全文获取类型
收费全文 | 310篇 |
免费 | 13篇 |
国内免费 | 2篇 |
专业分类
化学 | 247篇 |
力学 | 3篇 |
数学 | 53篇 |
物理学 | 22篇 |
出版年
2022年 | 6篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 8篇 |
2018年 | 2篇 |
2017年 | 5篇 |
2016年 | 21篇 |
2015年 | 7篇 |
2014年 | 5篇 |
2013年 | 16篇 |
2012年 | 20篇 |
2011年 | 25篇 |
2010年 | 9篇 |
2009年 | 10篇 |
2008年 | 17篇 |
2007年 | 23篇 |
2006年 | 23篇 |
2005年 | 13篇 |
2004年 | 18篇 |
2003年 | 18篇 |
2002年 | 10篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 1篇 |
1997年 | 6篇 |
1996年 | 1篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1967年 | 2篇 |
1964年 | 1篇 |
1962年 | 1篇 |
1960年 | 1篇 |
排序方式: 共有325条查询结果,搜索用时 0 毫秒
41.
The effect of confinement within some zeolitic structures on the activity and selectivity of metallocene catalysts for the ethylene oligomerization has been investigated using grand canonical Monte Carlo simulations (GCMC). The following zeolite (host) frameworks displaying different pore sizes, have been studied as solid hosts: mazzite (MAZ), AIPO-8 (AET), UTD-1F (DON), faujasite (FAU), and VPI-5 (VFI). Intermediates and transition states involved in the ethylene trimerization reaction catalyzed by a Ti-based catalyst [(η(5)-C(5)H(4)CMe(2)C(6)H(5))TiCl(3)/MAO] have been used as sorbates (guests). We have demonstrated linear correlations with slope a(H,j) between the adsorption enthalpy and the molecular volume V(m) of the sorbates, each holding for a given microporous host below a host-specific threshold V(mmax,j). Beyond this maximal molecular volume, the adsorption vanishes due to steric exclusion. a(H,j) increases, and V(mmax,j) decreases with decreasing host pore size, in line with the confinement concept. We moreover showed that, in the limit of vanishing loading (Henry regime), the enthalpies and entropies of adsorption in a given host are linearly correlated. We have defined a host-specific confinement compensation temperature a(j), which refers to a temperature where the stabilizing adsorption enthalpic interactions are canceled out against the loss in entropy. However, calculated a(j) are much larger than the operating temperatures. With a setup microkinetic model, we predict that the activity and selectivity of the confined Ti-catalyst in ethylene oligomerization can be significantly altered with respect to homogeneous phase conditions, since the adsorption free energies of transition states and intermediates also become functions of a(H,j) and V(m). We have applied this theory to predict the optimum host pore size to get maximum α-octene production, instead of α-hexene, which is primarily produced in the homogeneous phase. We also predict a significantly increased activity for confined catalysts. 相似文献
42.
Seguin J Moutiez M Li Y Belin P Lecoq A Fonvielle M Charbonnier JB Pernodet JL Gondry M 《Chemistry & biology》2011,18(11):1362-1368
Cyclodipeptide synthases (CDPSs) are small enzymes structurally related to class-I aminoacyl-tRNA synthetases (aaRSs). They divert aminoacylated tRNAs from their canonical role in ribosomal protein synthesis, for cyclodipeptide formation. All the CDPSs experimentally characterized to date are?bacterial. We show here that a predicted CDPS from the sea anemone Nematostella vectensis is an active CDPS catalyzing the formation of various cyclodipeptides, preferentially containing tryptophan. Our findings demonstrate that eukaryotes encode active CDPSs and suggest that all CDPSs have?a similar aminoacyl-tRNA synthetase-like architecture and ping-pong mechanism. They also raise questions about the biological roles of the cyclodipeptides produced in bacteria and eukaryotes. 相似文献
43.
Ferreira BS de Almeida CG Faza LP de Almeida A Diniz CG da Silva VL Grazul RM Le Hyaric M 《Molecules (Basel, Switzerland)》2011,16(7):5875-5885
Pequi (Caryocar brasiliense Camb.), baba?u (Orbignya phalerata Mart.), buriti (Mauritia flexuosa), and passion fruit (Passiflora edulis) oils were studied to determine their antibacterial, antioxidant and cytotoxic activities, as well as their total phenol and carotenoid contents. The fatty acid contents were determined by GC-MS. The three types of passion fruit oils studied were refined, cold pressed or extracted from seeds in a Soxhlet apparatus. The oils thus obtained showed differences in antioxidant activity and carotenoid content, but were similar in regard to total phenols. Buriti and pequi had the highest carotenoid contents, while refined and cold pressed passion fruit oil displayed the highest antioxidant activity. Pequi oil was the only oil to display antibacterial and cytotoxic activity. 相似文献
44.
Mireille Bossy Jean-François Jabir 《Stochastic Processes and their Applications》2011,121(12):2751-2775
We construct a confined Langevin type process aimed to satisfy a mean no-permeability condition at the boundary. This Langevin process lies in the class of conditional McKean Lagrangian stochastic models studied by Bossy, Jabir and Talay (2010) [5]. The confined process considered here is a first construction of solutions to the class of Lagrangian stochastic equations with boundary condition issued by the so-called PDF methods for Computational Fluid Dynamics. We prove the well-posedness of the confined system when the state space of the Langevin process is a half-space. 相似文献
45.
Mireille Bousquet-Mélou 《Journal of Algebraic Combinatorics》2011,33(4):571-608
We recover Gessel’s determinantal formula for the generating function of permutations with no ascending subsequence of length
m+1. The starting point of our proof is the recursive construction of these permutations by insertion of the largest entry.
This construction is of course extremely simple. The cost of this simplicity is that we need to take into account in the enumeration
m−1 additional parameters—namely, the positions of the leftmost increasing subsequences of length i, for i=2,…,m. This yields for the generating function a functional equation with m−1 “catalytic” variables, and the heart of the paper is the solution of this equation. 相似文献
46.
47.
Salas G Podgoršek A Campbell PS Santini CC Pádua AA Costa Gomes MF Philippot K Chaudret B Turmine M 《Physical chemistry chemical physics : PCCP》2011,13(30):13527-13536
Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface. 相似文献
48.
Four M Riehl D Mongin O Blanchard-Desce M Lawson-Daku LM Moreau J Chauvin J Delaire JA Lemercier G 《Physical chemistry chemical physics : PCCP》2011,13(38):17304-17312
In this article, the synthesis of a novel high-conjugated ligand and its corresponding Ru(II) complex PTFTF:Ru is reported, along with the linear and nonlinear optical characterizations. Two-photon absorption based optical power limiting properties (OPL), especially in the near infrared, are described and compared to those of the analogous complexes previously published. Combined with a preliminary theoretical approach, this allows us to highlight several key parameters for OPL optimization in such molecular systems and more particularly the spectral overlap between TPA and excited-state absorption. 相似文献
49.
Dr. Oumaïma Gharbi Dr. Mai T. T. Tran Prof. Mark E. Orazem Dr. Bernard Tribollet Dr. Mireille Turmine Dr. Vincent Vivier 《Chemphyschem》2021,22(13):1371-1378
The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution. 相似文献
50.
Gérald Perron François Quirion Daniel Lambert Jean Ledoux Lahouari Ghaicha R. Bennes Mireille Privat Jacques E. Desnoyers 《Journal of solution chemistry》1993,22(2):107-124
Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques. 相似文献