全文获取类型
收费全文 | 514篇 |
免费 | 18篇 |
国内免费 | 1篇 |
专业分类
化学 | 456篇 |
晶体学 | 1篇 |
数学 | 47篇 |
物理学 | 29篇 |
出版年
2023年 | 6篇 |
2022年 | 24篇 |
2021年 | 26篇 |
2020年 | 10篇 |
2019年 | 20篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 24篇 |
2015年 | 19篇 |
2014年 | 18篇 |
2013年 | 33篇 |
2012年 | 26篇 |
2011年 | 25篇 |
2010年 | 22篇 |
2009年 | 20篇 |
2008年 | 34篇 |
2007年 | 26篇 |
2006年 | 25篇 |
2005年 | 30篇 |
2004年 | 21篇 |
2003年 | 30篇 |
2002年 | 15篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1980年 | 3篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1974年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有533条查询结果,搜索用时 15 毫秒
61.
62.
The reaction of S-nitrosocaptopril (NOcap) formation was studied in both aqueous acid and basic medium. Captopril (cap) reacts rapidly with nitrous acid in strong acid medium to give the stable--in the timescale of the experiments--NOcap. The kinetic study of the reaction involving the use of stopped-flow, shows that at low sodium nitrite (nit) concentration, the reaction is first-order in both [nit], [H(+)], and is strongly catalysed by Cl(-) or Br(-) (= X(-)): rate = (k(3) + k(4)[X(-)])[H(+)][nit][cap]. In aqueous buffered solution of acetic acid-acetate the reaction rate is much slower and the decomposition of NOcap was observed; however, the rate of NOcap decay is more than 30-fold slower than its formation. In aqueous basic medium of carbonate-hydrogen carbonate buffer, as well as in alkaline medium, the kinetics of the nitroso group (NO) transfer from tert-butyl nitrite (tBN) to cap was studied using either conventional or stopped flow methods. In mild basic medium, the NOcap decomposes. The NOcap formation is first-order in both tBN and cap concentrations, and the reaction rate increases with pH until to, approximately, pH 11.5, above which value it becomes pH independent or even invariable with the [OH(-)]. Kinetic results show that the thiolate ion of cap is the reactive species. In fact, the presence of anionic micelles of sodium dodecyl sulfate (SDS) inhibits the reaction due to the separation of the reagents; whereas, cationic micelles of tetradecyltrimethylammonium bromide (TTABr) catalyse the reaction at low surfactant concentration due to reagents concentration in the small volume of the micelle. The rate equation is: rate = k(f) K(SH)[cap][tBN]/(K(SH) + [H(+)]). The rate of NOcap decomposition in mild basic medium is first-order in both [cap] and [NOcap], and decreases on increasing pH; but, in alkaline medium the NOcap is stable within the timescale of the experiments. Based on the results, the NOcap decomposition yields the disulfide compound that is formed in the nucleophilic attack of the -SH group of cap to the sulfur electrophilic center of NOcap, -S-N=O. The resulting rate equation is: rate = k(d)[H(+)][cap][NOcap]/(K(SH) + [H(+)]). 相似文献
63.
Muniz-Miranda M Del Rosso T Giorgetti E Margheri G Ghini G Cicchi S 《Analytical and bioanalytical chemistry》2011,400(2):361-367
We investigated the chemisorption of self-assembled monolayers of sulfur-functionalized 4-amino-7-nitrobenzofurazan on gold
and silver nanoisland films (NIFs) by means of surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS).
The ligand is a push–pull molecule, where an intramolecular charge transfer occurs between an electron-donor and an electron-acceptor
group, thus exhibiting nonlinear optical properties that are related to both SERS and SEF effects. The presence of different
heteroatoms in the molecule ensures the possibility of chemical interaction with both silver and gold substrates. The SERS
spectra suggest that furazan is bound to silver via lone pairs of the nitrogen atoms, whereas the ligand is linked to gold
via a sulfur atom. Silver NIFs provide more efficient enhancement of both fluorescence and Raman scattering in comparison
with gold NIFs. The present SEF and SERS investigation could provide useful information for foreseeing changes in the nonlinear
responses of this push–pull molecule. 相似文献
64.
Marcelo Kobelnik Douglas Lopes Cassimiro Adélia Emilia de Almeida Clóvis Augusto Ribeiro Marisa Spirandeli Crespi 《Journal of Thermal Analysis and Calorimetry》2011,105(2):415-419
The Al and In-diclofenac compounds were prepared. Thermogravimetry (TG) and X-ray diffraction powder patterns were used to
characterize these compounds. Details concerning the dehydration and thermal decomposition as well as data of kinetic parameters
have been described here. The kinetic studies of these stages were evaluated from several heating rates with mass sample of
2 and 5 mg in open crucibles under nitrogen atmosphere. The results of the present study improve the knowledge on these compounds
including their dehydration and thermal stability. The obtained data leads to a dependence on the sample mass, which results
in two kinetic behavior patterns. 相似文献
65.
Marandino A De Martino L Mancini E Milella L De Feo V 《Natural product communications》2011,6(11):1735-1738
The essential oils of Hypericum perforatum, H. perfoliatum and H. hircinum, growing in Southern Italy, were analyzed by GC and GC/MS. In the three oils, 111 compounds in all were identified: 53 for the oil of H. hircinum (93.7% of the total oil), 55 for H. perforatum (96.5% of the total oil) and 63 for H. perfoliatum (98.7% of the total oil). The major fraction of the essential oils of H. perforatum and H. hircinum was represented by sesquiterpene hydrocarbons, while the monoterpene alpha-pinene, and the phenol thymol were the most abundant compounds in the essential oil of H. perfoliatum. The oils were evaluated for their potential in vitro phytotoxic activity against germination and early radicle elongation of Raphanus sativus and Lepidium sativum. The germination of this latter was significantly inhibited by the essential oil of H. hircinum, at the highest doses tested, whereas radicle elongation of garden cress was significantly inhibited by the essential oils of H. perfoliatum and H. hircinum. The radicle elongation of radish was inhibited by the essential oil of H. hircinum to a major extent and by H. perforatum and perfoliatum in a minor measure. 相似文献
66.
This paper addresses the problem of determining the best scheduling for Bus Drivers, a $\mathcal{NP}$ -hard problem consisting of finding the minimum number of drivers to cover a set of Pieces-Of-Work (POWs) subject to a variety of rules and regulations that must be enforced such as spreadover and working time. This problem is known in literature as Crew Scheduling Problem and, in particular in public transportation, it is designated as Bus Driver Scheduling Problem. We propose a new mathematical formulation of a Bus Driver Scheduling Problem under special constraints imposed by Italian transportation rules. Unfortunately, this model can only be usefully applied to small or medium size problem instances. For large instances, a Greedy Randomized Adaptive Search Procedure (GRASP) is proposed. Results are reported for a set of real-word problems and comparison is made with an exact method. Moreover, we report a comparison of the computational results obtained with our GRASP procedure with the results obtained by Huisman et al. (Transp. Sci. 39(4):491?C502, 2005). 相似文献
67.
68.
A new, improved sensor for the electrocatalytic determination of ascorbate has been developed that has both a low applied operating potential and a low detection limit. The sensor was constructed by depositing copper hexacyanoferrate film either electrochemically or chemically onto carbon film electrode, and it was then characterised by cyclic voltammetry and electrochemical impedance spectroscopy. Chemically deposited films were shown to be the best for ascorbate determination and were used as an amperometric sensor at +0.05 V versus SCE to determine ascorbate in wines and juice. The linear range extended to 5 mM with a limit of detection of 2.1 M, the sensor was stable for more than four months, and it could be used continuously for at least 20 days. 相似文献
69.
Relating Categorical Semantics for Intuitionistic Linear Logic 总被引:1,自引:0,他引:1
Maria?Emilia?MaiettiEmail author Paola?Maneggia Valeria?de?Paiva Eike?Ritter 《Applied Categorical Structures》2005,13(1):1-36
There are several kinds of linear typed calculus in the literature, some with their associated notion of categorical model. Our aim in this paper is to systematise the relationship between three of these linear typed calculi and their models. We point out that mere soundness and completeness of a linear typed calculus with respect to a class of categorical models are not sufficient to identify the most appropriate class uniquely. We recommend instead to use the notion of internal language when relating a typed calculus to a class of models. After clarifying the internal languages of the categories of models in the literature we relate these models via reflections and coreflections.
Mathematics Subject Classifications (2000) 03G30, 03B15, 18C50, 03B20. 相似文献
70.
基于Ho等人的精确势能面(J. Chem. Phys. 119, 3063(2003))研究,运用准经典轨线方法计算了21.3 kJ/mol碰撞能下反应N(2D)+H2→NH+H和N(2D)+D2→ND+D的产物与反应物之间的矢量相关.发现两个反应的产物角分布都是前向和后向呈现峰值分布,产物的转动角动量矢量j′不仅是取向的,而且是在y轴负方向上定向的.两个反应显示出的同位素效应主要归因于同位素质量的差别. 相似文献