全文获取类型
收费全文 | 332篇 |
免费 | 9篇 |
专业分类
化学 | 211篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 37篇 |
物理学 | 46篇 |
无线电 | 42篇 |
出版年
2021年 | 2篇 |
2019年 | 1篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 10篇 |
2014年 | 9篇 |
2013年 | 11篇 |
2012年 | 18篇 |
2011年 | 24篇 |
2010年 | 17篇 |
2009年 | 8篇 |
2008年 | 26篇 |
2007年 | 31篇 |
2006年 | 29篇 |
2005年 | 21篇 |
2004年 | 25篇 |
2003年 | 20篇 |
2002年 | 12篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 2篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有341条查询结果,搜索用时 15 毫秒
331.
This article results from our collaborative project with a Finnish bank aiming to evaluate the sales performance of bank branches. The management wishes to evaluate the branches’ ability to generate profit, which rules out the pure technical efficiency considerations. The branches operate in heterogeneous environments. We deal with the heterogeneity by subdividing the branches according to the bank specification into overlapping clusters and analyze each cluster separately. The prices of the branch outputs are hard to assess as the results from the sales efforts can only be observed with long delays. We employ benchmark units similarly as in value efficiency analysis (VEA). However, we extend VEA in two ways. First, in standard VEA the benchmark unit is assumed to yield the maximum profit among the set of feasible technologies; instead, our benchmark technology may or may not be in the feasible set. Second, we consider efficiency tests employing a benchmark with respect to both profit and return. We propose a solution strategy for these extensions. The bank uses the study to support decisions concerning new branches, changes in the operations of inefficient branches, and actions aiming to more flexible deployment of the staff. 相似文献
332.
Sumerin V Schulz F Atsumi M Wang C Nieger M Leskelä M Repo T Pyykkö P Rieger B 《Journal of the American Chemical Society》2008,130(43):14117-14119
The first ansa-aminoborane N-TMPN-CH2C6H4B(C6F5)2 (where TMPNH is 2,2,6,6-tetramethylpiperidinyl) which is able to reversibly activate H2 through an intramolecular mechanism is synthesized. This new substance makes use of the concept of molecular tweezers where the active N and B centers are located close to each other so that one H2 molecule can fit in this void and be activated. Because of the fixed geometry of this ansa-ammonium-borate it forms a short N-H...H-B dihydrogen bond of 1.78 A as determined by X-ray analysis. Therefore, the bound hydrogen can be released above 100 degrees C. In addition, the short H...H contact and the N-H...H (154 degrees) and B-H...H (125 degrees) angles show that the dihydrogen interaction in N-TMPNH-CH2C6H4BH(C6F5)2 is partially covalent in nature. As a basis for discussing the mechanism, quantum chemical calculations are performed and it is found that the energy needed for splitting H2 can arise from the Coulomb attraction between the resulting ionic fragments, or "Coulomb pays for Heitler-London". The air- and moisture-stable N-TMPNH-CH2C6H4BH(C6F5)2 is employed in the catalytic reduction of nonsterically demanding imines and enamines under mild conditions (110 degrees C and 2 atm of H2) to give the corresponding amines in high yields. 相似文献
333.
The reaction of (1R,2R)‐(–)‐1,2‐diaminocyclohexane ( 1 ) [DACH] with the aldehyde (1R)‐(–)‐myrtenal ( 2 ) in MeOH afforded the bidentate diimine ligand, (1R,2R)‐(–)‐N1,N2‐bis{(1R)‐(–)myrtenylidene}‐1,2‐diaminocyclohexane ( 3 ) in a high yield. Reduction of 3 using LiAlH4 led to the formation of the desired ligand ( 4 ) (1R,2R)‐(–)‐N1,N2‐bis{(1R)‐(–)myrtenyl}‐1,2‐diaminocyclohexane. Treatment of compound 4 with K2PtCl4 or K2PdCl4 yielded the corresponding platinum(II) and palladium(II) complexes, Pt‐5 and Pd‐6 , respectively. The reaction of compound 3 with K2PtCl4 gave the diimine complex Pt‐7 . The cytotoxic activity of the complexes Pt‐5 , Pd‐6 and Pt‐7 was tested and compared to the approved drugs, cisplatin ( Cis ‐Pt ) and oxaliplatin ( Ox‐Pt ). The complexes ( Pt‐5 , Pd‐6 and Pt‐7 ) inhibit L1210 cell line proliferation with an IC50 of 0.6, 4.2, and 0.7 μL, respectively as evidenced by measuring thymidine incorporation. 相似文献
334.
Kocharova N Leiro J Lukkari J Heinonen M Skala T Sutara F Skoda M Vondracek M 《Langmuir : the ACS journal of surfaces and colloids》2008,24(7):3235-3243
Recently we reported noncovalent functionalization of nanotubes in an aqueous medium with ionic liquid-based surfactants, 1-dodecyl-3-methylimidazolium bromide (1) and 1-(12-mercaptododecyl)-3-methylimidazolium bromide (2), resulting in positively charged single-wall carbon nanotube (SWNT)-1,2 composites. Thiolation of SWNTs with 2 provides their self-assembly on gold as well as templating gold nanoparticles on SWNT sidewalls via a covalent -S-Au bond. In this investigation, we studied the electronic structure, intermolecular interactions, and packing within noncovalently thiolated SWNTs and also nanotube alignment in the bulk of SWNT-2 dried droplets and self-assembled submonolayers (SAMs) on gold by high-resolution X-ray photoemission spectroscopy (HRXPS), C K-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS). HRXPS data confirmed the noncovalent nature of interactions within the nanocomposite of thiolated nanotubes. In PM-IRRAS spectra of SWNT SAMs on gold, the IR-active vibrational SWNT modes have been observed and identified. According to PM-IRRAS data, the hydrocarbon chains of 2 are oriented with less tilt angle to the bare gold normal in a SAM deposited from an SWNT-2 dispersion than those of 1 deposited from an SWNT-1 dispersion on the mercaptoethanesulfonic acid-primed gold. For both the dried SWNT-2 bulk and the SWNT-2 SAM on gold, the C K-edge NEXAFS spectra revealed the presence of CH-pi interactions between hydrocarbon chains of 2 and the pi electronic nanotube structure due to the highly resolved vibronic fine structure of carbon 1s --> R*/sigma*C-H series of states in the alkyl chain of 2. For the SWNT-2 bulk, the observed splitting and upshift of the SWNT pi* orbitals in the NEXAFS spectrum indicated the presence of pi-pi interactions. In the NEXAFS spectrum of the SWNT-2 SAM on gold, the upshifted values of the photon energy for R*/sigma*C-H transitions indicated close contact of 2 with nanotubes and with a gold surface. The angle-dependent NEXAFS for the SWNT-2 bulk showed that most of the molecules of 2 are aligned along the nanotubes, which are self-organized with orientation parallel to the substrate plane, whereas the NEXAFS for the SWNT-2 SAM revealed a more normal orientation of functionality 2 on gold compared with that in the SWNT-2 bulk. 相似文献
335.
336.
By utilizing single particle interferometry, the fidelity or coherence of a pair of quantum states is identified with their capacity for interference. We consider processes acting on the internal degree of freedom (e.g., spin or polarization) of the interfering particle, preparing it in states rho_{A} or rho_{B} in the respective path of the interferometer. The maximal visibility depends on the choice of interferometer, as well as the locality or nonlocality of the preparations, but otherwise depends only on the states rho_{A} and rho_{B} and not the individual preparation processes themselves. This allows us to define interferometric measures which probe locality and correlation properties of spatially or temporally separated processes, and can be used to differentiate between processes that cannot be distinguished by direct process tomography using only the internal state of the particle. 相似文献
337.
Herrmann E Lihavainen H Hyvärinen AP Riipinen I Wilck M Stratmann F Kulmala M 《The journal of physical chemistry. A》2006,110(45):12448-12455
This work is an assessment of the capabilities of the FLUENT-FPM software package to simulate actual nucleation experiments. In the first step, we verified the FPM condensation routine with the NEWALC code. Next, homogeneous nucleation of n-butanol, n-pentanol, and n-hexanol in a laminar flow diffusion chamber (LFDC) was simulated and the results were compared to experimental data and an earlier model, which was described by Lihavainen and Viisanen (2001) and will be called femtube2 in the following. Models based on classical nucleation theory typically give too small nucleation rates for alcohol vapors. Also, the FPM underestimates particle production by several orders of magnitude, the factor being a constant for each nucleation isotherm (i.e., at constant nucleation temperature). However, experimental observations beyond exact particle concentrations can be reproduced. We found a behavior similar to the experiment for the dependence of the concentration of nucleated particles N on the flow rate. After correcting the FPM nucleation rate by a constant factor, experimentally found vapor depletion effects could be simulated. Comparing the FPM and femtube2, we observed that the FPM systematically predicts lower saturation ratio values. Further investigation of vapor depletion showed significant differences between the FPM and the femtube2 model. Furthermore, FPM simulations confirm the earlier found carrier gas effect (Lihavainen and Viisanen, 2001). 相似文献
338.
Marushkevich K Khriachtchev L Lundell J Räsänen M 《Journal of the American Chemical Society》2006,128(37):12060-12061
We prepared the first cis-trans dimer of formic acid and measured its vibrational spectrum in a low-temperature Ar matrix. This preparation was done by selective vibrational excitation of the trans-trans noncyclic dimer. It was found that the stability of the cis-trans dimer against proton tunneling is strongly improved compared to the monomer, especially at elevated temperatures (>30 K). This surprising phenomenon was explained by differences in dynamical, energetic, and vibrational properties of the dimer and monomer. The obtained results show that the proton tunneling reactions can be strongly modified in the hydrogen-bonded solid network compared to the monomeric species. 相似文献
339.
The light-induced H + XeC2 <--> HXeCC reaction is studied in solid Xe, and the full optical control of this reaction is demonstrated. By narrow-band excitation in the IR spectral region, HXeCC radicals can be decomposed to a local metastable configuration and then selectively recovered by resonant excitation of the XeC2 vibrations. The novel recovery process is explained by short-range mobility of the reagents promoted by vibrational energy redistribution near the absorbing XeC2 molecule. This means that a chemical reaction can be selectively promoted in a desired place where the chosen absorber locates. The obtained results make a strong case of solid-state reactive vibrational excitation spectroscopy of weak radiationless transitions. 相似文献
340.
Adnan S. Abu-Surrah Kristian Lappalainen Markku Leskelä Timo Repo 《Transition Metal Chemistry》2010,35(1):7-11
Aldimine 2,6-bis[(imino)methyl]pyridine iron(II) (1, 4, and 6) and cobalt(II) (3 and 5) complexes bearing bulky cycloaliphatic (bornyl and myrtanyl) or aromatic (naphthyl) terminal groups have been applied successfully,
after activation with methyl aluminoxane (MAO), as catalysts for the polymerization of tert-butylacrylate. For comparison reasons, complex 2 that contains the ketimine ligand, 2,6-bis[(−)-cis-myrtanylimino)ethyl]pyridine (BMEP), has also been utilized. All studied complexes showed moderate polymerization activities,
and they produced high molar mass syndiorich-atactic polymers. Surprisingly, the aldimine-based catalyst systems showed comparable
activities compared with the corresponding ketimine complex (2), and they produced high molar mass polymers. In addition, complexes with bulky terminal cycloaliphatic substituents on the
tridentate aldimine ligands showed higher polymerization activity compared with the aromatic ones (6). Polymerization activity and polymer molar masses are dependent on the ligand framework. 相似文献