全文获取类型
收费全文 | 2149篇 |
免费 | 65篇 |
国内免费 | 51篇 |
专业分类
化学 | 1225篇 |
晶体学 | 9篇 |
力学 | 85篇 |
综合类 | 12篇 |
数学 | 223篇 |
物理学 | 711篇 |
出版年
2021年 | 17篇 |
2020年 | 21篇 |
2019年 | 25篇 |
2018年 | 17篇 |
2017年 | 25篇 |
2016年 | 21篇 |
2015年 | 15篇 |
2014年 | 31篇 |
2013年 | 92篇 |
2012年 | 75篇 |
2011年 | 96篇 |
2010年 | 52篇 |
2009年 | 37篇 |
2008年 | 81篇 |
2007年 | 88篇 |
2006年 | 101篇 |
2005年 | 91篇 |
2004年 | 81篇 |
2003年 | 75篇 |
2002年 | 61篇 |
2001年 | 68篇 |
2000年 | 74篇 |
1999年 | 40篇 |
1998年 | 33篇 |
1997年 | 36篇 |
1996年 | 39篇 |
1995年 | 43篇 |
1994年 | 48篇 |
1993年 | 62篇 |
1992年 | 37篇 |
1991年 | 39篇 |
1990年 | 40篇 |
1989年 | 35篇 |
1988年 | 23篇 |
1987年 | 32篇 |
1986年 | 19篇 |
1985年 | 35篇 |
1984年 | 24篇 |
1983年 | 32篇 |
1982年 | 25篇 |
1981年 | 24篇 |
1980年 | 30篇 |
1979年 | 19篇 |
1978年 | 24篇 |
1977年 | 35篇 |
1975年 | 30篇 |
1974年 | 23篇 |
1973年 | 18篇 |
1972年 | 24篇 |
1966年 | 12篇 |
排序方式: 共有2265条查询结果,搜索用时 296 毫秒
71.
Tedesco E Della F Favaretto L Barbarella G Albesa-Jové D Pisignano D Gigli G Cingolani R Harris KD 《Journal of the American Chemical Society》2003,125(40):12277-12283
The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene-4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO. 相似文献
72.
A. I. Dikusar O. O. Redkozubova S. P. Yushchenko L. B. Kriksunov D. Harris 《Russian Journal of Electrochemistry》2003,39(10):1073-1077
Experimental study of the distribution of local rates of electrochemical micromachining in the presence of photoresist masks in various hydrodynamic conditions (macroscopically nonuniform rotating disk electrode, sprayer flow, an electrode placed into a cell with chaotic bulk electrolyte mixing) shows that the maximum etching localization is achieved at the control of the dissolution rate by the mass transport rate (at achieving the anodic limiting current). The localization enhancement as compared to the primary current distribution takes place in the case of a turbulent flow at hydrodynamic conditions where the removal of dissolution products from the undercutting region is hindered. These conditions (electrochemical reaction limited by the ion mass transport rate, high resistance to the mass transport in the undercutting region) are necessary for the localization enhancement using a pulsed anodic–cathodic treatment. 相似文献
73.
Integrals which are individually singular, but which may be combined to yield convergent expressions, are needed for computations of relativistic effects and various properties of atomic and quasiatomic systems. As computations become more detailed and precise, more such integrals are required. This paper presents general formulas for the radial parts of the singular and nonsingular (regular) integrals that occur when three-body systems are described using wave functions that include exponentials in all three interparticle coordinates. Our results are compared with those found in the literature for some of the integrals, and are also shown to be consistent with previously reported results for Hylleraas functions (a limiting case in which one of the exponential parameters is set to zero). 相似文献
74.
Williams JR Smalley AL Sellinschegg H Daniels-Hafer C Harris J Johnson MB Johnson DC 《Journal of the American Chemical Society》2003,125(34):10335-10341
A series of samples ((AB)(x)(CD)(y))(z) were prepared containing both short repeat units (AB and CD) and long repeat units ((AB)(x)(CD)(y)), where the short repeat units were designed to have the composition appropriate to form square M(4)Sb(12) skutterudites (M = Fe, Co, or Ir; square = vacancy, La, or Y). X-ray diffraction and reflectivity were used to follow the evolution of the films from amorphous, layered materials to crystalline skutterudite superlattices as a function of annealing temperature and time. In all cases, the short repeat units interdiffused and crystallized the expected skutterudite, while the long repeat period persisted after annealing. The skutterudites crystallize with random crystallographic orientation with respect to the substrate. The observed splitting of the peaks in the high-angle diffraction data from the IrSb(3)/CoSb(3) sample indicates the formation of a novel superlattice structure with each grain having a random crystallographic orientation of the skutterudite lattice with respect to the superlattice direction. 相似文献
75.
Bowmaker GA Harris RK Assadollahzadeh B Apperley DC Hodgkinson P Amornsakchai P 《Magnetic resonance in chemistry : MRC》2004,42(9):819-826
Solid-state cross-polarization magic-angle spinning (CP/MAS) NMR spectra were recorded for the compounds [Ag(NH3)2]2SO4, [Ag(NH3)2]2SeO4 and [Ag(NH3))]NO3, all of which contain the linear or nearly linear two-coordinate [Ag(NH3)2]+ ion. The 109Ag CP/MAS NMR spectra show centrebands and associated spinning sideband manifolds typical for systems with moderately large shielding anisotropy, and splittings due to indirect 1J(109Ag,14N) spin-spin coupling. Spinning sideband analysis was used to determine the 109Ag shielding anisotropy and asymmetry parameters Deltasigma and eta from these spectra, yielding anisotropies in the range 1500-1600 ppm and asymmetry parameters in the range 0-0.3. Spectra were also recorded for 15N and (for the selenate) 77Se. In all cases the number of resonances observed is as expected for the crystallographic asymmetric units. The crystal structure of the selenate is reported for the first time. One-bond (107, 109Ag,15N) coupling constants are found to have magnitudes in the range 60-65 Hz. Density functional calculations of the Ag shielding tensor for model systems yield results that are in good agreement with the experimentally determined shielding parameters, and suggest that in the solid compounds Deltasigma and eta are reduced and increased, respectively, from the values calculated for the free [Ag(NH3)2]+ ion (1920 ppm and 0, respectively), primarily as a result of cation-cation interactions, for which there is evidence from the presence of metal-over-metal stacks of [Ag(NH3)2]+ ions in the solid-state structures of these compounds. 相似文献
76.
A. W. Cooper P. J. Harris G. K. Kumar J. C. Tebby 《Journal of polymer science. Part A, Polymer chemistry》1989,27(6):1967-1974
The polymers of ethyl α-cyanopropenoate (widely known as cyanoacrylate) and dimethyl (α-ethoxycarbonyl)propenoylphosphonate have been hydrolyzed and their rates of degradation to formaldehyde have been compared. The phosphate polymer produced much less formaldehyde than the cyanopropenoate polymer as required for an improved surgical adhesive. In a comparative study, the rate of aqueous hydrolysis of a high molecular weight cyanoacrylate polymer differed from a previous report. The nature and the hydrolytic properties of the end groups in the two types of polymer are discussed. 相似文献
77.
This paper develops a quantitative k-nearest neighbors modeling technique. The technique is used to demonstrate that a compound's biological binding activity to a receptor can be calculated from the minimum of the square root of the sum of squared deviations (SSSD) of a structurally assigned chemical shift on a template between the unknown compound to be predicted and a set of known compounds with known activities. When building models of biological activity, nonlinear relationships are built into the input training data. If a model is developed by selecting only compounds with minimum structurally assigned chemical shift deviations from the unknown compound, some of the nonlinear relationships can be removed. The smaller the total chemical shift deviation between a compound with known activity and another compound with unknown activity, the more likely it will have similar biological, chemical, and physical properties. This means that a model can be produced without rigorous statistics or neural networks. This technique is similar to structure-activity relationship (SAR) modeling, but instead of relying on substructure fragments to produce a model, this new model is based on minimum chemical shift differences on those substructure fragments. We refer to this method as minimum deviation of structurally assigned spectra analysis (MiDSASA) modeling. Modeling by the minimum deviation concept can be applied to other chemoinformatic data analyses such as metabolite concentrations in metabolic pathways for metabolomics research. A MiDSASA template model for 30 steroids binding the corticosterone binding globulin based on the activity factors of the two nearest compounds had a correlation of 0.88. A MiDSASA template model for 50 steroids binding the aromatse enzyme based on the average activity of the four nearest compounds had a correlation of 0.71. 相似文献
78.
The FAKE method of approximate molecular-orbital calculations is presented and illustrated by application to a number of molecules. The method is of the extended Huckel type but uses accurately computed kinetic-energy matrix elements and avoids scale factors of the Wolfsberg—Helmholtz type. It also includes neighbor-atom charge effects and single-center off-diagonal matrix elements. These features permit FAKE occupied-orbital energies and charge distributions to come into close agreement with corresponding ab initio quantities. 相似文献
79.
Tao Huang Seyyedmohsen Hosseinibarkooie Adam L. Borne Mitchell E. Granade Jeffrey W. Brulet Thurl E. Harris Heather A. Ferris Ku-Lung Hsu 《Chemical science》2021,12(9):3295
Sulfonyl-triazoles are a new class of electrophiles that mediate covalent reaction with tyrosine residues on proteins through sulfur-triazole exchange (SuTEx) chemistry. Recent studies demonstrate the broad utility and tunability of SuTEx chemistry for chemical proteomics and protein ligand discovery. Here, we present a strategy for mapping protein interaction networks of structurally complex binding elements using functionalized SuTEx probes. We show that the triazole leaving group (LG) can serve as a releasable linker for embedding hydrophobic fragments to direct molecular recognition while permitting efficient proteome-wide identification of binding sites in live cells. We synthesized a series of SuTEx probes functionalized with a lipid kinase fragment binder for discovery of ligandable tyrosines residing in catalytic and regulatory domains of protein and metabolic kinases in live cells. We performed competition studies with kinase inhibitors and substrates to demonstrate that probe binding is occurring in an activity-dependent manner. Our functional studies led to discovery of probe-modified sites within the C2 domain that were important for downregulation of protein kinase C-alpha in response to phorbol ester activation. Our proof of concept studies highlight the triazole LG of SuTEx probes as a traceless linker for locating protein binding sites targeted by complex recognition elements in live cells.Sulfonyl-triazole probes modified with a kinase recognition element are developed for live cell activity-based profiling to identify tyrosine sites located in catalytic and regulatory domains that are important for kinase function. 相似文献
80.
The generation of metal cyanide ions in the gas phase by laser ablation of M(CN)(2) (M = Co, Ni, Zn, Cd, Hg), Fe(III)[Fe(III)(CN)(6)] x xH(2)O, Ag(3)[M(CN)(6)] (M = Fe, Co), and Ag(2)[Fe(CN)(5)(NO)] has been investigated using Fourier transform ion cyclotron resonance mass spectrometry. Irradiation of Zn(CN)(2) and Cd(CN)(2) produced extensive series of anions, [Zn(n)(CN)(2n+1)](-) (1 < or = n < or = 27) and [Cd(n)(CN)(2n+1)](-) (n = 1, 2, 8-27, and possibly 29, 30). Cations Hg(CN)(+) and [Hg(2)(CN)(x)](+) (x = 1-3), and anions [Hg(CN)(x)](-) (x = 2, 3), are produced from Hg(CN)(2). Irradiation of Fe(III)[Fe(III)(CN)(6)] x xH(2)O gives the anions [Fe(CN)(2)](-), [Fe(CN)(3)](-), [Fe(2)(CN)(3)](-), [Fe(2)(CN)(4)](-), and [Fe(2)(CN)(5)](-). When Ag(3)[Fe(CN)(6)] is ablated, [AgFe(CN)(4)](-) and [Ag(2)Fe(CN)(5)](-) are observed together with homoleptic anions of Fe and Ag. The additional heterometallic complexes [AgFe(2)(CN)(6)](-), [AgFe(3)(CN)(8)](-), [Ag(2)Fe(2)(CN)(7)](-), and [Ag(3)Fe(CN)(6)](-) are observed on ablation of Ag(2)[Fe(CN)(5)(NO)]. Homoleptic anions [Co(n)(CN)(n+1)](-) (n = 1-3), [Co(n)(CN)(n+2)](-) (n = 1-3), [Co(2)(CN)(4)](-), and [Co(3)(CN)(5)](-) are formed when anhydrous Co(CN)(2) is the target. Ablation of Ag(3)[Co(CN)(6)] yields cations [Ag(n)(CN)(n-1)](+) (n = 1-4) and [Ag(n)Co(CN)(n)](+) (n = 1, 2) and anions [Ag(n)(CN)(n+1)](-) (n = 1-3), [Co(n)(CN)(n-1)](-) (n = 1, 2), [Ag(n)Co(CN)(n+2)](-) (n = 1, 2), and [Ag(n)Co(CN)(n+3)](-) (n = 0-2). The Ni(I) species [Ni(n)(CN)(n-1)](+) (n = 1-4) and [Ni(n)(CN)(n+1)](-) (n = 1-3) are produced when anhydrous Ni(CN)(2) is irradiated. In all cases, CN(-) and polyatomic carbon nitride ions C(x)N(y)(-) are formed concurrently. On the basis of density functional calculations, probable structures are proposed for most of the newly observed species. General structural features are low coordination numbers, regular trigonal coordination stereochemistry for d(10) metals but distorted trigonal stereochemistry for transition metals, the occurrence of M-CN-M and M(-CN-)(2)M bridges, addition of AgCN to terminal CN ligands, and the occurrence of high spin ground states for linear [M(n)(CN)(n+1)](-) complexes of Co and Ni. 相似文献