全文获取类型
收费全文 | 1792篇 |
免费 | 400篇 |
国内免费 | 57篇 |
专业分类
化学 | 2033篇 |
晶体学 | 4篇 |
综合类 | 7篇 |
数学 | 27篇 |
物理学 | 178篇 |
出版年
2023年 | 20篇 |
2022年 | 26篇 |
2021年 | 72篇 |
2020年 | 158篇 |
2019年 | 100篇 |
2018年 | 86篇 |
2017年 | 63篇 |
2016年 | 122篇 |
2015年 | 122篇 |
2014年 | 120篇 |
2013年 | 139篇 |
2012年 | 101篇 |
2011年 | 93篇 |
2010年 | 81篇 |
2009年 | 75篇 |
2008年 | 84篇 |
2007年 | 106篇 |
2006年 | 101篇 |
2005年 | 79篇 |
2004年 | 76篇 |
2003年 | 79篇 |
2002年 | 38篇 |
2001年 | 26篇 |
2000年 | 24篇 |
1999年 | 33篇 |
1998年 | 26篇 |
1997年 | 38篇 |
1996年 | 29篇 |
1995年 | 26篇 |
1994年 | 17篇 |
1993年 | 17篇 |
1992年 | 12篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1970年 | 3篇 |
1968年 | 2篇 |
1966年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有2249条查询结果,搜索用时 15 毫秒
21.
Unraveling the Degradation Mechanism of Purine Nucleotides Photosensitized by Pterins: The Role of Charge‐Transfer Steps 下载免费PDF全文
Mariana P. Serrano Dr. Carolina Lorente Dr. Claudio D. Borsarelli Dr. Andrés H. Thomas 《Chemphyschem》2015,16(10):2244-2252
Photosensitized reactions contribute to the development of skin cancer and are used in many applications. Photosensitizers can act through different mechanisms. It is currently accepted that if the photosensitizer generates singlet molecular oxygen (1O2) upon irradiation, the target molecule can undergo oxidation by this reactive oxygen species and the reaction needs dissolved O2 to proceed, therefore the reaction is classified as 1O2‐mediated oxidation (type II mechanism). However, this assumption is not always correct, and as an example, a study on the degradation of 2′‐deoxyguanosine 5′‐monophosphate photosensitized by pterin is presented. A general mechanism is proposed to explain how the degradation of biological targets, such as nucleotides, photosensitized by pterins, naturally occurring 1O2 photosensitizers, takes place through an electron‐transfer‐initiated process (type I mechanism), whereas the contribution of the 1O2‐mediated oxidation is almost negligible. 相似文献
22.
Tianrong Yu Yang Gao Bo Wang Xing Dai Wanrun Jiang Ruixia Song Prof. Zhanwen Zhang Prof. Mingxing Jin Prof. Yongjian Tang Prof. Zhigang Wang 《Chemphyschem》2015,16(15):3308-3312
The mechanism of depolymerization is one of the most essential issues in chemical engineering and materials science. In this work, we investigate the depolymerization reactions of three typical free‐radical poly(alpha‐methylstyrene) tetramers by using first‐principles density functional theory. The calculated results show that these reactions all need to overcome the energy barriers in the range of 0.58 to 0.77 eV, and that breaking the C?C bond at the chain end leads to the dissociation of alpha‐methylstyrene monomers from the polymers. Electronic‐structure analysis indicates that the reactions occur easily at the CR3 unsaturated end, and that the frontier molecular orbitals that participate in the reactions are mainly localized at the unsaturated ends. Meanwhile, spin population analysis presents the unique net spin‐transfer process in free‐radical depolymerization reactions. We hope the current findings can contribute to understanding the free‐radical depolymerization mechanism and help guide future experiments. 相似文献
23.
Three unprecedented nitronyl nitroxide radical‐bridged 3d–4f clusters, [Ln2Cu2(hfac)10(NIT‐3py)2(H2O)2](LnIII=Y, Gd, Dy), have been obtained from the self‐assembly of Ln(hfac)3, Cu(hfac)2, and the radical ligand. The Dy complex shows a slow relaxation of magnetization, representing the first nitronyl nitroxide radical‐based 3d–4f cluster with single‐molecule magnet behavior. 相似文献
24.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(9):660-666
Nitrogen‐centered urazole radicals exist in equilibrium with tetrazane dimers in solution. The equilibrium established typically favors the free‐radical form. However, 1‐arylurazole radicals bearing substituents at the ortho position favor the dimeric form. We were able to determine the structure of one of the dimers (substituted at both ortho positions with methyl groups), namely 1,2‐(2,4‐dimethylphenyl)‐2‐[2‐(2,4‐dimethylphenyl)‐4‐methyl‐3,5‐dioxo‐1,2,4‐triazolidin‐1‐yl]‐4‐methyl‐1,2,4‐triazolidine‐3,5‐dione, C24H28N6O4, via X‐ray crystallography. The experimentally determined structure agreed well with the computationally obtained geometry at the B3LYP/6‐311G(d,p) level of theory. The preferred syn conformation of these 1‐arylurazole dimers results in the two aromatic rings being proximate and nearly parallel, which leads to some interesting shielding effects of certain signals in the 1H NMR spectrum. Armed with this information, we were able to decipher the more complicated 1H NMR spectrum obtained from a dimer that was monosubstituted at the ortho position with a methyl group. 相似文献
25.
M. Sc. Elena Kusevska Dr. M. Merced Montero-Campillo Prof. Otilia Mó Prof. Manuel Yáñez 《Angewandte Chemie (International ed. in English)》2017,56(24):6788-6792
Owing to its versatility in synthetic chemistry, TPB (tris[2-diisopropylphospino)phenyl]borane) is a very important frustrated Lewis Pair. The unusual stability of the neutral radical (TPB)Cu has been related to the presence of a one-electron B−Cu bond. Herein we show, through the use of different computational chemistry methods, that the existence and nature of this kind of A⋅⋅⋅M bond (A=donor atom, M=transition metal) depends on the surrounding chemical structure, and can be genuine one-electron sigma bonds only if appropriate metal ligands (Y), able to trap the charge in the desired region, are chosen. This ability is modulated by the subtle balance between the electronegativity of the different atoms along the A⋅⋅⋅M⋅⋅⋅Y bond paths. Most importantly, contrary to many TPB complexes in which boron acts as a Lewis acid, in one-electron-bond-containing structures boron behaves as a Lewis base. 相似文献
26.
Xiao-Qiang Wang Fan Gao Prof. Dr. Xian-Zheng Zhang 《Angewandte Chemie (International ed. in English)》2017,56(31):9029-9033
Tumor hypoxia greatly suppresses the therapeutic efficacy of photodynamic therapy (PDT), mainly because the generation of toxic reactive oxygen species (ROS) in PDT is highly oxygen-dependent. In contrast to ROS, the generation of oxygen-irrelevant free radicals is oxygen-independent. A new therapeutic strategy based on the light-induced generation of free radicals for cancer therapy is reported. Initiator-loaded gold nanocages (AuNCs) as the free-radical generator were synthesized. Under near-infrared light (NIR) irradiation, the plasmonic heating effect of AuNCs can induce the decomposition of the initiator to generate alkyl radicals (R.), which can elevate oxidative-stress (OS) and cause DNA damages in cancer cells, and finally lead to apoptotic cell death under different oxygen tensions. As a proof of concept, this research opens up a new field to use various free radicals for cancer therapy. 相似文献
27.
《Angewandte Chemie (International ed. in English)》2017,56(33):9670-9679
During the last 40 years, researchers investigating photoinitiated cationic polymerizations have delivered tremendous success in both industrial and academic settings. A myriad of photoinitiating systems have been developed, thus allowing polymerization of a broad array of monomers (e.g., epoxides, vinyl ethers, alkenes, cyclic ethers, and lactones) under practical, inexpensive, and environmentally benign conditions. More recently, owing to progress in photoredox catalysis, photocontrolled cationic polymerization has emerged as a means to precisely regulate polymer chain growth. This Minireview provides a concise historical perspective on cationic polymerization induced by light and discusses the latest advances in both photoinitiated and photocontrolled processes. The latter are exciting new directions for the field that will likely impact industries ranging from micropatterning to the synthesis of complex biomaterials and sequence‐controlled polymers. 相似文献
28.
Dr. Yan Li Dr. Yuk-Chi Chan Bi-Xiang Leong Dr. Yongxin Li Dr. Emma Richards Indu Purushothaman Dr. Susmita De Dr. Pattiyil Parameswaran Dr. Cheuk-Wai So 《Angewandte Chemie (International ed. in English)》2017,56(26):7573-7578
The trapping of a silicon(I) radical with N-heterocyclic carbenes is described. The reaction of the cyclic (alkyl)(amino) carbene [cAACMe] (cAACMe=:C(CMe2)2(CH2)NAr, Ar=2,6-iPr2C6H3) with H2SiI2 in a 3:1 molar ratio in DME afforded a mixture of the separated ion pair [(cAACMe)2Si:.]+I− ( 1 ), which features a cationic cAAC–silicon(I) radical, and [cAACMe−H]+I−. In addition, the reaction of the NHC–iodosilicon(I) dimer [IAr(I)Si:]2 (IAr=:C{N(Ar)CH}2) with 4 equiv of IMe (:C{N(Me)CMe}2), which proceeded through the formation of a silicon(I) radical intermediate, afforded [(IMe)2SiH]+I− ( 2 ) comprising the first NHC–parent-silyliumylidene cation. Its further reaction with fluorobenzene afforded the CAr−H bond activation product [1-F-2-IMe-C6H4]+I− ( 3 ). The isolation of 2 and 3 confirmed the reaction mechanism for the formation of 1 . Compounds 1 – 3 were analyzed by EPR and NMR spectroscopy, DFT calculations, and X-ray crystallography. 相似文献
29.
Kengo Asai Prof. Dr. Aiko Fukazawa Prof. Dr. Shigehiro Yamaguchi 《Angewandte Chemie (International ed. in English)》2017,56(24):6848-6852
A near-infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2-b;4,3-b′]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH-responsive changes in its photophysical properties due to a two-step acid–base equilibrium that produced a protonated cation ( 1H+ ) and an anion ( 1− ). While 1H+ showed an intense fluorescence in the red region of the visible spectrum, 1− exhibited a strong absorption in the NIR region. The tropylium ion character in 1H+ induces high pKa1 and pKa2 values for 1 . Moreover, a stable radical ( 1. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1. revealed a two-step reversible redox process that produced 1− and the cation 1+ , which is different from 1H+ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton. 相似文献
30.
Michael Teders Dr. Adrián Gómez-Suárez Lena Pitzer Prof. Dr. Matthew N. Hopkinson Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2017,56(3):902-906
Three new visible-light-promoted functionalizations of benzotriazole substrates were discovered using a mechanism-based screening method. ortho-Thiolated, borylated, and alkylated N-arylbenzamide products were obtained under mild reaction conditions in a new denitrogenative synthetic approach to functionalized aniline derivatives. The functional group tolerance of the borylation reaction was further analyzed in the first application of an additive-based robustness screen in a photocatalytic transformation. All the functionalizations proceed via photocatalytically initiated chain mechanisms as indicated by determination of the reaction quantum yields and Stern–Volmer analyses. 相似文献