全文获取类型
收费全文 | 318篇 |
免费 | 13篇 |
专业分类
化学 | 240篇 |
晶体学 | 1篇 |
力学 | 11篇 |
数学 | 31篇 |
物理学 | 48篇 |
出版年
2023年 | 5篇 |
2022年 | 5篇 |
2021年 | 7篇 |
2020年 | 7篇 |
2019年 | 14篇 |
2018年 | 5篇 |
2017年 | 4篇 |
2016年 | 7篇 |
2015年 | 11篇 |
2014年 | 8篇 |
2013年 | 8篇 |
2012年 | 18篇 |
2011年 | 29篇 |
2010年 | 7篇 |
2009年 | 17篇 |
2008年 | 15篇 |
2007年 | 11篇 |
2006年 | 11篇 |
2005年 | 8篇 |
2004年 | 8篇 |
2003年 | 6篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1973年 | 7篇 |
1972年 | 2篇 |
1956年 | 2篇 |
1928年 | 2篇 |
1919年 | 3篇 |
1905年 | 2篇 |
1901年 | 2篇 |
1895年 | 3篇 |
1883年 | 2篇 |
排序方式: 共有331条查询结果,搜索用时 109 毫秒
1.
Tay-Yean Lin Charles A. Kingsbury Jules Adelfang Norman H. Cromwell 《Journal of heterocyclic chemistry》1985,22(4):1017-1020
The synthesis and spectral characteristics of certain bis(1-alkyl-3-phenyl-2-aziridinyl)ketones are reported. The reactions of 1,2,4,5-tetrabromo-1,5-diphenyl-3-pentanone ( 2 ) with primary amines are assumed to have a mechanism similar to that of a simple dibromo-ketone. The so-called cis, cis- or trans, trans-configurations of the bis-aziridinylketones were determined by 1H and 13C nmr spectra. 相似文献
2.
Wolffs M Hoeben FJ Beckers EH Schenning AP Meijer EW 《Journal of the American Chemical Society》2005,127(39):13484-13485
Chiral aggregation of oligo(p-phenylene vinylene)-functionalized Zn and free-base porphyrins is observed in water. The formation of mixed assemblies containing both porphyrins results in sequential energy transfer from OPV via zinc porphyrin to free-base porphyrin. Furthermore, the incorporation of C60 as electron acceptor yields a charge separated state by ultimate electron transfer. 相似文献
3.
Burwell F. Powell Jules Reichenthal C. G. Overberger J.-P. Anselme 《Journal of heterocyclic chemistry》1980,17(2):219-224
The synthesis of cis- and trans-2,4-diphenylazetidines as well as that of their N-nitroso derivatives is described. The “abnormal” reduction of the N-nitrosamines gives a cis-trans mixture of the expected 1,2-diphenylcyclopropanes. However, no stereochemical correlations could be made owing to the base-induced isomerization of the starting N-nitrosamines during the course of the reaction. 相似文献
4.
Hyperoxygenation enhances the tumor cell killing of photofrin-mediated photodynamic therapy 总被引:8,自引:0,他引:8
Huang Z Chen Q Shakil A Chen H Beckers J Shapiro H Hetzel FW 《Photochemistry and photobiology》2003,78(5):496-502
Tumor hypoxia, either preexisting or as a result of oxygen depletion during photodynamic therapy (PDT) light irradiation, can significantly reduce the effectiveness of PDT-induced cell killing. To overcome tumor hypoxia and improve tumor cell killing, we propose using supplemental hyperoxygenation during Photofrin-PDT. The mechanism for the tumor cure enhancement of the hyperoxygenation-PDT combination is investigated using an in vivo-in vitro technique. A hypoxic tumor model was established by implanting mammary adenocarcinoma in the hind legs of mice. Light irradiation (200 J/cm2 at either 75 or 150 mW/cm2), under various oxygen supplemental conditions (room air, carbogen, 100% normobaric or hyperbaric oxygen), was delivered to animals that received 12.5 mg/kg Photofrin 24 h before light irradiation. Tumors were harvested at various time points after PDT and grown in vitro for colony formation analysis. Treated tumors were also analyzed histologically. The results show that when PDT is combined with hyperoxygenation, the hypoxic condition could be improved and the cell killing rate at various time points after PDT could be significantly enhanced over that without hyperoxygenation, suggesting an enhanced direct and indirect cell killing associated with high-concentration oxygen breathing. This study further confirms our earlier observation that when a PDT treatment is combined with hyperoxygenation it can be more effective in controlling hypoxic tumors. 相似文献
5.
In this article the methodology of the design of suitable background electrolytes (BGEs) in capillary zone electrophoresis (CZE) is described. The principal aspects of the role of a BGE in CZE are discussed with respect to an appropiate migration behavior of analytes, including the transport of the electric current, the buffering of pH, the Joule heat, the electro-endosmotic flow (EOF) and the principal migration and detection modes. The impact of the composition of the BGE upon migration and detection is discussed. It is shown that the total concentration of the BGE is a principal factor and the adjustment of migrating analyte zones according to the Kohlrausch regulating function (KRF) is the principal effect in most of the sample stacking techniques. The number of co-ions and their properties are of key importance for peak shapes of the analyte peaks and for the existence of system zones. The detection of UV-transparent analytes may advanteously be done in the indirect UV mode, by using UV-absorbing co-ions, however, both peaks and dips may be expected in the UV trace in case of multiple co-ionic BGEs. Properties of BGEs can be predicted applying mathematical models and it is shown that with SystCharts, predictions can be given concerning the existence of system zones, detection modes and the peak shapes of analytes for a given BGE. Practical examples of methodological considerations are given in the design of suitable BGEs for four principal combinations of migration and detection modes. The properties of the BGEs selected are exemplified with experimental results. Golden rules are summarized for the preparation of suitable BGEs in CZE. 相似文献
6.
We report the reactivity between the water stable Lewis acidic trioxatriangulenium ion (TOTA+) and a series of Lewis bases such as phosphines and N-heterocyclic carbene (NHC). The nature of the Lewis acid–base interaction was analyzed via variable temperature (VT) NMR spectroscopy, single-crystal X-ray diffraction, UV-visible spectroscopy, and DFT calculations. While small and strongly nucleophilic phosphines, such as PMe3, led to the formation of a Lewis acid–base adduct, frustrated Lewis pairs (FLPs) were observed for sterically hindered bases such as P(tBu)3. The TOTA+–P(tBu)3 FLP was characterized as an encounter complex, and found to promote the heterolytic cleavage of disulfide bonds, formaldehyde fixation, dehydrogenation of 1,4-cyclohexadiene, heterolytic cleavage of the C–Br bonds, and interception of Staudinger reaction intermediates. Moreover, TOTA+ and NHC were found to first undergo single-electron transfer (SET) to form [TOTA]·[NHC]˙+, which was confirmed via electron paramagnetic resonance (EPR) spectroscopy, and subsequently form a [TOTA–NHC]+ adduct or a mixture of products depending the reaction conditions used.Frustration at carbon! Herein, we present a frustrated Lewis pair system derived from a water stable carbon-based Lewis acid, trioxatriangulene (TOTA+), and a variety of Lewis bases, which successfully promotes bond cleavage and molecule fixation. 相似文献
7.
8.
Synthesis and structure–property relationship of carbazole‐alt‐benzothiadiazole copolymers 下载免费PDF全文
Jules Oriou Feifei Ng Georges Hadziioannou Cyril Brochon Eric Cloutet 《Journal of polymer science. Part A, Polymer chemistry》2015,53(17):2059-2068
A series of four π‐conjugated carbazole‐alt‐benzothiadiazole copolymers (PCBT) were prepared by Suzuki cross‐coupling reaction between synthesized dibromocarbazoles as electron‐rich subunits and 4,7‐bis(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)?2,1,3‐benzothiadiazole as electron‐deficient subunits. The subunits were directly linked through 2,7‐ or 3,6‐ positions of the carbazole. In addition, the carbazole monomers have been N‐substituted by a branched or a linear side‐chain. The chemical structure of the copolymers and their precursors was confirmed by NMR and IR spectroscopies, and their molar masses were estimated by SEC. Thermal analysis under N2 atmosphere showed no weight loss below 329°C, and no glass transition was observed in between 0 and 250°C. The band gaps of all PCBTs evaluated by optical spectroscopies and by cyclic voltammetry analysis were consistent with expectations and ranged between 2.2 and 2.3 eV. Finally, 2,7 and 3,6 linkages were shown to influence optical properties of PCBTs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2059–2068 相似文献
9.
10.
Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents 下载免费PDF全文
Jules Zeuna Nguendia Weiheng Zhong Alexandre Fleury Guillaume De Grandpré Prof. Armand Soldera Prof. Ribal Georges Sabat Prof. Jerome P. Claverie 《化学:亚洲杂志》2014,9(5):1356-1364
Copolymers of 2‐ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl‐2‐hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain‐transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high‐power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2‐hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non‐polar organic solvents, without altering the fundamental properties of the CNTs. 相似文献