全文获取类型
收费全文 | 390篇 |
免费 | 11篇 |
国内免费 | 1篇 |
专业分类
化学 | 212篇 |
晶体学 | 1篇 |
力学 | 13篇 |
数学 | 49篇 |
物理学 | 127篇 |
出版年
2022年 | 5篇 |
2021年 | 10篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 14篇 |
2015年 | 9篇 |
2014年 | 10篇 |
2013年 | 28篇 |
2012年 | 22篇 |
2011年 | 15篇 |
2010年 | 14篇 |
2009年 | 23篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 14篇 |
2005年 | 17篇 |
2004年 | 9篇 |
2003年 | 9篇 |
2002年 | 17篇 |
2001年 | 9篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 8篇 |
1995年 | 4篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1976年 | 4篇 |
1973年 | 1篇 |
1957年 | 1篇 |
1932年 | 1篇 |
排序方式: 共有402条查询结果,搜索用时 15 毫秒
11.
A. Mañanes M. Membrado J. Sañudo A. F. Pacheco L. C. Balbás 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,19(4):55-58
An analytic expression for the total energy of metallic clusters composed ofN identical atoms of valencev and with net chargeQ is obtained by means of a variational solution of the Thomas-Fermi-Weizsäcker energy density functional within the spherical jellium model. The minimum energy is given as an expansion in decreasing powers of the cluster radiusR=r s Z 1/3, withZ=vN andr s the radius per electron of the bulk metal. The coefficients are obtained as functions ofr s . Terms of volume (R 3), surface (R 2), curvature (R), constant (R 0), (1/R) and (1/R 2) are clearly separated in the formula, as well as the different contributions (kinetic, coulombic and exchange-correlation) to each of them. The asymptotic values (R→∞) for the work functions,W(r s ), and surface energies σ(r s ), are compared to analogous semiclassical and Kohn-Sham calculations of jellium-like surfaces and to the experimental values. The size dependent behaviour of chemical potentials, μ(R), electron affinities,AF(R), and ionization potentials,IP(R), are easily obtained for any kind of metallic clusters. In particular we discuss the Coulomb and quantum corrections to the coefficients β, δ in the asymptotic formulae:IP?W+β/R andAF?W+δ/R. 相似文献
12.
13.
Synthesis of the new l,3-dioxa-9-azaspiro[5.5]undecane ring, was realized by the scheme represented in Figure 2. Butyro-phenones 6 posses neuroleptic activity similar to that of halo-peridol. The pharmacological activity was reported in another publication (2). Conformational study of l,3-dioxa-9-azaspiro-[5.5]undecanes shows the existence of four conformations A, B, C and D, which are shown in Figure 4. The existence of these conformations depends on the nature of the substituents R and R' on the dioxane ring. Thus, in the compounds where R ≠ H, R' = H, the four conformations are possible with a preponderance of A and B. If R and R' are different from H only the conformation A is present in 99% concentration. Lastly, when R = R' = H, the four conformations are possible with equal population for the couple A, B and the couple C, D; the first couple predominating. The presence of a fluorophenylbutyric moiety on the piperidine nitrogen does not seem to stereochemically modify the heterocyclic group. 相似文献
14.
F.?Pacheco M.?González A.?Medina S.?Velumani J.A.?AscencioEmail author 《Applied Physics A: Materials Science & Processing》2004,78(4):531-536
In this work we report the synthesis of nanocomposites based on nanoparticles of cobalt titanate and titanium dioxide in their anatase crystalline phase by a sol–gel process. The synthesized nanoparticles of titanate vary from 1 to 6 nm in size. They are embedded in the anatase matrix, and they were obtained from TiO2 monoliths doped with Co2+. The formation of cobalt titanate nanoparticles showed a linear dependence on the cobalt concentration. The cobalt titanate nanocrystals are very stable even at temperatures higher than 1000 °C. The crystalline structures of the samples were examined using high-resolution transmission electron microscopy and X-ray diffraction. Molecular simulation methods were utilized for a better understanding and for improving the analytical data interpretation of the experimental results. PACS 61.16.Bg; 79.60.Jv; 61.46.+w; 61.50.Ah 相似文献
15.
Determination of selenium in bread-wheat samples grown under a Se-supplementation regime in actual field conditions 总被引:1,自引:0,他引:1
C. Galinha M. C. Freitas A. M. G. Pacheco J. Coutinho B. Maçãs A. S. Almeida 《Journal of Radioanalytical and Nuclear Chemistry》2012,291(1):231-235
Selenium is an essential micronutrient for humans and animals, yet it is deficient in at least one billion people worldwide.
Plants and plant-derived products transfer the soil-uptaken selenium to humans; therefore, the cultivation of plants enriched
in selenium can be an effective way to improve the selenium status on humankind. This paper focuses on determining the ability
of bread wheat to accumulate selenium after supplementation. One of the methods for supplementing this element in plants is
foliar application with selenium solutions. These supplemented crop of wheat samples—bread wheat; Triticum aestivum L.—were used to determine if there is an increase of selenium content in cereal grains by comparing them with cereals cultivated
in 2009 and harvested in 2010 with no supplementation. The experiments were done using sodium selenate and sodium selenite
at three different selenium concentrations: 4, 20 and 100 g per hectare. Total Se is assessed by cyclic neutron activation
analysis (CNAA), through short irradiations on the fast pneumatic system (SIPRA) of the Portuguese Research Reactor (RPI-ITN).
The short-lived nuclide 77mSe, that features a half-lifetime of 17.5 s, was used to determine the Se content in SIPRA. The experiment was successful,
since the selenium concentration increased in the cropped grains and reached values up to 35 times the non-supplemented ones. 相似文献
16.
Phosphane-free oxime-derived palladacycle 2 is an efficient precatalyst for the copper-free acylation of terminal alkynes with different carboxylic acid chlorides in toluene in the presence of 3 equiv of TEA as base, giving the corresponding ynones in good yields. The coupling reaction can normally be performed under air or under inert atmosphere when very low catalyst loadings (10(-3) mol % Pd) (turnover numbers (TONs) up to 23,000, turnover frequencies (TOFs) up to 958 h(-1)) or sensitive carboxylic acid chlorides are used. In addition, Pd(OAc)(2) has been shown as an efficient catalyst for the ligandless process, although usually working under higher loading conditions. This new protocol allows one to perform the synthesis of ynones at 110 degrees C, at room temperature, or under microwave irradiation conditions. 相似文献
17.
Pacheco Santos V Del Colle V Batista de Lima R Tremiliosi-Filho G 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):11064-11072
In the present work, ethanol electrooxidation on a Pt(100) electrode modified by different coverage degrees of osmium nanoislands obtained by spontaneous depositions, was extensively studied employing in situ FTIR spectroscopy. A collection of spectra of the ethanol adsorption and oxidation processes was acquired during the first series of a positive potential step, to determine the intermediate species, as well as the main products formed. The spectroscopic results obtained were correlated with conventional electrochemical results obtained by cyclic voltammetry. It was shown that the catalytic activity of Pt(100) for ethanol oxidation increases significantly after osmium deposition and that the mechanistic pathway for this reaction depends directly on the osmium coverage degree. Thus, for low osmium coverage (theta;( Os) up to 0.15) the formation of CO as an intermediate was favored and hence the full oxidation of adsorbed ethanol to CO(2) was increased. For higher osmium coverages (theta;(Os) up to 0.33), the higher the coverage is, the more the direct ethanol oxidation to acetaldehyde and acetic acid is favored. For osmium coverage degree of 0.40, the catalytic activity of the electrode for ethanol oxidation decreased. On an almost complete osmium layer (theta;(Os) = 0.92) obtained by electrodeposition at 50 mV vs reversible hydrogen electrode, the catalytic activity for ethanol oxidation shows a much lower value. 相似文献
18.
Dr. Krishna Kanti Dey Frances Ying Pong Dr. Jens Breffke Dr. Ryan Pavlick Dr. Emmanuel Hatzakis Dr. Carlos Pacheco Dr. Ayusman Sen 《Angewandte Chemie (International ed. in English)》2016,55(3):1113-1117
While momentum transfer from active particles to their immediate surroundings has been studied for both synthetic and biological micron‐scale systems, a similar phenomenon was presumed unlikely to exist at smaller length scales due to the dominance of viscosity in the ultralow Reynolds number regime. Using diffusion NMR spectroscopy, we studied the motion of two passive tracers—tetramethylsilane and benzene—dissolved in an organic solution of active Grubbs catalyst. Significant enhancements in diffusion were observed for both the tracers and the catalyst as a function of reaction rate. A similar behavior was also observed for the enzyme urease in aqueous solution. Surprisingly, momentum transfer at the molecular scale closely resembles that reported for microscale systems and appears to be independent of swimming mechanism. Our work provides new insight into the role of active particles on advection and mixing at the Ångström scale. 相似文献
19.
Pacheco WF Miguel EM Ramos GV Cardoso CE Farias PA Aucélio RQ 《Analytica chimica acta》2008,625(1):22-27
In this work, a new approach is presented to allow interference-free determination of Cu (II) by stripping voltammetry using the bismuth-film electrode. The addition of hydrogen peroxide to the electroanalytical cell has promoted complete resolution between re-dissolution peaks of Bi (III) and Cu (II). The absence of interference could be evaluated by the correlation coefficient (r > 0.99) between Cu (II) concentration and its shifted current peak (at +212 mV) while achieving a slightly fluctuation of the bismuth current peak at −180 mV. Studies were performed aiming towards the optimum conditions for trace determination of Cu (II) using hydrogen peroxide. The methodology was applied to a real sample (sugarcane spirits) and the results were compared to those from graphite furnace atomic absorption spectrometry. The analytical parameters of merit and the results of the analysis indicated that the analytical methodology could be readily used for trace determination of Cu (II). 相似文献
20.