全文获取类型
收费全文 | 1577篇 |
免费 | 91篇 |
国内免费 | 10篇 |
专业分类
化学 | 942篇 |
晶体学 | 5篇 |
力学 | 45篇 |
数学 | 401篇 |
物理学 | 285篇 |
出版年
2024年 | 6篇 |
2023年 | 25篇 |
2022年 | 37篇 |
2021年 | 33篇 |
2020年 | 45篇 |
2019年 | 46篇 |
2018年 | 32篇 |
2017年 | 24篇 |
2016年 | 76篇 |
2015年 | 72篇 |
2014年 | 69篇 |
2013年 | 112篇 |
2012年 | 116篇 |
2011年 | 152篇 |
2010年 | 87篇 |
2009年 | 51篇 |
2008年 | 97篇 |
2007年 | 86篇 |
2006年 | 82篇 |
2005年 | 69篇 |
2004年 | 67篇 |
2003年 | 51篇 |
2002年 | 42篇 |
2001年 | 17篇 |
2000年 | 12篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 13篇 |
1996年 | 17篇 |
1995年 | 22篇 |
1994年 | 11篇 |
1993年 | 3篇 |
1992年 | 13篇 |
1991年 | 4篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1982年 | 8篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1921年 | 1篇 |
排序方式: 共有1678条查询结果,搜索用时 15 毫秒
61.
Jan Rosenboom Dr. Lukas Chojetzki Dr. Tim Suhrbier Dr. Jabor Rabeah Dr. Alexander Villinger Dr. Ronald Wustrack Dr. Jonas Bresien Prof. Dr. Axel Schulz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202200624
The activation of C−Br bonds in various bromoalkanes by the biradical [⋅P(μ-NTer)2P⋅] ( 1 ) (Ter=2,6-bis-(2,4,6-trimethylphenyl)-phenyl) is reported, yielding trans-addition products of the type [Br−P(μ-NTer)2P−R] ( 2 ), so-called 1,3-substituted cyclo-1,3-diphospha-2,4-diazanes. This addition reaction, which represents a new easy approach to asymmetrically substituted cyclo-1,3-diphospha-2,4-diazanes, was investigated mechanistically by different spectroscopic methods (NMR, EPR, IR, Raman); the results suggested a stepwise radical reaction mechanism, as evidenced by the in-situ detection of the phosphorus-centered monoradical [⋅P(μ-NTer)2P-R].< To provide further evidence for the radical mechanism, [⋅P(μ-NTer)2P-Et] ( 3Et ⋅) was synthesized directly by reduction of the bromoethane addition product [Br-P(μ-NTer)2P-Et] ( 2 a ) with magnesium, resulting in the formation of the persistent phosphorus-centered monoradical [⋅P(μ-NTer)2P-Et], which could be isolated and fully characterized, including single-crystal X-ray diffraction. Comparison of the EPR spectrum of the radical intermediate in the addition reaction with that of the synthesized new [⋅P(μ-NTer)2P-Et] radical clearly proves the existence of radicals over the course of the reaction of biradical [⋅P(μ-NTer)2P⋅] ( 1 ) with bromoethane. Extensive DFT and coupled cluster calculations corroborate the experimental data for a radical mechanism in the reaction of biradical [⋅P(μ-NTer)2P⋅] with EtBr. In the field of hetero-cyclobutane-1,3-diyls, the demonstration of a stepwise radical reaction represents a new aspect and closes the gap between P-centered biradicals and P-centered monoradicals in terms of radical reactivity. 相似文献
62.
Felipe J. Llanes-Estrada Tim Van Cauteren Ángel P. Martín 《The European Physical Journal C - Particles and Fields》2007,51(4):945-952
We study the multiple solutions of the truncated propagator Dyson–Schwinger equation for a simple fermion theory with Yukawa
coupling to a scalar field. Upon increasing the coupling constant g, other parameters being fixed, more than one non-perturbative
solution breaking chiral symmetry becomes possible and we find these numerically. These “recurrences” appear as a mechanism
to generate different fermion generations as quanta of the same fundamental field in an interacting field theory, without
assuming any composite structure. The number of recurrences or flavors is reduced to the question of the value of the Yukawa
coupling, and it has no special profound significance in the standard model. The resulting mass function can have one or more
nodes and the measurement that potentially detects them can be thought of as a collider-based test of the virtual dispersion
relation for the charged lepton member of each family. This requires the three independent measurements of the charged lepton’s energy,
three-momentum and off-shellness. We illustrate how this can be achieved for the (more difficult) case of the tau lepton.
PACS 12.15.Ff; 11.30.Rd 相似文献
63.
We apply random matrix theory to compare correlation matrix estimators C obtained from emerging market data. The correlation matrices are constructed from 10 years of daily data for stocks listed on the Johannesburg stock exchange (JSE) from January 1993 to December 2002. We test the spectral properties of C against random matrix predictions and find some agreement between the distributions of eigenvalues, nearest neighbour spacings, distributions of eigenvector components and the inverse participation ratios for eigenvectors. We show that interpolating both missing data and illiquid trading days with a zero-order hold increases agreement with RMT predictions. For the more realistic estimation of correlations in an emerging market, we suggest a pairwise measured-data correlation matrix. For the data set used, this approach suggests greater temporal stability for the leading eigenvectors. An interpretation of eigenvectors in terms of trading strategies is given, as opposed to classification by economic sectors. 相似文献
64.
Kwan Ho Au-Yeung Tim Kühne Daniel Becker Dr. Marcus Richter Dr. Dmitry A. Ryndyk Prof. Dr. Gianaurelio Cuniberti Prof. Dr. Thomas Heine Prof. Dr. Xinliang Feng Dr. Francesca Moresco 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(69):17336-17340
The rapid development of on-surface synthesis provides a unique approach toward the formation of carbon-based nanostructures with designed properties. Herein, we present the on-surface formation of CN-substituted phenylene vinylene chains on the Au(111) surface, thermally induced by annealing the substrate stepwise at temperatures between 220 °C and 240 °C. The reaction is investigated by scanning tunneling microscopy and density functional theory. Supported by the calculated reaction pathway, we assign the observed chain formation to a Knoevenagel condensation between an aldehyde and a methylene nitrile substituent. 相似文献
65.
66.
Back Cover: Two‐Dimensional Tetrathiafulvalene Covalent Organic Frameworks: Towards Latticed Conductive Organic Salts (Chem. Eur. J. 45/2014)
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)
67.
Dr. Damien Hudry Dr. Christos Apostolidis Dr. Olaf Walter Dr. Arne Janßen Dr. Dario Manara Dr. Jean‐Christophe Griveau Dr. Eric Colineau Dr. Tonya Vitova Tim Prüßmann Dr. Di Wang Dr. Christian Kübel Dr. Daniel Meyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10431-10438
Apart from its technological importance, plutonium (Pu) is also one of the most intriguing elements because of its non‐conventional physical properties and fascinating chemistry. Those fundamental aspects are particularly interesting when dealing with the challenging study of plutonium‐based nanomaterials. Here we show that ultra‐small (3.2±0.9 nm) and highly crystalline plutonium oxide (PuO2) nanocrystals (NCs) can be synthesized by the thermal decomposition of plutonyl nitrate ([PuO2(NO3)2] ? 3 H2O) in a highly coordinating organic medium. This is the first example reporting on the preparation of significant quantities (several tens of milligrams) of PuO2 NCs, in a controllable and reproducible manner. The structure and magnetic properties of PuO2 NCs have been characterized by a wide variety of techniques (powder X‐ray diffraction (PXRD), X‐ray absorption fine structure (XAFS), X‐ray absorption near edge structure (XANES), TEM, IR, Raman, UV/Vis spectroscopies, and superconducting quantum interference device (SQUID) magnetometry). The current PuO2 NCs constitute an innovative material for the study of challenging problems as diverse as the transport behavior of plutonium in the environment or size and shape effects on the physics of transuranium elements. 相似文献
68.
In this work, the zero coverage adsorption properties of C5–C10 n- and iso-alkanes on the UiO-66, UiO-66-Me and UiO-66-NO2 metal–organic frameworks are studied by gas phase pulse chromatography. Analysis of enthalpy values, entropy values, Gibbs free energies and Henry constants reveals unusual chain length dependent adsorption behaviour of linear and branched alkanes, caused by the complex structure of the zirconium metal–organic framework UiO-66. The UiO-66 structure consists of a small, tetrahedral and large, octahedral cage. It is shown that at specific carbon chain lengths (e.g. C6–C7 for n-alkanes), distinctive jumps in adsorption enthalpy, entropy values and Henry constants occur. This chain length dependent effect is even more pronounced for 2- and 3-methyl alkanes and double branched alkanes. This distinctive shift in adsorption behaviour occurs at a molecular size that coincides with the cavity dimensions of the smallest, tetrahedral cage. The resulting selective adsorption arises from confinement effects and is function of both the molecular shape and size. 相似文献
69.
Hideyuki Tatsuno Kasper S. Kjr Kristjan Kunnus Tobias C. B. Harlang Cornelia Timm Meiyuan Guo Pavel Chbera Lisa A. Fredin Robert W. Hartsock Marco E. Reinhard Sergey Koroidov Lin Li Amy A. Cordones Olga Gordivska Om Prakash Yizhu Liu Mads G. Laursen Elisa Biasin Frederik B. Hansen Peter Vester Morten Christensen Kristoffer Haldrup Zoltn Nmeth Dorottya Srosin Szemes va Bajnczi Gyrgy Vank Tim B. Van Driel Roberto Alonso‐Mori James M. Glownia Silke Nelson Marcin Sikorski Henrik T. Lemke Dimosthenis Sokaras Sophie E. Canton Asmus O. Dohn Klaus B. Mller Martin M. Nielsen Kelly J. Gaffney Kenneth Wrnmark Villy Sundstrm Petter Persson Jens Uhlig 《Angewandte Chemie (International ed. in English)》2020,59(1):364-372
Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an FeIINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot 3MLCT state, from the initially excited 1MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the 3MC state, in competition with vibrational relaxation and cooling to the relaxed 3MLCT state. The relaxed 3MLCT state then decays much more slowly (7.6 ps) to the 3MC state. The 3MC state is rapidly (2.2 ps) deactivated to the ground state. The 5MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the 3MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance. 相似文献
70.
Zechao Yang Lukas Fromm Tim Sander Julian Gebhardt Tobias A. Schaub Andreas Grling Milan Kivala Sabine Maier 《Angewandte Chemie (International ed. in English)》2020,59(24):9549-9555
Demonstrated here is a supramolecular approach to fabricate highly ordered monolayered hydrogen‐ and halogen‐bonded graphyne‐like two‐dimensional (2D) materials from triethynyltriazine derivatives on Au(111) and Ag(111). The 2D networks are stabilized by N???H?C(sp) bonds and N???Br?C(sp) bonds to the triazine core. The structural properties and the binding energies of the supramolecular graphynes have been investigated by scanning tunneling microscopy in combination with density‐functional theory calculations. It is revealed that the N???Br?C(sp) bonds lead to significantly stronger bonded networks compared to the hydrogen‐bonded networks. A systematic analysis of the binding energies of triethynyltriazine and triethynylbenzene derivatives further demonstrates that the X3‐synthon, which is commonly observed for bromobenzene derivatives, is weaker than the X6‐synthon for our bromotriethynyl derivatives. 相似文献