全文获取类型
收费全文 | 1872篇 |
免费 | 83篇 |
国内免费 | 8篇 |
专业分类
化学 | 1438篇 |
晶体学 | 4篇 |
力学 | 50篇 |
数学 | 248篇 |
物理学 | 223篇 |
出版年
2023年 | 15篇 |
2022年 | 53篇 |
2021年 | 89篇 |
2020年 | 45篇 |
2019年 | 42篇 |
2018年 | 21篇 |
2017年 | 34篇 |
2016年 | 63篇 |
2015年 | 61篇 |
2014年 | 75篇 |
2013年 | 102篇 |
2012年 | 116篇 |
2011年 | 149篇 |
2010年 | 79篇 |
2009年 | 89篇 |
2008年 | 126篇 |
2007年 | 125篇 |
2006年 | 116篇 |
2005年 | 109篇 |
2004年 | 86篇 |
2003年 | 74篇 |
2002年 | 71篇 |
2001年 | 21篇 |
2000年 | 19篇 |
1999年 | 17篇 |
1998年 | 16篇 |
1997年 | 13篇 |
1996年 | 17篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 10篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 14篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1971年 | 2篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1911年 | 1篇 |
1909年 | 2篇 |
排序方式: 共有1963条查询结果,搜索用时 852 毫秒
61.
62.
Oxidation of 5×10−3 M noradrenaline in aqueous phosphate buffer, pH 7.4, with K3Fe(CN)6, NaIO4 or Fe2+/EDTA/H2O2 followed by extraction with ethyl acetate and acetylation with Ac2O/Pyr led to a main reaction product which was isolated and identified as 4-[bis-(1H-5,6-diacetoxyindol-2-yl)methyl]-1,2-diacetoxybenzene, an unprecedented [bis-(indol-2-yl)methyl]-benzene derivative unsubstituted on the 3-position of the indole rings. This product was also obtained in 40% yield by reaction of 5,6-dihydroxyindole with 3,4-dihydroxybenzaldehyde. Other components of the oxidation mixture were 1-acetyl-3,5,6-triacetoxyindole, derived from noradrenolutin, and 5,6-diacetoxyindole, originating from cyclisation/dehydration of the o-quinone of noradrenaline, along with some 3,4-diacetoxybenzaldehyde. Inspection of the aqueous phase revealed the presence of 3,4-dihydroxymandelic acid and 3,4-dihydroxybenzaldehyde, derived from oxidative breakdown of the 2-amino-1-hydroxyethyl chain via a p-quinomethane intermediate. These results disclose new aspects of the oxidative chemistry of noradrenaline beyond the aminochrome stage and provide a route to novel [bis-(indol-2-yl)methyl]-benzene derivatives of potential pharmacological interest. 相似文献
63.
Paola Maggiorotti 《Journal of Thermal Analysis and Calorimetry》1992,38(12):2749-2758
The RC1 calorimeter revealed itself a suitable instrument to obtain information about safety and mechanisms involved in the reaction between cyclohexanecarboxylic acid (AEB) and oleum. A previous hypothesis about the existence of an unstable intermediate was confirmed and its heat of formation was calculated. The heat of sulphonation related to undesirable by-products production and the heat of protonation of AEB with H2SO4 were also evaluated. Therefore, it was possible to distinguish the reactions involved in the process and, through their thermal behaviour, to determine the limit conditions to avoid the by-products formation.
Zusammenfassung Das RC1 Kalorimeter erwies sich als ein geeignetes Instrument, um Informationen über Sicherheit und Mechanismen bei der Reaktion von Cyclohexancarbonsäure (AEB) und Oleum zu gewinnen. Eine bereits bestehende Hypothese über die Existenz eines instabilen Zwischenproduktes konnte bestätigt und dessen Bildungswärme berechnet werden. Weiterhin wurde auch die Sulphonierungswärme bezogen auf die Entstehung von unerwünschten Nebenprodukten und die Protonierungswärme von AEB durch H2SO4 ermittelt. Es ist deshalb möglich, die einzelnen Reaktionen innerhalb dieses Prozesses über ihr thermisches Verhalten voneinander zu unterscheiden, um die Grenzbedingungen zur Vermei-dung der Bildung von Nebenprodukten zu ermitteln.相似文献
64.
(2S)- and (2R)-2-Amino-4-bromobutanoic acid were prepared starting from N-Boc-glutamic acid α tert-butyl ester. The double tert-butyl protection was necessary to prevent a partial racemisation during Barton’s radical decarboxylation used to transform the γ-carboxylic group into a bromide. This bromide reacted with different nitrogen, oxygen and sulphur nucleophiles to give nonnatural amino acids characterised by basic or heterocyclic side chains. The title compound was also used to prepare a conformationally constrained peptidomimetic. 相似文献
65.
S. M. Dal Bosco R. S. Jimenez C. Vignado J. Fontana B. Geraldo F. C. A. Figueiredo D. Mandelli W. A. Carvalho 《Adsorption》2006,12(2):133-146
The adsorption capacities of commercial and Brazilian natural clays were evaluated to test their applications in wastewater
control. We investigated the process of sorption of manganese(II) and cadmium(II) present in synthetic aqueous effluents,
by calculating the adsorption isotherms at 298 K using batch experiments. The influence of temperature and pH on the adsorption
process was also studied. Adsorption of metals was best described by a Langmuir isotherm, with values of Q
0 parameter, which is related to the sorption capacity, corresponding to 6.3 mg g− 1 for K-10/Cd(II), 4.8 mg g− 1 for K-10/Mn(II), 11.2 mg g− 1 for NT-25/Cd(II) and 6.0 mg g− 1 for NT-25/Mn(II). We observed two distinct adsorption mechanisms that may influence adsorption. At the first 5 min of interaction,
a cation exchange mechanism that takes place at exchange sites located on (001) basal planes is predominant. This process
is inhibited by low pH values. After this first and fast step, a second sorption mechanism can be related to formation of
inner-sphere surface complexes, which is formed at edges of the clay. The rate constants and the initial sorption rates correlate
positively with temperature in all studied systems, denoting the predominance of a physisorption process. The addition of
complexing agents that are incorporated within the K10 structure, enhance metal uptake by the adsorbent. The results have
shown that both Cd(II) and Mn(II) were totally retained from a 50 mg L− 1 solution when K10 grafted with ammonium pyrrolidinedithiocarbamate (APDC) was used as adsorbent. 相似文献
66.
Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces
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)
Essi Sariola‐Leikas Dr. Zafar Ahmed Dr. Paola Vivo Anniina Ojanperä Dr. Kimmo Lahtonen Jesse Saari Prof. Mika Valden Prof. Helge Lemmetyinen Dr. Alexander Efimov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1501-1510
Terpyridine‐substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl‐crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn2+ ions allowed for layer‐by‐layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid‐state dye‐sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed. 相似文献
67.
68.
Dr. Gabriel Menendez Rodriguez Dr. Francesco Zaccaria Leonardo Tensi Prof. Cristiano Zuccaccia Prof. Paola Belanzoni Prof. Alceo Macchioni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):2050-2064
The degradation pathways of highly active [Cp*Ir(κ2-N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO3), 2 undergoes partial protonation of the amide moiety, inducing rapid κ2-N,N to κ2-N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ2-N,N key intermediate of FA dehydrogenation ( INH ), bearing a N-protonated pica, can easily transform into the κ2-N,O analogue ( INH2 ; ΔG≠≈11 kcal mol−1, ΔG ≈−5 kcal mol−1). Intramolecular hydrogen liberation from INH2 is predicted to be rather prohibitive (ΔG≠≈26 kcal mol−1, ΔG≈23 kcal mol−1), indicating that FA dehydrogenation should involve mostly κ2-N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c . DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible. 相似文献
69.
Recently, some of us reviewed the synthes is and chemical reactions of conjugated azoalkenes.1 Emphasis was placed on the fact that these derivatives represent at the same time interesting products and useful intermediates in organic chemistry. In fact, conjugated azoolefins undergo a wide range of 1,4-additions, (3+2)- and (4+2)-cycloadditions allowing various functionalizations of the carbon atom adjacent to the carbonyl group, and the construction of many types of interesting five - and six-membered heterocycles, such as widely substituted pyrrole and pyridazine rings. These relevant synthetic objectives appear not to be smoothly obtained by other procedures. In addition, many of the compounds produced from conjugated azoalkenes can profitably be employed in the preparation of natural, pharmaceutical, and phytopharmaceutical products.1 相似文献
70.
Yanpeng Xue Eirini Maria Paschalidou Paola Rizzi Livio Battezzati Hans-Jörg Fecht 《哲学杂志》2018,98(30):2769-2781
Nanoporous gold thin films have been fabricated through chemical de-alloying of Au-based nanoglass with a nanocolumnar structure, with composition Au40Cu28Ag7Pd5Si20 (at.%), that had previously been deposited by magnetron sputtering. By varying the de-alloying conditions, gold ligaments ranging from 20 to 100?nm were obtained. The microstructure and chemical composition of the as-prepared films were characterised by various techniques. Surface-enhanced Raman scattering (SERS) of thin films was investigated using rhodamine 6G. The results indicate that the main microstructural features with interconnected ligaments and defects of nanoporous gold result in significant SERS enhancement. 相似文献