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61.
Jedlovszky P Pártay LB Bartók AP Garberoglio G Vallauri R 《The Journal of chemical physics》2007,126(24):241103
The structural changes occurring in supercooled liquid water upon moving from one coexisting liquid phase to the other have been investigated by computer simulation using a polarizable interaction potential model. The obtained results favorably compare with recent neutron scattering data of high and low density water. In order to assess the physical origin of the observed structural changes, computer simulation of several ice polymorphs has also been carried out. Our results show that there is a strict analogy between the structure of various disordered (supercooled) and ordered (ice) phases of water, suggesting that the occurrence of several different phases of supercooled water is rooted in the same physical origin that is responsible for ice polymorphism. 相似文献
62.
Romain Valentin Karine Molvinger Françoise Quignard Francesco Di Renzo 《Macromolecular Symposia》2005,222(1):93-102
Nitrogen adsorption at 77 K has been applied to the study of the texture of alginate aerogel microspheres obtained by CO2 supercritical drying of alcogels. The limited volume shrinkage suggests that the aerogels preserve the texture of the hydrogels. Alginate aerogels presents a N2 adsorption at small pressure higher than reference non-porous silica, to be attributed to the polarity of the surface or to a small microporous volume. The aggregated nanobead strings of the guluronic-rich gels accounts for a significant mesoporosity. The N2 adsorption results correspond to electron microscopy observations for features smaller than 50 nm. 相似文献
63.
Romain Valentin Raluca Horga Barbara Bonelli Edoardo Garrone Francesco Di Renzo Françoise Quignard 《Macromolecular Symposia》2005,230(1):71-77
Supercritical drying of alginate gels is an efficient way to prepare aerogels with high surface area (>300 m2 · g−1). FTIR spectroscopy allows to monitor the adsorption of NH3 from the gas phase onto the acid sites of the alginate. Free carboxylic groups are effective Brønsted sites, whereas the divalent cations used in the ionotropic gelation present the properties of Lewis sites. The ratio between Brønsted and Lewis sites provides infomation on the role of pH in alginate gelation and suggests that non-buffered gelation by transition-metal cations is a mixed ionotropic-acid process. 相似文献
64.
65.
Renzo Cimiraglia 《International journal of quantum chemistry》1996,60(1):167-171
Multireference perturbation theory is examined in connection with the two partitions in the Møller—Plesset and Epstein—Nesbet schemes. The implementation of an efficient diagrammatic technique is described and two examples of application (diazene and the Cr2 molecule), involving large variational spaces, are provided. © 1996 John Wiley & Sons, Inc. 相似文献
66.
Maddalena Corsini Piero Zanello Renzo Cini Gabriella Tamasi 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(6):m219-m223
The title compound, [Cu(C10H9N2O)2] or [CuII(CYMB)2], (I), was obtained in an attempt to reduce trans‐bis(2‐{[3,5‐bis(trifluoromethyl)phenyl]iminomethyl}phenolato)copper(II), [Cu(TIMB)2], (II), with bis(pentamethylcyclopentadienyl)cobalt(II) [decamethylcobaltocene, Cp*2Co, (III)]. The molecular structure of (I) has the CuII centre located on an inversion centre of the C2/c space group. A density functional theory (DFT) analysis at the B3LYP/Lanl2dz(CuF);6‐31G**(CHNO) level performed in order to optimize the structures of the free ligands CYMB− and TIMB−, and the metal complexes [CuI/II(CYMB)2]−/0 and [CuI/II(TIMB)2]−/0, reproduced well the X‐ray diffraction structure and allowed us to infer the insertion of the cyanomethide anion on the 3,5‐bis(trifluoromethyl)phenyl system from an evaluation of the Mulliken atomic charges and the electronic energies. 相似文献
67.
Capriati V Florio S Luisi R Perna FM Salomone A 《The Journal of organic chemistry》2006,71(10):3984-3987
A general method for the synthesis of hydroxyalkyl 1,3-dihydrobenzo[c]furans from ortho-lithiated aryloxiranes and carbonyl compounds is described. 相似文献
68.
Chen G Desinan S Rosei R Rosei F Ma D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(25):7925-7930
We report the synthesis and characterization of new Ni(x)Ru(1-x) (x = 0.56-0.74) alloy nanoparticles (NPs) and their catalytic activity for hydrogen release in the ammonia borane hydrolysis process. The alloy NPs were obtained by wet-chemistry method using a rapid lithium triethylborohydride reduction of Ni(2+) and Ru(3+) precursors in oleylamine. The nature of each alloy sample was fully characterized by TEM, XRD, energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We found that the as-prepared Ni-Ru alloy NPs exhibited exceptional catalytic activity for the ammonia borane hydrolysis reaction for hydrogen release. All Ni-Ru alloy NPs, and in particular the Ni(0.74)Ru(0.26) sample, outperform the activity of similar size monometallic Ni and Ru NPs, and even of Ni@Ru core-shell NPs. The hydrolysis activation energy for the Ni(0.74)Ru(0.26) alloy catalyst was measured to be approximately 37?kJ?mol(-1). This value is considerably lower than the values measured for monometallic Ni (≈70?kJ?mol(-1)) and Ru NPs (≈49?kJ?mol(-1)), and for Ni@Ru (≈44?kJ?mol(-1)), and is also lower than the values of most noble-metal-containing bimetallic NPs reported in the literature. Thus, a remarkable improvement of catalytic activity of Ru in the dehydrogenation of ammonia borane was obtained by alloying Ru with a Ni, which is a relatively cheap metal. 相似文献
69.
Arias-Ugarte R Sharma HK Morris AL Pannell KH 《Journal of the American Chemical Society》2012,134(2):848-851
We demonstrate that using Mo(CO)(6), Mo(CO)(5)NMe(3), and (η(5)-C(5)H(5))Mn(CO)(3) as catalysts for the silane, R(3)SiH, reduction of N,N-dimethylformamide (DMF), and N,N-diethylformamide (DEF), we can observe, intercept, and isolate, the important siloxymethylamine intermediates, R(3)SiOCH(2)NR'(2), R' = Me, Et, for the first time. In the presence of excess DMF such intermediates thermally react with a variety of silanes to form the corresponding disiloxanes in the absence of a metal catalyst. We also show that the germanium hydrides, Et(3)GeH and Bu(3)GeH, also reduce DMF to form trimethylamine and the corresponding digermoxane but observe no intermediates R(3)GeOCH(2)NMe(2). Bu(3)SnH reduces DMF, but along with the low yields of Bu(3)SnOSnBu(3) (but no Bu(3)SnOCH(2)NMe(2)) significant side products are obtained including (Bu(3)Sn)(2) and Bu(4)Sn. In the absence of DMF the siloxymethylamines can undergo metal-catalyzed reactions with silanes, germanes and stannanes to form disiloxanes, and R(3)SiOER(3) E = Ge, Sn, respectively. To date, the most efficient catalyst for this latter process is (η(5)-C(5)H(5))Mo(CO)(3)CH(3) via a photochemical reaction. 相似文献
70.
The equilibrium sorption of CI Direct Blue 1, as a model anionic adsorbate, from aqueous solution on cotton fabric was experimentally
studied. The equilibrium sorption data were employed to test the performance of a proposed nonlinear sorption model in describing
the sorption behavior of anionic adsorbates on cellulosic substrates. The analysis of data based on the nonlinear least-squares
curve fitting showed excellent correlation against experimental values as indicated by a high coefficient of determination
(R
2). The V and −Δμ° parameters were determined based on the nonlinear model and employed to represent the internal accessible volume of cotton
to CI Direct Blue 1 and the standard affinity of sorption. It was shown that variations in temperature and concentration of
electrolyte (e.g. NaCl) in the sorption system result in slight variations in V. The findings extend the scope of the previous study and indicate that the nonlinear sorption model can be used to accurately
determine the thermodynamic properties of a sorption system, such as the affinity (−Δμ°), enthalpy (ΔH°), and entropy (ΔS°), for anionic adsorbates on cellulosic substrates. 相似文献