary layer) and the snow and ice (e.g., by the *OH-mediated destruction of trace organics). To help understand these impacts, we have measured the quantum yield of *OH from the photolysis of HOOH on ice. Our measured quantum yields (Phi(HOOH --> *OH)) are independent of ionic strength, pH, and wavelength, but are dependent upon temperature. This temperature dependence for both solution and ice data is best described by the relationship ln(Phi(HOOH --> *OH)) = -(684 +/- 17)(1/T) + (2.27 +/- 0.064) (where errors represent 1 standard error). The corresponding activation energy (Ea) for HOOH (5.7 kJ mol(-1)) is much smaller than that for nitrate photolysis, indicating that the photochemistry of HOOH is less affected by changes in temperature. Using our measured quantum yields, we calculate that the photolytic lifetimes of HOOH in surface snow grains under midday, summer solstice sunlight are approximately 140 h at representative sites on the Greenland and Antarctic ice sheets. In addition, our calculations reveal that the majority of *OH radicals formed on polar snow grains are from HOOH photolysis, while nitrate photolysis is only a minor contributor. Similarly, HOOH appears to be much more important than nitrate as a photochemical source of *OH on cirrus ice clouds, where reactions of the photochemically formed hydroxyl radical could lead to the release of oxygenated volatile organic compounds to the upper troposphere. 相似文献
178.
Poly(N,N-dimethylacrylamide) (PDMA) with a molecular mass of 5.2 x 10(6) g/mol has been synthesized and used in DNA sequencing analysis by capillary electrophoresis (CE). A systematic investigation is presented on the effects of different separation conditions, such as injection amount, capillary inner diameter, polymer concentration, effective separation length, electric field and temperature, on the resolution. DNA sequencing up to 800 bases with a resolution (R) limit of 0.5 (and 1,000 bases with a resolution limit of 0.3) and a migration time of 96 min was achieved by using 2.5% w/v polymer, 150 V/cm separation electric field, and 60 cm effective separation length at room temperature on a DNA sample prepared with FAM-labeled--21M13 forward primer on pGEM3Zf(+) and terminated with ddCTP. Ultrafast and fast DNA sequencing up to 420 and 590 bases (R > or = 0.5) were also achieved by using 3% w/v polymer and 40 cm effective separation length with a separation electric field of 525 and 300 V/cm, and a migration time of 12.5 and 31.5 min, respectively. PDMA has low viscosity, long shelf life and dynamic coating ability to the glass surface. The unique properties of PDMA make it a very good candidate as a separation medium for large-scale DNA sequencing by capillary array electrophoresis (CAE). 相似文献
179.
180.
Jun Chu Qiulan Lv Chunliang Guo Dazhuang Xu Ke Wang Meiying Liu Hongye Huang Xiaoyong Zhang Yen Wei 《中国科学:化学(英文版)》2016,59(8):1003-1009
The synthesis of amphiphilic aggregation-induced emission(AIE) dyes based organic nanoparticles has recently attracted increasing attention in the biomedical fields. These AIE dyes based nanoparticles could effectively overcome the aggregation caused quenching effect of conventional organic dyes, making them promising candidates for fabrication of ultrabright organic luminescent nanomaterials. In this work, AIE-active luminescent polymeric nanoparticles(4-NH_2-PEG-TPE-E LPNs) were facilely fabricated through Michael addition reaction between tetraphenylethene acrylate(TPE-E) and 4-arm-poly(ethylene glycol)-amine(4-NH_2-PEG) in rather mild ambient. The 4-NH_2-PEG can not only endow these AIE-active LPNs good water dispersibility, but also provide functional groups for further conjugation reaction. The size, morphology and luminescent properties of 4-NH_2-PEG-TPE-E LPNs were characterized by a series of techniques in detail. Results suggested that these AIE-active LPNs showed spherical morphology with diameter about 100–200 nm. The obtained 4-NH_2-PEG-TPE-E LPNs display high water dispersibility and strong fluorescence intensity because of their self assembly and AIE properties of TPE-E.Biological evaluation results demonstrated that 4-NH_2-PEG-TPE-E LPNs showed negative toxicity toward cancer cells and good fluorescent imaging performance. All of these features make 4-NH_2-PEG-TPE-E LPNs promising candidates for biological imaging and therapeutic applications. 相似文献