全文获取类型
收费全文 | 1933篇 |
免费 | 52篇 |
国内免费 | 5篇 |
专业分类
化学 | 1455篇 |
晶体学 | 13篇 |
力学 | 89篇 |
数学 | 213篇 |
物理学 | 220篇 |
出版年
2023年 | 13篇 |
2022年 | 45篇 |
2021年 | 44篇 |
2020年 | 23篇 |
2019年 | 26篇 |
2018年 | 16篇 |
2017年 | 20篇 |
2016年 | 52篇 |
2015年 | 55篇 |
2014年 | 43篇 |
2013年 | 83篇 |
2012年 | 104篇 |
2011年 | 110篇 |
2010年 | 72篇 |
2009年 | 54篇 |
2008年 | 131篇 |
2007年 | 136篇 |
2006年 | 136篇 |
2005年 | 126篇 |
2004年 | 120篇 |
2003年 | 87篇 |
2002年 | 73篇 |
2001年 | 42篇 |
2000年 | 27篇 |
1999年 | 20篇 |
1998年 | 26篇 |
1997年 | 14篇 |
1996年 | 42篇 |
1995年 | 24篇 |
1994年 | 19篇 |
1993年 | 12篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 10篇 |
1982年 | 8篇 |
1981年 | 23篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 11篇 |
1977年 | 11篇 |
1974年 | 4篇 |
1970年 | 4篇 |
1929年 | 3篇 |
排序方式: 共有1990条查询结果,搜索用时 31 毫秒
101.
Transfer Hydrogenation of Ketones Catalyzed by Surface‐Active Ruthenium and Rhodium Complexes in Water
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Alexander M. Kalsin Dr. Tat'yana A. Peganova Dr. Valentin V. Novikov Alexandra I. Zhamoytina Dr. Luca Gonsalvi Dr. Maurizio Peruzzini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):846-854
An improved, high‐yield, one‐pot synthetic procedure for water‐soluble ligands functionalized with trialkyl ammonium side groups H2N(CH2)2NHSO2‐p‐C6H4CH2[NMe2(CnH2n+1)]+ ( [HL n ]+ ; n=8, 16) was developed. The corresponding new surface‐active complexes [(p‐cymene)RuCl( L n )] and [Cp*RhCl( L n )] (Cp*=η5‐C5Me5) were prepared and characterized. For n=16 micelles are formed in water at concentrations as low as 0.6 mM , as demonstrated by surface‐tension measurements. The complexes were used for catalytic transfer hydrogenation of ketones with formate in water. Highly active catalyst systems were obtained in the case of complexes bearing C16 tails due to their ability to be adsorbed at the water/substrate interface. The scope of these catalyst systems in aqueous solutions was extended from partially water soluble aryl alkyl ketones (acetophenone, butyrophenone) to hydrophobic dialkyl ketones (2‐dodecanone). 相似文献
102.
Michele Cacioppo Tobias Scharl Dr. Luka Đorđević Dr. Alejandro Cadranel Dr. Francesca Arcudi Prof. Dirk M. Guldi Prof. Maurizio Prato 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):12879-12884
Carbon dots (CDs) and their derivatives are useful platforms for studying electron-donor/acceptor interactions and dynamics therein. Herein, we couple amorphous CDs with phthalocyanines (Pcs) that act as electron donors with a large extended π-surface and intense absorption across the visible range of the solar spectrum. Investigations of the intercomponent interactions by means of steady-state and pump-probe transient absorption spectroscopy reveal symmetry-breaking charge transfer/separation and recombination dynamics within pairs of phthalocyanines. The CDs facilitate the electronic interactions between the phthalocyanines. Thus, our findings suggest that CDs could be used to support electronic couplings in multichromophoric systems and further increase their applicability in organic electronics, photonics, and artificial photosynthesis. 相似文献
103.
Maurizio Cossi Benedetta Mennucci Roberto Cammi 《Journal of computational chemistry》1996,17(1):57-73
We present analytical expressions for the first derivatives of area and other geometrical quantities of polygonal tesserae defined on molecular surfaces. This is a necessary step in the calculation of free energy derivatives with respect to nuclear coordinates for molecular solutes, in the framework of the polarizable continuum method. An application to solute-solvent dispersion energy derivatives is presented. © 1996 by John Wiley & Sons, Inc. 相似文献
104.
105.
106.
Enrico Albizzati Umberto Giannini Gianpiero Morini Maurizio Galimberti Luisa Barino Raimondo Scordamaglia 《Macromolecular Symposia》1995,89(1):73-89
The role of Lewis bases in MgCl2 supported catalysts for olefin polymerization is a subject of continuous interest and discussion in order to obtain more and more active and stereospecific catalysts and to explain their stereoregulating mechanism. Through molecular calculation and conformational analysis it was possible to identify chelating diethers that have the correct oxygen-oxygen distance necessary to tightly coordinate with the Mg ions of the support, even in the presence of other strong Lewis acids, and unable to give secondary reactions with TiCl4, AlR3, Ti-C and Ti-H bonds. The use of these donors has allowed the synthesis of catalytic systems that are both highly active and stereospecific even in the absence of external donors. Kinetic data of propylene polymerization with these catalyst systems are reported. The importance of the distance between the donor atoms in bifunctional Lewis bases has been proved also in the case of new classes of internal donors. Molecular modelling studies have enabled us to formulate models of active sites, located on some corners of MgCl2 crystallites, whose chirality is induced by the presence of a donor molecule in their environment. These models could explain, at least in part, the exceptional increase of isotactic polymer productivity observed for stereospecific catalyst systems, containing only the internal donor, with respect to catalysts lacking the Lewis base and could account for the influence of the donor on the molecular properties of the obtained polymers. 相似文献
107.
Sara Basile Natale Badalamenti Ornella Riccobono Salvatore Guarino Vincenzo Ilardi Maurizio Bruno Ezio Peri 《Molecules (Basel, Switzerland)》2022,27(3)
The problems of the environment and human health related to the use of synthetic and broad-spectrum insecticides have increasingly motivated scientific research on different alternatives and among these, the use of green systems, such as essential oils, have been explored. Several species of the Apiaceae and Asteraceae families, aromatic herbs rich in secondary bioactive metabolites, are used in the industrial field for pharmaceutical, cosmetic, and food purposes. Different essential oils extracted from some species of these families have shown acute toxicity and attractive and/or repellent effects towards different insects. In our work, we investigated the toxic potential of Calendula incana subsp. maritima and Laserpitium siler subsp. siculum essential oils against four insect species, Sitophilus oryzae, Lasioderma serricorne, Necrobia rufipes, and Rhyzoperta dominica, which are common pests of stored products. The composition of both oils, extracted by hydrodistillation from the aerial parts of the two plants, was evaluated by GC×GC-MS. Calendula incana subsp. maritima essential oil was rich in oxygenated sesquiterpenoids, such as cubebol (35.39%), 4-epi-cubebol (22.99%), and cubenol (12.77%), while the Laserpitium siler subsp. siculum essential oil was composed mainly of monoterpene hydrocarbons, such as β-phellandrene (42.16%), limonene (23.87%), and β-terpinene (11.80%). The toxicity Petri dish bioassays indicated that C. maritima oil killed a mean of 65.50% of S. oryzae and 44.00% of R. dominica adults, indicating a higher biocidal activity in comparison with L. siculum oil, while toward the other species, no significant differences in mortality were recorded. Calendula maritima oil could be, then, considered a promising candidate for further tests as an alternative biocide toward S. oryzae and R. dominica. The possibility that the relatively high content of oxygenated sesquiterpenoids in C. maritima essential oil determines its higher biocidal activity is discussed. 相似文献
108.
109.
Monica Bartolomei Maurizio Cignitti Marina Cotta Ramusino Gianfranco La Manna 《Journal of Molecular Structure》1995,330(1-3):431-435
7,8-dihydroquinoline-4,5 (1H,6H)-dione (1) and 7,8-dihydroquinoline-2,5-(1H,6H)-dione (2) in their tautomeric oxo and hydroxy forms have been studied by ab initio Hartree-Fock calculations; tautomerization energies predict a more stable hydroxy structure having an intramolecular hydrogen bond for compound 1, whereas the oxo form is slightly-preferred for compound 2. Fourier Transform-Infra Red (FT-IR) spectra in CHCl3 solution indicate that the predicted most stable tautomers in the vapour phase remain as such. 相似文献
110.
Carole Yaacoub Rim Wehbe Yahya Salma Dany El-Obeid Romeo El Bersaoui Bruno Coutard Ziad Fajloun 《Molecules (Basel, Switzerland)》2022,27(5)
Bee venom (BV) is one of the most remarkable natural products that has been a subject of studies since ancient times. Recent studies have shown that Apis mellifera syriaca venom possesses antibacterial as well as cytotoxic effects on cancer cell lines. The venom contains a variety of bioactive molecules—mainly melittin (MEL) and phospholipase A2 (PLA2), as well as other compounds that are not well characterized. In this work, we continue the biological characterization of A. mellifera syriaca venom by testing its anticoagulant effect on human plasma using the prothrombin time (PT) test, as well as assessing its proteolytic activity. In addition, the cytotoxicity of the crude venom—and of its two main components, MEL and PLA2—was tested on HeLa cancer cell lines for the first time. The results obtained showed the capacity of A. mellifera syriaca venom to increase clotting time, thereby proving its anticoagulant effect. Moreover, the venom did not demonstrate a significant proteolytic activity unless administrated at concentrations ≥ 5 mg/mL. Finally, we showed that crude A. mellifera syriaca venom, along with MEL, exhibit a strong in vitro cytotoxic effect on HeLa cancer cell lines, even at low concentrations. In summary, our findings could serve as a basis for the development of new natural-based drug candidates in the therapeutic field. 相似文献