全文获取类型
收费全文 | 3024篇 |
免费 | 154篇 |
国内免费 | 7篇 |
专业分类
化学 | 2085篇 |
晶体学 | 23篇 |
力学 | 87篇 |
数学 | 404篇 |
物理学 | 586篇 |
出版年
2023年 | 23篇 |
2022年 | 25篇 |
2021年 | 38篇 |
2020年 | 48篇 |
2019年 | 51篇 |
2018年 | 50篇 |
2017年 | 64篇 |
2016年 | 123篇 |
2015年 | 78篇 |
2014年 | 128篇 |
2013年 | 222篇 |
2012年 | 227篇 |
2011年 | 244篇 |
2010年 | 142篇 |
2009年 | 139篇 |
2008年 | 169篇 |
2007年 | 143篇 |
2006年 | 119篇 |
2005年 | 156篇 |
2004年 | 108篇 |
2003年 | 110篇 |
2002年 | 89篇 |
2001年 | 25篇 |
2000年 | 33篇 |
1999年 | 23篇 |
1998年 | 35篇 |
1997年 | 37篇 |
1996年 | 22篇 |
1995年 | 20篇 |
1994年 | 25篇 |
1993年 | 28篇 |
1992年 | 21篇 |
1991年 | 17篇 |
1990年 | 16篇 |
1989年 | 21篇 |
1988年 | 23篇 |
1987年 | 17篇 |
1986年 | 19篇 |
1985年 | 16篇 |
1984年 | 30篇 |
1983年 | 16篇 |
1982年 | 17篇 |
1981年 | 19篇 |
1980年 | 20篇 |
1979年 | 17篇 |
1978年 | 20篇 |
1977年 | 25篇 |
1976年 | 12篇 |
1975年 | 16篇 |
1974年 | 15篇 |
排序方式: 共有3185条查询结果,搜索用时 15 毫秒
81.
Landa Purushottam Unnikrishnan V. B. Dattatraya Gautam Rawale Mansi Gujrati Surya Dev Mishra Sajeev T. K. Neelesh C. Reddy Srinivasa Rao Adusumalli Ram Kumar Mishra Vishal Rai 《Chemical science》2020,11(48):13137
Analytically pure proteins are indispensable for diverse applications, including therapeutics. Here, we report a methodology where a single amino acid, glycine, enables metal-free protein purification. This robust platform is enabled by a Gly-tag resin for site-specific capture, enrichment, and release through chemically triggered C–C bond dissociation by resonance-assisted electron density polarization.Gly-tag resin precisely captures and releases a protein with one glycine at the N-terminus. The user-friendly protocol delivers analytically pure protein free of metal contaminants. 相似文献
82.
Velázquez MM Ortega F Monroy F Rubio RG Pegiadou S Pérez L Infante MR 《Journal of colloid and interface science》2005,283(1):144-152
We report the formation of Langmuir monolayers of pure zwitterionic hexadecyl 1-N-L-tryptophan glycerol ether (C(16)-TGE) surfactant and mixed monolayers of cationic-zwitterionic surfactant obtained modifying the pH of the subphase. The pressure-area and surface potential-area isotherms and fluorescence microscopy measurements have been used to characterize the surface phase transitions in the monolayers. These transitions appeared at larger areas as the pH decreased from 6.0 to 2.0 and almost disappeared as the pH decreased further. The analysis of the surface potential and the infrared reflection-absorption spectroscopy data suggests that the phase transition is associated with a change of orientation of both the hydrocarbon chain and the aromatic group of the surfactant with respect to the air-water surface. The surface rheology of the monolayers was studied by quasielastic light scattering and by the oscillatory barrier technique. The results indicate that there is at least one relaxation process in the monolayer. 相似文献
83.
Solid phase crystallization of plasma-enhanced chemical-vapor-deposited (PECVD) amorphous silicon (alpha-Si:H) in alpha-Si:H/Al and Al/alpha-Si:H structures has been investigated using transmission electron microscopy (TEM) and X-ray diffraction (XRD). Radiative heating has been used to anneal films deposited on carbon-coated nickel (Ni) grids at temperatures between 200 and 400 degrees C for TEM studies. alpha-Si:H films were deposited on c-Si substrates using high vacuum (HV) PECVD for the XRD studies. TEM studies show that crystallization of alpha-Si:H occurs at 200 degrees C when Al film is deposited on top of the alpha-Si:H film. Similar behavior was observed in the XRD studies. In the case of alpha-Si:H deposited on top of Al films, the crystallization could not be observed at 400 degrees C by TEM and even up to 500 degrees C as seen by XRD. 相似文献
84.
Some aspects of resonant vibrations of self-interstitials in the 100-dumbbell configuration are discussed by using a simple defect model incorporating nearest-neighbour interactions, with parameters fitted to the results of computer simulation. Especially we calculate the change of the lattice specific heat due to interstitials. An appreciable increase of the specific heat is obtained yielding a peak at 9–10 K in C/C for Cu. Following a recent suggestion of W. Schilling the diffuse inelastic one-phonon scattering is calculated in the range of the resonance frequencies forq-values away from the phonon-line. In particular, an appreciable diffuse intensity is obtained for theE
g-mode making an experimental observation by neutron scattering feasible. 相似文献
85.
Summary Novel bimetallic alkoxides of copper(II) of the type Cu[M(OPr-i)6]2 (M = Nb or Ta) have been synthesised by the interaction of CuCl2 (1 mol) with K[M(OPr-i)6] (2 mol). These bimetallic isopropoxides undergo facile alcohol interchange with primary alcohols such as MeOH, EtOH,n-PrOH andn-BuOH. However, witht-BuOH, the reaction cannot be driven to completion even under prolonged continuous azeotropic fractionation of the liberatedi-PrOH and the final product corresponded in analysis to Cu[Ta(OPr-i)2(OBu-t)4]2.I.r., electronic and electron spin resonance spectral and magnetic susceptibility measurements indicate a distorted octahedralD
4h geometry for copper(II) in these bimetallic alkoxides. 相似文献
86.
Full details on a very efficient transamination reaction for the synthesis of zwitterionic N,N-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives [C6H2(=NHR)2(=O)2] 5-16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5.H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(=NH2)2(=O)2] 4 in 4.H2O have been established by single-crystal X-ray diffraction. This one-pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N-substituents bearing functionalities such as -OMe (13), -OH (9-12), NR1R2 with R1 = or not equal R2 (14-16) or an alkene (8), leading to a rich coordination chemistry and allowing fine-tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral Zn(II) complex [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20), ligands 13 and 16 with coordinating "arms" afforded with Zn(acac)2 the 2:1 adducts [Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral Zn(II) center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized Zn(II) zwitterionic complexes [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)]] 22 (R1=R2=Me) and 23 (R1=Et, R2=H) by means of an unprecedented, tandemlike synthesis in which 1) the two pendant amino groups of the organic benzoquinonemonoimine zwitterionic precursor favor metal coordination and proton transfer and 2) the saturated linker prevents pi-conjugation between the charges. The nature of the structural arrangements in the solid state for both inorganic (20, 22, 23) and organic (5, 9, 13, and 15) molecules is determined by subtle variations in the nature of the N-substituent on the zwitterion precursor. 相似文献
87.
Badorrey R Cativiela C Díaz-de-Villegas MD Díez R Galbiati F Gálvez JA 《The Journal of organic chemistry》2005,70(24):10102-10105
[reaction: see text] Addition of trimethylsilyl cyanide to ketimines derived from (R)-2,2-dimethyl-1,3-dioxolan-4-yl methyl ketone to generate a quaternary stereocenter has been achieved with high yields and excellent diastereoselectivity. The stereoselectivity was found to be temperature and solvent dependent. The beta-hydroxy-alpha-amino nitrile of syn configuration was the major compound in kinetically controlled reactions, whereas the anti stereoisomer was obtained in excess in thermodynamically controlled reactions. Double stereodifferentiation under kinetic control conditions was successful, and the cyanation reaction occurred with complete syn diastereoselectivity using the matched pair. The versatility of the resulting amino nitrile as a synthetic intermediate was tested by performing the synthesis of orthogonally protected (R)-(2-aminomethyl)alanine. 相似文献
88.
The thermolysis of sodium hexa/benzoato/ferrate/III/, i. e. Na3[Fe/C6H5COO/6].4.5H2O has been investigated at different temperatures in air using Mössbauer, infrared spectroscopic and derivatographic techniques /DTG, DTA, TG/. The thermal decomposition proceeds without the reduction of iron/III/. An increase in particle size of -Fe2O3 formed during thermolysis has been observed with increasing temperature. The end product, -NaFeO2 is formed as a result of the solid state reaction between -Fe2O3 and sodium carbonate. 相似文献
89.
Gupta Madan Mohan Srivastava Alpana Tripathi Arvind Kumar Misra Himanshu Verma Ram Kishore 《平面色谱法杂志一现代薄层色谱法》2006,19(4):282-287
JPC – Journal of Planar Chromatography – Modern TLC - High-performance thin-layer chromatography (HPTLC) has been used for normal-phase separation of the components of hexane,... 相似文献
90.
[reaction: see text] Optically pure allylic amines have been synthesized from alpha,beta-unsaturated aldehydes via allylboration with (-)-B-allyldiisopinocampheylborane, followed by Overman rearrangement. By incorporating crotyl and alkoxyallylboration, functionalization at delta-position was readily accomplished. By applying this methodology, the synthesis of several chiral alpha-amino acids has been achieved. 相似文献