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61.
Gas-chromatographic experiments were carried out in various phases of the solvents 4-acetoxy-N-[4-methoxy-benzylidene]-aniline, dibutoxyazoxybenzene, lithium stearate, dihexoxyazoxybenzene, and diheptoxyazoxybenzene. The solutes were linear, branched and cyclic alkanes, and substituted benzenes. Excess enthalpies, entropies, and free entropies were calculated from net retention volumes. In the nematic liquid crystalline phases the effect of order disturbance was significant in
and
but it was, by enthalpy-entropy compensation, not demonstrable in
. Differences in flexibility and degree of expansion of the solutes did not result in significantly different values of the excess quantities. 相似文献
62.
Elena V. Parfenyuk Olga I. Davydova Nataliya Sh. Lebedeva 《Journal of solution chemistry》2004,33(1):1-10
Calorimetric titrations have been performed at 298.15 K in aqueous solutions to derive the stability constants and thermodynamic parameters of the interactions of D-maltose and sucrose with some amino acids (glycine, DL-alanine, DL-leucine, and L-serine). The apparent molal volumes of the disaccharides in dilute aqueous solutions of the amino acids have been determined from density measurements at 298.15 K. In contrast to D-maltose, sucrose was found to associate with the amino acids and these associated species are preferentially entropy stabilized. These results are interpreted in terms of the influence of the nature of the solutes, their specific conformations, and hydration, on the ability of the disaccharides to form associated complexes with the amino acids. 相似文献
63.
Paul W. Chun 《International journal of quantum chemistry》2001,85(6):697-712
This communication will demonstrate the existence of a thermodynamic molecular switch in the pairwise, sequence‐specific hydrophobic interaction of Ile–Ile, Leu–Ile, Val–Leu, or Ala–Leu over the temperature range of 273–333 K reported by Nemethy and Scheraga in 1962. Based on Chun's development of the Planck–Benzinger methodology, the change in inherent chemical bond energy at 0 K, ΔH°(T0), is 3.0 kcal mol?1 for Ile–Ile, 2.4 for Leu–Ile, 1.8 for Val–Leu, and 1.2 kcal mol?1 for Ala–Leu. The value of ΔH°(T0) decreases as the length of the hydrophobic side chain decreases. It is clear that the strength and stability of the hydrophobic interaction is determined by the packing density of the side chains, with Ala–Leu being the most stable. At 〈Tm〉, the thermal agitation energy, $\int^{T}_{0}\Delta Cp^{\circ}(T)\,dT$, is about five times greater than ΔH°(T0) in each case. Additionally, the thermal agitation energy for the same series, evaluated at 〈Tm〉, decreases in the same order, that is, as the length of the side chain decreases. This pairwise, sequence‐specific hydrophobic interaction is highly similar in its thermodynamic behavior to that of other biological systems, except that the negative Gibbs free energy change minimum at 〈Ts〉 occurs at a considerably higher temperature, 355 K compared to about 300 K. The melting temperature, 〈Tm〉, is also high, 470 K compared to 343 K in a biological system. The implication is that the negative Gibbs free energy minimum at a well‐defined 〈Ts〉 has it origin in the hydrophobic interactions, which are highly dependent on details of molecular structure. In addition to the four specific dipeptide interactions described, we have shown in our unpublished work the existence of a thermodynamic molecular switch in the interactions of 32 dipeptides wherein a change of sign in ΔCp°(T)reaction leads to a true negative minimum in the Gibbs free energy of reaction, and hence, a maximum in the related Keq. Indeed, all interacting biological systems that we have thus far examined using the Planck–Benzinger approach point to the universality of thermodynamic molecular switches. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
64.
Piotr Kujawa Annie Audibert‐Hayet Joseph Selb Franoise Candau 《Journal of Polymer Science.Polymer Physics》2004,42(9):1640-1655
Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (NH). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (NH = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the NH value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (NH = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004 相似文献
65.
THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT 总被引:2,自引:0,他引:2
Ai-minLi Hai-suoWu Quan-xingZhang Gen-chengZhang ChaoLong Zheng-haoFei Fu-qiangLiu Jin-longChen 《高分子科学》2004,(3):259-267
Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate. 相似文献
66.
Moon Hwan Cho Seung Chang Yang Nam Keun Yang Yongjin Kang Jaejung Ko 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):279-287
The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, andAg+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C.Ag+ exhibited remarkably higher complexation selectivity.Ag+ and several transition metal ions have been transportedusing this ligand as carrier in a bulk liquid membrane. CompetitiveAg+–M2+ transport studies have also beencarried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitiveAg+–M2+ transport studies. The complexformation of N,N-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver,[Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 ismonoclinic, space group P21/n (No. 14), with cell dimensionsa = 13.398(4) , b=12.577(5) , c = 21.521(4) , =100.14(2) , V = 3570(2) 3 and Z = 4. 相似文献
67.
68.
蛋白质变性机理与变性时的热力学参数研究进展 总被引:7,自引:0,他引:7
生物大分子是近年来生命科学的研究热点和难点之一,而对蛋白质变性的研究有助于深刻揭示生命现象的机理.利用光谱学和热力学可以分别从微观和宏观角度对蛋白质变性进行研究,并由此得到表征蛋白质变性的热力学参数.这对深入了解蛋白质的折叠与伸展、变性机理、结构稳定性及生命体的新陈代谢等问题具有很大意义.近年来,国内外学者在此方面做了大量的工作,主要涉及蛋白质在水溶液中的变性机理、在有变性剂存在下水溶液中的变性机理及在含有其它物质水溶液中的变性机理.用来表征蛋白质变性的热力学参数有热容、变性自由能、变性焓和变性熵等.本文对这些研究进行了概述. 相似文献
69.
Jose L. Zurita Maria L. G. de Soria Miguel A. Postigo Miguel Katz 《Journal of solution chemistry》1987,16(2):163-170
Densities, viscosities, enthalpies, vapor-liquid equilibria, and surface tensions were determined at 25°C for the 2-propanol+dichloromethane system. From the experimental results excess volumes, viscosities, enthalpies, Gibbs energies, and excess surface tensions were calculated. An attempt has been made to explain the observed deviations from ideal behavior on the basis of intermolecular interactions. 相似文献
70.
The main thermodynamic characteristics of the adsorption of haloadamantanes on graphitized thermal carbon black were determined by experimental measurements and by calculations in terms of molecular-statistic theory of adsorption. Using experimental data, the Kovac retention indices were calculated and the optimum conditions for gas-chromatographic separation of haloadamantanes on stationary phases with different polarity were elucidated. The influence of the cage effect in the adamantane unit on the chromatographic properties of haloadamantanes was established. 相似文献