全文获取类型
收费全文 | 4878篇 |
免费 | 84篇 |
国内免费 | 17篇 |
专业分类
化学 | 2709篇 |
晶体学 | 22篇 |
力学 | 104篇 |
数学 | 519篇 |
物理学 | 1625篇 |
出版年
2020年 | 37篇 |
2019年 | 35篇 |
2018年 | 28篇 |
2016年 | 69篇 |
2015年 | 56篇 |
2014年 | 62篇 |
2013年 | 200篇 |
2012年 | 172篇 |
2011年 | 205篇 |
2010年 | 115篇 |
2009年 | 95篇 |
2008年 | 185篇 |
2007年 | 247篇 |
2006年 | 207篇 |
2005年 | 221篇 |
2004年 | 226篇 |
2003年 | 159篇 |
2002年 | 133篇 |
2001年 | 110篇 |
2000年 | 108篇 |
1999年 | 63篇 |
1998年 | 46篇 |
1997年 | 61篇 |
1996年 | 68篇 |
1995年 | 55篇 |
1994年 | 68篇 |
1993年 | 83篇 |
1992年 | 109篇 |
1991年 | 72篇 |
1990年 | 82篇 |
1989年 | 68篇 |
1988年 | 49篇 |
1987年 | 63篇 |
1986年 | 66篇 |
1985年 | 104篇 |
1984年 | 92篇 |
1983年 | 73篇 |
1982年 | 70篇 |
1981年 | 82篇 |
1980年 | 61篇 |
1979年 | 67篇 |
1978年 | 68篇 |
1977年 | 61篇 |
1976年 | 53篇 |
1975年 | 67篇 |
1974年 | 70篇 |
1973年 | 80篇 |
1972年 | 57篇 |
1971年 | 41篇 |
1970年 | 40篇 |
排序方式: 共有4979条查询结果,搜索用时 46 毫秒
261.
Joseph T. Hill-Cousins Sofia S. Salim Youssef M. Bakar Richard K. Bellingham Mark E. Light Richard C.D. Brown 《Tetrahedron》2014
Ring-closing metathesis (RCM) and sequential Yb(OTf)3 promoted Diels–Alder reactions of sulfamide-linked enynes proceeded selectively in one-pot to afford a series of bicyclic and tricyclic sulfamides. Excellent levels of diastereoselectivity are observed for the cycloaddition step, with only the endo-adducts being isolated. The protocol was further extended to incorporate a one-pot RCM–cross metathesis (CM)–Diels–Alder sequence, permitting rapid access to high levels of molecular complexity from simple and easily accessible precursors. 相似文献
262.
Vaman C Andreoiu C Bazin D Becerril A Brown BA Campbell CM Chester A Cook JM Dinca DC Gade A Galaviz D Glasmacher T Hjorth-Jensen M Horoi M Miller D Moeller V Mueller WF Schiller A Starosta K Stolz A Terry JR Volya A Zelevinsky V Zwahlen H 《Physical review letters》2007,99(16):162501
Rare isotope beams of neutron-deficient 106,108,110Sn from the fragmentation of 124Xe were employed in an intermediate-energy Coulomb excitation experiment. The measured B(E2,0(1)(+)-->2(1)(+)) values for 108Sn and 110Sn and the results obtained for the 106Sn show that the transition strengths for these nuclei are larger than predicted by current state-of-the-art shell-model calculations. This discrepancy might be explained by contributions of the protons from within the Z = 50 shell to the structure of low-energy excited states in this region. 相似文献
263.
Adare A Afanasiev S Aidala C Ajitanand NN Akiba Y Al-Bataineh H Alexander J Al-Jamel A Aoki K Aphecetche L Armendariz R Aronson SH Asai J Atomssa ET Averbeck R Awes TC Azmoun B Babintsev V Baksay G Baksay L Baldisseri A Barish KN Barnes PD Bassalleck B Bathe S Batsouli S Baublis V Bauer F Bazilevsky A Belikov S Bennett R Berdnikov Y Bickley AA Bjorndal MT Boissevain JG Borel H Boyle K Brooks ML Brown DS Bucher D Buesching H Bumazhnov V Bunce G Burward-Hoy JM Butsyk S Campbell S Chai JS Chang BS 《Physical review letters》2007,98(16):162301
Differential measurements of elliptic flow (v2) for Au+Au and Cu+Cu collisions at sqrt[sNN]=200 GeV are used to test and validate predictions from perfect fluid hydrodynamics for scaling of v2 with eccentricity, system size, and transverse kinetic energy (KE T). For KE T identical with mT-m up to approximately 1 GeV the scaling is compatible with hydrodynamic expansion of a thermalized fluid. For large values of KE T mesons and baryons scale separately. Quark number scaling reveals a universal scaling of v2 for both mesons and baryons over the full KE T range for Au+Au. For Au+Au and Cu+Cu the scaling is more pronounced in terms of KE T, rather than transverse momentum. 相似文献
264.
Aubert B Barate R Bona M Boutigny D Couderc F Karyotakis Y Lees JP Poireau V Tisserand V Zghiche A Grauges E Palano A Chen JC Qi ND Rong G Wang P Zhu YS Eigen G Ofte I Stugu B Abrams GS Battaglia M Brown DN Button-Shafer J Cahn RN Charles E Gill MS Groysman Y Jacobsen RG Kadyk JA Kerth LT Kolomensky YG Kukartsev G Lynch G Mir LM Orimoto TJ Pripstein M Roe NA Ronan MT Wenzel WA del Amo Sanchez P Barrett M Ford KE Harrison TJ Hart AJ Hawkes CM Morgan SE Watson AT Held T Koch H Lewandowski B 《Physical review letters》2007,98(5):051802
We present an observation of B-->eta'K*. The data sample corresponds to 232x10(6) BB[over ] pairs collected with the BABAR detector at the PEP-II asymmetric-energy B factory at the Stanford Linear Accelerator Center. We measure the branching fractions (in units of 10(-6)) B(B(0)-->eta'K*0)=3.8+/-1.1+/-0.5 and B(B+-->eta'K*+)=4.9(1.7)(+1.9)+/-0.8, where the first error is statistical and the second systematic. A simultaneous fit results in the observation of B-->eta'K* with B(B-->eta'K*)=4.1(-0.9)(+1.0)+/-0.5. We also search for B-->eta'rho and eta'f(0)(980)(f(0)-->pi+pi-) with results and 90% confidence level upper limits B(B+-->eta'rho+)=8.7(-2.8-1.3)(+3.1+2.3) (<14), B(B(0)-->eta'rho0)<3.7, and B(B(0)-->eta'f(0)(980)(f(0)-->pi+pi-))<1.5. Charge asymmetries in the channels with significant yields are consistent with zero. 相似文献
265.
Pileio G Concistrè M McLean N Gansmüller A Brown RC Levitt MH 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,186(1):65-74
Many important double-quantum recoupling techniques in solid-state NMR are classified as being gamma-encoded. This means that the phase of the double-quantum effective Hamiltonian, but not its amplitude, depends on the third Euler angle defining the orientation of the molecular spin system in the frame of the magic-angle-spinning rotor. In this paper, we provide closed analytical solutions for the dependence of the powder-average double-quantum-filtered signal on the recoupling times, within the average Hamiltonian approximation for gamma-encoded pulse sequences. The validity of the analytical solutions is tested by numerical simulations. The internuclear distance in a (13)C(2)-labelled retinal is estimated by fitting the analytical curves to experimental double-quantum data. 相似文献
266.
Cadars S Sein J Duma L Lesage A Pham TN Baltisberger JH Brown SP Emsley L 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,188(1):24-34
The robustness of the refocused INADEQUATE MAS NMR pulse sequence for probing through-bond connectivities has been demonstrated in a large range of solid-state applications. This pulse sequence nevertheless suffers from artifacts when applied to multispin systems, e.g. uniformly labeled (13)C solids, which distort the lineshapes and can potentially result in misleading correlation peaks. In this paper, we present a detailed account that combines product-operator analysis, numerical simulations and experiments of the behavior of a three-spin system during the refocused INADEQUATE pulse sequence. The origin of undesired anti-phase contributions to the spectral lineshapes are described, and we show that they do not interfere with the observation of long-range correlations (e.g. two-bond (13)C-(13)C correlations). The suppression of undesired contributions to the refocused INADEQUATE spectra is shown to require the removal of zero-quantum coherences within a z-filter. A method is proposed to eliminate zero-quantum coherences through dephasing by heteronuclear dipolar couplings, which leads to pure in-phase spectra. 相似文献
267.
A feasibility study of X‐ray phase‐contrast mammographic tomography at the Imaging and Medical beamline of the Australian Synchrotron
下载免费PDF全文
![点击此处可从《Journal of synchrotron radiation》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yakov I. Nesterets Timur E. Gureyev Sheridan C. Mayo Andrew W. Stevenson Darren Thompson Jeremy M. C. Brown Marcus J. Kitchen Konstantin M. Pavlov Darren Lockie Francesco Brun Giuliana Tromba 《Journal of synchrotron radiation》2015,22(6):1509-1523
Results are presented of a recent experiment at the Imaging and Medical beamline of the Australian Synchrotron intended to contribute to the implementation of low‐dose high‐sensitivity three‐dimensional mammographic phase‐contrast imaging, initially at synchrotrons and subsequently in hospitals and medical imaging clinics. The effect of such imaging parameters as X‐ray energy, source size, detector resolution, sample‐to‐detector distance, scanning and data processing strategies in the case of propagation‐based phase‐contrast computed tomography (CT) have been tested, quantified, evaluated and optimized using a plastic phantom simulating relevant breast‐tissue characteristics. Analysis of the data collected using a Hamamatsu CMOS Flat Panel Sensor, with a pixel size of 100 µm, revealed the presence of propagation‐based phase contrast and demonstrated significant improvement of the quality of phase‐contrast CT imaging compared with conventional (absorption‐based) CT, at medically acceptable radiation doses. 相似文献
268.
Copper‐Catalyzed Cross‐Coupling of Boronic Esters with Aryl Iodides and Application to the Carboboration of Alkynes and Allenes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Yiqing Zhou Wei You Kevin B. Smith Prof. M. Kevin Brown 《Angewandte Chemie (International ed. in English)》2014,53(13):3475-3479
Copper‐catalyzed Suzuki–Miyaura‐type cross‐coupling and carboboration processes are reported. The cross‐couplings function well with a variety of substituted aryl iodides and aryl boronic esters and allows for orthogonal reactivity compared to palladium‐catalyzed processes. The carboboration method includes both alkynes and allenes and provides access to highly substituted and stereodefined vinyl boronic esters. The alkyne carboboration method is highlighted in the simple one‐pot synthesis of Tamoxifen. 相似文献
269.
Oxidative Addition to Palladium(0) Diphosphine Complexes: Observations of Mechanistic Complexity with Iodobenzene as Reactant
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Almira Kurbangalieva Dr. Duncan Carmichael Dr. K. K. Hii Dr. Anny Jutand Dr. John M. Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1116-1125
Using a combination of electrochemical and NMR techniques, the oxidative addition of PhX to three closely related bis‐diphosphine P2Pd0 complexes, where the steric bulk of just one substituent was varied, has been analysed quantitatively. For the complex derived from MetBu2P, a rapid reaction ensued with PhI following an associative mechanism, and data was also obtained by cyclic voltammetry for PhOTs, PhBr and PhCl, revealing distinct relative reactivities from the related (PCx3)2Pd complex (Cx=cyclohexyl) previously studied. The corresponding EttBu2P complex reacted more slowly with PhI and was studied by NMR spectroscopy. The reaction course indicated a mixture of pathways, with contribution from a component that was [PhI] independent. For the CxtBu2P complex, reaction was again monitored by NMR spectroscopy, and was even slower. At high PhI concentrations reaction was predominantly linear in [PhI], but at lower concentrations the [PhI] independent pathway was again observed, and an accelerating influence of the reaction product was observed over the concentration range. The NMR spectra of the EttBu2P and CxtBu2P complexes conducted in C6D6 shows some line broadening that was augmented on addition of PhI. NMR experiments carried out in parallel show that there is rapid ligand exchange between free phosphine and the Pd2Pd complex and also a slow ligand crossover between different P2Pd complexes. DFT calculations were carried out to further test the feasibility of C6D6 involvement in the oxidative addition process, and located Van der Waals complexes for association of the P2Pd0 complexes with either PhI or benzene. PhI or solvent‐assisted pathways for ligand loss are both lower in energy than direct ligand dissociation. Taken all together, these results provide a consistent explanation for the surprising complexity of an apparently simple reaction step. The clear dividing line between reactions that give a di‐ or monophosphine palladium complex after oxidative addition clarifies the participation of the ligand in coupling catalysis. 相似文献
270.
Boryl‐Functionalized σ‐Alkynyl and Vinylidene Rhodium Complexes: Synthesis and Electronic Properties
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Holger Braunschweig Christopher K. L. Brown Dr. Rian D. Dewhurst Dr. J. Oscar C. Jimenez‐Halla Thomas Kramer Dr. Ivo Krummenacher Dr. Bernd Pfaffinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1427-1433
The synthesis, reactivity, and properties of boryl‐functionalized σ‐alkynyl and vinylidene rhodium complexes such as trans‐[RhCl(?C?CHBMes2)(PiPr3)2] and trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] are reported. An equilibrium was found to exist between rhodium vinylidene complexes and the corresponding hydrido σ‐alkynyl complexes in solution. The complex trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2] (IMe=1,3‐dimethylimidazol‐2‐ylidene) was found to exhibit solvatochromism and can be quasireversibly oxidized and reduced electrochemically. Density functional calculations were performed to determine the reaction mechanism and to help rationalize the photophysical properties of trans‐[Rh(C?CBMes2)(IMe)(PiPr3)2]. 相似文献