全文获取类型
收费全文 | 617篇 |
免费 | 30篇 |
专业分类
化学 | 532篇 |
晶体学 | 2篇 |
力学 | 13篇 |
数学 | 54篇 |
物理学 | 46篇 |
出版年
2024年 | 1篇 |
2023年 | 8篇 |
2022年 | 21篇 |
2021年 | 26篇 |
2020年 | 22篇 |
2019年 | 13篇 |
2018年 | 18篇 |
2017年 | 3篇 |
2016年 | 28篇 |
2015年 | 33篇 |
2014年 | 19篇 |
2013年 | 37篇 |
2012年 | 32篇 |
2011年 | 52篇 |
2010年 | 31篇 |
2009年 | 33篇 |
2008年 | 45篇 |
2007年 | 38篇 |
2006年 | 27篇 |
2005年 | 36篇 |
2004年 | 19篇 |
2003年 | 25篇 |
2002年 | 22篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1971年 | 1篇 |
1935年 | 2篇 |
1933年 | 1篇 |
1928年 | 4篇 |
1924年 | 2篇 |
排序方式: 共有647条查询结果,搜索用时 0 毫秒
21.
Pereira C Patrício S Silva AR Magalhães AL Carvalho AP Pires J Freire C 《Journal of colloid and interface science》2007,316(2):570-579
Copper (II) acetylacetonate was immobilised directly onto two clays, laponite (Lap) and K10-montmorillonite (K10), and after their amine functionalisation with (3-aminopropyl)triethoxysilane (APTES). All the materials were characterised by nitrogen adsorption isotherms at -196 degrees C, elemental analysis, TG-DSC, XRD, and IR spectroscopy. The K10-based materials were also characterised by XPS. The APTES-functionalised K10 showed higher copper loading than K10, indicating that the clay functionalisation enhanced the complex immobilisation; on the contrary, in Lap-based materials higher metal content was obtained by direct complex anchoring, probably due to the delaminated nature of Lap which induced the particles aggregation on functionalisation with APTES. All the results pointed out that the Cu complex was anchored onto the amine-functionalised clays by Schiff condensation between the amine groups of anchored APTES and the carbonyl groups of the acetylacetonate ligand, whereas direct immobilisation proceeded mostly through interaction between the metal centre and the clay surface hydroxyl groups. 相似文献
22.
Dr. Clara Illescas 《Chemphyschem》2023,24(20):e202300307
A computational study of Be4++H(2s, 2p) collisions has been carried out employing the Classical Trajectory Monte Carlo (CTMC) method for the impact energy range from 20 keV/u to 1000 keV/u. The integral n partial cross sections for H(n) excitation and Be3+(n) electron capture and, the total ionization and electron capture cross sections are calculated and compared to recent semiclassical results. A general good agreement is observed for the n partial and total electron capture and ionization cross sections. The comparative study of the three inelastic processes show no significant differences between both excited targets. 相似文献
23.
From an Icosahedron to a Plane: Flattening Dodecaiodo‐dodecaborate by Successive Stripping of Iodine
Dr. Pau Farràs Dr. Nina Vankova Lei Liu Zeonjuk Jonas Warneke Dr. Thomas Dülcks Prof. Dr. Thomas Heine Prof. Dr. Clara Viñas Prof. Dr. Francesc Teixidor Prof. Dr. Detlef Gabel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(41):13208-13212
It has been shown by electrospray ionization–ion‐trap mass spectrometry that B12I122? converts to an intact B12 cluster as a result of successive stripping of single iodine radicals or ions. Herein, the structure and stability of all intermediate B12In? species (n=11 to 1) determined by means of first‐principles calculations are reported. The initial predominant loss of an iodine radical occurs most probably via the triplet state of B12I122?, and the reaction path for loss of an iodide ion from the singlet state crosses that from the triplet state. Experimentally, the boron clusters resulting from B12I122? through loss of either iodide or iodine occur at the same excitation energy in the ion trap. It is shown that the icosahedral B12 unit commonly observed in dodecaborate compounds is destabilized while losing iodine. The boron framework opens to nonicosahedral structures with five to seven iodine atoms left. The temperature of the ions has a considerable influence on the relative stability near the opening of the clusters. The most stable structures with five to seven iodine atoms are neither planar nor icosahedral. 相似文献
24.
Dr. Albert Ferrer‐Ugalde Dr. Arántzazu González‐Campo Prof. Dr. Clara Viñas Dr. Jesús Rodríguez‐Romero Dr. Rosa Santillan Dr. Norberto Farfán Prof. Dr. Reijo Sillanpää Dr. Antonio Sousa‐Pedrares Dr. Rosario Núñez Prof. Dr. Francesc Teixidor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9940-9951
Two sets of o‐carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene‐containing carboranes 6 – 9 , was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1‐[(9,9‐dioctyl‐fluorene‐2‐yl)ethynyl]carborane ( 11 ) was synthesized by the reaction of 9,9‐dioctyl‐2‐ethynylfluorene and decaborane (B10H14). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4‐(chloromethyl)styrene or 9‐(chloromethyl)anthracene yielded compounds 12 and 13 . Members of the second set of derivatives, comprising anthracene‐containing carboranes, were synthesized by reactions of monolithium or dilithium salts of 1‐Me‐1,2‐C2B10H11, 1‐Ph‐1,2‐C2B10H11, and 1,2‐C2B10H12 with 1 or 2 equivalents of 9‐(chloromethyl)anthracene, respectively, to produce compounds 14 – 16 . In addition, 2 equivalents of the monolithium salts of 1‐Me‐1,2‐C2B10H11 (Me‐o‐carborane) and 1‐Ph‐1,2‐C2B10H11 (Ph‐o‐carborane) were reacted with 9,10‐bis(chloromethyl)anthracene to produce compounds 17 and 18 , respectively. Fluorene derivatives 6 – 9 exhibit moderate fluorescence quantum yields (32–44 %), whereas 11 – 13 , in which the fluorophore is bonded to the Ccluster (Cc), show very low emission intensity (6 %) or complete fluorescence quenching. The anthracenyl derivatives containing the Me‐o‐carborane moiety exhibit notably high fluorescence emissions, with ?F=82 and 94 %, whereas their Ph‐o‐carborane analogues are not fluorescent at all. For these compounds, we have observed a correlation between the Cc?Cc bond length and the fluorescence intensity in CH2Cl2 solution, comparable to that observed for previously reported styrene‐containing carboranes. Thus, our hypothesis is that for systems of this type the fluorescence may be tuned and even predicted by changing the substituent on the adjacent Cc. 相似文献
25.
Clara Strandberg 《European Polymer Journal》2006,42(8):1855-1865
In an earlier study, we have shown that chemiluminescence (CL) and the total luminescence intensity (TLI) method are highly sensitive to oxidation in degradable PE. In this study, stabilised PE and PP were characterised with CL in an inert (TLI) and in an oxygen atmosphere (CL-OIT) and the results were compared to those obtained by the commonly used techniques, FT-IR (carbonyl index (CI)) and thermal analysis (DSC-OIT). PE was aged at a low temperature (80 °C) and PP was aged at temperatures between 60 and 120 °C. Non-Arrhenius behaviour was observed in the oxidation of PP. This showed the importance of aging at a low temperature to obtain realistic results. TLI and CI of stabilised PP and most of the stabilised PE gave comparable results with the same sensitivity for oxidation detection. This was in contrast to our previous results for degradable PE. However, TLI of unstabilised PE showed earlier oxidation detection than CI, which agreed with our earlier results. TLI of PE had a higher sensitivity than CL-OIT, and both TLI and CI of PP were sufficiently sensitive to detect the effect of aging at different temperatures, whereas DSC-OIT was not. 相似文献
26.
We have recently described the synthesis of two porphyrogenic macrocycles: 20-phenyl-2,13-dimethyl-3,7,8,12-tetraethyl-[24]iso-pentaphyrin (1) and 20-phenyl-2,13-dimethyl-3,7,8,12-tetraethyl-[22]pentaphyrin (2) (J. Med. Chem.2006, 49, 196-204). We found that the structure of iso-pentaphyrin is influenced by the acidity of the medium. By adjusting the TFA concentration, we solved two isomers of iso-pentaphyrin: 1 and 1A. At high TFA concentration iso-pentaphyrin is present only as 1, which is slowly oxidized into the aromatic macrocycle 2 upon exposure to air. The correlation between acidic conditions, isomer structures, and oxidation is discussed. 相似文献
27.
28.
29.
30.
Luis H. Mendoza-Huizar Clara H. Rios-Reyes 《Journal of Solid State Electrochemistry》2011,15(4):737-745
An electrochemical study of cobalt electrodeposition onto a polycrystalline platinum electrode from an aqueous solution (10−2 M CoCl2 + 1 M NH4Cl (pH 9.5)) was carried out through cyclic voltammetry and potential step techniques. Analysis of the voltammetric data clearly
showed that a cobalt adlayer is formed during the application of potential in the underpotential deposition (upd) region.
Formation of this cobalt adlayer involved the simultaneous presence of both adsorption and 2D nucleation processes. Cobalt
adlayers obtained by linear voltammetry in upd region were analyzed employing diffuse reflectance spectroscopy (DRS). By using
theoretical quantum studies at PM6//HF/LANL1MB level, it was possible to assign the peaks obtained by DRS at 328 and 337 nm
to the cobalt adsorption on Pt(111) and Pt(100), respectively, while the signals recorded at 355 and 362 nm were related with
the clean platinum surfaces Pt(100) and Pt(111). Also, quantum calculations at the PM6 level indicated that the energy formation
order is Co-Pt(100) > Co-Pt(111) > Co-Pt(110) > Co-Co(surface). 相似文献