全文获取类型
收费全文 | 1469篇 |
免费 | 76篇 |
国内免费 | 9篇 |
专业分类
化学 | 1181篇 |
晶体学 | 16篇 |
力学 | 22篇 |
数学 | 156篇 |
物理学 | 179篇 |
出版年
2023年 | 19篇 |
2022年 | 23篇 |
2021年 | 47篇 |
2020年 | 45篇 |
2019年 | 50篇 |
2018年 | 29篇 |
2017年 | 23篇 |
2016年 | 72篇 |
2015年 | 46篇 |
2014年 | 48篇 |
2013年 | 67篇 |
2012年 | 136篇 |
2011年 | 167篇 |
2010年 | 69篇 |
2009年 | 61篇 |
2008年 | 110篇 |
2007年 | 89篇 |
2006年 | 107篇 |
2005年 | 89篇 |
2004年 | 55篇 |
2003年 | 44篇 |
2002年 | 40篇 |
2001年 | 10篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 8篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 6篇 |
1990年 | 3篇 |
1988年 | 2篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 2篇 |
1967年 | 1篇 |
1876年 | 1篇 |
排序方式: 共有1554条查询结果,搜索用时 15 毫秒
211.
Kiani A Alpuche-Aviles MA Eggers PK Jones M Gooding JJ Paddon-Row MN Bard AJ 《Langmuir : the ACS journal of surfaces and colloids》2008,24(6):2841-2849
Electron transfer (ET) rate kinetics through n-alkanethiol self-assembled monolayers (SAMs) of alkanethiols of different chain lengths [Me(CH2)nSH; n=8, 10, 11, 15] on Au and Hg surfaces and ferrocene (Fc)-terminated SAMs (poly-norbornylogous and HS(CH2)12CONHCH2Fc) on Au were studied using cyclic voltammetry and scanning electrochemical microscopy (SECM). The SECM results allow determination of the ET kinetics of solution-phase Ru(NH3)63+/2+ through the alkanethiol SAMs on Au and Hg. A model using the potential dependence of the measured rate constants is proposed to compensate for the pinhole contribution. Extrapolated values of koML for Ru(NH3)63+/2+ using the model follow the expected exponential decay (beta is 0.9) for different chain lengths. For a Fc-terminated poly-norbornyl SAM, the standard rate constant of direct tunneling (ko is 189+/-31 s(-1)) is in the same order as the ko value of HS(CH2)12CONHCH2Fc. In blocking and Fc SAMs, the rates of ET are demonstrated to follow Butler-Volmer kinetics with transfer coefficients alpha of 0.5. Lower values of alpha are treated as a result of the pinhole contribution. The normalized rates of ET are 3 orders of magnitude higher for Fc-terminated than for blocking monolayers. Scanning electron microscopy imaging of Pd nanoparticles electrochemically deposited in pinholes of blocking SAMs was used to confirm the presence of pinholes. 相似文献
212.
Hall WP Anker JN Lin Y Modica J Mrksich M Van Duyne RP 《Journal of the American Chemical Society》2008,130(18):5836-5837
A plasmonic switch based on the calcium-induced conformational changes of calmodulin is shown to exhibit reversible wavelength modulations in response to changing calcium concentration. The extinction maximum (lambdamax) of a localized surface plasmon resonance (LSPR) sensor functionalized with a novel calmodulin construct, cutinase-calmodulin-cutinase (CutCaMCut), reversibly shifts by 2-3 nm. A high-resolution (HR) LSPR spectrometer with a wavelength resolution (3sigma) of 1.5 x 10-2 nm was developed to detect these wavelength modulations in real-time, providing information about the dynamics and structure of the protein. The rate of conversion from open (Ca2+-bound) to closed (Ca2+-free) calmodulin is shown to be 4-fold faster than the reverse process, with a closing rate of 0.127 s-1 and opening rate of 0.034 s-1. As far as we are aware, this plasmonic switch marks the first use of LSPR spectroscopy to detect reversible conformational changes in an unlabeled protein. 相似文献
213.
Westenhoff S Howard IA Hodgkiss JM Kirov KR Bronstein HA Williams CK Greenham NC Friend RH 《Journal of the American Chemical Society》2008,130(41):13653-13658
A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount. 相似文献
214.
215.
A peptide-modified electrode array with a different peptide on each electrode is compared with a single electrode modified with many peptides for the voltammetric measurement of concentrations of Cu(2+), Cd(2+) and Pb(2+) in solution. The single gold electrode was modified simultaneously with peptides Gly-Gly-His, glutathione and angiotensin I each coupled to thioctic acid, and thioctic acid itself, and the calibration of mixtures of ions was compared with previously published data from an array of four sensors each with an individual modification. Calibration at the multi-peptide single-electrode sensor was by two-way partial least squares (voltammetric current measured with variables 'sample' x 'potential') and for the electrode array by three-way NPLS1 ('sample' x 'potential' x 'electrode'). The advantage of designing experiments to yield multi-way data is demonstrated and discussed. 相似文献
216.
Alexander WA Day BS Moore HJ Lee TR Morris JR Troya D 《The Journal of chemical physics》2008,128(1):014713
The effect of mass on gas/organic-surface energy transfer is explored via investigation of the scattering dynamics of rare gases (Ne, Ar, and Kr) from regular (CH3-terminated) and omega-fluorinated (CF3-terminated) alkanethiol self-assembled monolayers (SAMs) at 60 kJmol collision energy. Molecular-beam scattering experiments carried out in ultrahigh vacuum and molecular-dynamics simulations based on high-accuracy potentials are used to obtain the rare-gases' translational-energy distributions after collision with the SAMs. Simulations indicate that mass is the most important factor in determining the changes in the energy exchange dynamics for Ne, Ar, and Kr collisions on CH3- and CF3-terminated SAMs at 60 kJmol collision energy. Other factors, such as changes in the gas-surface potential and intrasurface interactions, play only a minor role in determining the differential dynamics behavior for the systems studied. 相似文献
217.
Since the discovery of ozone depletion, the doublet electronic states of the ozone radical cation have received much attention in experimental and theoretical investigations, while the low-lying quartet states have not. In the present research, viable pathways to the quartet states from the lowest three triplet states of ozone, (3)A(2), (3)B(2), and (3)B(1), and excitations from the (2)A(1) and (2)B(2) states of the ozone radical cation have been studied in detail. The potential energy surfaces, structural optimizations, and vibrational frequencies for several states of ozone and its radical cation have been thoroughly investigated using the complete active space self-consistent field, unrestricted coupled cluster theory from a restricted open-shell Hartree-Fock reference including all single and double excitations (UCCSD), UCCSD method with the effects of connected triple excitations included perturbatively, and unrestricted coupled cluster including all single, double, and triple excitations with the effects of connected quadruple excitations included perturbatively. These methods used Dunning's correlation-consistent polarized core-valence basis sets, cc-pCVXZ (X = D, T, Q, and 5). The most feasible pathways (symmetry and spin allowed transitions) to the quartet states are (4)A(1)<--(3)A(2), (4)A(2)<--(3)A(2), (4)A(1)<--(3)B(2), (4)A(2)<--(3)B(1), (4)B(2)<--(3)B(1), (4)A(2)<--(1)A(1), (4)B(2)<--(1)A(1), and (4)A(1)<--(1)A(1) with vertical ionization potentials of 12.46, 12.85, 12.82, 12.46, 12.65, 13.43, 13.93, and 14.90 eV, respectively. 相似文献
218.
Ariën S. Rustenburg Justin Dancer Baiwei Lin Jianwen A. Feng Daniel F. Ortwine David L. Mobley John D. Chodera 《Journal of computer-aided molecular design》2016,30(11):945-958
Small molecule distribution coefficients between immiscible nonaqueuous and aqueous phases—such as cyclohexane and water—measure the degree to which small molecules prefer one phase over another at a given pH. As distribution coefficients capture both thermodynamic effects (the free energy of transfer between phases) and chemical effects (protonation state and tautomer effects in aqueous solution), they provide an exacting test of the thermodynamic and chemical accuracy of physical models without the long correlation times inherent to the prediction of more complex properties of relevance to drug discovery, such as protein-ligand binding affinities. For the SAMPL5 challenge, we carried out a blind prediction exercise in which participants were tasked with the prediction of distribution coefficients to assess its potential as a new route for the evaluation and systematic improvement of predictive physical models. These measurements are typically performed for octanol-water, but we opted to utilize cyclohexane for the nonpolar phase. Cyclohexane was suggested to avoid issues with the high water content and persistent heterogeneous structure of water-saturated octanol phases, since it has greatly reduced water content and a homogeneous liquid structure. Using a modified shake-flask LC-MS/MS protocol, we collected cyclohexane/water distribution coefficients for a set of 53 druglike compounds at pH 7.4. These measurements were used as the basis for the SAMPL5 Distribution Coefficient Challenge, where 18 research groups predicted these measurements before the experimental values reported here were released. In this work, we describe the experimental protocol we utilized for measurement of cyclohexane-water distribution coefficients, report the measured data, propose a new bootstrap-based data analysis procedure to incorporate multiple sources of experimental error, and provide insights to help guide future iterations of this valuable exercise in predictive modeling. 相似文献
219.
We consider an inverse source problem for an inhomogeneous wave equation with discrete-in-time sources, modeling a seismic rupture. The inverse source problem, with an arbitrary source term on the right-hand side of the wave equation, is not uniquely solvable. Here we formulate conditions on the source term that allow us to show uniqueness and that provide a reasonable model for the application of interest. We assume that the source term is supported on a finite set of times and that the support in space moves with subsonic velocity. Moreover, we assume that the spatial part of the source is singular on a hypersurface, an application being a seismic rupture along a fault plane. Given data collected over time on a detection surface that encloses the spatial projection of the support of the source, we show how to recover the times and locations of sources microlocally and then reconstruct the smooth part of the source assuming that it is the same at each source location. 相似文献
220.
Hiu C. Lam Justin T. J. Spence Dr. Jonathan H. George 《Angewandte Chemie (International ed. in English)》2016,55(35):10368-10371
Hyperjapones A–E and hyperjaponols A–C are complex natural products of mixed aromatic polyketide and terpene biosynthetic origin that have recently been isolated from Hypericum japonicum. We have synthesized hyperjapones A–E using a biomimetic, oxidative hetero‐Diels–Alder reaction to couple together dearomatized acylphloroglucinol and cyclic terpene natural products. Hyperjapone A is proposed to be the biosynthetic precursor of hyperjaponol C through a sequence of: 1) epoxidation; 2) acid‐catalyzed epoxide ring‐opening; and 3) a concerted, asynchronous alkene cyclization and 1,2‐alkyl shift of a tertiary carbocation. Chemical mimicry of this proposed biosynthetic sequence allowed a concise total synthesis of hyperjaponol C to be completed in which six carbon–carbon bonds, six stereocenters, and three rings were constructed in just four steps. 相似文献