全文获取类型
收费全文 | 903篇 |
免费 | 29篇 |
国内免费 | 5篇 |
专业分类
化学 | 632篇 |
晶体学 | 9篇 |
力学 | 12篇 |
数学 | 85篇 |
物理学 | 199篇 |
出版年
2023年 | 8篇 |
2022年 | 10篇 |
2021年 | 10篇 |
2020年 | 18篇 |
2019年 | 13篇 |
2018年 | 14篇 |
2016年 | 9篇 |
2015年 | 18篇 |
2014年 | 16篇 |
2013年 | 44篇 |
2012年 | 79篇 |
2011年 | 78篇 |
2010年 | 31篇 |
2009年 | 15篇 |
2008年 | 60篇 |
2007年 | 56篇 |
2006年 | 67篇 |
2005年 | 55篇 |
2004年 | 44篇 |
2003年 | 39篇 |
2002年 | 31篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 11篇 |
1996年 | 11篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 11篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 8篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1977年 | 6篇 |
1975年 | 3篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1968年 | 4篇 |
1961年 | 3篇 |
1960年 | 3篇 |
1941年 | 4篇 |
1939年 | 3篇 |
1907年 | 5篇 |
排序方式: 共有937条查询结果,搜索用时 390 毫秒
91.
Seth C. Rasmussen Jason C. Pickens James E. Hutchison 《Journal of heterocyclic chemistry》1997,34(1):285-288
A new synthetic route to 4-substituted-2,2′-bithiophenes has been developed utilizing 4-bromo-2,2′-bithiophene ( 1 ). Formation of the bithienyllithium adduct via halogen-metal exchange was found to be problematic and resulted in complex mixtures of products. The Grignard reagent of 1 can be obtained easily via the “entrainment” method, allowing the production of 4-substituted-2,2′-bithiophenes (where sub-stituent = octyl, hydroxyethyl, hydroxymethyl, carboxy, carbomethoxy, acetoxyethyl, and acetoxymethyl). 相似文献
92.
Contrasting Response of Two Dipolar Fluorescence Probes in a Leucine‐Based Organogel and Its Implications
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Sivalingam Soumya Sudipta Seth Sneha Paul Prof. Dr. Anunay Samanta 《Chemphyschem》2015,16(11):2440-2446
The microenvironments of a leucine‐based organogel are probed by monitoring the fluorescence behavior of coumarin 153 (C153) and 4‐aminophthalimide (AP). The steady‐state data reveals distinctly different locations of the two molecules in the gel. Whereas AP resides close to the hydroxyl moieties of the gelator and engages in hydrogen‐bonding interactions, C153 is found in bulk‐toluene‐like regions. In contrast to C153, AP exhibits excitation‐wavelength‐dependent emission, indicating that the environments of the hydrogen‐bonded AP molecules are not all identical. A two‐component fluorescence decay of AP in gel, unlike C153, supports this model. A time‐resolved fluorescence anisotropy study of the rotational motion of the molecules also reveals the strong association of only AP with the gelator. That AP influences the critical gelation concentration implies its direct involvement in the gel‐formation process. The results highlight the importance of guest–gelator interactions in gels containing guest molecules. 相似文献
93.
Synthesis of 8‐Aminoquinolines by Using Carbamate Reagents: Facile Installation and Deprotection of Practical Amidating Groups
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hye Kyung Kim Prof. Dr. Seth R. Marder Prof. Dr. Sukbok Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17200-17204
Described herein is the development of practical routes to 8‐aminoquinolines by using readily installable and easily deprotectable amidating reagents. Two scalable procedures were optimized under RhIII‐catalyzed conditions: i) the use of pre‐generated chlorocarbamates and ii) a two‐step one‐pot process that directly employs carbamates. Both approaches are highly convenient for the gram‐scale synthesis of 8‐aminoquinolines under mild conditions. Facile deprotection of the synthetically versatile amidating groups was achieved under the Pd‐catalyzed transfer hydrogenation conditions with simultaneous deoxygenation of quinoline N‐oxides, thus yielding 8‐aminoquinolines in excellent overall efficiency. 相似文献
94.
Lomaiviticins A and B are complex antitumor antibiotics that were isolated from a strain of Micromonospora. A confluence of several unusual structural features renders the lomaiviticins exceedingly challenging targets for chemical synthesis. We report an 11-step, enantioselective synthetic route to lomaiviticin aglycon. Our route proceeds by late-stage, stereoselective dimerization of two equivalent monomeric intermediates, a transformation that may share parallels with the natural products' biosyntheses. The route we describe is scalable and convergent, and it lays the foundation for determination of the mode of action of these natural products. 相似文献
95.
Fedorov O Huber K Eisenreich A Filippakopoulos P King O Bullock AN Szklarczyk D Jensen LJ Fabbro D Trappe J Rauch U Bracher F Knapp S 《Chemistry & biology》2011,18(1):67-76
There is a growing recognition of the importance of protein kinases in the control of alternative splicing. To define the underlying regulatory mechanisms, highly selective inhibitors are needed. Here, we report the discovery and characterization of the dichloroindolyl enaminonitrile KH-CB19, a potent and highly specific inhibitor of the CDC2-like kinase isoforms 1 and 4 (CLK1/CLK4). Cocrystal structures of KH-CB19 with CLK1 and CLK3 revealed a non-ATP mimetic binding mode, conformational changes in helix αC and the phosphate binding loop and halogen bonding to the kinase hinge region. KH-CB19 effectively suppressed phosphorylation of SR (serine/arginine) proteins in cells, consistent with its expected mechanism of action. Chemical inhibition of CLK1/CLK4 generated a unique pattern of splicing factor dephosphorylation and had at low nM concentration a profound effect on splicing of the two tissue factor isoforms flTF (full-length TF) and asHTF (alternatively spliced human TF). 相似文献
96.
Altun M Kramer HB Willems LI McDermott JL Leach CA Goldenberg SJ Kumar KG Konietzny R Fischer R Kogan E Mackeen MM McGouran J Khoronenkova SV Parsons JL Dianov GL Nicholson B Kessler BM 《Chemistry & biology》2011,18(11):1401-1412
Converting lead compounds into drug candidates is a crucial step in drug development, requiring early assessment of potency, selectivity, and off-target effects. We have utilized activity-based chemical proteomics to determine the potency and selectivity of deubiquitylating enzyme (DUB) inhibitors in cell culture models. Importantly, we characterized the small molecule PR-619 as a broad-range DUB inhibitor, and P22077 as a USP7 inhibitor with potential for further development as a chemotherapeutic agent in cancer therapy. A striking accumulation of polyubiquitylated proteins was observed after both selective and general inhibition of cellular DUB activity without direct impairment of proteasomal proteolysis. The repertoire of ubiquitylated substrates was analyzed by tandem mass spectrometry, identifying distinct subsets for general or specific inhibition of DUBs. This enabled identification of previously unknown functional links between USP7 and enzymes involved in DNA repair. 相似文献
97.
Wan S Wu F Rech JC Green ME Balachandran R Horne WS Day BW Floreancig PE 《Journal of the American Chemical Society》2011,133(41):16668-16679
The potent cytotoxins pederin and psymberin have been prepared through concise synthetic routes (10 and 14 steps in the longest linear sequences, respectively) that proceed via a late-stage multicomponent approach to construct the N-acyl aminal linkages. This route allowed for the facile preparation of a number of analogs that were designed to explore the importance of the alkoxy group in the N-acyl aminal and functional groups in the two major subunits on biological activity. These analogs, including a pederin/psymberin chimera, were analyzed for their growth inhibitory effects, revealing several new potent cytotoxins and leading to postulates regarding the molecular conformational and hydrogen bonding patterns that are required for biological activity. Second generation analogs have been prepared based on the results of the initial assays and a structure-based model for the binding of these compounds to the ribosome. The growth inhibitory properties of these compounds are reported. These studies show the profound role that organic chemistry in general and specifically late-stage multicomponent reactions can play in the development of unique and potent effectors for biological responses. 相似文献
98.
He F Wang W Chen W Xu T Darling SB Strzalka J Liu Y Yu L 《Journal of the American Chemical Society》2011,133(10):3284-3287
A series of semiconducting copolymers (PTAT-x) containing extended π-conjugated tetrathienoanthracene units have been synthesized. It was shown that the extended conjugation system enhanced the π-π stacking in the polymer/PC(61)BM blend films and facilitated the charge transport in heterojunction solar cell devices. After structural fine-tuning, the polymer with bulky 2-butyloctyl side chains (PTAT-3) exhibited a PCE of 5.6% when it was blended with PC(61)BM. 相似文献
99.
A postsynthetic modification (PSM) scheme for metal-organic frameworks (MOFs) has been developed using a tetrazine-based "Click" reaction. It was found that the efficacy of this modification procedure was dependent on the MOF topology and, in the case of an isoreticular MOF (IRMOF) system, required the formation of a mixed-ligand IRMOF with a suitable ratio of 1,4-benzenedicarboxylate (BDC) and an olefin-tagged BDC derivative. On the basis of the versatile use of tetrazine "Click" chemistry in bioconjugate chemistry, we expect that this scheme will prove to be a useful reaction for preparing functionalized materials, including MOFs. 相似文献
100.
We derive structure-property relationships for methine ("Brooker") dyes relating the color of the dye and its symmetric parents to its bond alternation in the ground state and also to the dipole properties associated with its low-lying charge-resonance (or charge-transfer) transition. We calibrate and test these relationships on an array of different protonation states of the green fluorescent protein chromophore motif (an asymmetric halochromic methine dye) and its symmetric parent dyes. The relationships rely on the assumption that the diabatic states that define the Platt model for methine dye color [J. R. Platt, J. Chem. Phys. 25, 80 (1956)] can also be distinguished by their single-double bond alternation and by their charge localization character. These assumptions are independent of the primary constraint that defines the diabatic states in the Platt model--specifically, the Brooker deviation rule for methine dyes [L. G. S. Brooker, Rev. Mod. Phys. 14, 275 (1942)]. Taking these assumptions, we show that the Platt model offers an alternate route to known structure-property relationships between the bond length alternation and the quadratic nonlinear polarizability β. We show also that the Platt model can be parameterized without the need for synthesis of the symmetric parents of a given dye, using the dipole data obtained through spectroscopic measurements. This suggests that the Platt model parameters may be used as independent variables in free-energy relationships for chromophores whose symmetric parents cannot be synthesized or chromophores strongly bound to biomolecular environments. The latter category includes several recently characterized biomolecular probe constructs. We illustrate these concepts by an analysis of previously reported electroabsorption and second-harmonic generation experiments on green fluorescent proteins. 相似文献