全文获取类型
收费全文 | 1075篇 |
免费 | 37篇 |
国内免费 | 7篇 |
专业分类
化学 | 664篇 |
晶体学 | 6篇 |
力学 | 86篇 |
数学 | 202篇 |
物理学 | 161篇 |
出版年
2023年 | 8篇 |
2022年 | 14篇 |
2021年 | 19篇 |
2020年 | 28篇 |
2019年 | 21篇 |
2018年 | 9篇 |
2017年 | 11篇 |
2016年 | 30篇 |
2015年 | 28篇 |
2014年 | 28篇 |
2013年 | 69篇 |
2012年 | 53篇 |
2011年 | 76篇 |
2010年 | 34篇 |
2009年 | 46篇 |
2008年 | 72篇 |
2007年 | 67篇 |
2006年 | 54篇 |
2005年 | 53篇 |
2004年 | 52篇 |
2003年 | 43篇 |
2002年 | 42篇 |
2001年 | 13篇 |
2000年 | 17篇 |
1999年 | 14篇 |
1998年 | 6篇 |
1997年 | 9篇 |
1996年 | 23篇 |
1995年 | 16篇 |
1994年 | 35篇 |
1993年 | 16篇 |
1992年 | 7篇 |
1991年 | 9篇 |
1990年 | 7篇 |
1989年 | 3篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 11篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1969年 | 4篇 |
排序方式: 共有1119条查询结果,搜索用时 15 毫秒
1.
Tony Donnelly 《Applied Surface Science》2006,252(13):4445-4448
Ultra-thin (0.5-5 nm) films of Ag have been prepared by pulsed laser deposition in vacuum using a 26 ns KrF excimer laser at 1 J cm−2. The deposition was controlled using a Langmuir ion probe and a quartz crystal thickness monitor. Transmission electron microscopy showed that the films are not continuous, but are structured on nanometer size scales. Optical absorption spectra showed the expected surface plasmon resonance feature, which shifted to longer wavelength and increased in strength as the equivalent film thickness was increased. It is shown that Maxwell Garnett effective medium theory can be used to calculate the main features of optical absorption spectra. 相似文献
2.
Tony Burkitt 《Nuclear Physics B》1983,220(4):401-414
A variety of techniques for the inclusion of dynamical fermions in lattice gauge theory is examined. Three pseudo-fermionic techniques that have the characteristics desirable for an unquenched simulation of four-dimensional QCD are studied in detail. Langevin and Metropolis pseudo-fermionic techniques are implemented for a 64×64 lattice on the Distributed Array Processor and their relative merits examined both for free fermions and the lattice Schwinger model. 相似文献
3.
The fluid flow through a rotating straight pipe is considered, the axis of rotation being perpendicular to the pipe axis. The flow of the fluid is taken as fully developed, i.e. the velocity field is assumed to be the same in all transverse cross sections of the pipe. The derivation presented applies to viscous and nonviscous incompressible fluids. For constant angular pipe velocity a simple and exact (Coriolis type) relationF=2Q(t) is derived between the forceF by which the fluid acts on the (unit length of the) pipe in the direction perpendicular to the two axes, the fluid mass flow rateQ(t) through the pipe, and the angular velocity. Variable angular velocities, i.e.
, introduce an additional term into the expression for the inertial forceF, which depends only on
and on known (constant) parameters; this term is known for given angular velocity(t). The flow configuration investigated here is an idealization of those appearing (over short space and time intervals) in the devices measuring mass flow rateQ(t) through the (Coriolis) forceF. Therefore the exact results derived here cast some light on the degree of precision one expects in these devices, where more complicated flow configurations are present than those looked at in this paper. 相似文献
4.
Martinho M Banse F Bartoli JF Mattioli TA Battioni P Horner O Bourcier S Girerd JJ 《Inorganic chemistry》2005,44(25):9592-9596
The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved. 相似文献
5.
The benzene dimer is the simplest prototype of pi-pi interactions and has been used to understand the fundamental physics of these interactions as they are observed in more complex systems. In biological systems, however, aromatic rings are rarely found in isolated pairs; thus, it is important to understand whether aromatic pairs remain a good model of pi-pi interactions in clusters. In this study, ab initio methods are used to compute the binding energies of several benzene trimers and tetramers, most of them in 1D stacked configurations. The two-body terms change only slightly relative to the dimer, and except for the cyclic trimer, the three- and four-body terms are negligible. This indicates that aromatic clusters do not feature any large nonadditive effects in their binding energies, and polarization effects in benzene clusters do not greatly change the binding that would be anticipated from unperturbed benzene-benzene interactions, at least for the 1D stacked systems considered. Three-body effects are larger for the cyclic trimer, but for all systems considered, the computed binding energies are within 10% of what would be estimated from benzene dimer energies at the same geometries. 相似文献
6.
Treatment of [Ti(O-i-Pr)(2)Cl(2)] with NaL(OEt) (L(OEt)(-) = [CpCo[P(O)(OEt)(2)](3)](-), Cp = eta(5)-C(5)H(5)) afforded [L(OEt)Ti(O-i-Pr)(2)Cl] that reacted with HCl in ether to give [L(OEt)TiCl(3)] (1). The average Ti-O and Ti-Cl distances in 1 are 1.975 and 2.293 A, respectively. Reaction of titanyl sulfate with NaL(OEt) in water followed by addition of HBF(4) afforded [L(OEt)TiF(3)] (2), the Ti-O and Ti-F distances of which are 2.020(2) and 1.792(2) A, respectively. The Zr(IV) analogue [L(OEt)ZrF(3)] (3) was prepared similarly from zirconyl nitrate, NaL(Oet), and HBF(4) in water. The Zr-O and average Zr-F distances in 3 are 2.139(2) and 1.938(2) A, respectively. Treatment of 1 with tetrachlorocatechol (H(2)Cl(4)cat) afforded [L(OEt)Ti(Cl(4)cat)Cl] (4). The average Ti-O(P), Ti-O(C), and Ti-Cl distances in 4 are 1.972, 1.926, and 2.334 A, respectively. Hydrolysis of 4 in the presence of Et(3)N yielded the mu-oxo dimer [(L(OEt))(2)Ti(2)(Cl(4)cat)(2)(mu-O)] (5). The average Ti-O(P), Ti-O(C), and Ti-O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) A. Treatment of 1 with 1,1'-binaphthol (BINOLH(2)) in the presence of Et(3)N afforded [(L(OEt))(2)Ti(2)(mu-O)(2)(mu-BINOL)] x 2BINOLH(2) (6.2BINOLH(2)). Complex 1 is capable of catalyzing ring opening of epoxides with Me(3)SiN(3) under solvent-free conditions presumably via a Ti-azide intermediate. 相似文献
7.
Hussain HH Babic G Durst T Wright JS Flueraru M Chichirau A Chepelev LL 《The Journal of organic chemistry》2003,68(18):7023-7032
We are attempting to develop novel synthetic antioxidants aimed at retarding the effects of free-radical induced cell damage. In this paper we discuss the design strategy and report the synthesis of seven novel antioxidants, including six catechols and a benzylic phenol. The bond dissociation enthalpy (BDE) for the most active (weakest) OH bond in each molecule was calculated by theoretical methods, as well as the BDE for the semiquinone radical. Reaction rates with the nitrogen-centered free radical DPPH(*) were measured in ethyl acetate. The log of k(DPPH) for bimolecular reaction correlated well with the primary BDE. The correlation between rate constants and calculated BDEs shows that the BDE is a good predictor of antioxidant activity with DPPH(*), suggesting that our design criteria are useful and that these compounds should undergo further testing in cell cultures and in animal models. 相似文献
8.
H. Dupont Durst Luis Echegoyen George W. Gokel Angel Kaifer 《Tetrahedron letters》1982,23(43):4449-4452
The 13C spin-lattice relaxation times (T1's) of cryptands [2.1.1], [2.2.1] and [2.2.2] as well as those of the corresponding cryptate complexes with Li+, Na+, and K+ in CDCl3 and CH3OH:D2O (90:10) were measured and the results are interpreted in terms of molecular compression and desolvation effects. 相似文献
9.
Lazarus EA Navratil GA Greenfield CM Strait EJ Austin ME Burrell KH Casper TA Baker DR DeBoo JC Doyle EJ Durst R Ferron JR Forest CB Gohil P Groebner RJ Heidbrink WW Hong R Houlberg WA Howald AW Hsieh C Hyatt AW Jackson GL Kim J Lao LL Lasnier CJ Leonard AW Lohr J La Haye RJ Maingi R Miller RL Murakami M Osborne TH Perkins LJ Petty CC Rettig CL Rhodes TL Rice BW Sabbagh SA Schissel DP Scoville JT Snider RT Staebler GM Stallard BW Stambaugh RD St John HE Stockdale RE Taylor PL Thomas DM 《Physical review letters》1996,77(13):2714-2717
10.
Imazethapyr is the herbicide developed for use in leguminous crops. In this study, flow-injection liposome immunoanalysis (FILIA) has been shown to be capable of measuring imazethapyr in a buffered solution with a detection limit of 0.1 ppb through the optimization process. Protein A coated glass beads covalently conjugated with antibody were contained in a glass column, and this column was used as an immunoreactor. Liposomes which encapsulated a fluorescent dye, sulforhodamine B (SRB) or carboxyfluorescein (CF), generated the analytical signal. By loading larger volumes of sample onto the column, it was shown that the detection limit could be lowered. Liposomes containing carboxyfluorescein gave more sensitive response and a lower detection limit than those with sulforhodamine B. Also, improved response was obtained by using a smaller flow cell in the fluorescence detector due to the reduced dilution effect. 相似文献