全文获取类型
收费全文 | 483篇 |
免费 | 41篇 |
专业分类
化学 | 390篇 |
力学 | 6篇 |
数学 | 61篇 |
物理学 | 67篇 |
出版年
2023年 | 13篇 |
2022年 | 9篇 |
2021年 | 20篇 |
2020年 | 16篇 |
2019年 | 9篇 |
2018年 | 18篇 |
2017年 | 6篇 |
2016年 | 24篇 |
2015年 | 28篇 |
2014年 | 33篇 |
2013年 | 40篇 |
2012年 | 38篇 |
2011年 | 52篇 |
2010年 | 31篇 |
2009年 | 17篇 |
2008年 | 35篇 |
2007年 | 20篇 |
2006年 | 34篇 |
2005年 | 17篇 |
2004年 | 19篇 |
2003年 | 21篇 |
2002年 | 8篇 |
2000年 | 7篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
排序方式: 共有524条查询结果,搜索用时 15 毫秒
71.
Gaertner S Bourennane M Kurtsiefer C Cabello A Weinfurter H 《Physical review letters》2008,100(7):070504
We introduce a new quantum protocol for solving detectable Byzantine agreement (also called detectable broadcast) between three parties, and also for solving the detectable liar detection problem. The protocol is suggested by the properties of a four-qubit entangled state, and the classical part of the protocol is simpler than that of previous proposals. In addition, we present an experimental implementation of the protocol using four-photon entanglement. 相似文献
72.
We demonstrate the generation of high-energy picosecond pulses directly from a thin-disk laser oscillator by employing a self-imaging active multipass geometry. Stable single-pulse operation has been obtained with an average output power in excess of 50 W, excluding a cw background of 8%, at a repetition rate of 3.8 MHz. Self-starting passive mode locking was accomplished using a semiconductor saturable absorber mirror. The maximum pulse energy was 13.4 microJ at a pulse duration of 1.36 ps with a time-bandwidth product of 0.34. Single-pass external frequency doubling with a conversion efficiency of 60% yielded >28 W of average power at 515 nm. 相似文献
73.
We investigate few-boson tunneling in a one-dimensional double well, covering the full crossover from weak interactions to the fermionization limit of strong correlations. Based on exact quantum-dynamical calculations, it is found that the tunneling dynamics of two atoms evolves from Rabi oscillations to correlated pair tunneling as we increase the interaction strength. Near the fermionization limit, fragmented-pair tunneling is observed and analyzed in terms of the population imbalance and two-body correlations. For more atoms, the tunneling dynamics near fermionization is shown to be sensitive to both atom number and initial configuration. 相似文献
74.
Philipp Kulas Martin Seidel Alessandro Bozzato Bernhard Schick Daniel I. Sessler Sascha Kreuer Tobias Hüppe 《Biomedical chromatography : BMC》2020,34(5):e4811
Owing to the lack of specific symptoms, diagnosis of head and neck squamous cell carcinoma (HNSCC) may be delayed. We evaluated volatile organic compounds in tumor samples from patients suffering from HNSCC and tested the hypothesis that there is a characteristic altered composition in the headspace of HNSCC compared with control samples from the same patient with normal squamous epithelium. These results provide the basis for future noninvasive breath analysis in HNSCC. Headspace air of suspected tumor and contralateral control samples in 20 patients were analyzed using ion-mobility spectrometry. Squamous cell carcinoma was diagnosed in 16 patients. In total, we observed 93 different signals in headspace measurements. Squamous cell carcinomas revealed significantly higher levels of volatile cyclohexanol (0.54 ppbv, 25th to 75th percentiles 0.35–0.86) compared with healthy squamous epithelium (0.24 ppbv, 25th to 75th percentiles 0.12–0.3; p < 0.001). In conclusion, head and neck squamous cell carcinoma emitted significantly higher levels of volatile cyclohexanol in headspace compared with normal squamous epithelium. These findings form the basis for future breath analysis for diagnosis, therapy control and the follow-up of HNSSC to improve therapy and aftercare. 相似文献
75.
76.
We studied the thermal diffusion behavior of the nonionic surfactant solutions C 12E 6/water and C 12E 5/water at different concentrations and temperatures using thermal diffusion forced Rayleigh scattering (TDFRS). Two different types of TDFRS setups have been applied. In the classical TDFRS, we use an argon laser to write the optical grating into the sample by using a small amount of ionic dye to convert the optical grating into a temperature grating. In the other setup, called IR-TDFRS, we use an infrared laser as the writing beam, which utilizes the water absorption band to convert the optical grating into a temperature grating. The measurements by IR-TDFRS show a one-mode signal for all concentrations and temperatures, while the signal in the classical TDFRS consists of two modes for higher temperatures and lower surfactant concentrations (Ning, H.; et al. J. Phys. Chem. B 2006, 110, 10746). We find good agreement between the Soret coefficient determined in the IR-TDFRS and the one derived from the first fast mode in the previous studies. The Soret coefficient of the nonionic solutions is positive and enhanced at the critical point. In general, the Soret coefficient of the micelles tends to increase with temperature. We found that the presence of the second mode observed in the classical TDFRS is related to the addition of the ionic dye, but even with the ionic dye it is not possible to observe a second mode in the IR-TDFRS. The origin of the second mode is discussed in terms of charged micelles and an inhomogenous dye distribution in the temperature gradient. 相似文献
77.
Novel calix[4]arene amides have been synthesized and their interaction with alkaline cations has been evaluated through extracting aqueous solutions of Li-, Na- and K-picrates with solutions of calix[4]arene amides in CH2Cl2. Electron-withdrawing groups on the upper rim of the calix[4]arene scaffold were found to have a negative effect on the absolute amount of metal ions extracted. The decreased extraction ability is accompanied by a higher selectivity towards sodium cations. 相似文献
78.
Ina Heckelmann Zifei Lu Dr. Joseph C. A. Prentice Dr. Florian Auras Dr. Tanya K. Ronson Prof. Dr. Richard H. Friend Prof. Dr. Jonathan R. Nitschke Dr. Sascha Feldmann 《Angewandte Chemie (International ed. in English)》2023,62(12):e202301806
Organic semiconductors are promising for efficient, printable optoelectronics. However, strong excited-state quenching due to uncontrolled aggregation limits their use in devices. We report on the self-assembly of a supramolecular pseudo-cube formed from six perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDIs and suppresses intramolecular rotations and vibrations, leading to non-aggregated, monomer-like properties in solution and the solid state, in contrast to the fast fluorescence quenching in the free ligand. The stabilized excited state and electronic purity in the cage enables the observation of delayed fluorescence due to a bright excited multimer, acting as excited-state reservoir in a rare case of benign inter-chromophore interactions in the cage. We show that self-assembly provides a powerful tool for retaining and controlling the electronic properties of chromophores, and to bring molecular electronics devices within reach. 相似文献
79.
The development of the first highly active enantioselective catalyst for the aza-Claisen rearrangement of Z-configured allylic trifluoroacetimidates generating valuable almost enantiopure protected allylic amines is described. Usually Z-configured allylic imidates react significantly slower than their E-configured counterparts, but in the present study the opposite effect was observed. Z-Configured olefins have the principal practical advantage that a geometrically pure C=C double bond can be readily obtained, for example, by semihydrogenations of alkynes. Our catalyst, a C(2)-symmetric planar chiral bispalladacycle complex, is rapidly prepared from ferrocene in four simple steps. Key step of this protocol is an unprecedented highly diastereoselective biscyclopalladation providing dimeric macrocyclic complexes of fascinating structure. In the present study as little as 0.1 mol % of catalyst precursor were sufficient for most of the alkyl substituted substrates to give in general almost quantitative yields. NMR investigations revealed a monomeric structure for the active catalyst species. The bispalladacycle can also be used for the formation of almost enantiomerically pure allylic amines (ee > or =96 %) substituted with important functional groups such as ester, ketone, ether, silyl ether, acetal or protected amino moieties providing high-added-value allylic amine building blocks in excellent yield (> or =94 %). The preparative advantages should render this methodology highly appealing as a practical and valuable tool for the formation of allylic amines in target oriented synthesis. 相似文献
80.
Baumann S Schoof S Harkal SD Arndt HD 《Journal of the American Chemical Society》2008,130(17):5664-5666
Proximity-induced covalent capture (PICC) has been established for the investigation of ligand binding to composite protein/oligonucleotide target complexes. The RNA-induced attachment of the thiopeptides Thiostrepton and Nosiheptide to engineered Cys mutants of the ribosomal protein L11 was highly position selective and allowed mapping of their binding site at amino acid resolution. 相似文献