全文获取类型
收费全文 | 1227篇 |
免费 | 85篇 |
国内免费 | 1篇 |
专业分类
化学 | 922篇 |
晶体学 | 10篇 |
力学 | 23篇 |
数学 | 173篇 |
物理学 | 185篇 |
出版年
2023年 | 9篇 |
2022年 | 18篇 |
2021年 | 21篇 |
2020年 | 34篇 |
2019年 | 25篇 |
2018年 | 14篇 |
2017年 | 17篇 |
2016年 | 52篇 |
2015年 | 48篇 |
2014年 | 69篇 |
2013年 | 91篇 |
2012年 | 89篇 |
2011年 | 86篇 |
2010年 | 61篇 |
2009年 | 53篇 |
2008年 | 64篇 |
2007年 | 57篇 |
2006年 | 52篇 |
2005年 | 43篇 |
2004年 | 39篇 |
2003年 | 24篇 |
2002年 | 35篇 |
2001年 | 21篇 |
2000年 | 16篇 |
1999年 | 7篇 |
1997年 | 7篇 |
1996年 | 12篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 9篇 |
1992年 | 18篇 |
1991年 | 11篇 |
1989年 | 12篇 |
1988年 | 6篇 |
1987年 | 11篇 |
1986年 | 16篇 |
1985年 | 17篇 |
1984年 | 8篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1977年 | 9篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 7篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1970年 | 6篇 |
排序方式: 共有1313条查询结果,搜索用时 15 毫秒
61.
We propose a model to describe correlated two-electron dynamics in strong laser fields during laser-induced recollision between an electron and its parent ion. We derive an effective interaction potential which describes the effect of the laser-driven electron collision with an ion while retaining the correlation between the colliding and the bound electron. Using dissociative ionization of molecular hydrogen as an example, we analyze the dynamics of correlation-driven electron localization in a dissociating hydrogen molecular ion. 相似文献
62.
A novel dihydroazepine-bridged BIPHEP phosphoramidite ligand with an amino acid moiety in the backbone was synthesized and evaluated in the Rh-catalyzed asymmetric hydrogenation. The scorpion tail-like amino acid backbone is capable of hydrogen bond formation and able to shift the rotamer composition of the biphenyl axis with the two scissor-like arms. Pivaloyl-l -valine was studied as chiral selector unit and compared with pivaloylglycine as the achiral reference substance. The enantiomerization barrier of the pivaloylglycine-modified biphenylamide was determined to be ΔG≠=110 kJ/mol. In the case of pivaloyl-l -valine, the (Sax) isomer is thermodynamically favored. Due to the relatively high barrier, the ligand is atropisomeric at room temperature and allows the preparative separation of the stereoisomers. The obtained phosphoramidite ligands were separated by chiral HPLC. For the first eluting rotamer, Rh complex ([Rh(cod)(L)2]BF4) was generated in situ and examined in the enantioselective hydrogenation of 2-acetamidoacrylate and methyl 2-acetamido-3-phenylacrylate, achieving enantiomeric excesses of up to 94 %. 相似文献
63.
We prove part of a conjecture by Johansson, Kahn, and Vu (Factors in random graphs, Random Struct. Algorithms 33 (2008), 1, 1–28.) regarding threshold functions for the existence of an H‐factor in a random graph . We prove that the conjectured threshold function is correct for any graph H which is not covered by its densest subgraphs. We also demonstrate that the main result of Johansson, Kahn, and Vu (Factors in random graphs, Random Struct. Algorithms 33 (2008), 1, 1–28) generalizes to multigraphs, digraphs, and a multipartite model. 相似文献
64.
Dipl.‐Chem. Günther Thiele Thomas Krüger Prof. Dr. Stefanie Dehnen 《Angewandte Chemie (International ed. in English)》2014,53(18):4699-4703
The first inorganic lead(IV) compound without oxygen, nitrogen or halogen ligands attached to the lead atom was obtained as the potassium salt of the tetraselenidoplumbate(IV) anion [PbIVSe4]4?. It is stable under inert conditions which may enable the transfer of the chemistry of chalcogenidogermanate(IV) or chalcogenidostannate(IV) materials, to the lead homologues. 相似文献
65.
Coverage‐ and Temperature‐Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111)
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)
Michael Röckert Matthias Franke Quratulain Tariq Stefanie Ditze Michael Stark Patrick Uffinger Daniel Wechsler Upendra Singh Dr. Jie Xiao Dr. Hubertus Marbach Prof. Dr. Hans‐Peter Steinrück Dr. Ole Lytken 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8948-8953
Using temperature‐programmed desorption, supported by X‐ray photoelectron spectroscopy and scanning tunneling microscopy, a comprehensive overview of the main reactions of 5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin (2HTPP) on Cu(111) as a function of coverage and temperature is obtained. Three reactions were identified: metalation with Cu substrate atoms, stepwise partial dehydrogenation, and finally complete dehydrogenation. At low coverage the reactions are independent of coverage, but at higher coverage metalation becomes faster and partial dehydrogenation slower. This behavior is explained by a weaker interaction between the iminic nitrogen atoms and the Cu(111) surface in the high‐coverage checkerboard structure, leading to faster metalation, and the stabilizing effect of T‐type interactions in the CuTPP islands formed at high coverage after metalation, leading to slower dehydrogenation. Based on the amount of hydrogen released and the appearance in STM, a structure of the partially dehydrogenated molecule is suggested. 相似文献
66.
Organotin–Oxido Cluster‐Based Multiferrocenyl Complexes Obtained by Hydrolysis of Ferrocenyl‐Functionalized Organotin Chlorides
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)
Zhiliang You Robert Möckel Jakob Bergunde Prof. Dr. Stefanie Dehnen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13491-13496
Three organotin–oxido clusters were formed by hydrolysis of ferrocenyl‐functionalized organotin chloride precursors in the presence of NaEPh (E=S, Se). [RFcSnCl3?HCl] ( C ; RFc = CMe2CH2C(Me)?N?N?C(Me)Fc) and [SnCl6]2? formed {(RFcSnCl2)3[Sn(OH)6]}[SnCl3] ( 3 a ) and {(RFcSnCl2)3[Sn(OH)6]}[PhSeO3] ( 3 b ), bearing an unprecedented [Sn4O6] unit, in a one‐pot synthesis or stepwise through [(RFcSnCl2)2Se] ( 1 ) plus [(RFcSnCl2)SePh] ( 2 ). A one‐pot reaction starting out from FcSnCl3 gave [(FcSn)9(OH)6O8Cl5] ( 4 ), which represents the largest Fc‐decorated Sn/O cluster reported to date. 相似文献
67.
Determination of the Absolute Configuration of Perylene Quinone‐Derived Mycotoxins by Measurement and Calculation of Electronic Circular Dichroism Spectra and Specific Rotations
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)
Prof. Dr. Joachim Podlech Dr. Stefanie C. Fleck Prof. Dr. Manfred Metzler Dr. Jochen Bürck Prof. Dr. Anne S. Ulrich 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(36):11463-11470
Altertoxins I–III, alterlosins I and II, alteichin (alterperylenol), stemphyltoxins I–IV, stemphyperylenol, stemphytriol, 7‐epi‐8‐hydroxyaltertoxin I, and 6‐epi‐stemphytriol are mycotoxins derived from perylene quinone, for which the absolute configuration was not known. Electronic circular dichroism (ECD) spectra were calculated for these compounds and compared with measured spectra of altertoxins I–III, alteichin, and stemphyltoxin III and with reported Cotton effects. Specific rotations were calculated and compared with reported specific rotations. The absolute configuration of all the toxins, except for stemphyltoxin IV, could thus be determined. The validity of the assignment was high whenever reported ECD data were available for comparison, and the validity was lower when the assignment was based only on the comparison of calculated and reported specific rotations. ECD spectra are intrinsically different for toxins with a biphenyl substructure and for toxins derived from dihydroanthracene. 相似文献
68.
One‐Step Multicomponent Self‐Assembly of a First‐Generation Sierpiński Triangle: From Fractal Design to Chemical Reality
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Rajarshi Sarkar Kai Guo Dr. Charles N. Moorefield Prof. Mary Jane Saunders Prof. Chrys Wesdemiotis Prof. George R. Newkome 《Angewandte Chemie (International ed. in English)》2014,53(45):12182-12185
A novel terpyridine‐based architecture that mimics a first‐generation Sierpiński triangle has been synthesized by multicomponent assembly and features tpy? CdII? tpy connectivity (tpy=terpyridine). The key terpyridine ligands were synthesized by the Suzuki cross‐coupling reaction. Mixing two different terpyridine‐based ligands and CdII in a precise stoichiometric ratio (1:1:3) produced the desired fractal architecture in near‐quantitative yield. Characterization was accomplished by NMR spectroscopy, mass spectrometry, and transmission electron microscopy. 相似文献
69.
Origin and Location of Electrons and Protons during the Formation of Intermetalloid Clusters [Sm@Ga3−xH3−2xBi10+x]3− (x=0, 1)
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dipl.‐Chem. Bastian Weinert B.Sc. Fabian Müller Dr. Klaus Harms Dr. Rodolphe Clérac Prof. Dr. Stefanie Dehnen 《Angewandte Chemie (International ed. in English)》2014,53(44):11979-11983
Reaction of [GaBi3]2? with [Sm(C5Me4H)3] yielded the first protonated ternary intermetalloid clusters [Sm@Ga3?xH3?2xBi10+x]3? ( 1 ; x=0,1). The presence of the Ga? H bonds and the transfer of electrons and protons during the formation of 1 were elucidated by a combination of experimental and quantum chemical methods, thereby rationalizing the role of the solvent ethane‐1,2‐diamine as a Brønsted acid. As an organic by‐product, we observed the previously unknown octamethylfulvene ( 2 ) upon C? C coupling of (C5Me4H)?. 相似文献
70.
Tuija Jokinen Dr. Mikko Sipilä Stefanie Richters Prof. Veli‐Matti Kerminen Dr. Pauli Paasonen Dr. Frank Stratmann Dr. Douglas Worsnop Prof. Markku Kulmala Dr. Mikael Ehn Prof. Hartmut Herrmann Dr. Torsten Berndt 《Angewandte Chemie (International ed. in English)》2014,53(52):14596-14600
Gas‐phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α‐pinene) form highly oxidized RO2 radicals with up to 12 O atoms, along with related closed‐shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O2 addition generating a next R′OO radical, is similar to the well‐known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical). Field measurements show the relevance of this process to atmospheric chemistry. Thus, the well‐known reaction principle of autoxidation is also applicable to the atmospheric gas‐phase oxidation of hydrocarbons leading to extremely low‐volatility products which contribute to organic aerosol mass and hence influence the aerosol–cloud–climate system. 相似文献