全文获取类型
收费全文 | 9155篇 |
免费 | 552篇 |
国内免费 | 42篇 |
专业分类
化学 | 6735篇 |
晶体学 | 32篇 |
力学 | 157篇 |
数学 | 1478篇 |
物理学 | 1347篇 |
出版年
2023年 | 75篇 |
2022年 | 63篇 |
2021年 | 145篇 |
2020年 | 229篇 |
2019年 | 199篇 |
2018年 | 146篇 |
2017年 | 120篇 |
2016年 | 415篇 |
2015年 | 378篇 |
2014年 | 401篇 |
2013年 | 476篇 |
2012年 | 661篇 |
2011年 | 704篇 |
2010年 | 503篇 |
2009年 | 410篇 |
2008年 | 652篇 |
2007年 | 576篇 |
2006年 | 541篇 |
2005年 | 554篇 |
2004年 | 459篇 |
2003年 | 301篇 |
2002年 | 218篇 |
2001年 | 77篇 |
2000年 | 56篇 |
1999年 | 63篇 |
1998年 | 55篇 |
1997年 | 136篇 |
1996年 | 82篇 |
1995年 | 103篇 |
1994年 | 97篇 |
1993年 | 85篇 |
1992年 | 80篇 |
1991年 | 56篇 |
1990年 | 37篇 |
1989年 | 68篇 |
1988年 | 51篇 |
1987年 | 31篇 |
1986年 | 31篇 |
1985年 | 45篇 |
1984年 | 36篇 |
1983年 | 22篇 |
1982年 | 45篇 |
1981年 | 30篇 |
1980年 | 25篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1977年 | 18篇 |
1975年 | 21篇 |
1973年 | 15篇 |
1968年 | 14篇 |
排序方式: 共有9749条查询结果,搜索用时 15 毫秒
61.
Functionalization of Intramolecular Frustrated Lewis Pairs by 1,1‐Carboboration with Conjugated Enynes 下载免费PDF全文
Dr. Andreas Feldmann Dr. Gerald Kehr Dr. Constantin G. Daniliuc Dr. Christian Mück‐Lichtenfeld Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(35):12456-12464
The vicinal P/B frustrated Lewis pair (FLP) Mes2PCH2CH2B(C6F5)2 undergoes 1,1‐carboboration reactions with the Me3Si‐substituted enynes to give ring‐enlarged functionalized C3‐bridged P/B FLPs. These serve as active FLPs in the activation of dihydrogen to give the respective zwitterionic [P]H+/[B]H? products. One such product shows activity as a metal‐free catalyst for the hydrogenation of enamines or a bulky imine. The ring‐enlarged FLPs contain dienylborane functionalities that undergo “bora‐Nazarov”‐type ring‐closing rearrangements upon photolysis. A DFT study had shown that the dienylborane cyclization of such systems itself is endothermic, but a subsequent C6F5 migration is very favorable. Furthermore, substituted 2,5‐dihydroborole products are derived from cyclization and C6F5 migration from the photolysis reaction. In the case of the six‐membered annulation product, a subsequent stereoisomerization reaction takes place and the resultant compound undergoes a P/B FLP 1,2‐addition reaction with a terminal alkyne with rearrangement. 相似文献
62.
Metal‐Catalyzed β‐Functionalization of Michael Acceptors through Reductive Radical Addition Reactions 下载免费PDF全文
Dr. Jan Streuff Prof. Dr. Andreas Gansäuer 《Angewandte Chemie (International ed. in English)》2015,54(48):14232-14242
Transition‐metal‐catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β‐unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today′s developments. 相似文献
63.
Boryl (Hetero)aryne Precursors as Versatile Arylation Reagents: Synthesis through CH Activation and Orthogonal Reactivity 下载免费PDF全文
Dr. Emilien Demory Karthik Devaraj Dr. Andreas Orthaber Dr. Paul J. Gates Dr. Lukasz T. Pilarski 《Angewandte Chemie (International ed. in English)》2015,54(40):11765-11769
(Pinacolato)boryl ortho‐silyl(hetero)aryl triflates are presented as a new class of building blocks for arylation. They demonstrate unique versatility by delivering boronate or (hetero)aryne reactivity chemoselectively in a broad range of transformations. This approach enables the unprecedented postfunctionalization of fluoride‐activated (hetero)aryne precursors, for example, as substrates in transition‐metal catalysis, and offers valuable new possibilities for aryl boronate postfunctionalization without the use of specialized protecting groups. 相似文献
64.
Chemical Synthesis Elucidates the Immunological Importance of a Pyruvate Modification in the Capsular Polysaccharide of Streptococcus pneumoniae Serotype 4 下载免费PDF全文
Dr. Claney L. Pereira Andreas Geissner Dr. Chakkumkal Anish Prof. Dr. Peter H. Seeberger 《Angewandte Chemie (International ed. in English)》2015,54(34):10016-10019
Carbohydrate modifications are believed to strongly affect the immunogenicity of glycans. Capsular polysaccharides (CPS) from bacterial pathogens are frequently equipped with a pyruvate that can be placed across the 4,6‐, 3,4‐, or 2,3‐positions. A trans‐2,3‐linked pyruvate is present on the CPS of the Gram‐positive bacterium Streptococcus pneumoniae serotype 4 (ST4), a pathogen responsible for pneumococcal infections. To assess the immunological importance of this modification within the CPS repeating unit, the first total synthesis of the glycan was carried out. Glycan microarrays containing a series of synthetic antigens demonstrated how antibodies raised against natural ST4 CPS specifically recognize the pyruvate within the context of the tetrasaccharide repeating unit. The pyruvate modification is a key motif for designing minimal synthetic carbohydrate vaccines for ST4. 相似文献
65.
Corrigendum: Crystallographic Snapshot of an Arrested Intermediate in the Biomimetic Activation of CO2 下载免费PDF全文
66.
67.
Dendronized Hyperbranched Macromolecules: Soft Matter with a Novel Type of Segmental Distribution 下载免费PDF全文
Priv.‐Doz. Dr. Albena Lederer Prof. Dr. Walther Burchard Tobias Hartmann Johannes S. Haataja Dr. Nikolay Houbenov Andreas Janke Dr. Peter Friedel Dr. Ralf Schweins Dr. Peter Lindner 《Angewandte Chemie (International ed. in English)》2015,54(43):12578-12583
Dendronization of a hyperbranched polyester with different generation dendrons leads to pseudo‐dendritic structures. The hyperbranched core is modified by the divergent coupling of protected monomer units to the functional groups. Compared to dendrimers, the synthetic effort is significantly less, but the properties are very close to those of high‐generation dendrimers. The number of functional groups, molar mass, and rheology behavior even in the early generation (G1–G4) pseudo‐dendrimers strongly resembles the behavior of dendrimers in higher generations (G5–G8). Comparison of the segmental and internal structure with perfect dendrimers is performed using SANS, dynamic light scattering and viscosity analysis, microscopy and molecular dynamics simulation. The interpretation of the results reveals unique structural characteristics arising from lower segmental density of the core, which turns into a soft nano‐sphere with a smooth surface even in the first generation. 相似文献
68.
Thomas Heuser Elisabeth Weyandt Dr. Andreas Walther 《Angewandte Chemie (International ed. in English)》2015,54(45):13258-13262
Switchable self‐assemblies respond to external stimuli with a transition between near‐equilibrium states. Although being a key to present‐day advanced materials, these systems respond rather passively, and do not display autonomous dynamics. For autonomous behavior, approaches must be found to orchestrate the time domain of self‐assemblies, which would lead to new generations of dynamic and self‐regulating materials. Herein, we demonstrate catalytic control of the time domain of pH‐responsive peptide hydrogelators in a closed system. We program transient acidic pH states by combining a fast acidic activator with the slow, enzymatic, feedback‐driven generation of a base (dormant deactivator). This transient state can be programmed over orders of magnitude in time. It is coupled to dipeptides to create autonomously self‐regulating, dynamic gels with programmed lifetimes, which are used for fluidic guidance, burst release, and self‐erasing rapid prototyping. 相似文献
69.
Cover Picture: Metal‐Free Addition/Head‐to‐Tail Polymerization of Transient Phosphinoboranes,RPH‐BH2: A Route to Poly(alkylphosphinoboranes) (Angew. Chem. Int. Ed. 46/2015) 下载免费PDF全文
70.
Synthesis,Structure, and Properties of SrC(NH)3, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif 下载免费PDF全文
M. Sc. Ronja Missong M. Sc. Janine George Dr. Andreas Houben Dr. Markus Hoelzel Prof. Dr. Richard Dronskowski 《Angewandte Chemie (International ed. in English)》2015,54(41):12171-12175
Strontium guanidinate, SrC(NH)3, the first compound with a doubly deprotonated guanidine unit, was synthesized from strontium and guanidine in liquid ammonia and characterized by X‐ray and neutron diffraction, IR spectroscopy, and density‐functional theory including harmonic phonon calculations. The compound crystallizes in the hexagonal space group P63/m, constitutes the nitrogen analogue of strontium carbonate, SrCO3, and its structure follows a layered motif between Sr2+ ions and complex anions of the type C(NH)32?; the anions adopt the peculiar trinacria shape. A comparison of theoretical phonons with experimental IR bands as well as quantum‐chemical bonding analyses yield a first insight into bonding and packing of the formerly unknown anion in the crystal. 相似文献