全文获取类型
收费全文 | 831篇 |
免费 | 83篇 |
国内免费 | 1篇 |
专业分类
化学 | 704篇 |
晶体学 | 1篇 |
力学 | 16篇 |
数学 | 118篇 |
物理学 | 76篇 |
出版年
2024年 | 1篇 |
2023年 | 7篇 |
2022年 | 16篇 |
2021年 | 21篇 |
2020年 | 35篇 |
2019年 | 25篇 |
2018年 | 11篇 |
2017年 | 15篇 |
2016年 | 53篇 |
2015年 | 47篇 |
2014年 | 70篇 |
2013年 | 63篇 |
2012年 | 78篇 |
2011年 | 76篇 |
2010年 | 55篇 |
2009年 | 48篇 |
2008年 | 43篇 |
2007年 | 40篇 |
2006年 | 32篇 |
2005年 | 32篇 |
2004年 | 33篇 |
2003年 | 11篇 |
2002年 | 23篇 |
2001年 | 11篇 |
2000年 | 3篇 |
1999年 | 7篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1988年 | 1篇 |
1986年 | 5篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 1篇 |
1941年 | 2篇 |
1938年 | 2篇 |
1934年 | 2篇 |
1916年 | 1篇 |
1915年 | 1篇 |
排序方式: 共有915条查询结果,搜索用时 15 毫秒
51.
52.
Fuxing Pan Lukas Guggolz Florian Weigend Stefanie Dehnen 《Angewandte Chemie (International ed. in English)》2020,59(38):16638-16643
The Zintl anion (Ge2As2)2? represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh3)AuMe] into the 1,2‐diaminoethane (en) solution of (Ge2As2)2?, the heterometallic cluster anion [Au6(Ge3As)(Ge2As2)3]3? is obtained as its salt [K(crypt‐222)]3[Au6(Ge3As)(Ge2As2)3]?en?2 tol ( 1 ). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non‐bonding) octahedron of six Au atoms that is face‐capped by four (GexAs4?x)x? (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge3As)3? unit besides three (Ge2As2)2? units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au6(Ge3As)(Ge2As2)3]3?. Reactions of the heavier homologues (Tt2Pn2)2? (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1 , but dimers of ternary nine‐vertex clusters, {[AuTt5Pn3]2}4? (in 2 – 4 ; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo‐tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge2As2)2?, according to the DFT calculations. 相似文献
53.
Dr. Yumei Lin Dewang Xie Prof. Dr. Werner Massa Dr. Leonhard Mayrhofer Sina Lippert Benjamin Ewers Dr. Alexey Chernikov Prof. Dr. Martin Koch Prof. Dr. Stefanie Dehnen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):8806-8813
In situ transformations of selenidostannate frameworks in ionic liquids (ILs) were initiated by treatment of the starting phase K2[Sn2Se5] and the consecutive reaction products by means of temperature increase and/or amine addition. Along the reaction pathway, the framework dimensionalities of the five involved selenidostannate anions develop from 3D to 1D and back, both in top‐down and bottom‐up style. Addition of ethane‐1,2‐diamine (en) led to the reversion of the 2D→1D step from 2D‐{[Sn24Se56]16?} to 1D‐{[Sn6Se14]4?}. As rationalized by DFT investigations, the 2D anion is thermodynamically favored. Photoconductivity measurements reveal that all samples show Schottky contact behavior with absolute thresholds below 10 V. One of the samples exhibits conductive states within the energy range of visible photons. 相似文献
54.
Three one‐dimensional coordination polymers, [MnCl2(4‐pyterpy)]∙2CHCl3 ( 1 ), [Mn(NO3)2(4‐pyterpy)]∙CHCl3 ( 2 ) and [Ag(NO3)(3‐pyterpy)]∙H2O ( 3 ) (4‐pyterpy = 4′‐(4‐pyridyl)‐2,2′:6′,2″‐terpyridine and 3‐pyterpy = 4′‐(3‐pyridyl)‐2,2′:6′,2″‐terpyridine) were synthesized and characterized by X‐ray diffraction. All three compounds exhibit a rare “head‐to‐tail” coordination of the multidentate ligand, but differ significantly in their polymer chain conformations. Additionally, the fluorescent properties of all three compounds were investigated and show a weak, ligand‐centered fluorescence at 416–418 nm. 相似文献
55.
56.
Thermal fluctuations of surfactant bilayers in an aqueous solution produce an effective, long-range repulsion that can lead to a continuous unbinding transition. We report on an optical interferometry study of the thermal fluctuations of multicomponent bilayers close to the unbinding transition. We find that, in contrast to the case of single-component bilayers, the thermal fluctuation spectrum of multicomponent bilayers does not agree with a continuous unbinding transition but instead indicates the proximity of an unbinding tricritical point. 相似文献
57.
58.
G. Alexander L. Criegee H.C. Dehne K. Derikum R. Devenish G. Flügge G. Franke Ch. Gerke E. Hackmack P. Harms G. Horlitz Th. Kahl G. Knies E. Lehmann R. Schmitz U. Timm P. Waloschek K. Wacker 《Physics letters. [Part B]》1978,78(1):162-166
The decay of the heavy lepton τ into πv has been established using the magnetic detector PLUTO. The branching ratio is determined to be BR(τ→πv)=(9.0 ± 2.9)% with an additional systematic uncertainty of 2.5%. This value is in good agreement with the theoretical prediction. 相似文献
59.
Melting curves of Cu and Ni were measured in the laser-heated diamond cell to 97 GPa (3800 K) and 60 GPa (2970 K), respectively. The temperatures of Cu are in good agreement with recent theoretical calculations. The Cu melting slope (dT/dP) is about 2.5 times steeper than for Ni. The present results confirm the key role d-shell electrons play in determining the temperature dependence of high pressure melting curves in transition metals that have filled or partially filled d electron bands. 相似文献
60.
Klaassen T Kasel D Harlfinger S Fuhr U 《Rapid communications in mass spectrometry : RCM》2004,18(15):1675-1680
A reliable and easy to use liquid chromatography/tandem mass spectrometry (LC/MS/MS) method without the use of sample extraction was developed for the simultaneous quantification of urinary concentrations of mephenytoin, a standard phenotyping substrate for the cytochrome P450 enzyme CYP2C19, and its phase I metabolites 4'-hydroxymephenytoin and nirvanol. Fifty microL of urine were diluted with a buffered beta-glucuronidase solution and incubated at 37 degrees C for 6 h followed by addition of methanol, containing the internal standard 4'-methoxymephenytoin. The chromatographic separation was achieved using a 100 x 3 mm, 5 micro Thermo Electron Aquasil C18 column with a gradient flow, increasing the organic fraction (acetonitrile/methanol 50:50) of the mobile phase from 10 to 90%. Quantification by triple-stage mass spectrometry (TSQ Quantum, Thermo Electron) was accomplished by negative electrospray ionization in the selected reaction monitoring mode. Linearity was observed for all substances in the concentration range 15-10 000 ng/mL. The lower limit of quantification (LLOQ) was 20 ng/mL for 4'-hydroxymephenytoin and 30 ng/mL for nirvanol and mephenytoin, respectively. Intra- and inter-day inaccuracy did not exceed 9.5% for all substances from LLOQ to 10 000 ng/mL. Intra- and inter-day precision were in the range of 0.8-10.5%. The method was validated according to international ICH and FDA guidelines and successfully applied for phenotyping of Caucasian male volunteers who received an oral dose of 50 mg mephenytoin. 相似文献