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71.
Details of structural changes that take place in water near an apolar solute have been studied by Monte Carlo simulations for hard sphere solutes of increasing size, including the limiting case of water at a hard structureless wall. Water has been modelled by two different types of extended primitive model, the four-site EPM4 model and five-site EPM5 model. Two different patterns of the orientational ordering of the water molecules around the solute as a function of its size have been found. For the EPM5 model, the structure of water and the orientation of its molecules near an apolar solute of finite diameter do not seem to be sensitive to the size of the solute, and only become more pronounced when the solute becomes a hard wall. On the other hand, the orientation ordering of the EPM4 molecules gradually changes with increasing size of the solute, and for solutes larger than approximately five times the size of the water molecule it is opposite to that near a small solute. A novel method to evaluate the excess chemical potential of large solutes has been implemented, and some thermodynamic quantities for water (distribution of hydrogen bonds and the excess chemical potential) have been computed as a function of the distance from the solute. 相似文献
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In a recent paper the author showed that the distribution ofleading significant digits, l.s.d., resulting from successivemultiplications is logarithmic. In this paper these resultsare extended by establishing, still without any assumptionsof invariance to scaling, that this distribution remains invariantunder all further arithmetic operationsboth multiplicativeand additive. The fact that 30% of decimal numbers have l.s.d.1 persists. 相似文献
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Abstract— The 1(N)-(2,6-dichlorobenzyl)-1,4-dihydronicotinamide (I), N-methyl- and N,N-dimethyl-1(N)-(2,6-dichlorobenzyl)-1,4-dihydronicotinamide (II and III), respectively), and 1(N)-(2,6-dichloro-benzyl)-2-aminomethyl-1,4-dihydronicotinic acid lactame (IV) were synthesized as model compounds for natural coenzymes, and systematically studied by 1H NMR, UV/V1S absorption and fluorescence spectroscopy. The absorption at ∼ 340 nm argues for an effective conjugation between dihydropyridine and carboxamide π-system, and rules out any severely twisted conformation. For the natural coenzymes NADH and NMNH, as well as for I and II (with no or only one N-amide substituent), 1H NMR definitively establishes a transoid conformation in solution, with the carbonyl O close to 2-H of the dihydropyridine ring. N,N-dimethyl substitution effectively inverts the carboxamide orientation into the cisoid form. The 1H NMR data (as well as molar extinctions) for the fused-ring derivatives IV and V, with a fixed cisoid and transoid structure, respectively, provide final proof for the conformational assignment.
Absorption maxima are shifted to lower energies with increasing solvent polarity. In solvents which can act as hydrogen bond acceptors to the carboxamide N-H, absorption shows a general blue-shift of ∼ 10 nm. H-bond donor solvents do not affect absorption maxima but enhance molar extinction. Fluorescence maxima show a similar dependence on solvent polarity but no specific hydrogen-bonding effect. Fluorescence quantum yields appear increased tenfold in solvents donating H-bonds to the carboxamide C=O group. These results are interpreted in terms of the vinylogous amide resonance between C=O function and ring-N lone pair being the electronic interaction dominating in the ground state of dihydronicotinamides. 相似文献
Absorption maxima are shifted to lower energies with increasing solvent polarity. In solvents which can act as hydrogen bond acceptors to the carboxamide N-H, absorption shows a general blue-shift of ∼ 10 nm. H-bond donor solvents do not affect absorption maxima but enhance molar extinction. Fluorescence maxima show a similar dependence on solvent polarity but no specific hydrogen-bonding effect. Fluorescence quantum yields appear increased tenfold in solvents donating H-bonds to the carboxamide C=O group. These results are interpreted in terms of the vinylogous amide resonance between C=O function and ring-N lone pair being the electronic interaction dominating in the ground state of dihydronicotinamides. 相似文献
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Abstract— –An attempt was made to identify some of the ultraviolet (u.v.) photoproducts of 5-bromouracil-labeled DNA (BrU-DNA). Two synthetic dinucleotides, 5-bromodeoxyuridylyl-(3' →5 ')-thymidine (BrdUpT) and 5-bromodeoxyuridylyl-(3' → 5')-deoxycytidine (BrdUpdC), were prepared. Each gave a single u.v. photoproduct which in turn gave a single acid hydrolysis product. 2-14 C-BrU-DNA. prepared from E. coli B3, was irradiated (275–280 nm), hydrolyzed, and paper chromatographed in four systems. Comparison with the two synthetic photoproducts showed that if present at all, BrdUpT and BrdUpdC photoproducts could account for no more than 10 and 3.5 per cent respectively of the total photoproducts. At 55 per cent conversion of BrU into photoproducts, the major 14 C-photoproduct was uracil (78 per cent); the remaining 22 per cent was made up of at least six products, three of which were reversed by 232 nm irradiation.
The debrominated cyclobutane structure proposed by Haug for BrdUpT photoproduct has been shown to be incorrect. It was found to contain one atom of bromine per molecule. On the basis of nuclear magnetic resonance and u.v. spectra, two possible structures are proposed for the photoproduct, each containing an eight-membered ring. 相似文献
The debrominated cyclobutane structure proposed by Haug for BrdUpT photoproduct has been shown to be incorrect. It was found to contain one atom of bromine per molecule. On the basis of nuclear magnetic resonance and u.v. spectra, two possible structures are proposed for the photoproduct, each containing an eight-membered ring. 相似文献
78.
We define quadrature formulas for integrals with weight functionsby applying a given approximation method locally. This allowsthe generalisation of different quadrature formulas, e.g., thecompound Newton-Cotes formulas, Gauss summation formulas, orGregory's formulas, to the case of weighted integrals, as wellas to construct new quadrature formulas, and to derive errorestimates for all these quadrature formulas. The estimates consideredhere are mainly of the form |R[f]|c||f(r)||, provided the underlyingapproximation method is exact for polynomials of degree <r(R[f] is the quadrature error). Explicit, asymptotically sharperror estimates are obtained for arbitrary integrable weightfunctions. Further, estimates are obtained for the case thatthe quadrature error is of higher order than the approximationerror. 相似文献
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ANALYSIS OF SENSITIVITY AND UNCERTAINTY IN AN INDIVIDUAL‐BASED MODEL OF A THREATENED WILDLIFE SPECIES 下载免费PDF全文
Sensitivity analysis—determination of how prediction variables affect response variables—of individual‐based models (IBMs) are few but important to the interpretation of model output. We present sensitivity analysis of a spatially explicit IBM (HexSim) of a threatened species, the Northern Spotted Owl (NSO; Strix occidentalis caurina) in Washington, USA. We explored sensitivity to HexSim variables representing habitat quality, movement, dispersal, and model architecture; previous NSO studies have well established sensitivity of model output to vital rate variation. We developed “normative” (expected) model settings from field studies, and then varied the values of ≥ 1 input parameter at a time by ±10% and ±50% of their normative values to determine influence on response variables of population size and trend. We determined time to population equilibration and dynamics of populations above and below carrying capacity. Recovery time from small population size to carrying capacity greatly exceeded decay time from an overpopulated condition, suggesting lag time required to repopulate newly available habitat. Response variables were most sensitive to input parameters of habitat quality which are well‐studied for this species and controllable by management. HexSim thus seems useful for evaluating potential NSO population responses to landscape patterns for which good empirical information is available. 相似文献