全文获取类型
收费全文 | 1568篇 |
免费 | 29篇 |
国内免费 | 17篇 |
专业分类
化学 | 1056篇 |
晶体学 | 11篇 |
力学 | 23篇 |
数学 | 308篇 |
物理学 | 216篇 |
出版年
2023年 | 6篇 |
2022年 | 36篇 |
2021年 | 37篇 |
2020年 | 22篇 |
2019年 | 28篇 |
2018年 | 27篇 |
2017年 | 25篇 |
2016年 | 56篇 |
2015年 | 33篇 |
2014年 | 50篇 |
2013年 | 104篇 |
2012年 | 89篇 |
2011年 | 97篇 |
2010年 | 69篇 |
2009年 | 86篇 |
2008年 | 93篇 |
2007年 | 92篇 |
2006年 | 96篇 |
2005年 | 72篇 |
2004年 | 74篇 |
2003年 | 41篇 |
2002年 | 54篇 |
2001年 | 20篇 |
2000年 | 28篇 |
1999年 | 16篇 |
1998年 | 18篇 |
1997年 | 16篇 |
1996年 | 19篇 |
1995年 | 18篇 |
1994年 | 8篇 |
1993年 | 15篇 |
1992年 | 12篇 |
1991年 | 7篇 |
1990年 | 16篇 |
1989年 | 10篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 13篇 |
1984年 | 15篇 |
1983年 | 12篇 |
1982年 | 14篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1973年 | 6篇 |
1966年 | 2篇 |
排序方式: 共有1614条查询结果,搜索用时 15 毫秒
131.
Simultaneous confidence bands for the integrated hazard function 总被引:1,自引:1,他引:0
The construction of the simultaneous confidence bands for the integrated hazard function is considered. The Nelson–Aalen estimator
is used. The simultaneous confidence bands based on bootstrap methods are presented. Four methods of construction of such
confidence bands are proposed. The weird and conditional bootstrap methods are used for resampling. Simulations are made to
compare the actual coverage probability of the bootstrap and the asymptotic simultaneous confidence bands. It is shown that
the equal-tailed bootstrap confidence band has the coverage probability closest to the nominal one. We also present application
of our confidence bands to the data regarding survival after heart transplant.
This research was partly supported by AGH grant No. 10.420.03. 相似文献
132.
133.
134.
The objective of this paper is to provide information about application of solid-phase extraction (SPE) for isolation of nine high-intensity sweeteners (acesulfame-K, alitame, aspartame, cyclamate, dulcin, neotame, saccharin, sucralose and neohesperidin dihydrochalcone) from aqueous solutions. The influence of several types of LC-MS compatible buffers (different pH values and compositions) on their recovery has been studied and discussed. A number of commercially available SPE cartridges, such as Chromabond C18ec, Strata-X RP, Bakerbond Octadecyl, Bakerbond SDB-1, Bakerbond SPE Phenyl, Oasis HLB, LiChrolut RP-18, Supelclean LC-18, Discovery DSC-18 and Zorbax C18 were tested in order to evaluate their applicability for the isolation of analytes. Very high recoveries (better than 92%) of all studied compounds were obtained using formic acid-N,N-diisopropylethylamine buffer adjusted to pH 4.5 and C18-bonded silica sorbents. Behaviour of polymeric sorbents strongly depends on their structure. Strata-X RP behaves much like a C18-bonded silica sorbent. Recoveries obtained using Oasis HLB were comparable with those observed for silica-based sorbents. The only compound less efficiently (83%) retained by this sorbent was cyclamate. Bakerbond SDB-1 shows unusual selectivity towards aspartame and alitame. Recoveries of these two sweeteners were very low (26 and 42%, respectively). It was also found that aspartame and alitame can be selectively separated from the mixture of sweeteners using formic acid-triethylamine buffer at pH 3.5. 相似文献
135.
Pijanka JK Kumar D Dale T Yousef I Parkes G Untereiner V Yang Y Dumas P Collins D Manfait M Sockalingum GD Forsyth NR Sulé-Suso J 《The Analyst》2010,135(12):3126-3132
Over the last few years, there has been an increased interest in the study of stem cells in biomedicine for therapeutic use and as a source for healing diseased or injured organs/tissues. More recently, vibrational spectroscopy has been applied to study stem cell differentiation. In this study, we have used both synchrotron based FTIR and Raman microspectroscopies to assess possible differences between human pluripotent (embryonic) and multipotent (adult mesenchymal) stem cells, and how O(2) concentration in cell culture could affect the spectral signatures of these cells. Our work shows that infrared spectroscopy of embryonic (pluripotent) and adult mesenchymal (multipotent) stem cells have different spectral signatures based on the amount of lipids in their cytoplasm (confirmed with cytological staining). Furthermore, O(2) concentration in cell culture causes changes in both the FTIR and Raman spectra of embryonic stem cells. These results show that embryonic stem cells might be more sensitive to O(2) concentration when compared to mesenchymal stem cells. While vibrational spectroscopy could therefore be of potential use in identifying different populations of stem cells further work is required to better understand these differences. 相似文献
136.
Izabela Franssen Szydłowska Jacek Nowacki Jerzy Herbich 《Journal of photochemistry and photobiology. A, Chemistry》2010,209(2-3):135-146
The electronic structure of the lowest excited singlet states and molecular geometries of a series of dialkylaminopyridines (DAAPs) representing electron donor–acceptor systems were studied by photostationary and time-resolved UV–vis spectroscopic methods and quantum chemical calculations. The comparative studies allow us to rationalize dual luminescence of 4-DAAPs in terms of the TICT state model—the analysis of the electronic transition dipole moments indicates a nearly orthogonal conformation of the fluorescent ICT states. Introduction of the amino group at meta position as in 3-diisopropylaminopyridine completely changes photophysics of these pyridine derivatives: (i) the Franck-Condon excited state initially reached upon excitation and the solvent equilibrated fluorescent state are most probably of the same nature (both excited states do not correspond to a full separation of charges) and (ii) the electronic structure and geometry of the fluorescent CT states of m-DIAP are solvent dependent. 相似文献
137.
The equilibrium structure and the three-dimensional potential energy surface of the Mg-HF van der Waals complex in its ground electronic state have been determined from accurate ab initio calculations using the coupled-cluster method, CCSD(T), in conjunction with the basis sets of triple- through quintuple-zeta quality. The core-electron correlation, high-order valence-electron correlation, and scalar relativistic effects were investigated. The Mg-HF complex was confirmed to be linear at equilibrium, with a vibrationless dissociation energy (into Mg and HF) D(e) of 280 cm(-1). The vibration-rotation energy levels of two isotopologues, (24)Mg-HF and (24)Mg-DF, were predicted using the variational method. The predicted spectroscopic constants can be useful in a further analysis of high-resolution vibration-rotation spectra of the Mg-HF complex. 相似文献
138.
Vyas S Muthukrishnan S Kubicki J McCulla RD Burdzinski G Sliwa M Platz MS Hadad CM 《Journal of the American Chemical Society》2010,132(47):16796-16804
The photochemistry of diphenylphosphoryl azide was studied by femtosecond transient absorption spectroscopy, by chemical analysis of light-induced reaction products, and by RI-CC2/TZVP and TD-B3LYP/TZVP computational methods. Theoretical methods predicted two possible mechanisms for singlet diphenylphosphorylnitrene formation from the photoexcited phosphoryl azide. (i) Energy transfer from the (π,π*) singlet excited state, localized on a phenyl ring, to the azide moiety, thereby leading to the formation of the singlet excited azide, which subsequently loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. (ii) Direct irradiation of the azide moiety to form an excited singlet state of the azide, which in turn loses molecular nitrogen to form the singlet diphenylphosphorylnitrene. Two transient species were observed upon ultrafast photolysis (260 nm) of diphenylphosphoryl azide. The first transient absorption, centered at 430 nm (lifetime (τ) ~ 28 ps), was assigned to a (π,π*) singlet S(1) excited state localized on a phenyl ring, and the second transient observed at 525 nm (τ ~ 480 ps) was assigned to singlet diphenylphosphorylnitrene. Experimental and computational results obtained from the study of diphenyl phosphoramidate, along with the results obtained with diphenylphosphoryl azide, supported the mechanism of energy transfer from the singlet excited phenyl ring to the azide moiety, followed by nitrogen extrusion to form the singlet phosphorylnitrene. Ultrafast time-resolved studies performed on diphenylphosphoryl azide with the singlet nitrene quencher, tris(trimethylsilyl)silane, confirmed the spectroscopic assignment of singlet diphenylphosphorylnitrene to the 525 nm absorption band. 相似文献
139.
We report the structural evolution of zeolitic imidazolate framework-8 (ZIF-8) as a function of time at room temperature. We have identified the different stages of ZIF-8 formation (nucleation, crystallization, growth, and stationary periods) and elucidated its kinetics of transformation. We hypothesize that the observed semicrystalline-to-crystalline transformation may take place via solution- and solid-mediated mechanisms, as suggested by the observed phase transformation evolution and Avrami's kinetics, respectively. A fundamental understanding of ZIF-8 structural evolution as demonstrated in this study should facilitate the preparation of functional metal-organic framework phases with controlled crystal size and extent of crystallinity. 相似文献
140.
The absolute configurations of 2-cyclohexenone cis-diol metabolites resulting from the biotransformation of the corresponding phenols have been determined by comparison of their experimental and calculated circular dichroism spectra (TDDFT at the PCM/B2LYP/Aug-cc-pVTZ level), optical rotations (calculated at the PCM/B3LYP/Aug-cc-pVTZ level) and by stereochemical correlation. It is found that circular dichroism spectra and optical rotations of 2-cyclohexenone derivatives are strongly dependent on the ring conformation (M or P sofa S(5) or half-chair), enone non-planarity and the nature and positions of the hydroxy and alkyl substituents. The effect of non-planarity of the enone chromophore, including the distortion of the C=C bond, is determined for the model structures by TDDFT calculations at the PCM/B2LYP/6-311++G(2d,2p) level. Non-planarity of the C=C bond in the enone chromophore is commonly encountered in 2-cyclohexenone derivatives and it is a source of significant rotatory strength contribution to the electronic circular dichroism spectra. It is shown that the two lowest-energy transitions in acrolein and 2-cyclohexenone and its derivatives are n(C=O)-π(C=O)* and π(C=C)-π(C=O)*, as expected, while the shorter-wavelength (below 200 nm) transitions are of more complex nature. In 2-cyclohexenone and its alkyl derivatives it is predominantly a mixture of π(C=C)-π(C=C)* and π(C=C)-σ* transitions, whereas the presence of hydroxy substituent results in a dominant contribution due to the n(OH)-π(C=O)* transition. A generalized model for correlation of the CD spectra of 2-cyclohexenones with their structures is presented. 相似文献