全文获取类型
收费全文 | 424996篇 |
免费 | 6247篇 |
国内免费 | 1910篇 |
专业分类
化学 | 238070篇 |
晶体学 | 6263篇 |
力学 | 16749篇 |
综合类 | 66篇 |
数学 | 48262篇 |
物理学 | 123743篇 |
出版年
2018年 | 4040篇 |
2017年 | 4063篇 |
2016年 | 6650篇 |
2015年 | 4788篇 |
2014年 | 6598篇 |
2013年 | 17756篇 |
2012年 | 13639篇 |
2011年 | 16831篇 |
2010年 | 11351篇 |
2009年 | 11024篇 |
2008年 | 15582篇 |
2007年 | 15813篇 |
2006年 | 14864篇 |
2005年 | 13477篇 |
2004年 | 12032篇 |
2003年 | 10678篇 |
2002年 | 10448篇 |
2001年 | 12037篇 |
2000年 | 9306篇 |
1999年 | 7046篇 |
1998年 | 5739篇 |
1997年 | 5765篇 |
1996年 | 5829篇 |
1995年 | 5246篇 |
1994年 | 5257篇 |
1993年 | 5105篇 |
1992年 | 5719篇 |
1991年 | 5541篇 |
1990年 | 5327篇 |
1989年 | 5269篇 |
1988年 | 5131篇 |
1987年 | 5135篇 |
1986年 | 4918篇 |
1985年 | 6605篇 |
1984年 | 6693篇 |
1983年 | 5595篇 |
1982年 | 5995篇 |
1981年 | 5718篇 |
1980年 | 5444篇 |
1979年 | 5724篇 |
1978年 | 6133篇 |
1977年 | 5999篇 |
1976年 | 5901篇 |
1975年 | 5511篇 |
1974年 | 5594篇 |
1973年 | 5660篇 |
1972年 | 4040篇 |
1971年 | 3314篇 |
1968年 | 3605篇 |
1967年 | 3778篇 |
排序方式: 共有10000条查询结果,搜索用时 667 毫秒
141.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
142.
Daniel Heinz Annette Meister Hazrat Hussain Karsten Busse Jörg Kressler 《Journal of polymer science. Part A, Polymer chemistry》2020,58(23):3322-3335
Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy. 相似文献
143.
Dr. Zhoulong Fan Katherine L. Bay Dr. Xiangyang Chen Zhe Zhuang Han Seul Park Dr. Kap-Sun Yeung Prof. Dr. K. N. Houk Prof. Dr. Jin-Quan Yu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4800-4807
A simple and efficient nitrile-directed meta-C−H olefination, acetoxylation, and iodination of biaryl compounds is reported. Compared to the previous approach of installing a complex U-shaped template to achieve a molecular U-turn and assemble the large-sized cyclophane transition state for the remote C−H activation, a synthetically useful phenyl nitrile functional group could also direct remote meta-C−H activation. This reaction provides a useful method for the modification of biaryl compounds because the nitrile group can be readily converted to amines, acids, amides, or other heterocycles. Notably, the remote meta-selectivity of biphenylnitriles could not be expected from previous results with a macrocyclophane nitrile template. DFT computational studies show that a ligand-containing Pd–Ag heterodimeric transition state (TS) favors the desired remote meta-selectivity. Control experiments demonstrate the directing effect of the nitrile group and exclude the possibility of non-directed meta-C−H activation. Substituted 2-pyridone ligands were found to be key in assisting the cleavage of the meta-C−H bond in the concerted metalation–deprotonation (CMD) process. 相似文献
144.
L. Resse L.G.S. Oliveira C.I.L. de Araujo A.R. Pereira R.L. Silva 《Physics letters. A》2019,383(14):1655-1659
In this work, we have used the MuMax3 software to simulate devices consisting of a ferromagnetic thin film placed over a heavy metal thin film. The devices are two interconnected partial-disks where a Néel domain wall is formed in the disks junction. In our simulations we investigate devices with disk radius nm and different distance d between the disks centers (from nm to nm). By applying strong sinusoidal external magnetic fields, we find a mechanism able to create, annihilate and even manipulate a skyrmion in each side of the device. This mechanism is discussed in terms of interactions between skyrmion and domain wall. The Néel domain wall formed in the center of the device interacts with the Néel skyrmion, leading to a process of transporting a skyrmion from one disk to the other periodically. Our results have relevance for potential applications in spintronics such as logical devices. 相似文献
145.
146.
147.
The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters (PE-S) to the corresponding sulfoxide (PE-SO) and then sulfone (PE-SO2) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO2 > PE-SO. The relative mechanical strength as a function of oxidation state is revealed through the use of gem-dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling.The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. 相似文献
148.
149.
Markus Bödenler Ludovic de Rochefort P. James Ross Nicolas Chanet Geneviève Guillot Gareth R. Davies 《Molecular physics》2019,117(7-8):832-848
ABSTRACTFast field-cycling (FFC) nuclear magnetic resonance relaxometry is a well-established method to determine the relaxation rates as a function of magnetic field strength. This so-called nuclear magnetic relaxation dispersion gives insight into the underlying molecular dynamics of a wide range of complex systems and has gained interest especially in the characterisation of biological tissues and diseases. The combination of FFC techniques with magnetic resonance imaging (MRI) offers a high potential for new types of image contrast more specific to pathological molecular dynamics. This article reviews the progress in FFC-MRI over the last decade and gives an overview of the hardware systems currently in operation. We discuss limitations and error correction strategies specific to FFC-MRI such as field stability and homogeneity, signal-to-noise ratio, eddy currents and acquisition time. We also report potential applications with impact in biology and medicine. Finally, we discuss the challenges and future applications in transferring the underlying molecular dynamics into novel types of image contrast by exploiting the dispersive properties of biological tissue or MRI contrast agents. 相似文献
150.
Dr. Felipe L. Coelho Eduarda S. Gil Dr. Paulo F. B. Gonçalves Dr. Leandra F. Campo Dr. Paulo H. Schneider 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8157-8162
In this work, a series of 2-chalcogenylindoles was synthesized by an efficient methodology, starting from chalcogenoalkynes, including a previously unreported tellurium indole derivative. For the first time, these 2-substituted chalcogenylindoles were obtained in the absence of metal catalyst or base, under thermal conditions only. In addition, the results described herein represent a methodology with inverse regioselectivity for the chalcogen functionalization of indoles. 相似文献