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711.
W. Zielenkiewicz A. Zielenkiewicz K. L. Wierzchowski 《Journal of solution chemistry》1994,23(10):1125-1131
Enthalpies of solution in water, H
sol
o
, and enthalpies of sublimation, H
sub
o
, were determined experimentally for a number of crystalline derivatives of adenine: 6,8,9-trimethyladenine; 6,9-dimethyl-8-ethyladenine; 6,9-dimethyl-8-propyladenine; 6,9-dimethyl-8-butyladenine; 8,9-dimethyl-adenine and 9-methyl-8-ethyladenine. Standard enthalpies of hydration, H
hydr
o
, derived from these data were calculated. The latter were discussed together with the values for variously alkylated adenines, determined previously. The data obtained show that the dependence of enthalpy of hydration on the number of methylene groups added upon substitution with 8-n-alkyl groups of 9-methyladenine and 6,9-dimethyladenine is nonlinear. 相似文献
712.
W. Zielenkiewicz A. Zielenkiewicz K. L. Wierzchowski 《Journal of solution chemistry》1993,22(11):975-981
Enthalpies of solution in water H
sol
o
and enthalpies of sublimation H
sub
o
were determined for a number of crystalline derivatives of uracil: 1,6-dimethyluracil (m
2
1,6
Ura), 1,3,6-trimethyluracil (m
3
1,3,6
Ura), 6-ethyl-1,3-dimethyluracil (e6m
2
1,3
Ura), 6-propyl-1,3-dimethyluracil (pr6m
2
1,3
Ura) and 6-butyl-1,3-dimethyluracil (but6m
2
1,3
Ura). Standard enthalpies of hydration H
hydr
o
and standard enthalpies of interaction H
int
o
of the solutes with their hydration shells were calculated. The data obtained show that dependence of H
int
o
on the number of-CH2- groups of n-alkyl chain added upon substitution of diketopyrimidine ring is nonlinear. This finding is discussed in connection with results of X-ray diffraction structure determinations for the crystalline compounds. 相似文献
713.
Nonconventional gels formed by lecithin in hydrocarbon oils containing a small amount of water have been studied with the help of temperature- and water-content-dependent phase transitions,31P NMR and FT-IR techniques. Gels are obtained in cyclohexane,n-octane, andn-dodecane. Addition of cholesterol in lecithin/water/oil ternary system either eliminates the gelation or shifts the transition temperature to higher values. The gels are thermoreversible, optically clear and are not birefringent. The composition of these gels indicates that the gelation takes place even at 15 weight % of lecithin and water. The lateral motion of the phosphate part of lecithin head group along surfactant monolayer, as well as the tumbling motion of the entangled assemblies of the rodshaped aggregates are fast enough to average out the chemical shift anisotropy of31P NMR spectra. From the FT-IR studies, it has been concluded that the gel formation involves the conformational changes in the polar head part of lecithin molecules in such a way that further hydration of phosphate group is drastically hindered.This paper is respectfully dedicated to the sixtieth birthday of Professor Hans F. Eicke, University of Basel, Switzerland 相似文献
714.
K. B. Bazhykova I. A. Poplavskaya K. D. Praliev 《Chemistry of Heterocyclic Compounds》2005,41(11):1386-1389
The reaction of 1-(2-ethoxyethyl)piperidin-4-one with ethynylcyclohexanol led to the synthesis of a glycol, the hydration
of which gave a mixture of spirocyclic compounds with a carbonyl group at various positions in the furan ring.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1649–1652, November, 2005. 相似文献
715.
The heats of solution of the sodium n-alkyl sulfonates from methyl to octyl have been measured at 25°C in water, D2O, and three alcohol-rich mixtures with water, all at solute concentrations low enough so that solute-solute interaction is negligible. Methylene-group contributions to the enthalpies of transfer are readily identified. Collation with the results of earlier studies of enthalpies of transfer leads to the conclusion that methylene-group enthalpies of transfer can be identified as follows: 0.87 kcal-mole–1 for transfers to the gas phase from water and –0.035 kcal-mole–1 for transfers to D2O from H2O, independent of the solute type provided only that methylene-group contributions can be identified in the data. Compared to other solvents, water is about as lipophilic as dimethylsulfoxide or a mixture of 27 moles of water with 73 moles of methanol. However, the range of the interactions between different groups on a given solute molecule seems to be much greater in water than in any of the other solvents studied, making it more difficult to identify group contributions to solvation in water. Another example of the complexity of the solvation of alkyl groups in water is encountered when one compares the solvation enthalpy of hexane in various solvents with some of the above results. 相似文献
716.
Rudovský J Cígler P Kotek J Hermann P Vojtísek P Lukes I Peters JA Vander Elst L Muller RN 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2373-2384
A monophosphonate analogue of H4dota, 1,4,7,10-tetraazacyclododecane-4,7,10-tris(carboxymethyl)-1-methylphosphonic acid (H5do3aP), and its complexes with lanthanides were synthesized. Multinuclear NMR studies reveal that, in aqueous solution, lanthanide(III) complexes of the ligand exhibit structures analogous to those of H4dota complexes. Thus, the central ion is nine-coordinate, surrounded by four nitrogen atoms, three acetate and one phosphonate oxygen atoms, and one water molecule in an apical position. For complexes of H5do3aP with Ln(III) ions in the middle of the series, the abundance of the desired twisted square-antiprismatic (TSAP) isomer is higher than for the corresponding H4dota complexes. The TSAP/square-antiprismatic (SAP) isomer ratio is highly sensitive to protonation of the phosphonate group: a higher abundance of the TSAP isomer was found in acidic solutions. The microscopic protonation constants of the TSAP isomers are higher than those of the SAP isomers. The presence of one water molecule in the first coordination sphere of the complexes in the pH region studied (pH 2.5-7.0) is confirmed by 17O NMR spectroscopy. The results of a simultaneous fit of variable-temperature 17O NMR relaxation data and 1H NMRD profiles show that the residence time of water (tauM) in the Gd(III) complex is much smaller than for [Gd(dota)(H2O)]-. The exchange rate appears to be dependent on the pH of the solution. The values of tauM are 37, 40, and 14 ns at pH 2.5, 4.7, and 7.0, respectively. These observations can be explained by an extensive second-sphere hydrogen-bonding network that varies with the state of protonation of the phosphonate moiety. Upon protonation of the complex, the second-sphere hydration probably becomes more ordered, which may result in a decrease in penetrability and an increase in tauM. The relaxivity of the Gd(III) complex is almost independent of the pH and is equal to 4.7 s(-1) mM(-1) (20 MHz, pH 7 and 37 degrees C). The solid-state structure was determined for the Nd(III) complex. It crystallizes as the TSAP isomer and the unit cell contains two independent molecules of the complex with different Nd-O(water) bond lengths of 2.499 and 2.591 A. 相似文献
717.
The affects of alkali metal cations on the retention behavior of halide ions has been investigated. In general, the retention times of the anions were found to decrease as the size of the metal ion increased, although an inversion was observed for the rubidium and cesium ions. A similar inversion has been reported for calculated anion polarizabilities. 相似文献
718.
Dielectric properties of ethanol and 1-hexanol solutions containing LiCl, CaCl2·2H2O and Ca(NO3)2·4H2O, respectively, have been determined. It is found that LiCl reduces the static permittivity in ethanol, but CaCl2·2H2O and Ca(NO3)2·4H2O both give an initial increase in s. All the electrolytes studied increase the mean relaxation time of the ethanol solutions. In 1-hexanol the static permittivity is rather invariant for all studied electrolytes at low concentrations, while the same lengthening of the mean relaxation time is observed. When water is added in addition to the hydration water of the electrotyte, the static permittivity in hexanol is almost unaltered while the relaxation time is drastically shortened. The experimental result is discussed in terms of a formation of ion pairs, solvation sheaths, and kinetic depolarization, a partial release of hydration water and a structuring influence on the alcohol structure by the hydrated cation. 相似文献
719.
The hydration structure of human lysozyme was studied with cryogenic X-ray diffraction experiment and molecular dynamics simulations. The crystal structure analysis at a resolution of 1.4 A provided 405 crystal water molecules around the enzyme. In the simulations at 300 K, the crystal structure was immersed in explicit water molecules. We examined correlations between crystal water sites and two physical quantities calculated from the 1-ns simulation trajectories: the solvent density reflecting the time-averaged distribution of water molecules, and the solvent dipole measuring the orientational ordering of water molecules around the enzyme. The local high solvent density sites were consistent with the crystal water sites, and better correlation was observed around surface residues with smaller conformational fluctuations during the simulations. Solvent dipoles around those sites exhibited coherent and persistent ordering, indicating that the hydration water molecules at the crystal water sites were highly oriented through the interactions with hydrophilic residues. Those water molecules restrained the orientational motions of adjoining water molecules and induced a solvent dipole field, which was persistent during the simulations around the enzyme. The coherent ordering was particularly prominent in and around the active site cleft of the enzyme. Because the ordering was significant up to the third to fourth solvent layer region from the enzyme surface, the coherently ordered solvent dipoles likely contributed to the molecular recognition of the enzyme in a long-distance range. The present work may provide a new approach combining computational and the experimental studies to understand protein hydration. 相似文献
720.
Amedeo Marini Vittorio Berbenni Giovanna Bruni Piercarlo Mustarelli Ferdinando Giordano Marco Villa 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(3):221-234
A method to determine the composition and hydration state of the complexes formed in aqueous solution by cyclodextrins (CD) is presented and applied to the -CD/ketoprofen system; it is based on a combination of spectroscopic, calorimetric, and thermogravimetric analyses. The complexes have, on average and per -CD mole, more than eleven water molecules, which are present in completely different bound states. 相似文献