全文获取类型
收费全文 | 1001篇 |
免费 | 57篇 |
国内免费 | 1篇 |
专业分类
化学 | 686篇 |
晶体学 | 2篇 |
力学 | 53篇 |
数学 | 152篇 |
物理学 | 166篇 |
出版年
2024年 | 4篇 |
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 49篇 |
2020年 | 39篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 20篇 |
2016年 | 71篇 |
2015年 | 40篇 |
2014年 | 42篇 |
2013年 | 69篇 |
2012年 | 82篇 |
2011年 | 113篇 |
2010年 | 53篇 |
2009年 | 34篇 |
2008年 | 50篇 |
2007年 | 57篇 |
2006年 | 53篇 |
2005年 | 55篇 |
2004年 | 30篇 |
2003年 | 33篇 |
2002年 | 23篇 |
2001年 | 5篇 |
2000年 | 11篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
1961年 | 1篇 |
1948年 | 1篇 |
1938年 | 1篇 |
1937年 | 1篇 |
1918年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有1059条查询结果,搜索用时 78 毫秒
101.
Maffeo D Velkov Z Misiakos K Mergia K Paulidou A Zavali M Mavridis IM Yannakopoulou K 《Journal of colloid and interface science》2011,358(2):369-375
The monitoring of the antibacterial agent triclosan binding at nanomolar concentration from an aqueous solution by employing a well-packed monolayer with a predetermined single orientation made of specifically synthesized 2,3-dimethyl-6-(undec-10-enamide)-6-deoxy-β-cyclodextrin (DMBUA) on a silicon wafer (Si/SiO(2)) coated with a novolac resin is reported. A white light reflectance spectroscopy (WLRS) setup was used for the real-time monitoring of the DMBUA deposition and triclosan binding processes. Film thicknesses obtained by WLRS were in very good agreement with the ones measured by X-ray reflectivity (XRR) experiments. Triclosan binds strongly to the DMBUA monolayer (logK(assoc)=6.68). NMR studies in aqueous solution indicated that the chlorophenolyl ring rather than the dichlorophenyl ring is preferentially inserted into DMBUA cups. The current detecting system that requires no tedious surface chemistry, no thiolated cyclodextrins, no gold surfaces, and no expensive equipment may be useful in capturing small molecules and may permit various applications, e.g., preparation of antimicrobial surfaces. 相似文献
102.
Recently, a simple scaling argument was introduced that allows us to map, with some precautions, Brownian and Monte Carlo dynamics for spherical particles. Here, we extend the scaling to study systems that have orientational degrees of freedom and carefully asses its validity over a wide region of temperature and density. Our work allows us to devise a Brownian Monte Carlo algorithm that produces, to a good approximation, physically meaningful trajectories with a minimum programming effort, although at the expense of some sampling efficiency. 相似文献
103.
104.
Collini D De Biani FF Dolzhnikov DS Femoni C Iapalucci MC Longoni G Tiozzo C Zacchini S Zanello P 《Inorganic chemistry》2011,50(7):2790-2798
The previously ill-characterized [H(x)Rh(22)(CO)(35)](4-/5-) carbonyl cluster has been obtained as a byproduct of the synthesis of [H(3)Rh(13)(CO)(24)](2-) and effectively separated by metathesis of their sodium salts with [NEt(4)]Cl. Although the yields are modest and never exceed 10-15% (based on Rh), this procedure affords spectroscopically pure [H(3)Rh(22)(CO)(35)](5-) anion. Formation of the latter in mixture with other Rh clusters was also observed by electrospray ionization-mass spectrometry (ESI-MS) in the oxidation of [H(2)Rh(13)(CO)(24)](3-) with Cu(2+) salts. The recovery of further amounts of [H(3)Rh(22)(CO)(35)](5-) was hampered by too similar solubility of the salts composing the mixture. Conversely, the reaction in CH(3)CN of [H(2)Rh(13)(CO)(24)](3-) with [Cu(MeCN)(4)](+)[BF(4)](-) leads to the [H(2)Rh(13)(CO)(24){Cu(MeCN)}(2)](-) bimetallic cluster. The X-ray crystal structures of [H(4)Rh(22)(CO)(35)](4-), [H(3)Rh(22)(CO)(35)](5-), and [H(2)Rh(13)(CO)(24){Cu(MeCN)}(2)](-) are reported. From a formal point of view, the metal frame of the former two species can be derived by interpenetration along two orthogonal axes of two moieties displaying the structure of the latter. The availability of [H(8-n)Rh(22)(CO)(35)](n-) salts prompted their detailed chemical, spectroscopic, and electrochemical characterization. The presence of hydride atoms has been directly proved both by ESI-MS and (1)H NMR. Moreover, both [H(4)Rh(22)(CO)(35)](4-) and [H(3)Rh(22)(CO)(35)](5-) undergo distinctive electrochemically reversible redox changes. This allows to assess electrochemical studies as indisputable though circumstantial evidence of the presence of (1)H NMR-silent hydride atoms in isostructural anions of different charge. 相似文献
105.
Glass-forming liquids have been extensively studied in recent decades, but there is still no theory that fully describes these systems, and the diversity of treatments is in itself a barrier to understanding. Here we introduce a new simple model that (possessing both liquid-crystal and glass transition) unifies different approaches, producing most of the phenomena associated with real glasses, without loss of the simplicity that theorists require. Within the model we calculate energy relaxation, nonexponential slowing phenomena, the Kauzmann temperature, and other classical signatures. Moreover, the model reproduces a subdiffusive exponent observed in experiments of dense systems. The simplicity of the model allows us to identify the microscopic origin of glassification, leaving open the possibility for theorists to make further progress. 相似文献
106.
Audisio D Messaoudi S Peyrat JF Brion JD Alami M 《The Journal of organic chemistry》2011,76(12):4995-5005
3-(N-Substituted) 4(1H)-quinolinones were synthesized using the copper-catalyzed Ullmann C-N bond forming strategy in moderate to quantitative yields. Starting from 3-halo-4(1H)-quinolones, various nucleophiles including amides, lactams, sulfonamides and NH-containing azoles have been used successfully. In all cases, the reactions take place rapidly in toluene and proceed by using copper powder as a catalyst, DMEDA as a ligand and K(2)CO(3) as a base. In addition, other related heterocycles such as 3-bromoquinolin-2(1H)-ones, 3-bromocoumarin, and 3,5-dibromo-2-pyridone show good to very high reactivity with various nucleophiles under our Cu/DMEDA catalyst system. 相似文献
107.
Giust D Albasanz JL Martín M Marega R Delforge A Bonifazi D 《Chemical communications (Cambridge, England)》2011,47(38):10617-10619
Here we report on the surface immobilization of redox-active [60]fullerene derivatives and the consequent neuroprotective effects toward l-glutamate induced excitotoxicity in human derived undifferentiated neuroblastoma cells. 相似文献
108.
Zeitouny J Belbakra A Llanes-Pallas A Barbieri A Armaroli N Bonifazi D 《Chemical communications (Cambridge, England)》2011,47(1):451-453
The synthesis, photoswitchability and NIR emitting properties of a novel π-extended pyrene derivative, peripherally decorated with four azobenzenyl-ethynyl legs, are reported. 相似文献
109.
110.