全文获取类型
收费全文 | 477篇 |
免费 | 139篇 |
国内免费 | 16篇 |
专业分类
化学 | 612篇 |
物理学 | 20篇 |
出版年
2023年 | 6篇 |
2022年 | 14篇 |
2021年 | 28篇 |
2020年 | 34篇 |
2019年 | 23篇 |
2018年 | 12篇 |
2017年 | 11篇 |
2016年 | 35篇 |
2015年 | 55篇 |
2014年 | 37篇 |
2013年 | 43篇 |
2012年 | 43篇 |
2011年 | 55篇 |
2010年 | 50篇 |
2009年 | 39篇 |
2008年 | 33篇 |
2007年 | 15篇 |
2006年 | 23篇 |
2005年 | 18篇 |
2004年 | 19篇 |
2003年 | 16篇 |
2002年 | 6篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1988年 | 3篇 |
排序方式: 共有632条查询结果,搜索用时 31 毫秒
21.
Jason P. Seeley Dr. Mircea Cotlet Aileen M. Eagleton Seiichiro Higashiya Prof. John T. Welch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(4):961-965
The fluorescence intensity of a C-terminal acceptor chromophore, N-(7-dimethylamino-4-methyl coumarin (DACM), increased proportionally with 280 nm irradiation of an increasing number of donor tryptophan residues located on a β-sheet forming polypeptide. The fluorescence intensity of the acceptor chromophore increased even as the length of the β-sheet edge approached 256 Å, well beyond the Förster radius for the tryptophan–acceptor chromophore pair. The folding of the peptides under investigation was verified by circular dichroism (CD) and deep UV resonance Raman experiments. Control experiments showed that the enhancement of DACM fluorescence occurred concomitantly with peptide folding. In other control experiments, the DACM fluorescence intensity of the solutions of tryptophan and DACM did not show any enhancement of DACM fluorescence with increasing tryptophan concentrations. Formation of fibrillar aggregates of the substrate peptides prepared for the fluorescence studies was undetectable by thioflavin T (ThT) fluorescence. 相似文献
22.
Kentaro Mishiba Dr. Yuya Tanaka Prof. Dr. Munetaka Akita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(17):5432-5438
Herein, we report the synthesis and electrochemical and photophysical properties of aromatic hydrocarbons having one or two dimesitylborylethynyl peripherals. The mono- ( 1 ) and diboryl compounds ( 2 ), readily prepared by nucleophilic substitution reaction, are fairly stable to air and moisture in the solid state. The inserted ethynediyl (C≡C) spacer cancels the steric hindrance between the bulky dimesitylboryl groups and aromatic rings, leading to effective π conjugation over the B−C≡C−Ar linkages, as revealed by cyclic voltammetry. Despite the small structural differences, the photophysical properties of the benzene, naphthalene, and anthracene derivatives are different. Virtually no emission was observed from the benzene derivatives, whereas the anthracene derivatives emitted with high quantum yields both in solution and in the solid state. Notably, the naphthalene derivatives showed aggregation-induced emission behavior. Unlike the common sterically congested triarylborane derivatives reported so far, the anthracene derivatives showed π–π*-type absorption and emission bands, which derive from efficient intramolecular orbital interactions between the boron centers and anthracene moieties, as supported by DFT calculations. As a result, the dimesitylborylethynyl substituents effectively lower the LUMO levels of the aromatic hydrocarbon parts, whereas the HOMO levels are almost unaffected, thereby leading to materials with controllable HOMO–LUMO gaps. 相似文献
23.
Juan Luis Vázquez Ivan Velazco-Cabral Dr. Marcos Flores-Álamo Gleb Turlakov Geraldina Rodríguez Dr. Ivana Moggio Dr. Eduardo Arias Dr. Eduardo Peña-Cabrera Dr. Miguel A. Vázquez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(71):e202202446
A series of new symmetrical highly substituted BODIPYs 6 a – l was synthesized through a prefunctionalization approach in 35 %–89 % yields from the pyrrole core. This strategy allowed modulation of the substituents at the different positions based on the choice of Fischer's alkynyl carbenes, oxazolones and aldehydes used as precursors. The substituent variation at positions 2, 6, 3 and 5 had the greatest effect on the modulation of their photophysical properties such as absorption (λabs) and emission (λem) wavelengths, extinction coefficient (ϵ), quantum yields (ϕ), Stokes shifts (Δν), fluorescence decay, radiative (krad) and non-radiative (knr) constants and the CIE 1931 coordinates. Theoretical calculations allowed to corroborate the effect of the substituents of meso-position on the modification of the dihedral angles. Cyclic voltammetry studies revealed that the BODIPY series presents similar redox potential behavior, being electrochemically active even in successive cycles, which suggests that transport by diffusion is the dominant process. 相似文献
24.
Juan Carlos López-López Dr. Delia Bautista Dr. Pablo González-Herrero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(49):11307-11315
A stereoselective synthetic route to homo- and heteroleptic facial tris-cyclometalated PtIV complexes is reported, involving the oxidative addition of 2-(2-pyridyl)- or 2-(1-isoquinolinyl)benzenediazonium salts to cis-[Pt(C^N)2] precursors, with C^N=cyclometalated 2-(p-tolyl)pyridine (tpy), 2-phenylquinoline (pq), 2-(2-thienyl)pyridine or 1-phenylisoquinoline (piq), to produce labile diazenide intermediates that undergo photochemical or thermal elimination of N2. The method allows the preparation of derivatives bearing cyclometalated ligands of low π–π* transition energies. The new complexes exhibit phosphorescence in fluid solution at room temperature arising from triplet ligand-centered (3LC) excited states, which, in the cases of the heteroleptic derivatives, involve the ligand with the lowest π–π* gap. The heteroleptic piq derivatives exhibit fluorescence and dual phosphorescence from different ligand-centered excited states in rigid media, demonstrating the potential of cyclometalated PtIV complexes as multi-emissive materials. 相似文献
25.
Lingjie Sun Dr. Weigang Zhu Wei Wang Dr. Fangxu Yang Congcong Zhang Prof. Shufeng Wang Dr. Xiaotao Zhang Prof. Rongjin Li Prof. Huanli Dong Prof. Wenping Hu 《Angewandte Chemie (International ed. in English)》2017,56(27):7831-7835
Cocrystals of 4-styrylpyridine and 1,2,4,5-tetracyanobenzene were successfully prepared by supramolecular self-assembly. Donor–acceptor interactions between the molecular components are the main driving force for self-assembly and contribute to intermolecular charge transfer. The cocrystals possess two-photon absorption properties that are not observed in the individual components; suggesting that two-photon absorption originates from intermolecular charge-transfer interactions in the donor–acceptor system. The origin of two-photon absorption in multichromophore systems remains under-researched; thus, the system offers a rare demonstration of two-photon absorption by cocrystallization. Cocrystal engineering may facilitate further design and development of novel materials for nonlinear optical and optoelectronic applications. 相似文献
26.
27.
Dr. Sylvain Achelle Dr. Jean‐Pierre Malval Dr. Stéphane Aloïse Dr. Alberto Barsella Dr. Arnaud Spangenberg Dr. Loic Mager Dr. Huriye Akdas‐Kilig Dr. Jean‐Luc Fillaut Prof. Bertrand Caro Prof. Françoise Robin‐le Guen 《Chemphyschem》2013,14(12):2725-2736
The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching. 相似文献
28.
Dr. Ángel J. Jiménez Michael Sekita Dr. Esmeralda Caballero Dr. M. Luisa Marcos Dr. M. Salomé Rodríguez‐Morgade Prof. Dr. Dirk M. Guldi Prof. Tomás Torres 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14506-14514
In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of PtII disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of PtII between Pc and PDI impacts the results in a longer‐lived Pc . +/PDI . ? radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 . 相似文献
29.
Dr. Ádám Eördögh Annabell Martin Prof. Dr. Pablo Rivera-Fuentes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(71):e202202832
Single-molecule localization microscopy (SMLM) can reveal nanometric details of biological samples, but its high phototoxicity hampers long-term imaging in live specimens. A significant part of this phototoxicity stems from repeated irradiations that are necessary for controlled switching of fluorophores to maintain the sparse labeling of the sample. Lower phototoxicity can be obtained using fluorophores that blink spontaneously, but controlling the density of single-molecule emitters is challenging. We recently developed photoregulated fluxional fluorophores (PFFs) that combine the benefits of spontaneously blinking dyes with photocontrol of emitter density. These dyes, however, were limited to imaging acidic organelles in live cells. Herein, we report a systematic study of PFFs that culminates in probes that are functional at physiological pH and operate at longer wavelengths than their predecessors. Moreover, these probes are compatible with HaloTag labeling, thus enabling timelapse, single-molecule imaging of specific protein targets for exceptionally long times. 相似文献
30.
Xing Chen Dr. Guoyun Meng Guanming Liao Dr. Florian Rauch Dr. Jiang He Dr. Alexandra Friedrich Prof. Dr. Todd B. Marder Dr. Nan Wang Dr. Pangkuan Chen Prof. Dr. Suning Wang Dr. Xiaodong Yin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(20):6274-6282
A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m−2. These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability. 相似文献