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71.
Arthur J. Carty Shaun F. Malone Nicholas J. Taylor 《Journal of organometallic chemistry》1979,172(2):201-211
The synthesis of selenium bound selenourea complexes of methylmercury, [CH3HgSeC(NH2)2]X (X=Cl, Br, NO3, ClO4) are described. A single crystal X-Ray analysis of the nitrate salt has provided for the first time bond length data pertinent to the biologically important mercury-selenium interaction. Crystals of [CH3HgSeC(NH2)2] NO3 belong to the space group PnZic with a = 7.524(1), b = 11.204(2), c = 9.738(2)Å, and z = 4. The structure was solved and refined using 561 observed reflections measured on a Syntex P21 diffractometer to a final R value of 0.037. The mercury atom is linearly coordinated to the methyl group and the selenium atom of the selenourea with Hg-Se of 2.477(3)Å. Strong Hg-Se bonding is indicated by the X-Ray data and by the 1H - 199Hg nmr coupling constants. A comparison of spectroscopic data for analogous thio and selenourea complexes is presented. 相似文献
72.
Brightness reversion of softwood (SW) and hardwood (HW) bleached chemithermomechanical pulps (BCTMP) with a 300–400nm light source under argon, oxygen, and air were studied in the absence and presence of UV-screens using UV–Vis reflectance difference spectroscopy. The UV-Vis difference absorption spectra of control SW and HW BCTMP testsheets indicate that as the concentration of atmospheric oxygen is increased, the absorption at max 360nm increases and a blue shift occurs. In all of the cases studied, brightness reversion was observed to occur under an argon atmosphere. The addition of benzophenone and benzotriazole additives to BCTMP testsheets resulted in a significant decrease in formation of chromophores absorbed at 400nm and 360nm. The possible mechanisms contributing to these effects are discussed in terms of the photoformation of lignin chromophoric structures. 相似文献
73.
We study positive solutions of the Dirichlet problem: u(x)+f(u(x))=0,xD
n
,u(x)=0,xD
n
, whereD
n
is ann-ball. We find necessary and sufficient conditions for solutions to be nondegenerate. We also give some new existence and uniqueness theorems.Research supported in part by NSF Contract Number MCS 80-02337 相似文献
74.
Simple two-parameter Hückel and Pitzer equations were used for the calculation of the activity coefficients of aqueous hydrochloric acid at temperatures 0–60°C up to a molality of 2.0 mol-kg–1. The data obtained by Harned and Ehlers(2,3) on galvanic cells without a liquid junction were used in the parameter estimations of these equations. These data consist of sets of measurements at the temperature intervals of 5°C. It was observed that all estimated parameters follow very simple equations with respect to temperature. They are either constant or depend linearly on the temperature. The values for the activity coefficient parameters calculated by these simple equations are recommended here. The recommended parameter values were tested by predicting the data of Gupta, Hills, and Ives,(5) consisting of cell measurements from 5 to 45°C and molalities up to 1.0 mol-kg–1, and the data of Bates and Bower,(4) which extend to 95°C but measurements were only made on molalities less than about 0.1 mol-kg–1. The activity coefficients obtained by the new equations were also compared to those calculated by the Pitzer equations with the parameter values determined by Saluja, Pitzer, and Phutela(6) from calorimetric data. The agreement observed was excellent up to a molality of 1.5 mol-kg–1 at temperatures from 0 to 60°C. 相似文献
75.
Matthias Weil 《无机化学与普通化学杂志》2004,630(7):1048-1053
Single crystals of HgII(H4TeVIO6) (colourless to light‐yellow, rectangular plates) and HgI2(H4TeVIO6)(H6TeVIO6)·2H2O (colourless, irregular) were grown from concentrated solutions of orthotelluric acid, H6TeO6, and respective solutions of Hg(NO3)2 and Hg2(NO3)2. The crystal structures were solved and refined from single crystal diffractometer data sets (HgII(H4TeVIO6): space group Pna21, Z = 4, a =10.5491(17), b = 6.0706(9), c = 8.0654(13)Å, 1430 structure factors, 87 parameters, R[F2 > 2σ(F2)] = 0.0180; HgI2(H4TeVIO6)(H6TeVIO6)·2H2O: space group P1¯, Z = 1, a = 5.7522(6), b = 6.8941(10), c = 8.5785(10)Å, α = 90.394(8), β = 103.532(11), γ = 93.289(8)°, 2875 structure factors, 108 parameters, R[F2 > 2σ(F2)] = 0.0184). The structure of HgII(H4TeVIO6) is composed of ribbons parallel to the b axis which are built of [H4TeO6]2— anions and Hg2+ cations held together by two short Hg—O bonds with a mean distance of 2.037Å. Interpolyhedral hydrogen bonding between neighbouring [H4TeO6]2— groups, as well as longer Hg—O bonds between Hg atoms of one ribbon to O atoms of adjacent ribbons lead, to an additional stabilization of the framework structure. HgI2(H4TeVIO6)(H6TeVIO6)·2H2O is characterized by a distorted hexagonal array made up of [H4TeO6]2— and [H6TeO6] octahedra which spread parallel to the bc plane. Interpolyhedral hydrogen bonding between both building units stabilizes this arrangement. Adjacent planes are stacked along the a axis and are connected by Hg22+ dumbbells (d(Hg—Hg) = 2.5043(4)Å) situated in‐between the planes. Additional stabilization of the three‐dimensional network is provided by extensive hydrogen bonding between interstitial water molecules and O and OH‐groups of the [H4TeO6]2— and [H6TeO6] octahedra. Upon heating HgI2(H4TeVIO6)(H6TeVIO6)·2H2O decomposes into TeO2 under formation of the intermediate phases HgII3TeVIO6 and the mixed‐valent HgIITeIV/VI2O6. 相似文献
76.
Cheng X Kelso C Hornak V de los Santos C Grollman AP Simmerling C 《Journal of the American Chemical Society》2005,127(40):13906-13918
The process by which DNA repair enzymes recognize and selectively excise damaged bases in duplex DNA is fundamental to our mechanistic understanding of these critical biological reactions. 8-Oxoguanine (8-oxoG) is the most common form of oxidative DNA damage; unrepaired, this lesion generates a G:C-->T:A mutation. Central to the recognition and repair of DNA damage is base extrusion, a process in which the damaged base lesion or, in some cases, its partner disengages from the helix and is bound to the enzyme's active site where base excision takes place. The conformation adopted by 8-oxoG in duplex DNA is affected by the base positioned opposite this lesion; conformational changes may also take place when the damaged base binds to its cognate repair enzyme. We performed unrestrained molecular dynamics simulations for several 13-mer DNA duplexes. Oligomers containing G:C and 8oxoG:C pairs adopted Watson-Crick geometries in stable B-form duplexes; 8oxoG showed increased local and global flexibility and a reduced barrier to base extrusion. Duplexes containing the G:A mismatch showed much larger structural fluctuations and failed to adopt a well-defined structure. For the 8oxoG:A mismatch that is recognized by the DNA glycosylase MutY, the damaged nucleoside underwent spontaneous and reproducible anti-->syn transitions. The syn conformation is thermodynamically preferred. Steric hindrance and unfavorable electrostatics associated with the 8oxoG O8 atom in the anti conformation were the major driving forces for this transition. Transition events follow two qualitatively different pathways. The overall anti-->syn transition rate and relative probability of the two transition paths were dependent on local sequence context. These simulations indicate that both the dynamic and equilibrium behavior of the duplex change as a result of oxidation; these differences may provide valuable new insight into the selective action of enzymes on damaged DNA. 相似文献
77.
P. F. Crain James A. McCloskey Arthur F. Lewis Karl H. Schram Leroy B. Townsend 《Journal of heterocyclic chemistry》1973,10(5):843-847
The mass spectrum of pyrazomycin has been obtained and reveals a fragmentation pattern with several important peaks which are not normally found in the mass spectra of C-nucleosides. It has now been established, using model compounds, that these unusual fragment ions are a direct result of the juxtaposition of the exocyclic hydroxy and carboxamido groups of the aglycon. It appears that a facile elimination of ammonia and ethanol from o-hydroxycarboxamides and o-hydroxyethylesters, respectively, may be a general fragmentation reaction for aromatic heterocycles. A mass spectrum of the TMS derivative of pyrazomycin has also been obtained and factors which may result in exceptions to the empirical B+30 (M-103) rule for C-nucleosides are discussed. 相似文献
78.
Arthur A. Santilli Stephen V. Wanser Dong H. Kim Anthony C. Scotese 《Journal of heterocyclic chemistry》1975,12(2):311-316
Dieckmann ring closure reactions of 4-[(2-cyanoethyl)substituted amino]-2-phenyl-5-pyrimidinecarboxylates (Ha-f) afforded several 5,6,7,8-tetrahydro-5-oxo-2-phenylpyrido[2,3-d]pyrimidine-6- carbonitriles (IIIa-f). The open-chain intermediates (IIa-f) were prepared by dechloroamination of 5-carbethoxy-4-chloro-2-phenylpyrimidine (1a) with several 3-substituted amino- propionitriles. Alkylation of the sodium salt of 5,6,7,8-tetrahydro-8-methyl-5-oxo-2-phenyl-pyrido[2,3-d]pyrimidine-6- carbonitrile (IIIa) with methyl iodide in DMF resulted in methylation at C-6 to afford IV. Tosylation of IIIa in pyridine gave the corresponding tosyl ester (V) of the enolic form. Oxidative dehydrogenation at the 6,7-position resulted when IIIa reacted with thionyl chloride, affording 5,8-dihydro-8-methyl-5-oxo-2-phenylpyrido[2,3-d]pyrimidine-6- carbonitrile (VII). Dechloroamination of la or 5-carbethoxy-4-chloro-2-methylthiopyrimidine (Ib) with ethyl 3-ethylaminopropionate followed by Dieckmann cyclization of the resulting open-chain intermediates gave the corresponding ethyl 5,6,7,8-tetrahydro-5-oxopyrido[2,3-d]pyrimidine-6-carboxylates IX'a and IX'b, respectively. These exist predominately in the enol form and undergo alkylation and oxidation reactions similar to IIIa. 相似文献
79.
Wolfgang Weil 《manuscripta mathematica》1981,36(1):1-18
It is shown that there exists a distribution T on n ( unit sphere of Euclidean n-space) such that the mixed volume V(K1,...,Kn) equals
for all convex bodies Ki, where
is the support function of ki and denotes the tensor product. As a consequence, mixed volumes are approximated uniformly by n-fold integrals of the corresponding support functions. 相似文献
80.
Arthur M. Geoffrion 《Mathematical Programming》1977,13(1):23-37
Mathematical programming applications often require an objective function to be approximated by one of simpler form so that an available computational approach can be used. An a priori bound is derived on the amount of error (suitably defined) which such an approximation can induce. This leads to a natural criterion for selecting the best approximation from any given class. We show that this criterion is equivalent for all practical purposes to the familiar Chebyshev approximation criterion. This gains access to the rich legacy on Chebyshev approximation techniques, to which we add some new methods for cases of particular interest in mathematical programming. Some results relating to post-computational bounds are also obtained.This paper was partially supported by the National Science Foundation and by the Office of Naval Research, and was the basis for a plenary lecture delivered at the IX International Symposium on Mathematical Programming in Budapest, Hungary, August 1976. 相似文献