全文获取类型
收费全文 | 518篇 |
免费 | 40篇 |
国内免费 | 4篇 |
专业分类
化学 | 355篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 25篇 |
物理学 | 165篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 21篇 |
2019年 | 8篇 |
2018年 | 9篇 |
2017年 | 3篇 |
2016年 | 8篇 |
2015年 | 11篇 |
2014年 | 26篇 |
2013年 | 29篇 |
2012年 | 33篇 |
2011年 | 21篇 |
2010年 | 21篇 |
2009年 | 22篇 |
2008年 | 32篇 |
2007年 | 30篇 |
2006年 | 30篇 |
2005年 | 39篇 |
2004年 | 33篇 |
2003年 | 24篇 |
2002年 | 6篇 |
2001年 | 16篇 |
2000年 | 15篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 7篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1967年 | 2篇 |
1943年 | 1篇 |
排序方式: 共有562条查询结果,搜索用时 375 毫秒
211.
Qiyao Li Junyi Gong Ying Li Ruoyao Zhang Haoran Wang Jianquan Zhang He Yan Jacky W. Y. Lam Herman H. Y. Sung Ian D. Williams Ryan T. K. Kwok Min-Hui Li Jianguo Wang Ben Zhong Tang 《Chemical science》2021,12(2):709
Developing versatile synthetic methodologies with merits of simplicity, efficiency, and environment friendliness for five-membered heterocycles is of incredible importance to pharmaceutical and material science, as well as a huge challenge to synthetic chemistry. Herein, an unexpected regioselective photoreaction to construct a fused five-membered azaheterocycle with an aggregation-induced emission (AIE) characteristic is developed under mild conditions. The formation of the five-membered ring is both thermodynamically and kinetically favored, as justified by theoretical calculation and experimental evidence. Markedly, a light-driven amplification strategy is proposed and applied in selective mitochondria-targeted cancer cell recognition and fluorescent photopattern fabrication with improved resolution. The work not only delivers the first report on efficiently generating a fused five-membered azaheterocyclic AIE luminogen under mild conditions via photoreaction, but also offers deep insight into the essence of the photosynthesis of fused five-membered azaheterocyclic compounds.A multifunctional, AIE-based, fused five-membered azaheterocycle is photogenerated with light-driven amplification to combat the photobleaching issue and fabricate display materials. 相似文献
212.
Matthew Kwok Wai Choi 《Tetrahedron》2004,60(12):2875-2879
A new cross-linked polystyrene-supported thioanisole reagent is reported. This reagent incorporates the flexible JandaJel™ cross-linker and can be treated with methyl trifluoromethanesulfonate to form the corresponding sulfonium salt. This salt can in turn be deprotonated to form a polymer-supported sulfur ylide that is able to react with aldehydes and ketones to form epoxides. The thioanisole reagent can also be oxidized to form an insoluble sulfoxide reagent that is useful in Swern oxidation reactions. In these reactions, the polymer-supported thioanisole-based reagents can be recovered, regenerated and reused. 相似文献
213.
The ultraviolet photolysis of CH(2)I(2) was studied in water and salt water solutions using photochemistry and picosecond time-resolved resonance Raman spectroscopy. Photolysis in both types of environments produces mainly CH(2)(OH)(2) and HI products. However, photolysis of CH(2)I(2) in salt water leads to the formation of different products/intermediates (CH(2)ICl and Cl(2) (-)) not observed in the absence of salt in aqueous solutions. The amount of CH(2)(OH)(2) and HI products appears to decrease after photolysis of CH(2)I(2) in salt water compared to pure water. We briefly discuss possible implications of these results for photolysis of CH(2)I(2) and other polyhalomethanes in sea water and other salt aqueous environments compared to nonsalt water solvated environments. 相似文献
214.
Xiao ZL Han CY Kwok WK Wang HH Welp U Wang J Crabtree GW 《Journal of the American Chemical Society》2004,126(8):2316-2317
When the dimension of materials decreases to mesoscale, their properties can change dramatically, depending on the boundary conditions imposed by the sample architecture including geometry, morphology, and hierarchical structures. Here we show that electrodeposition, a method for reducing materials from a solution onto a substrate, can provide a versatile pathway to tailor the architecture of mesostructures. Novel lead (Pb) structures ranging from nanowires, mesoparticles with octahedral, decahedral, and icosahedral shapes to porous nanowires, multipods, nanobrushes, and even snowflake-shaped structures were synthesized through systematically exploring electrodeposition parameters including reduction potentials, solution concentration, starting materials, supporting electrolytes, and surfactants. 相似文献
215.
Picosecond and nanosecond time-resolved resonance Raman spectroscopy combined with density functional theory calculations have been performed to characterize the structure, dynamics, and hydrogen-bonding effects on the triplet state of the phototrigger model compound p-methoxyacetophenone (MAP) in cyclohexane, MeCN, and 50% H2O/50% MeCN (v:v) mixed solvent. Analogous work has also been done to study the corresponding ground state properties. The ground and triplet states of MAP were both found to be associated strongly with the water solvent molecules in the 50% H2O/50% MeCN solvent system. A hydrogen-bond complex model involving one or two water molecules bonded with the oxygen atoms of the MAP carbonyl and methoxy moieties has been employed to explore the hydrogen-bond interactions and their influence on the geometric and electronic properties for the ground and triplet states of MAP. Among the various hydrogen-bond configurations examined, the carbonyl hydrogen-bond configuration involving one water molecule was calculated to lead to the most stable hydrogen-bond complex for both the ground and the triplet states with the strength of the hydrogen-bond interaction being stronger in the triplet state than the ground state. The increased carbonyl located hydrogen-bond strength in the triplet state results in substantial modification of both the electronic and the structural conformation so that the triplet of the hydrogen-bond complex can be considered as a distinct species from the free MAP triplet state. This provides a framework to interpret the differences observed in the TR3 spectral and triplet lifetime obtained in the neat MeCN solvent (attributed to the free MAP triplet state) and the 50% H2O/50% MeCN solvent (due to the triplet of the hydrogen-bond complex). Temporal evolution at early picosecond times indicates rapid ISC conversion, and subsequent relaxation of the excess energy of the initially formed energetic triplets occurs for both the free MAP and the hydrogen-bond complex. The triplet of the carbonyl hydrogen-bond complex appears to be generated directly from the corresponding ground state complex and it does not dissociate back to the free triplet state within the triplet state lifetime. We briefly discuss the influence of the carbonyl hydrogen-bond effect on the pi pi* triplet reactivity for MAP and closely related compounds. 相似文献
216.
The interpretation of contact angles in terms of solid surface tensions is not trivial. In the past, we and others have postulated that contact angles should be measured with liquid of surface tension larger than the anticipated solid surface tension, i.e., gamma(lv)>gamma(sv). This has recently been disputed. It is also not entirely obvious how to proceed experimentally since gamma(sv) is not known initially. Typically, one starts with a liquid of high gamma(lv) (such as water) and goes lower. We have stopped in the past when the contact angles became small. A question arises as to what would happen if we would go on. Contact angles of liquids with gamma(lv) less than or near gamma(sv) were measured on eight polymer-coated solid surfaces. The experimental contact angle patterns for gamma(lv)gamma(sv) were compared. Results suggest that contact angle interpretation in terms of solid surface tensions requires contact angles to be measured for gamma(lv)>gamma(sv) because the Young equation is not applicable for gamma(lv)相似文献
217.
Jing Liang Guangxue Feng Ryan Tsz Kin Kwok Dan Ding Benzhong Tang Bin Liu 《中国科学:化学(英文版)》2016,59(1):53-61
Fluorescent light-up probes comprising a tetraphenylethene unit with aggregation-induced emission (AIE) characteristics and a water-soluble peptide have been designed and synthesized which provide cell membrane and nuclear permeability to live cells. This strategy has offered new opportunities for the development of probes with light-up ability and good signal-to-noise ratio. The selectivity or targeting specificity is determined by the peptide sequence, i.e. a nuclear localization signal that leads to nucleus imaging and a cell biomarker targeting peptide that offers specific light-up imaging of HT-29 cells. 相似文献
218.
Ultraviolet irradiation of DNA produces electronic excited states that predominantly eliminate the excitation energy by returning to the ground state (photostability) or following minor pathways into mutagenic photoproducts (photodamage). The cyclobutane pyrimidine dimer (CPD) formed from photodimerization of thymines in DNA is the most common form of photodamage. The underlying molecular processes governing photostability and photodamage of thymine-constituted DNA remain unclear. Here, a combined femtosecond broadband time-resolved fluorescence and transient absorption spectroscopies were employed to study a monomer thymidine and a single-stranded thymine oligonucleotide. We show that the protecting deactivation of a thymine multimer is due to an ultrafast single-base localized stepwise mechanism where the initial excited state decays via a doorway state to the ground state or proceeds via the doorway state to a triplet state identified as a major precursor for CPD photodamage. These results provide new mechanistic characterization of and a dynamic link between the photoexcitation of DNA and DNA photostability and photodamage. 相似文献
219.
A whole-cell environmental biosensor was fabricated on a diamond electrode. Unicellular microalgae Chlorella vulgaris was entrapped in the bovine serum albumin (BSA) membrane and immobilized directly onto the surface of a diamond electrode for heavy metal detection. We found that the unique surface properties of diamond reduce the electrode fouling problem commonly encountered with metal electrodes. The cell-based diamond biosensor can attain a detection limit of 0.1 ppb for Zn(2+) and Cd(2+), and exhibits higher detection sensitivity and stability compared to platinum electrodes. 相似文献
220.
Glucose oxidase showed direct electrochemical transfer at glassy carbon electrodes immobilized with carbon nanotube‐gold colloid (CNT‐Au) composites with poly(diallydimethylammonium chloride) (PDDA) coatings. The modified electrode (GC/CNT/Au/PDDA‐GOD) was employed for the amperometric determination of glucose. Under optimal conditions, the biosensor displayed linear response to glucose from 0.5 to 5 mM with a sensitivity of 2.50 mA M?1 at an applied potential of ?0.3 V (vs. Ag|AgCl reference). 相似文献