全文获取类型
收费全文 | 366篇 |
免费 | 33篇 |
国内免费 | 2篇 |
专业分类
化学 | 255篇 |
晶体学 | 2篇 |
力学 | 17篇 |
数学 | 30篇 |
物理学 | 97篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 3篇 |
2020年 | 3篇 |
2019年 | 7篇 |
2018年 | 10篇 |
2017年 | 1篇 |
2016年 | 16篇 |
2015年 | 14篇 |
2014年 | 16篇 |
2013年 | 28篇 |
2012年 | 36篇 |
2011年 | 20篇 |
2010年 | 16篇 |
2009年 | 13篇 |
2008年 | 15篇 |
2007年 | 32篇 |
2006年 | 19篇 |
2005年 | 12篇 |
2004年 | 5篇 |
2003年 | 14篇 |
2002年 | 8篇 |
2001年 | 15篇 |
2000年 | 10篇 |
1999年 | 14篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1969年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有401条查询结果,搜索用时 15 毫秒
41.
The carbamoylating agents carbamoyl azides and carbamoyl cyanides (aka cyanoformamides) react with hydroxylamine in different ways, leading in the first case to N-hydroxyureas and, in the case of carbamoyl cyanides, to carbamoyl amidoxime derivatives. The synthetic procedure developed for the latter type of compound, which represents an interesting precursor for heterocyclic structures, allowed the highly efficient preparation of a wide selection of examples. The Z configuration of the double bond in the amidoxime moiety was proposed on the basis of comparison between experimental and calculated (13)C and (15)N NMR chemical shift values for the isopropyl and benzyl derivatives. 相似文献
42.
43.
44.
45.
In this article the dynamics of generic Cr (r ≥ 3) perturbations of complex polynomials are considered. The attention is focused on the determination of the existence
of large or invariant components of the complement of the basin of ∞, where the interesting dynamics occur. 相似文献
46.
Summary This paper discusses the problems associated with the symbolic treatment of functional equations and presents a Mathematica
package for the solution of real functional equations of real variables. The package includes a minimal basic database which
contains a reduced set of functional equations with its four components: equation, domain, class and the corresponding solution.
The word minimal is used in the sense that any equation that is solvable by the system using non-searching methods is excluded
from the database. The package incorporates a searching algorithm which can solve functional equations independently of their
notation and their algebraic representation. Not only general solutions but particular and candidate solutions are dealt with.
This implies a careful analysis of domains and classes. The package includes some methods for solving functional equations,
which are used when the input functional equations are not found in the database. Some methods have been implemented internally
and some are in an external package. Finally, some examples illustrate the use of the package. 相似文献
47.
Macrocyclic Gd3+ Complexes with Pendant Crown Ethers Designed for Binding Zwitterionic Neurotransmitters
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Fatima Oukhatar Hervé Meudal Dr. Céline Landon Prof. Dr. Nikos K. Logothetis Prof. Dr. Carlos Platas‐Iglesias Priv.‐Doz. Dr. Goran Angelovski Dr. Éva Tóth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11226-11237
A series of Gd3+ complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd3+ chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen‐type macrocycle that binds the Ln3+ ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM ?1 s?1 at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by 1H relaxometric titrations of the Gd3+ complexes and by luminescence measurements on the Eu3+ and Tb3+ analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu3+ complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non‐amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved. 相似文献
48.
Carlos A. Iglesias 《High Energy Density Physics》2005,1(1):42-51
It is shown that a quantum kinetic theory approach to line broadening, extended to stationary non-equilibrium states, yields corrections to the standard electron impact widths of isolated lines that depend on the population of the radiator internal levels. A consistent classical limit from a general quantum treatment of the perturbing electrons also introduces corrections to the isolated line widths. Both effects are essential in preserving detailed-balance relations. Preliminary analysis indicates that these corrections may resolve existing discrepancies between theoretical and experimental widths of isolated lines. An experimental test of the results is proposed. 相似文献
49.
Díaz de Greñu B Iglesias Hernández P Espona M Quiñonero D Light ME Torroba T Pérez-Tomás R Quesada R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14074-14083
Synthetic prodiginine obatoclax shows promise as a potential anticancer drug. This compound promotes apoptosis of cancer cells, although the mechanism of action is unclear. To date, only the inhibition of BCL-2 proteins has been proposed as a mechanism of action. To gain insight into other possible modes of action, we have studied the anion-binding properties of obatoclax and related analogues in solution, in the solid state, and by means of density functional theory calculations. These compounds are well suited to interact with anions such as chloride and bicarbonate. The anion-transport properties of the compounds synthesized were assayed in model phospholipid liposomes by using a chloride-selective-electrode technique and (13)C NMR spectroscopy. The results demonstrated that these compounds are efficient anion exchangers that promote chloride, bicarbonate, and nitrate transport through lipid bilayers at very low concentrations. In vitro studies on small-cell lung carcinoma cell line GLC4 showed that active ionophores are able to discharge pH gradients in living cells and the cytotoxicity of these compounds correlates well with ionophoric activity. 相似文献
50.
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