全文获取类型
收费全文 | 6647篇 |
免费 | 275篇 |
国内免费 | 45篇 |
专业分类
化学 | 4651篇 |
晶体学 | 40篇 |
力学 | 146篇 |
数学 | 1120篇 |
物理学 | 1010篇 |
出版年
2023年 | 42篇 |
2022年 | 88篇 |
2021年 | 172篇 |
2020年 | 115篇 |
2019年 | 139篇 |
2018年 | 110篇 |
2017年 | 92篇 |
2016年 | 218篇 |
2015年 | 193篇 |
2014年 | 225篇 |
2013年 | 398篇 |
2012年 | 444篇 |
2011年 | 513篇 |
2010年 | 324篇 |
2009年 | 320篇 |
2008年 | 417篇 |
2007年 | 427篇 |
2006年 | 404篇 |
2005年 | 391篇 |
2004年 | 279篇 |
2003年 | 208篇 |
2002年 | 212篇 |
2001年 | 91篇 |
2000年 | 82篇 |
1999年 | 71篇 |
1998年 | 54篇 |
1997年 | 58篇 |
1996年 | 87篇 |
1995年 | 51篇 |
1994年 | 48篇 |
1993年 | 50篇 |
1992年 | 62篇 |
1991年 | 45篇 |
1990年 | 39篇 |
1989年 | 43篇 |
1988年 | 35篇 |
1987年 | 37篇 |
1986年 | 38篇 |
1985年 | 47篇 |
1984年 | 33篇 |
1983年 | 26篇 |
1982年 | 40篇 |
1981年 | 25篇 |
1980年 | 22篇 |
1979年 | 19篇 |
1978年 | 16篇 |
1977年 | 15篇 |
1975年 | 13篇 |
1974年 | 12篇 |
1973年 | 9篇 |
排序方式: 共有6967条查询结果,搜索用时 46 毫秒
71.
Barberá J Puig L Romero P Serrano JL Sierra T 《Journal of the American Chemical Society》2005,127(1):458-464
The work described here concerns a challenge of general interest in supramolecular chemistry: the achievement of chiral helical organizations with controlled structures. This work provides a strategy to obtain supramolecular polymers in which a chiral helical conformation has been induced by a noncovalent association, that is, through hydrogen bonding. Polycatenar 2,4,6-triarylamino-1,3,5-triazines, which organize into columnar mesophases and are susceptible to H-bonding interactions, were chosen as a starting point to build up the chiral supramolecular structure. The stacking of these mesogens has been forced to wind in a helical way by means of H-bond association with (R)-3-methyladipic acid, within the mesophase. The optically active columnar organization has been studied in depth by optical microscopy, differential scanning calorimetry (DSC), X-ray diffraction, and circular dichroism. Formation of stable complexes between the triazine units and (R)-3-methyladipic acid has also been investigated by means of NMR diffusion-ordered spectroscopy (DOSY) experiments in chloroform. 相似文献
72.
C. Joly S. Goizet J. C. Schrotter J. Sanchez M. Escoubes 《Journal of membrane science》1997,130(1-2):63-74
The effect of introduction of silica particles prepared by the sol-gel technique on the gas transport properties of a polyimide film was studied. The sorption and permeation of N2, O2, CO2, H2 and CH4 were studied and correlated with morphological changes in the polymer structure. From sorption isotherms, we observed that the composite membrane presents higher solubility coefficients than the polyimide one. The solubility coefficient ratio between the composite and the polyimide is about 1.5–2.0. The isotherms were analyzed in terms of the dual mode sorption. The Henry's coefficient and the Langmuir's affinity and saturation constants were obtained allowing to calculate the Langmuir to Henry concentration ratios as function of the gas pressure. These ratios decrease until zero within a certain pressure range as long as the Langmuir's mode is acting and they are higher for the polyimide membrane when compared with the composite one. This study was completed with calorimetric measurements during the sorption. The gas interaction energy in kJ/mol decreases within the same pressure range as previously described. The measured energies are higher for the polyimide film when compared with the composite one because the polyimide membrane presents a stronger energetic effect caused by a higher Langmuir's contribution. From permeation studies at 3.155 Pa, the composite membrane showed higher permeability coefficients and permselectivities than the polyimide one. All these results were explained, taking into account the difference on the imidization degree of both membranes and the morphological changes which may be induced by the silica nodules in the organic/inorganic interphases. 相似文献
73.
Ignacio Gimeno Ainhoa Urtizberea Juan Romn-Roche David Zueco Agustín Camn Pablo J. Alonso Olivier Roubeau Fernando Luis 《Chemical science》2021,12(15):5621
We explore how to encode more than a qubit in vanadyl porphyrin molecules hosting a S = 1/2 electronic spin coupled to a I = 7/2 nuclear spin. The spin Hamiltonian and its parameters, as well as the spin dynamics, have been determined via a combination of electron paramagnetic resonance, heat capacity, magnetization and on-chip magnetic spectroscopy experiments performed on single crystals. We find low temperature spin coherence times of micro-seconds and spin relaxation times longer than a second. For sufficiently strong magnetic fields (B > 0.1 T, corresponding to resonance frequencies of 9–10 GHz) these properties make vanadyl porphyrin molecules suitable qubit realizations. The presence of multiple equispaced nuclear spin levels then merely provides 8 alternatives to define the ‘1’ and ‘0’ basis states. For lower magnetic fields (B < 0.1 T), and lower frequencies (<2 GHz), we find spectroscopic signatures of a sizeable electronuclear entanglement. This effect generates a larger set of allowed transitions between different electronuclear spin states and removes their degeneracies. Under these conditions, we show that each molecule fulfills the conditions to act as a universal 4-qubit processor or, equivalently, as a d = 16 qudit. These findings widen the catalogue of chemically designed systems able to implement non-trivial quantum functionalities, such as quantum simulations and, especially, quantum error correction at the molecular level.We show that a sizeable electronuclear entanglement of the S = 1/2 and I = 7/2 spins of a vanadyl porphyrin provides the conditions to act as a universal 4-qubit processor, and thus implement quantum error correction at the molecular level. 相似文献
74.
Chemical, structural, and thermal properties of Zn(II)-Cr(III) layered double hydroxides intercalated with sulfated and sulfonated surfactants 总被引:1,自引:0,他引:1
Crepaldi EL Pavan PC Tronto J Valim JB 《Journal of colloid and interface science》2002,248(2):429-442
Zn(II)-Cr(III)-LDHs (layered double hydroxides) containing sulfated or sulfonated surfactants as the interlamellar anion were synthesized by the coprecipitation method. The syntheses were conducted under various different experimental conditions, such as the Zn : Cr ratio, pH, and aging time. In each of the prepared materials, unlike previously reported data, the interlayer anion arrangement did not change, being consistent with a perpendicular monolayer. The thermal decomposition process of the prepared materials was studied by a set of analysis methods, such as TG/DTA, TG/MS, PXRD, and FT-IR. From the results obtained it was possible to conclude that, in an air atmosphere, the anions decomposed by a partial combustion, leading to the formation of sulfide. The results also showed that sulfonated surfactants containing LDHs are much more stable than those containing sulfated surfactants. A mechanism was proposed for the thermal decomposition of such LDHs based on the experimental results. 相似文献
75.
Boev VI Pérez-Juste J Pastoriza-Santos I Silva CJ Gomes Mde J Liz-Marzán LM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):10268-10272
Hybrid organic-inorganic nanocomposites containing uniform distributions of metal nanoparticles have been prepared by mixing a preformed nanoparticle colloid with the precursors of a ureasil, prior to the sol-gel transition. These nanocomposites possess not only high optical quality and optical features dictated by the size and shape of the nanoparticle dopants but also a high degree of flexibility, which can largely enhance the range of applications in practical devices. The deposition of a uniform silica shell on the nanoparticle surface prior to the sol-gel transition was found to be required to maintain the colloidal stability during the process and, thus, to retain the optical properties in the final nanocomposite material. This method can be readily extended to other materials, such as semiconductor and magnetic nanoparticles. 相似文献
76.
A variational method called discrete variable representation is applied to study the energy spectra of two interacting electrons in a quantum dot with a three-dimensional anisotropic harmonic confinement potential. This method, applied originally to problems in molecular physics and theoretical chemistry, is here used to solve the eigenvalue equation to relative motion between the electrons. The two-electron quantum dot spectrum is determined then with a precision of at least six digits. Moreover, the electron correlation energies for various potential confinement parameters are investigated for singlet and triplet states. When possible, the present results are compared with the available theoretical values. 相似文献
77.
78.
Luis C. Mendes Andrea D. Tedesco Mauro S. Miranda Marcia R. Benzi Beatriz S. Chagas 《Polymer Testing》2005,24(8):963-968
In this third work, we evaluated the degree of conversion (DC) versus depth of dental filling composite named Prodigy Condensable™ using infrared spectroscopy. Confirming previous results, there was a gradual reduction of DC with increasing depth but the composite exhibited extreme values of DC, an upper value (45.9%) on the surface and a lower one (6.1%) at a depth of 5 mm. The composite presented the worst performance among materials studied. The composite formulation was 80% of inorganic fillers and BisfenolA/dimethacrylate (BisGMA) (18%)/triethyleneglycoldimethacrylate (TEGDMA) (2.0%) as monomers. As stated before, type/ratio/viscosity of monomers and type, amount, size and size distribution of fillers all together had an important role in the cure reaction contributing to the final performance of the composite. 相似文献
79.
Rafael Usón Pascual Lahuerta Daniel Carmona Luis A. Oro 《Transition Metal Chemistry》1980,5(1):327-329
Summary The preparation of the covalent Rh(OCIO3)(CS)(PCy3)2 and Rh(OClO3)(CS)(PPh3)(PCy3) perchlorato complexes is described, These complexes react with mono- or bidentate nitrogen donor ligands to give new cationic complexes of the [Rh(CS)(PCY3)2L]ClO4 and [Rh(CS)(PPh,)(PCy3)L]ClO4 types, 相似文献
80.
Kujawa P Moraille P Sanchez J Badia A Winnik FM 《Journal of the American Chemical Society》2005,127(25):9224-9234
The layer-by-layer growth of multilayer assemblies of two polysaccharides, the polyanion hyaluronan (HA) and the polycation chitosan (CH), was investigated using atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy, with primary emphasis on the effect of the polysaccharide molecular weights on the film thickness and surface morphology. The HA/CH multilayers exhibit an exponential increase of the optical film thickness with the number of deposited bilayers. We show that the multilayer thickness at a given stage depends on the size of both CH, the diffusing polyelectrolyte, and HA, the non-diffusing species. Assemblies (12 bilayers) of high molecular weight polysaccharides (HA, 360,000; CH, 160,000) were twice as thick (approximately 900 nm vs approximately 450 nm) as those obtained with low molecular weight polymers (HA, 30,000; CH, 31,000), as assessed by AFM scratch tests. The exponential growth rate is the same for the high and low molecular weight pairs; the larger film thicknesses observed by SPR and by AFM arising from an earlier onset of the steep exponential growth phase in the case of the high molecular weight pair. In all cases, isolated islets form during the deposition of the first CH layer onto the underlying HA. Upon further film growth, individual islets coalesce into larger vermiculate features. The transition from distinct islands to vermiculate structures depends on the molecular weights of the polysaccharides and the lower molecular weight construct presents larger worm-like surface domains than the high molecular weight pair. 相似文献