全文获取类型
收费全文 | 295篇 |
免费 | 14篇 |
专业分类
化学 | 215篇 |
力学 | 8篇 |
数学 | 43篇 |
物理学 | 43篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 19篇 |
2020年 | 8篇 |
2019年 | 11篇 |
2018年 | 5篇 |
2017年 | 8篇 |
2016年 | 8篇 |
2015年 | 10篇 |
2014年 | 8篇 |
2013年 | 10篇 |
2012年 | 8篇 |
2011年 | 14篇 |
2010年 | 20篇 |
2009年 | 17篇 |
2008年 | 15篇 |
2007年 | 15篇 |
2006年 | 12篇 |
2005年 | 22篇 |
2004年 | 15篇 |
2003年 | 11篇 |
2002年 | 8篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1983年 | 5篇 |
1982年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1933年 | 2篇 |
1929年 | 1篇 |
排序方式: 共有309条查询结果,搜索用时 15 毫秒
1.
Two different problems are proposed as approximations of the usual system modelling natural convection under the Oberbeck-Boussinesq assumptions. The error is evaluated by means of the norm of its gradient in the Hilbert space. The average Nusselt number is also estimated. 相似文献
2.
M. A. Macrì C. Del Gratta L. Di Donato S. Di Luzio G. L. Romani S. Della Penna A. Pasquarelli 《Il Nuovo Cimento D》1994,16(5):425-432
Summary A preliminary study is here reported on a new potential marker for biomagnetic measurements. The marker consists of superparamagnetic
polymer microspheres which were detected in the presence of external steady magnetic fields by means of an r.f.-SQUID magnetometer.
The particles were prepared in samples differing in the concentration value and immersed in a homogeneous magnetic field of
variable intensity. A simple model was taken into account for the distribution of the microspheres in the samples, so that
the theoretical values were compared to the marker field values measured by the biomagnetic sensor. The overall sensitivity
of the experimental apparatus and the minimum concentration value of the marker were then estimated. 相似文献
3.
Extremely localized molecular orbitals (ELMOs), namely orbitals strictly localized on molecular fragments, are easily transferable from one molecule to another one. Hence, they provide a natural way to set up the electronic structure of large molecules using a data base of orbitals obtained from model molecules. However, this procedure obviously increases the energy with respect to a traditional MO calculation. To gain accuracy, it is important to introduce a partial electron delocalization. This can be carried out by defining proper optimal virtual orbitals that supply an efficient set for nonorthogonal configurations to be employed in VB-like expansions. 相似文献
4.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
5.
Summary The aim of this investigation was to obtain qualitative and quantitative profiles of the flavonoid and biflavonoid composition
of six cypress species—Cupressus funebris L.,Cupressus sempervirens L.,Cupressus glabra L.,Cupressus arizonica L.,Cupressus goveniana L., andCupressus lusitanica L. HPLC-diode-array detection (DAD), HPLC-MS, and HPTLC were used to identify the individual compounds. A chromatographic
method was optimized for identification and quantification of the main flavonoid glycosides and biflavonoids. The flavonoids
identified and calibrated were: rutin, quercetin glucoside, quercetin rhamnoside, and kaempferol 3-O-rhamnoside. The biflavonoids identified and calibrated were: cupressuflavone, amentoflavone, robustaflavone, hinokiflavone,
methylrobustaflavone, methylamentoflavone, and dimethylcupressuflavone. 相似文献
6.
Organic templates for the generation of inorganic materials 总被引:6,自引:0,他引:6
van Bommel KJ Friggeri A Shinkai S 《Angewandte Chemie (International ed. in English)》2003,42(9):980-999
Mankind's fascination with shapes and patterns, many examples of which come from nature, has greatly influenced areas such as art and architecture. Science too has long since been interested in the origin of shapes and structures found in nature. Whereas organic chemistry in general, and supramolecular chemistry especially, has been very successful in creating large superstructures of often stunning morphology, inorganic chemistry has lagged behind. Over the last decade, however, researchers in various fields of chemistry have been studying novel methods through which the shape of inorganic materials can be controlled at the micro- or even nanoscopic level. A method that has proven very successful is the formation of inorganic structures under the influence of (bio)organic templates, which has resulted in the generation of a large variety of structured inorganic structures that are currently unattainable through any other method. 相似文献
7.
Friggeri A Gronwald O van Bommel KJ Shinkai S Reinhoudt DN 《Journal of the American Chemical Society》2002,124(36):10754-10758
The synthesis of a new saccharide-based gelator (2) containing a donor moiety has been described. Gelation experiments of a dual-component gel consisting of a saccharide-based gelator bearing an acceptor group (1) and of 2 have been performed in a variety of organic solvents and water. Moreover, gelation tests at different molar ratios of 1 and 2 have been performed in water, octanol, and diphenyl ether. In these last two solvents a gel color change was observed, from colorless to yellow, upon cooling of the sample to room temperature. This phenomenon was further investigated by UV-visible spectroscopy, which revealed the presence of charge-transfer interactions in the gel, in octanol. Temperature-dependence UV spectroscopy confirmed that such interactions occur in the gel but not in the corresponding solution sample. Furthermore, T(gel) measurements show that dual-component gels of 1 and 2 present increased thermal stability at a 50:50 ratio of the two gelators, in dependence of the solvent. Transmission electron microscopy (TEM) images of the single-component gels in diphenyl ether revealed that they consist of a fibrous network, while the dual-component gel presents a novel, helical, fibrous-bundle structure. 相似文献
8.
Atmospheric bulk deposition of major and trace elements was measured at Venice from November 1995 to October 1997. Collection was carried out using polyethylene bulk passive samplers, samples being collected bi-weekly. In order to highlight the contribution of the atmosphere to water chemistry and particle budgets in the Lagoon of Venice, the geochemical composition (Si, Al, Ca, Mg, K, Na, Mn, Cr, Zn, Pb, Cd, Cu, As) of dissolved and insoluble bulk fractions was determined by AAS + ICP mass spectrometry. Great sample variability was found, with almost two orders of magnitude between maximum and minimum values for several metals. All fluxes in 1995/96 were 30% lower than in 1996/97, ranging from -3% (Ca) to -57% (Li), except for Zn, Cd and As. On the contrary, the solubility of all elements decreased during 1996/97. Partitioning between soluble and insoluble phases shows that Al, Cr, Fe and Si are mainly in the insoluble form, whereas for As, Ca, Cu, Mg, Na, Ni, K, Pb and Zn the dissolved fraction represents 50-90% of total input. The amount of particle load affects partitioning between dissolved and particulate, especially for Al and Pb. Seasonal variability was evident. The lowest pH values (approximately 5.2) were recorded in winter, causing an increase of solubility for all metals except for As, which showed the highest solubility in summer. 相似文献
9.
Gianfranco Cainelli Paola Galletti Daria Giacomini Andrea Gualandi Arianna Quintavalla 《Helvetica chimica acta》2003,86(11):3548-3559
The enantiomeric ratio E of enzyme‐catalyzed (Candida antarctica lipase and lipase PS) and chemo‐catalyzed (L ‐proline‐based diamines) acylation reactions of 1‐(naphthalen‐2‐yl)ethanol, 2‐phenylpropanol, and 2‐benzylpropane‐1,3‐diol is dependent on solvent and temperature. Plots of ln E vs. 1/T showed the presence of inversion temperatures (Tinv). The Tinv values for the bio‐catalyzed and the chemo‐catalyzed reactions are fairly in agreement, and correspond as well to the TNMR values obtained by variable‐temperature 13C‐NMR experiments on the substrates in the same solvent of the resolution. This result demonstrates that clustering effects in the substrate solvation manage the chemical and the enzymatic enantioselectivity, and, moreover, that the solute? solvent cluster is always the real reacting species in solution for chemical as well as for enzymatic reactions. 相似文献
10.
Eulogio Jimenez Luis Romani Maria Inmaculada Paz Andrade Geneviève Roux-Desgranges Jean-Pierre E. Grolier 《Journal of solution chemistry》1986,15(11):879-890
Molar excess volumes V
E
at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H
2m+1
C
m
COOC
n
H
2n+1
)+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C
p
E
at constant pressure at the same temperature. V
E
is positive for all systems and rather symmetric, with V
E
(x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C4H8O2, C5H10O2, or C6H12O2). The composition dependence of C
p
E
is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane. 相似文献