全文获取类型
收费全文 | 286篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 244篇 |
数学 | 12篇 |
物理学 | 33篇 |
无线电 | 13篇 |
出版年
2022年 | 3篇 |
2021年 | 10篇 |
2020年 | 3篇 |
2019年 | 2篇 |
2017年 | 2篇 |
2016年 | 15篇 |
2015年 | 2篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 13篇 |
2011年 | 8篇 |
2010年 | 5篇 |
2009年 | 10篇 |
2008年 | 9篇 |
2007年 | 8篇 |
2006年 | 13篇 |
2005年 | 15篇 |
2004年 | 12篇 |
2003年 | 13篇 |
2002年 | 8篇 |
2001年 | 6篇 |
2000年 | 5篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 5篇 |
1979年 | 6篇 |
1978年 | 1篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 5篇 |
1974年 | 4篇 |
1973年 | 5篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1970年 | 3篇 |
1969年 | 3篇 |
1967年 | 2篇 |
1965年 | 2篇 |
1964年 | 1篇 |
1963年 | 1篇 |
排序方式: 共有302条查询结果,搜索用时 156 毫秒
91.
92.
93.
94.
Botta M Quici S Pozzi G Marzanni G Pagliarin R Barra S Geninatti Crich S 《Organic & biomolecular chemistry》2004,2(4):570-577
Five novel Gd(iii) complexes based on the structure of the heptadentate macrocyclic 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) ligand have been synthesized and their (1)H and (17)O NMR relaxometric properties investigated in detail. The complexes have been functionalised on the secondary nitrogen atom of the macrocyclic ring with different pendant groups for promoting their ability to interact non-covalently with human serum albumin (HSA). The analysis of the proton relaxivity, measured as a function of pH and magnetic field strength, have revealed that the three complexes bearing a poly(ethylene glycol)(PEG) chain possess a single coordinated water molecule, whereas the complexes functionalised with 1-[3-(2-hydroxyphenyl)]-propyl and 1-[3-(2-carboxyphenyloxy)]-propyl pendant groups have two inner sphere water molecules. The water exchange rates, measured by variable temperature (17)O NMR, cover a broad range of values (from 18 to 770 ns) as a function of their charge, the chemical nature of the substituent and its ability to organize a second sphere of hydration near the water(s) binding site. All the complexes have shown some degree of interaction with HSA, with a stronger binding affinity measured for those bearing an aromatic moiety on the pendant group. However, upon binding the expected relaxation enhancement has not been observed and this has been explained with the displacement of the coordinated water molecules by the protein and formation of ternary adducts. 相似文献
95.
[reaction: see text] A new cellulose-supported reagent for the synthesis of guanidine in aqueous medium is reported starting from commercially available functionalized cellulose beads. Primary and secondary amines, anilines, and amino acids were transformed to the corresponding guanidines in high yields and under very mild conditions. 相似文献
96.
Gabriella Pinto Sabrina De Pascale Maria Aponte Andrea Scaloni Francesco Addeo Simonetta Caira 《Molecules (Basel, Switzerland)》2021,26(8)
Plant polyphenols have beneficial antioxidant effects on human health; practices aimed at preserving their content in foods and/or reusing food by-products are encouraged. The impact of the traditional practice of the water curing procedure of chestnuts, which prevents insect/mould damage during storage, was studied to assess the release of polyphenols from the fruit. Metabolites extracted from pericarp and integument tissues or released in the medium from the water curing process were analyzed by matrix-assisted laser desorption ionization-time of flight-mass spectrometry (MALDI-TOF-MS) and electrospray-quadrupole-time of flight-mass spectrometry (ESI-qTOF-MS). This identified: (i) condensed and hydrolyzable tannins made of (epi)catechin (procyanidins) and acid ellagic units in pericarp tissues; (ii) polyphenols made of gallocatechin and catechin units condensed with gallate (prodelphinidins) in integument counterparts; (iii) metabolites resembling those reported above in the wastewater from the chestnut curing process. Comparative experiments were also performed on aqueous media recovered from fruits treated with processes involving: (i) tap water; (ii) tap water containing an antifungal Lb. pentosus strain; (iii) wastewater from a previous curing treatment. These analyses indicated that the former treatment determines a 6–7-fold higher release of polyphenols in the curing water with respect to the other ones. This event has a negative impact on the luster of treated fruits but qualifies the corresponding wastes as a source of antioxidants. Such a phenomenon does not occur in wastewater from the other curing processes, where the release of polyphenols was reduced, thus preserving the chestnut’s appearance. Polyphenol profiling measurements demonstrated that bacterial presence in water hampered the release of pericarp metabolites. This study provides a rationale to traditional processing practices on fruit appearance and qualifies the corresponding wastes as a source of bioactive compounds for other nutraceutical applications. 相似文献
97.
We correct a Feynman diagram presented in the paper ‘Heavy neutral gauge bosons at the LHC in an extended MSSM’, published in Nuclear Physics B 866 (2013) 293. 相似文献
98.
Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations
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. Debora Scuderi Prof. Enrico Bodo Dr. Barbara Chiavarino Prof. Simonetta Fornarini Prof. Maria Elisa Crestoni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17239-17250
The redox activity of cysteine sulfur allows numerous post‐translational protein modifications involved in the oxidative regulation of metabolism, in metal binding, and in signal transduction. A combined approach based on infrared multiple photon dissociation spectroscopy at the Centre Laser Infrarouge d'Orsay (CLIO) free electron laser facility, calculations of IR frequencies, and finite temperature ab initio molecular dynamics simulations has been employed to characterize the gas‐phase structures of deprotonated cysteine sulfenic, sulfinic, and sulfonic acids, [cysSOx]? (x=1, 2, 3, representing the number of S‐bound oxygen atoms), which are key intermediates in the redox‐switching chemistry of proteins. The ions show different structural motifs owing to preferential binding of the proton to either the carboxylate or sulfur‐containing group. Due to the decreasing basicity of the sulfenic, sulfinic, and sulfonic terminals, the proton bound to SO? in [cysSO]? migrates to the carboxylate in [cysSO3]?, whereas it turns out to be shared in [cysSO2]?. Evidence is gathered that a mixture of close‐lying low‐energy conformers is sampled for each cysteine oxo form in a Paul ion trap at room temperature. 相似文献
99.
100.
Effects of Aromatic Fluorine Substitution on Protonated Neurotransmitters: The Case of 2‐Phenylethylamine
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)
M. Sc. Markus Schütz Dr. Aude Bouchet Prof. Barbara Chiavarino Prof. Maria Elisa Crestoni Prof. Simonetta Fornarini Prof. Otto Dopfer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8124-8136
Fluorination of pharmaceutical compounds is a common tool to modulate their physiochemical properties. We determine the effects of site‐specific aromatic fluorine substitution on the geometric, energetic, vibrational, and electronic properties of the protonated neurotransmitter 2‐phenylethylamine (xF‐H+PEA, x=ortho, meta, para) by infrared multiphoton photodissociation (IRMPD) in the fingerprint range (600–1750 cm?1) and quantum chemical calculations at the B3LYP‐D3/aug‐cc‐pVTZ level. The IRMPD spectra of all ions are assigned to their folded gauche conformers stabilized by intramolecular NH+???π hydrogen bonds (H‐bonds) between the protonated amino group and the aromatic ring. H→F substitution reduces the symmetry and allows for additional NH+???F interactions in oF‐H+PEA, leading to three distinct gauche conformers. In comparison to oF‐H+PEA, the fluorination effects on the energy landscape (energy ordering and isomerization barriers) in pF‐H+PEA and mF‐H+PEA with one and two gauche conformers are less pronounced. The strengths of the intramolecular NH+???F and NH+???π bonds are analyzed by the noncovalent interaction (NCI) method. 相似文献