全文获取类型
收费全文 | 2106篇 |
免费 | 107篇 |
国内免费 | 8篇 |
专业分类
化学 | 1521篇 |
晶体学 | 13篇 |
力学 | 65篇 |
数学 | 317篇 |
物理学 | 305篇 |
出版年
2023年 | 18篇 |
2022年 | 15篇 |
2021年 | 50篇 |
2020年 | 62篇 |
2019年 | 45篇 |
2018年 | 28篇 |
2017年 | 26篇 |
2016年 | 68篇 |
2015年 | 50篇 |
2014年 | 67篇 |
2013年 | 112篇 |
2012年 | 157篇 |
2011年 | 201篇 |
2010年 | 110篇 |
2009年 | 91篇 |
2008年 | 153篇 |
2007年 | 147篇 |
2006年 | 147篇 |
2005年 | 127篇 |
2004年 | 111篇 |
2003年 | 81篇 |
2002年 | 67篇 |
2001年 | 40篇 |
2000年 | 21篇 |
1999年 | 17篇 |
1998年 | 14篇 |
1997年 | 23篇 |
1996年 | 25篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 16篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 3篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 4篇 |
1978年 | 4篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1939年 | 3篇 |
1915年 | 4篇 |
1913年 | 3篇 |
1903年 | 2篇 |
1889年 | 3篇 |
排序方式: 共有2221条查询结果,搜索用时 93 毫秒
971.
Belegrinou S Mannelli I Lisboa P Bretagnol F Valsesia A Ceccone G Colpo P Rauscher H Rossi F 《Langmuir : the ACS journal of surfaces and colloids》2008,24(14):7251-7261
The interaction of the proteins bovine serum albumin (BSA), lysozyme (Lys), lactoferrin (Lf), and fibronectin (Fn) with surfaces of protein-resistant poly(ethylene oxide) (PEO) and protein-adsorbing poly(acrylic acid) (PAA) fabricated by plasma-enhanced chemical vapor deposition has been studied with quartz crystal microbalance with dissipation monitoring (QCM-D). We focus on several parameters which are crucial for protein adsorption, i.e., the isoelectric point (pI) of the proteins, the pH of the solution, and the charge density of the sorbent surfaces, with the zeta-potential as a measure for the latter. The measurements reveal adsorption stages characterized by different segments in the plots of the dissipation vs frequency change. PEO remains protein-repellent for BSA, Lys, and Lf at pH 4-8.5, while weak adsorption of Fn was observed. On PAA, different stages of protein adsorption processes could be distinguished under most experimental conditions. BSA, Lys, Lf, and Fn generally exhibit a rapid initial adsorption phase on PAA, often followed by slower processes. The evaluation of the adsorption kinetics also reveals different adsorption stages, whereas the number of these stages does not always correspond to the structurally different phases as revealed by the D- f plots. The results presented here, together with information obtained in previous studies by other groups on the properties of these proteins and their interaction with surfaces, allow us to develop an adsorption scenario for each of these proteins, which takes into account electrostatic protein-surface and protein-protein interaction, but also the pH-dependent properties of the proteins, such as shape and exposure of specific domains. 相似文献
972.
Soussan E Mille C Blanzat M Bordat P Rico-Lattes I 《Langmuir : the ACS journal of surfaces and colloids》2008,24(6):2326-2330
A new sugar-derived tricatenar catanionic surfactant (TriCat) was developed to obtain stable vesicles that could be exploited for drug encapsulation. The presence of the sugar moiety led to the formation of highly hydrophilic stoichiometric catanionic surfactant systems. The three hydrophobic chains permitted vesicles to form spontaneously. The self-assembly properties (morphology, size, and stability) of TriCat were examined in water and in buffer solution. Encapsulation studies of a hydrophilic probe, arbutin, commonly used in cosmetics for its whitening properties, were performed to check the impermeability of the vesicle bilayer. The enhancement of hydrophobic forces by the three chains of TriCat prevented surfactant equilibrium between the bilayer and the solution and enabled the probe to be retained in the aqueous cavity of the vesicles for at least 30 h. Thus, the present study suggests that this tricatenar catanionic surfactant could be a promising delivery system for hydrophilic drugs. 相似文献
973.
Kuchta B Firlej L Marzec M Boulet P 《Langmuir : the ACS journal of surfaces and colloids》2008,24(8):4013-4019
We study the microscopic mechanism of adsorption in nanometric cylindrical pores with strongly heterogeneous walls using grand canonical Monte Carlo simulations. The pore surface structure is modeled by a new lattice-site approach. Each site is characterized by two amplitudes--structural and energetic--that locally modify the structural and energetic properties of the surface. The amplitudes are randomly distributed over the pore wall. We have shown that different structural and energetic distribution functions lead to different mechanism of adsorption. The energetic site distribution plays the most crucial role in the submonolayer region. The structural site distribution modifies the multilayer adsorption. A method to analyze the stability of the adsorbed system using static susceptibility is proposed. Potential applications in multiscale modeling are discussed. 相似文献
974.
Dietzel PD Johnsen RE Blom R Fjellvåg H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(8):2389-2397
Porous metal-organic framework compounds with coordinatively unsaturated metal sites on the inner surface of the pores promise to be valuable adsorbents and catalyst systems, either in industrial applications or as model systems to study interactions with guest molecules. The dehydration process of two isostructural microporous coordination polymers, [M2(dhtp)(H2O)2].8 H2O, termed CPO-27-M (M=Co, Zn; H(4)dhtp=2,5-dihydroxyterephthalic acid) was investigated by in situ variable temperature X-ray diffraction. Both compounds contain accessible coordination sites at the metal after complete removal of the solvent. However, despite the analogy of their crystal structures, they behave differently during dehydration. For CPO-27-Co, water desorption is a smooth topotactic process of second order with no concomitant space group change and no increase in microstrain, which is beneficial for the applicability of the material. Removal of the water propagates from the center of the channels outwards. The coordinating water molecule at the metal desorbs only when almost all the bulk water in the pores has disappeared. In contrast, discontinuities in the powder pattern of CPO-27-Zn indicate the occurrence of first-order transitions. The crystal structures of four of the five individual phases could be determined. The structure of the intermediate phase occurring just before the framework is completely evacuated was elusive in respect to full structure solution and refinement, but it is most probably related to the removal of the axis of threefold symmetry. The zinc-based material experiences a significant amount of strain. 相似文献
975.
Computational analyses of the longitudinally twisted polycyclic aromatic hydrocarbons 9,18-diphenyltetrabenz[a,c,h,j]anthracene (1), 9,10,19,20-tetraphenyltetrabenzo[a,c,j,l]naphthacene (2), and 9,10,11,20,21,22-hexaphenyltetrabenzo[a,c,l,n]pentacene (3) were performed at the B3LYP/6-31G(d) level of theory. Ground state and transition state structures were located for two classes of conformational reactions in these molecules: twist inversions (enantiomerization or racemization reactions) and phenyl rotations, and the free energies of activation for these processes were calculated. Where possible, the computational results were compared with both new and existing experimental data for the rates of these conformational reactions. Multiple pathways were identified for some processes, but the low-energy transition states were often quite different from those that common chemical intuition might suggest. 相似文献
976.
Rémy Morgentin Georges Pasquet Pascal Boutron Frédéric Jung Maryannick Lamorlette Mickaël Maudet Patrick Plé 《Tetrahedron》2008,64(12):2772-2782
This paper describes the different strategies devised and applied to overcome the selectivity issues in the syntheses of 6,7-disubstituted-1H-quinolin-4-one, 7-substituted-1H-1,6-naphthyridin-4-one and 6-substituted-1H-1,7-naphthyridin-4-one derivatives. They allowed us to improve the overall yields and the scaling-up feasibility. Several examples illustrate these strategies with their advantages and drawbacks. 相似文献
977.
Christian Lherbet David Soupaya Cécile Baudoin-Dehoux Chantal André Casimir Blonski Pascal Hoffmann 《Tetrahedron letters》2008,49(38):5449-5451
A new route to functionalized iso(thio)chromans is described. The compounds are accessible easily in a one pot-reaction by using different benzaldehydes and phenylethanethiol or phenylethanol in presence of bismuth triflate. 相似文献
978.
Applying semianalytical models of nonideal plasma, we evaluate the behavior of the metallic phase in metal-ammonia solutions (MAS). This behavior is mainly controlled by the degenerate electron gas, which remains stable down to 5 MPM due to high solvent polarizability and strong dielectric screening of solvated ions. Comparing the behavior of the metallic state with those of localized solvated electrons, we have estimated the miscibility gap Delta n for various alkali metals and found Delta n(Na)>Delta n(K). It is rather narrow in Rb-NH3 and does not occur in Cs-NH3 solutions, which is in full agreement with the experiments. The case of Li is discussed separately. The difference calculated in the excess free energies of the metallic and nonmetallic phases is in the order of kBT, yielding a thermally fluctuating mixed state at intermediate metal concentrations. It results in a continuous metal-nonmetal (MNM) transition above the consolute point Tc and a phase separation below Tc. We propose a criterion for the MNM transition which may be attributed to the line of the maximum of compressibility above Tc. This line crosses the spinodal one at the critical temperature. Finally, we assert that a new electronic phase similar to microemulsion should also arise between the spinodal and the binodal lines. 相似文献
979.
Belorizky E Fries PH Helm L Kowalewski J Kruk D Sharp RR Westlund PO 《The Journal of chemical physics》2008,128(5):052315
The enhancement of the spin-lattice relaxation rate for nuclear spins in a ligand bound to a paramagnetic metal ion [known as the paramagnetic relaxation enhancement (PRE)] arises primarily through the dipole-dipole (DD) interaction between the nuclear spins and the electron spins. In solution, the DD interaction is modulated mostly by reorientation of the nuclear spin-electron spin axis and by electron spin relaxation. Calculations of the PRE are in general complicated, mainly because the electron spin interacts so strongly with the other degrees of freedom that its relaxation cannot be described by second-order perturbation theory or the Redfield theory. Three approaches to resolve this problem exist in the literature: The so-called slow-motion theory, originating from Swedish groups [Benetis et al., Mol. Phys. 48, 329 (1983); Kowalewski et al., Adv. Inorg. Chem. 57, (2005); Larsson et al., J. Chem. Phys. 101, 1116 (1994); T. Nilsson et al., J. Magn. Reson. 154, 269 (2002)] and two different methods based on simulations of the dynamics of electron spin in time domain, developed in Grenoble [Fries and Belorizky, J. Chem. Phys. 126, 204503 (2007); Rast et al., ibid. 115, 7554 (2001)] and Ann Arbor [Abernathy and Sharp, J. Chem. Phys. 106, 9032 (1997); Schaefle and Sharp, ibid. 121, 5387 (2004); Schaefle and Sharp, J. Magn. Reson. 176, 160 (2005)], respectively. In this paper, we report a numerical comparison of the three methods for a large variety of parameter sets, meant to correspond to large and small complexes of gadolinium(III) and of nickel(II). It is found that the agreement between the Swedish and the Grenoble approaches is very good for practically all parameter sets, while the predictions of the Ann Arbor model are similar in a number of the calculations but deviate significantly in others, reflecting in part differences in the treatment of electron spin relaxation. The origins of the discrepancies are discussed briefly. 相似文献
980.
Zeghida W Debray J Chierici S Dumy P Demeunynck M 《The Journal of organic chemistry》2008,73(6):2473-2475
A novel and simple method of preparation of 2-alkylaminoquinazolin-4-ones with fused heteroaromatic rings from easily accessible (hetero)aromatic amines is described. The method is very efficient, and the 2-alkylaminoquinazolinone derivatives are obtained in three steps without chromatographic purification. The key step is the ring closure of the N-protected guanidine intermediates by intramolecular Friedel-Craft's type substitution. 相似文献