全文获取类型
收费全文 | 3079篇 |
免费 | 199篇 |
国内免费 | 14篇 |
专业分类
化学 | 2344篇 |
晶体学 | 13篇 |
力学 | 81篇 |
数学 | 442篇 |
物理学 | 412篇 |
出版年
2023年 | 47篇 |
2022年 | 38篇 |
2021年 | 61篇 |
2020年 | 124篇 |
2019年 | 139篇 |
2018年 | 61篇 |
2017年 | 39篇 |
2016年 | 161篇 |
2015年 | 152篇 |
2014年 | 160篇 |
2013年 | 181篇 |
2012年 | 252篇 |
2011年 | 353篇 |
2010年 | 172篇 |
2009年 | 130篇 |
2008年 | 204篇 |
2007年 | 165篇 |
2006年 | 140篇 |
2005年 | 174篇 |
2004年 | 122篇 |
2003年 | 99篇 |
2002年 | 35篇 |
2001年 | 38篇 |
2000年 | 24篇 |
1999年 | 41篇 |
1998年 | 18篇 |
1997年 | 12篇 |
1996年 | 18篇 |
1995年 | 12篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1975年 | 8篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1971年 | 3篇 |
1963年 | 5篇 |
1956年 | 3篇 |
1905年 | 2篇 |
1904年 | 2篇 |
排序方式: 共有3292条查询结果,搜索用时 593 毫秒
161.
The pyrophoric compound Rb2[U(NH2)6] was obtained as a grey to black powder from the reaction of more than three equivalents of RbNH2 with UI3 in anhydrous liquid ammonia. During the process, UIII is oxidized to UIV and ammonia is reduced under evolution of H2. Rb2[U(NH2)6] crystallizes in the cubic crystal system, space group Fm3 m, with the lattice parameter a = 9.7870(12) Å, V = 937.4(2) Å3, Z = 4 at T = 293 K. It is isotypic to K2PtCl6. The compound contains the unprecedented hexaamidouranate(IV) anion [U(NH2)6]2–. 相似文献
162.
The Al45Cr7 compound is considered to exhibit an approximant structure of the icosahedral Al4Cr phase. Its (010) surface has been investigated in detail using density functional calculations. Surface energy calculations show that the stable terminations result from a cleavage of the crystal between adjacent atomic planes, in agreement with the layered structure of the compound. The integrity of the icosahedral atomic arrangements (icosahedral clusters) found in the bulk structure, is predicted to be removed at the surface. This result is in contrast to what has been previously concluded for the (010) surface of the Al13Fe4 quasicrystal approximant. Our findings are discussed in relation to the bonding network in the compound, calculated using the Crystal Orbital Hamiltonian Population approach, as possible reasons for such contrasted behavior. 相似文献
163.
Fabian Dankert H. Lars Deubner Matthias Müller Magnus R. Buchner Florian Kraus Carsten von Hänisch 《无机化学与普通化学杂志》2020,646(18):1501-1507
The work describes unexpected stoichiometric C–F bond cleavage reactions of beryllium, magnesium, gallium, hafnium and thorium halides with α,α,α-trifluorotoluene. The reaction of BeBr2 / GaBr3 or MgBr2 / GaBr3 mixtures as well as neat GaI3 with α,α,α-trifluorotoluene in the presence of (OSi2Me4)2 ( I ) yields the carbenium ion containing compounds [Ph-C(O2Si2Me4)][GaX4] (X = Br: 1 , X = I/F: 2 ). Both compounds were successfully characterized and a defluorination type reaction under incorporation of a siloxy unit was observed. Compound 1 was also characterized by single-crystal X-ray diffraction analysis. The conversion of α,α,α-trifluorotoluene with BeI2, HfI4 or ThI4 turned out to be a halodefluorination-type reaction with formation of α,α,α-triiodotoluene ( 3 ). An adequate NMR spectroscopic and the X-ray crystallographic characterization of 3 were performed for the first time. 相似文献
164.
Junting Chen Dr. Jiakun Li Dr. Matthew B. Plutschack Dr. Florian Berger Prof. Dr. Tobias Ritter 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5665-5669
Herein, we report a regioselective alkenyl electrophile synthesis from unactivated olefins that is based on a direct and regioselective C−H thianthrenation reaction. The selectivity is proposed to arise from an unusual inverse-electron-demand hetero-Diels–Alder reaction. The alkenyl sulfonium salts can serve as electrophiles in palladium- and ruthenium-catalyzed cross-coupling reactions to make alkenyl C−C, C−Cl, C−Br, and C−SCF3 bonds with stereoretention. 相似文献
165.
Dirk Schlüter Florian Kleemiss Dr. Malte Fugel Dr. Enno Lork Prof. Dr. Kunihisa Sugimoto PD Dr. Simon Grabowsky Prof. Dr. Jeffrey R. Harmer Dr. Matthias Vogt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1335-1343
Derivatives of 1,2-dithienylethene (DTE) have superb photochromic properties due to an efficient reversible photocyclization reaction of their hexatriene structure and, thus, have application potential in materials for optoelectronics and (multi-responsive) molecular switches. Transition-metal complexes bearing switchable DTE motifs commonly incorporate their coordination site rather distant from the hexatriene system. In this work the redox active ligand 1,2-bis(2,5-dimethylthiophen-3-yl)ethane-1,2-dione is described, which reacts with [V(TMEDA)2Cl2] to give a rare non-oxido vanadium(IV) species 3(M,M/P,P) . This blue complex has two bidentate en-diolato ligands which chelate the VIV center and give rise to two five-membered metallacycles with the adjacent hexatriene DTE backbone bearing axial chirality. Upon irradiation with UVA light or prolonged heating in solution, the blue compound 3(M,M/P,P) converts into the purple atropisomer 4(para,M/para,P) . Both complexes were isolated and structurally characterized by single-crystal X-ray diffraction analysis (using lab source and synchrotron radiation). The antiparallel configuration (M or P helicity) present in both 3(M,M/P,P) and 4(para,M/para,P) is a prerequisite for (reversible) 6π cyclization reactions. A CW EPR spectroscopic study reveals the metalloradical character for 3(M,M/P,P) and 4(para,M/para,P) and indicates dynamic reversible cyclization of the DTE backbone in complex 3(M,M/P,P) at ambient temperature in solution. 相似文献
166.
Florian M. Kruse Jennifer S. Teichert Prof. Dr. Oliver Trapp 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14776-14790
Ever since the discovery of nucleic acids 150 years ago,[1] major achievements have been made in understanding and decrypting the fascinating scientific questions of the genetic code.[2] However, the most fundamental question about the origin and the evolution of the genetic code remains a mystery. How did nature manage to build up such intriguingly complex molecules able to encode structure and function from simple building blocks? What conditions were required? How could the precursors survive the unhostile environment of early Earth? Over the past decades, promising synthetic concepts were proposed providing clarity in the field of prebiotic nucleic acid research. In this Minireview, we show the current status and various approaches to answer these fascinating questions. 相似文献
167.
Florian Ritter Dr. Lukas John Dr. Tobias Schindler Julian P. Schroers Simon Teeuwen Dr. Michael E. Tauchert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(59):13436-13444
The dative Pd→B interaction in a series of RDPBR’ Pd0 and PdII complexes (RDPBR’=(o-PR2C6H4)2BR’, diphosphinoborane) was analyzed using XRD, 11B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state PdII and Pd0, stabilizing the latter. Reaction of lithium amides with [(RDPBR’)PdII(4-NO2C6H4)I] chemoselectively yields the C−N coupling product. DFT modelling indicates no significant impact of PdII→B coordination on the inner-sphere reductive elimination rate. 相似文献
168.
Dr. Florian Rauch Peter Endres Dr. Alexandra Friedrich Dr. Daniel Sieh Dr. Martin Hähnel Dr. Ivo Krummenacher Prof. Dr. Holger Braunschweig Prof. Dr. Maik Finze Prof. Dr. Lei Ji Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12951-12963
Using a new divergent approach, conjugated triarylborane dendrimers were synthesized up to the 2nd generation. The synthetic strategy consists of three steps: 1) functionalization, via iridium catalyzed C−H borylation; 2) activation, via fluorination of the generated boronate ester with K[HF2] or [N(nBu4)][HF2]; and 3) expansion, via reaction of the trifluoroborate salts with aryl Grignard reagents. The concept was also shown to be viable for a convergent approach. All but one of the conjugated borane dendrimers exhibit multiple, distinct and reversible reduction potentials, making them potentially interesting materials for applications in molecular accumulators. Based on their photophysical properties, the 1st generation dendrimers exhibit good conjugation over the whole system. However, the conjugation does not increase further upon expansion to the 2nd generation, but the molar extinction coefficients increase linearly with the number of triarylborane subunits, suggesting a potential application as photonic antennas. 相似文献
169.
Ina Vollmer Michael J. F. Jenks Mark C. P. Roelands Robin J. White Toon van Harmelen Paul de Wild Gerard P. van der Laan Florian Meirer Jos T. F. Keurentjes Bert M. Weckhuysen 《Angewandte Chemie (International ed. in English)》2020,59(36):15402-15423
Increasing the stream of recycled plastic necessitates an approach beyond the traditional recycling via melting and re‐extrusion. Various chemical recycling processes have great potential to enhance recycling rates. In this Review, a summary of the various chemical recycling routes and assessment via life‐cycle analysis is complemented by an extensive list of processes developed by companies active in chemical recycling. We show that each of the currently available processes is applicable for specific plastic waste streams. Thus, only a combination of different technologies can address the plastic waste problem. Research should focus on more realistic, more contaminated and mixed waste streams, while collection and sorting infrastructure will need to be improved, that is, by stricter regulation. This Review aims to inspire both science and innovation for the production of higher value and quality products from plastic recycling suitable for reuse or valorization to create the necessary economic and environmental push for a circular economy. 相似文献
170.
Florian A. Mann Niklas Herrmann Felipe Opazo Sebastian Kruss 《Angewandte Chemie (International ed. in English)》2020,59(40):17732-17738
Single‐walled carbon nanotubes (SWCNTs) are a 1D nanomaterial that shows fluorescence in the near‐infrared (NIR, >800 nm). In the past, covalent chemistry was less explored to functionalize SWCNTs as it impairs NIR emission. However, certain sp3 defects (quantum defects) in the carbon lattice have emerged that preserve NIR fluorescence and even introduce a new, red‐shifted emission peak. Here, we report on quantum defects, introduced using light‐driven diazonium chemistry, that serve as anchor points for peptides and proteins. We show that maleimide anchors allow conjugation of cysteine‐containing proteins such as a GFP‐binding nanobody. In addition, an Fmoc‐protected phenylalanine defect serves as a starting point for conjugation of visible fluorophores to create multicolor SWCNTs and in situ peptide synthesis directly on the nanotube. Therefore, these quantum defects are a versatile platform to tailor both the nanotube's photophysical properties as well as their surface chemistry. 相似文献