全文获取类型
收费全文 | 425篇 |
免费 | 55篇 |
国内免费 | 49篇 |
专业分类
化学 | 335篇 |
晶体学 | 3篇 |
力学 | 1篇 |
综合类 | 4篇 |
数学 | 23篇 |
物理学 | 163篇 |
出版年
2023年 | 8篇 |
2022年 | 19篇 |
2021年 | 21篇 |
2020年 | 36篇 |
2019年 | 21篇 |
2018年 | 4篇 |
2017年 | 9篇 |
2016年 | 19篇 |
2015年 | 20篇 |
2014年 | 23篇 |
2013年 | 37篇 |
2012年 | 20篇 |
2011年 | 14篇 |
2010年 | 21篇 |
2009年 | 18篇 |
2008年 | 24篇 |
2007年 | 27篇 |
2006年 | 26篇 |
2005年 | 21篇 |
2004年 | 16篇 |
2003年 | 16篇 |
2002年 | 8篇 |
2001年 | 19篇 |
2000年 | 10篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1980年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有529条查询结果,搜索用时 0 毫秒
21.
MA Jianhua LIN Weizhen DU Fuqiang HAN Zhenhui YAO Side & LIN Nianyun .College of Biology Engineering Jimei University Xiamen China .Laboratory of Nanobiomedicine & Laboratory of Radiation Chemistry Shanghai Institute of Applied Physics Chinese Acade Sciences Shanghai China 《中国科学B辑(英文版)》2005,48(4):292-296
Quinones including menadione are ubiquitous in nature. They play important roles in aerobic respira- tion and photosynthesis[1,2]. In addition, exogenous quinones are used as antibiotics and anticancer drugs. Their function is closely related to their red… 相似文献
22.
Nagappanpillai Adarsh Madhesh Shanmugasundaram Dr. Rekha R. Avirah Dr. Danaboyina Ramaiah 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(40):12655-12662
A new series of aza‐BODIPY derivatives ( 4 a – 4 c , 5 a , c , and 6 b , c ) were synthesized and their excited‐state properties, such as their triplet excited state and the yield of singlet‐oxygen generation, were tuned by substituting with heavy atoms, such as bromine and iodine. The effect of substitution has been studied in detail by varying the position of halogenation. The core‐substituted dyes showed high yields of the triplet excited state and high efficiencies of singlet‐oxygen generation when compared to the peripheral‐substituted systems. The dye 6 c , which was substituted with six iodine atoms on the core and peripheral phenyl ring, showed the highest quantum yields of the triplet excited state (ΦT=0.86) and of the efficiency of singlet‐oxygen generation (ΦΔ=0.80). Interestingly, these dyes were highly efficient as photooxygenation catalysts under artificial light, as well as under normal sunlight conditions. The uniqueness of these aza‐BODIPY systems is that they are stable under irradiation conditions, possess strong red‐light absorption (620–680 nm), exhibit high yields of singlet‐oxygen generation, and act as efficient and sustainable catalysts for photooxygenation reactions. 相似文献
23.
The fluorescent properties, structure, and electronic structure of the ground and excited singlet and triplet electronic states of the cis and trans forms of 4,5-dihydro-2-(2-furyl)oxazole, 4,4-dihydro-2-(2-thienyl)oxazole, 2-(2-furyl)oxazole (FO), and 2-(2-thienyl)oxazole (TO) have been studied. The orbital nature of the lower excited singlet and triplet states has been studied by the semiempirical INDO/S (valence approximation) and PPP/S ( approximation) methods. It was shown that for FO and TO molecules the lower triplet state is of the * type, for which delocalization of the electronic excitation on atoms is characteristic. In the singlet excitation state inversion was observed of the energy levels of the delocalized * states and n* states localized over several bonds (for the free TO and FO molecules the lower excited singlet states S1* were assigned to * and n* types respectively). Owing to the low position of the T
* and T
n* levels relative to the singlet level of * type, the rate constant for intercombination conversion is greater than the rate constant for radiative decay. Consequently an efficient population of the triplet states of the molecules occurs under conditions of electronic-vibrational excitation. The direction of reactions during synthesis was compared with the localization indices in the ground state for electrophilic, nucleophilic, and radical substitution, and also with the excitation localization numbers L for a wide selection of electronically excited states. It was concluded that the change in the structure of the azole molecule on replacing an O atom by an S atom, or on changing from a partially hydrogenated to a heteroaromatic system, was the main reason for the change of all the spectral parameters characterizing the electronic-vibrational or the spin-orbital interaction of the most reactive groups of atoms in the molecular structure. 相似文献
24.
一种新型香豆素酮可见光敏化染料的合成及其光引发性质的研究 总被引:3,自引:0,他引:3
高效的可见光光敏引发体系是目前光聚合研究中的重要领域.3,3′-二(7-二乙胺基)香豆素酮(R)已被公认为一种高效的可见光聚合敏化染料,并可以与Ar+激光488 nm波长匹配.本文新合成了一种染料3-(4-二乙胺基-苯丙烯酰基)-7-二乙胺基香豆素(S).实验发现在普通碘钨灯照射下,S/邻氯六芳基双咪唑(HABI)体系具有比已有高效染料R/HABI体系更快的光漂白速度和更高的引发聚合效率,是一种新型高效的可见光光敏聚合引发体系.而且S在不同溶剂中的最大吸收波长在452~489 nm之间,比R红移16~30 nm,因此该体系可以更好地与Ar+ (488 nm)激光器匹配.本文对该染料的光敏化机理进行了探讨. 相似文献
25.
Iridium(III) Complexes Bearing Pyrene‐Functionalized 1,10‐Phenanthroline Ligands as Highly Efficient Sensitizers for Triplet–Triplet Annihilation Upconversion 下载免费PDF全文
Yue Lu Junsi Wang Dr. Niamh McGoldrick Xiaoneng Cui Prof. Dr. Jianzhang Zhao Colin Caverly Dr. Brendan Twamley Dr. Gearoid M. Ó Máille Bryan Irwin Robert Conway‐Kenny Prof. Dr. Sylvia M. Draper 《Angewandte Chemie (International ed. in English)》2016,55(47):14688-14692
“Chemistry‐on‐the‐complex” synthetic methods have allowed the selective addition of 1‐ethynylpyrene appendages to the 3‐, 5‐, 3,8‐ and 5,6‐positions of IrIII‐coordinated 1,10‐phenanthroline via Sonogashira cross‐coupling. The resulting suite of complexes has given rise to the first rationalization of their absorption and emission properties as a function of the number and position of the pyrene moieties. Strong absorption in the visible region (e.g. 3,8‐substituted Ir‐3 : λabs=481 nm, ?=52 400 m ?1 cm?1) and long‐lived triplet excited states (e.g. 5‐substituted Ir‐2 : τT=367.7 μs) were observed for the complexes in deaerated CH2Cl2. On testing the series as triplet sensitizers for triplet–triplet annihilation upconversion, those IrIII complexes bearing pyrenyl appendages at the 3‐ and 3,8‐positions ( Ir‐1 , Ir‐3 ) were found to give optimal upconversion quantum yields (30.2 % and 31.6 % respectively). 相似文献
26.
Reactions of singlet and triplet carbon atoms with water are explored theoretically using CASSCF–MCQDPT2, CCSD, and DFT methodologies. The 1S carbons are found to be unreactive. Depending on the carbon atom generation method and the reaction medium, gas‐phase C(3P) attacking water may generate CO and atomic hydrogen as the end products. Reaction paths of the C(1D) + H2O system are complicated due to the involvement of two reactive potential energy surfaces with branchings occurring along each. Modifications in product distributions for reactions taking place in condensed phases are elaborated. The decisive reaction conditions, under which the oxygen abstraction and intermolecular formaldehyde generation dominate, are suggested to clarify the discrepancy related with experimental CO observation. The findings are consistent with available experimental data on this system. Oxygen abstraction and intermolecular formaldehyde generation mechanisms suggested here are capable of serving as models for similar reactions of alcohols. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012 相似文献
27.
28.
29.
Dr. Debangshu Chaudhuri Dr. Eva Sigmund Annemarie Meyer Lisa Röck Philippe Klemm Sebastian Lautenschlager Agnes Schmid Shane R. Yost Prof. Dr. Troy Van Voorhis Dr. Sebastian Bange Prof. Dr. Sigurd Höger Prof. Dr. John M. Lupton 《Angewandte Chemie (International ed. in English)》2013,52(50):13449-13452
30.
San-E Zhu Jian-Hui Zhang Yu Gong Li-Feng Dou Li-Hua Mao Hong-Dian Lu Chun-Xiang Wei Hong Chen Xue-Fei Wang Wei Yang 《Molecules (Basel, Switzerland)》2021,26(5)
A broadband visible light-absorbing [70]fullerene-BODIPY-triphenylamine triad (C70-B-T) has been synthesized and applied as a heavy atom-free organic triplet photosensitizer for photooxidation. By attaching two triphenylmethyl amine units (TPAs) to the π-core of BODIPY via ethynyl linkers, the absorption range of the antenna is extended to 700 nm with a peak at 600 nm. Thus, the absorption spectrum of C70-B-T almost covers the entire UV–visible region (270–700 nm). The photophysical processes are investigated by means of steady-state and transient spectroscopies. Upon photoexcitation at 339 nm, an efficient energy transfer (ET) from TPA to BODIPY occurs both in C70-B-T and B-T, resulting in the appearance of the BODIPY emission at 664 nm. Direct or indirect (via ET) excitation of the BODIPY-part of C70-B-T is followed by photoinduced ET from the antenna to C70, thus the singlet excited state of C70 (1C70*) is populated. Subsequently, the triplet excited state of C70 (3C70*) is produced via the intrinsic intersystem crossing of C70. The photooxidation ability of C70-B-T was studied using 1,5-dihydroxy naphthalene (DHN) as a chemical sensor. The photooxidation efficiency of C70-B-T is higher than that of the individual components of C70-1 and B-T, and even higher than that of methylene blue (MB). The photooxidation rate constant of C70-B-T is 1.47 and 1.51 times as that of C70-1 and MB, respectively. The results indicate that the C70-antenna systems can be used as another structure motif for a heavy atom-free organic triplet photosensitizer. 相似文献