全文获取类型
收费全文 | 586篇 |
免费 | 33篇 |
专业分类
化学 | 504篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 38篇 |
物理学 | 72篇 |
出版年
2024年 | 2篇 |
2023年 | 7篇 |
2022年 | 9篇 |
2021年 | 11篇 |
2020年 | 10篇 |
2019年 | 15篇 |
2018年 | 9篇 |
2017年 | 3篇 |
2016年 | 21篇 |
2015年 | 19篇 |
2014年 | 25篇 |
2013年 | 28篇 |
2012年 | 43篇 |
2011年 | 50篇 |
2010年 | 42篇 |
2009年 | 26篇 |
2008年 | 49篇 |
2007年 | 41篇 |
2006年 | 29篇 |
2005年 | 38篇 |
2004年 | 31篇 |
2003年 | 28篇 |
2002年 | 12篇 |
2001年 | 3篇 |
2000年 | 5篇 |
1999年 | 7篇 |
1998年 | 4篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有619条查询结果,搜索用时 218 毫秒
11.
Senge MO Hatscher SS Wiehe A Dahms K Kelling A 《Journal of the American Chemical Society》2004,126(42):13634-13635
Vilsmeier formylation is one of the most widely used substitution reactions for the functionalization of porphyrins. However, its utility is limited by the electrophilic/acidic reaction conditions, deactivation of the aromatic system and regiochemical problems, the requirement for metal complexes and necessity for subsequent demetalation under harsh conditions, and low functional group tolerance. To overcome these limitations, the dithianyl group has been utilized as a latent formyl synthon in porphyrin chemistry. 2-Formyl-1,3-dithiane can be used directly in pyrrole condensation reactions to regioselectively yield porphyrins with up to four dithianyl residues. Likewise, 5-dithianyldipyrromethane could be prepared quantitatively as a key building block for various porphyrin condensation reactions yielding the respective free base formylporphyrins after deprotection. Additionally, dithianyllithium can be used as a reagent for the direct aromatic substitution of metallo- and free base porphyrins under nucleophilic conditions. 相似文献
12.
13.
14.
15.
16.
Oliver Back Dr. Christoph Förster Prof. Dr. Thomas Basché Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6542-6552
2-Iminopyrroles [HtBuL, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(tBuL), aggregate to dimers, [M(tBuL)(NCR)]2 (M=Li, R=CH3, CH(CH3)CNH2), or polymers, [M(tBuL)]n (M=Na, K). In solution (solv=CH3CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(tBuL)(solv)m with N,N′-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(tBuL) chromophore possesses a low-energy intraligand charge-transfer (ILCT) excited state. The chelated alkali cations rigidify the chromophore, restricting intramolecular motions (RIM) by the chelation-enhanced fluorescence (CHEF) effect in solution and, consequently, switch-on a blue fluorescence emission. 相似文献
17.
Vincent S. D. Voet Gerrit ten Brinke Katja Loos 《Journal of polymer science. Part A, Polymer chemistry》2014,52(20):2861-2877
Poly(vinylidene fluoride) (PVDF) has reached the second largest production volume of fluoropolymers in recent years, and its popularity can be ascribed to high thermal stability and chemical inertness combined with its ferroelectric behavior. Copolymerization of vinylidene fluoride with other monomers leads to a wide variety of products with modified or improved properties. Besides commercially available fluorinated random copolymers, well‐defined block‐, graft, and alternating copolymers based on PVDF received more attention in recent years. PVDF‐containing block copolymers that may self‐assemble into well‐ordered morphologies are of particular interest, being potential precursors for functional nanostructured materials applicable in membranes and electronics. This Highlight provides an overview of the routes developed towards these materials via conventional and controlled polymerization techniques. In addition, it discusses their nanoscopic phase behavior and current and potential applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2861–2877 相似文献
18.
Aaron Breivogel Michael Meister Dr. Christoph Förster Dr. Frédéric Laquai Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(41):13745-13760
The synergy of push–pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the 1MLCT absorption and the 3MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the 3MLCT excited‐state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC‐tpy)][PF6]2, [Ru(ddpd‐NH2)(EtOOC‐tpy)][PF6]2, [Ru(ddpd){(MeOOC)3‐tpy}][PF6]2, and [Ru(ddpd‐NH2){(EtOOC)3‐tpy}][PF6]2 the combination of the electron‐accepting 2,2′;6′,2′′‐terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron‐donating N,N′‐dimethyl‐N,N′‐dipyridin‐2‐ylpyridine‐2,6‐diamine (ddpd) ligand decorated with none or one NH2 group enforces spatially separated and orthogonal frontier orbitals with a small HOMO–LUMO gap resulting in low‐energy 1MLCT and 3MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating 3MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time‐resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge n=0–4) and on triplet excited states (3MLCT and 3MC) as well as by time‐dependent density functional calculations (excited singlet states). 相似文献
19.
20.
Assessment of ionic liquid stationary phases for the GC analysis of fatty acid methyl esters 总被引:1,自引:0,他引:1
Katja Dettmer 《Analytical and bioanalytical chemistry》2014,406(20):4931-4939
The gas chromatographic separation of fatty acid methyl esters (FAMEs) on ionic liquid stationary phases was investigated. Seven commercially available ionic liquid columns were tested using a test mixture containing 37 fatty acid methyl esters. The influence of column temperature on the elution order was studied using five different temperature programs. Retention times were highly reproducible. Similar retention behavior was observed for the IL59, IL60, and IL61 columns. The peak pair C18:1 cis/trans was not baseline resolved on these columns, whose stationary phases are highly similar. C18:2 cis/trans, C18:3 n6/n3, and C20:3 n6/n3 were baseline separated on all columns. Baseline separation of the complete test mix was only obtained on the IL82 column using a heating rate of 5 K/min. In general, retention times decreased with increasing column polarity but unsaturated FAMEs were retained stronger compared to their saturated counterparts. Except for the IL59 column, retention crossover was observed when the temperature program was changed. 相似文献