全文获取类型
收费全文 | 298篇 |
免费 | 13篇 |
专业分类
化学 | 233篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 1篇 |
物理学 | 74篇 |
出版年
2021年 | 2篇 |
2019年 | 8篇 |
2017年 | 2篇 |
2016年 | 16篇 |
2015年 | 10篇 |
2014年 | 3篇 |
2013年 | 13篇 |
2012年 | 16篇 |
2011年 | 14篇 |
2010年 | 5篇 |
2009年 | 3篇 |
2008年 | 6篇 |
2007年 | 4篇 |
2006年 | 9篇 |
2005年 | 9篇 |
2004年 | 7篇 |
2003年 | 7篇 |
2002年 | 4篇 |
2001年 | 6篇 |
2000年 | 2篇 |
1999年 | 5篇 |
1998年 | 14篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 10篇 |
1994年 | 16篇 |
1993年 | 2篇 |
1992年 | 11篇 |
1991年 | 12篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 3篇 |
1979年 | 8篇 |
1978年 | 3篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1972年 | 3篇 |
1971年 | 2篇 |
1969年 | 4篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1961年 | 2篇 |
1935年 | 2篇 |
1932年 | 2篇 |
1921年 | 2篇 |
排序方式: 共有311条查询结果,搜索用时 31 毫秒
51.
Claudia J. Diehl Thomas Scattolin Ulli Englert Franziska Schoenebeck 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(1):217-221
While there is a growing interest in harnessing synergistic effects of more than one metal in catalysis, relatively little is known beyond bimetallic systems. This report describes the straightforward access to an air‐stable Pd trimer and presents unambiguous reactivity data of its privileged capability to differentiate C?I over C?Br bonds in C?C bond formations (arylation and alkylation) of polyhalogenated arenes, which typical Pd0 and PdI‐PdI catalysts fail to deliver. Experimental and computational reactivity data, including the first location of a transition state for bond activation by the trimer, are presented, supporting direct trimer reactivity to be feasible. 相似文献
52.
Hassan Osseili Khai‐Nghi Truong Thomas P. Spaniol Laurent Maron Ulli Englert Jun Okuda 《Angewandte Chemie (International ed. in English)》2019,58(6):1833-1837
Facile α‐H elimination from tetrakis(trimethylsilylmethyl)titanium precursors to give adducts of (alkylidene)bis(alkyl)titanium complexes is induced by light alkali metal amides of the NNNN‐type macrocyclic anionic ligand Me3TACD [(Me3TACD)H=1,4,7‐trimethyl‐1,4,7,10‐tetraazacyclododecane]. In the crystal, the alkali metal interacts with the carbene carbon atom or with the CH2 group of the trimethylsilymethyl ligand. The nucleophilic character of the carbene carbon atom was shown by the reaction with benzophenone and terminal acetylenes. 相似文献
53.
Hendrik Schneider Lukas Deweid Thomas Pirzer Desislava Yanakieva Simon Englert Bastian Becker Dr. Olga Avrutina Prof. Dr. Harald Kolmar 《ChemistryOpen》2019,8(3):354-357
Antibody-drug conjugates (ADCs) are multicomponent biomolecules that have emerged as a powerful tool for targeted tumor therapy. Combining specific binding of an immunoglobulin with toxic properties of a payload, they however often suffer from poor hydrophilicity when loaded with a high amount of toxins. To address these issues simultaneously, we developed dextramabs, a novel class of hybrid antibody-drug conjugates. In these architectures, the therapeutic antibody trastuzumab is equipped with a multivalent dextran polysaccharide that enables efficient loading with a potent toxin in a controllable fashion. Our modular chemoenzymatic approach provides an access to synthetic dextramabs bearing monomethyl auristatin as releasable cytotoxic cargo. They possess high drug-to-antibody ratios, remarkable hydrophilicity, and high toxicity in vitro. 相似文献
54.
55.
Christoph Englert Dr. Ivo Nischang Cornelia Bader Philipp Borchers Julien Alex Michael Pröhl Martin Hentschel Dr. Matthias Hartlieb Dr. Anja Traeger Prof. Dr. Georg Pohnert Dr. Stephanie Schubert Dr. Michael Gottschaldt Prof. Dr. Ulrich S. Schubert 《Angewandte Chemie (International ed. in English)》2018,57(9):2479-2482
A benzoin‐derived diol linker was synthesized and used to generate biocompatible polyesters that can be fully decomposed on demand upon UV irradiation. Extensive structural optimization of the linker unit was performed to enable the defined encapsulation of diverse organic compounds in the polymeric structures and allow for a well‐controllable polymer cleavage process. Selective tracking of the release kinetics of encapsulated model compounds from the polymeric nano‐ and microparticle containers was performed by confocal laser scanning microscopy in a proof‐of‐principle study. The physicochemical properties of the incorporated and released model compounds ranged from fully hydrophilic to fully hydrophobic. The demonstrated biocompatibility of the utilized polyesters and degradation products enables their use in advanced applications, for example, for the smart packaging of UV‐sensitive pharmaceuticals, nutritional components, or even in the area of spatially selective self‐healing processes. 相似文献
56.
A series of cocrystals of an organometallic tungsten complex with organic small molecules has been prepared and studied by single-crystal X-ray diffraction. Comparison of the five structures thus obtained allowed the measurement of the effects of the crystal environment on the molecular structure under investigation. Not only soft torsional degrees of freedom but also bond angles, the point symmetry, and other geometrical features of the reference molecule have been found to vary significantly. It is concluded that parameters commonly ascribed to themolecular structure may in reality depend onintermolecular interactions.Dedicated to Prof. Dr. J. Strähle on the occasion of his 60th birthday. 相似文献
57.
The solid-state structure of the triple-decker salt [Cp*Fe(-5:5-C4Me4P)RuCp*] · CF3SO3 shows orientational disorder for the pseudosymmetric cations. A chemically related compound was used to define a restrained structure model. Comparison of different refinement strategies proves that this restrained model is superior to an unrestrained treatment. 相似文献
58.
Latronico M Polini F Gallo V Mastrorilli P Calmuschi-Cula B Englert U Re N Repo T Räisänen M 《Inorganic chemistry》2008,47(21):9779-9796
The protonation of the dinuclear phosphinito bridged complex [(PHCy2)Pt(mu-PCy2){kappa(2)P,O-mu-P(O)Cy2}Pt(PHCy2)] (Pt-Pt) (1) by Br?nsted acids affords hydrido bridged Pt-Pt species the structure of which depends on the nature and on the amount of the acid used. The addition of 1 equiv of HX (X = Cl, Br, I) gives products of formal protonation of the Pt-Pt bond of formula syn-[(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(O)Cy2}] (Pt-Pt) (5, X = Cl; 6, X = Br; 8, X = I), containing a Pt-X bond and a dangling kappa P-P(O)Cy2 ligand. Uptake of a second equivalent of HX results in the protonation of the P(O)Cy2 ligand with formation of the complexes [(PHCy2)(X)Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappaP-P(OH)Cy2}]X (Pt-Pt) (3, X = Cl; 4, X = Br; 9, X = I). Each step of protonation is reversible, thus reactions of 3, 4, with NaOH give, first, the corresponding neutral complexes 5, 6, and then the parent compound 1. While the complexes 3 and 4 are indefinitely stable, the iodine analogue 9 transforms into anti-[(PHCy2)(I)Pt(mu-PCy2)(mu-H)Pt(PHCy2)(I)] (Pt-Pt) (7) deriving from substitution of an iodo group for the P(OH)Cy2 ligand. Complexes 3 and 4 are isomorphous crystallizing in the triclinic space group P1 and show an intramolecular hydrogen bond and an interaction between the halide counteranion and the POH hydrogen. The occurrence of such an interaction also in solution was ascertained for 3 by (35)Cl NMR. Multinuclear NMR spectroscopy (including (31)P-(1)H HOESY) and density-functional theory calculations indicate that the mechanism of the reaction starts with a prior protonation of the oxygen with formation of an intermediate (12) endowed with a six membered Pt(1)-X...H-O-P-Pt(2) ring that evolves into thermodynamically stable products featuring the hydride ligand bridging the Pt atoms. Energy profiles calculated for the various steps of the reaction between 1 and HCl showed very low barriers for the proton transfer and the subsequent rearrangement to 12, while a barrier of 29 kcal mol(-1) was found for the transformation of 12 into 5. 相似文献
59.
Dr. Takahito Mukai Dr. Markus Englert Dr. H. James Tripp Dr. Corwin Miller Dr. Natalia N. Ivanova Dr. Edward M. Rubin Dr. Nikos C. Kyrpides Prof. Dieter Söll 《Angewandte Chemie (International ed. in English)》2016,55(17):5337-5341
Selenocysteine (Sec or U) is encoded by UGA, a stop codon reassigned by a Sec‐specific elongation factor and a distinctive RNA structure. To discover possible code variations in extant organisms we analyzed 6.4 trillion base pairs of metagenomic sequences and 24 903 microbial genomes for tRNASec species. As expected, UGA is the predominant Sec codon in use. We also found tRNASec species that recognize the stop codons UAG and UAA, and ten sense codons. Selenoprotein synthesis programmed by UAG in Geodermatophilus and Blastococcus, and by the Cys codon UGU in Aeromonas salmonicida was confirmed by metabolic labeling with 75Se or mass spectrometry. Other tRNASec species with different anticodons enabled E. coli to synthesize active formate dehydrogenase H, a selenoenzyme. This illustrates the ease by which the genetic code may evolve new coding schemes, possibly aiding organisms to adapt to changing environments, and show the genetic code is much more flexible than previously thought. 相似文献
60.