全文获取类型
收费全文 | 3980篇 |
免费 | 87篇 |
国内免费 | 22篇 |
专业分类
化学 | 2536篇 |
晶体学 | 23篇 |
力学 | 159篇 |
数学 | 666篇 |
物理学 | 705篇 |
出版年
2021年 | 27篇 |
2020年 | 31篇 |
2019年 | 34篇 |
2018年 | 39篇 |
2017年 | 38篇 |
2016年 | 62篇 |
2015年 | 73篇 |
2014年 | 86篇 |
2013年 | 233篇 |
2012年 | 170篇 |
2011年 | 200篇 |
2010年 | 126篇 |
2009年 | 119篇 |
2008年 | 172篇 |
2007年 | 165篇 |
2006年 | 178篇 |
2005年 | 197篇 |
2004年 | 158篇 |
2003年 | 145篇 |
2002年 | 123篇 |
2001年 | 45篇 |
2000年 | 57篇 |
1999年 | 34篇 |
1998年 | 31篇 |
1997年 | 67篇 |
1996年 | 66篇 |
1995年 | 63篇 |
1994年 | 52篇 |
1993年 | 57篇 |
1992年 | 47篇 |
1991年 | 49篇 |
1990年 | 37篇 |
1989年 | 39篇 |
1988年 | 33篇 |
1987年 | 29篇 |
1985年 | 78篇 |
1984年 | 59篇 |
1983年 | 51篇 |
1982年 | 63篇 |
1981年 | 72篇 |
1980年 | 53篇 |
1979年 | 69篇 |
1978年 | 68篇 |
1977年 | 78篇 |
1976年 | 52篇 |
1975年 | 53篇 |
1974年 | 50篇 |
1973年 | 37篇 |
1971年 | 36篇 |
1968年 | 27篇 |
排序方式: 共有4089条查询结果,搜索用时 31 毫秒
1.
Habarurema Gratien Gerber Thomas Mukabagorora Theonille Hosten Eric Ndayambaje Jean Bernard Betz Richard 《Transition Metal Chemistry》2020,45(1):55-63
Transition Metal Chemistry - Rhenium(I) and (VII) complexes with cyclohex-1-enylolonium cation and bridging pyridyl derivatives are reported. Additionally, the CO-bridged pyridyl and their related... 相似文献
2.
Dergez Timea Por Viktria Anditi Bernard Collins Knig-Pter Anik 《Journal of Analytical Chemistry》2022,77(4):513-518
Journal of Analytical Chemistry - Polycyclic aromatic hydrocarbons (PAHs) can be extremely hazardous to human health due to their carcinogenicity and toxicity. Following mother exposure, a part of... 相似文献
3.
Prof. Piotr Bałczewski Dr. Emilia Kowalska Dr. Ewa Różycka-Sokołowska Dr. Joanna Skalik Dr. Krzysztof Owsianik Dr. Marek Koprowski Dr. Bernard Marciniak Dr. Dariusz Guziejewski Prof. Witold Ciesielski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14148-14161
The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen. 相似文献
4.
Manuel
Bernard Ghislain Lartigue Guillaume Balarac Vincent Moureau Guillaume Puigt 《国际流体数值方法杂志》2020,92(11):1551-1583
In this article, a new framework to design high-order approximations in the context of node-centered finite volumes on simplicial meshes is proposed. The major novelty of this method is that it relies on very simple and compact differential operators, which is a critical point to achieve good performances in the High-performance computing context. This method is based on deconvolution between nodal and volume-average values, which can be conducted to any order. The interest of the new method is illustrated through three different applications: mesh-to-mesh interpolation, levelset curvature computation, and numerical scheme for convection. Higher order can also be achieved within the present framework by introducing high-rank tensors. Although these tensors feature much symmetries, their manipulation can quickly become an overwhelming task. For this reason and without loss of generality, the present articles are limited to third-order expansion. This method, although tightly connected to the k-exact schemes theory, does not rely on successive corrections: the high-order property is obtained in a single operation, which makes them more attractive in terms of performances. 相似文献
5.
Inside Back Cover: 9H‐Quinolino[3,2,1‐k]phenothiazine: A New Electron‐Rich Fragment for Organic Electronics (Chem. Eur. J. 50/2016) 下载免费PDF全文
6.
Modulation of the Physicochemical Properties of Donor–Spiro–Acceptor Derivatives through Donor Unit Planarisation: Phenylacridine versus Indoloacridine—New Hosts for Green and Blue Phosphorescent Organic Light‐Emitting Diodes (PhOLEDs) 下载免费PDF全文
Dr. Sébastien Thiery Dr. Denis Tondelier Bernard Geffroy Dr. Olivier Jeannin Dr. Joëlle Rault‐Berthelot Dr. Cyril Poriel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10136-10149
This work reports a detailed structure–property relationship study of a series of efficient host materials based on the donor–spiro–acceptor (D‐spiro‐A) design for green and sky‐blue phosphorescent organic light‐emitting diodes (PhOLEDs). The electronic and physical effects of the indoloacridine (IA) fragment connected through a spiro bridge to different acceptor units, namely, fluorene, dioxothioxanthene or diazafluorene moiety, have been investigated in depth. The resulting host materials have been easily synthesised through short, efficient, low‐cost, and highly adaptable synthetic routes by using common intermediates. The dyes possess a very high triplet energy (ET) and tuneable HOMO/LUMO levels, depending on the strength of the donor/acceptor combination. The peculiar electrochemical and optical properties of the IA moiety have been investigated though a fine comparison with their phenylacridine counterparts to study the influence of planarisation. Finally, these molecules have been incorporated as hosts in green and sky‐blue PhOLEDs. For the derivative SIA‐TXO2 as a host, external quantum efficiencies as high as 23 and 14 % have been obtained for green and sky‐blue PhOLEDs, respectively. 相似文献
7.
Ivan Dragičević Dr. Danijela Barić Dr. Borislav Kovačević Prof. Bernard T. Golding Dr. David M. Smith 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6132-6143
Model studies of prebiotic chemistry have revealed compelling routes for the formation of the building blocks of proteins and RNA, but not DNA. Today, deoxynucleotides required for the construction of DNA are produced by reduction of nucleotides catalysed by ribonucleotide reductases, which are radical enzymes. This study considers potential non‐enzymatic routes via intermediate radicals for the ancient formation of deoxynucleotides. In this context, several mechanisms for ribonucleotide reduction, in a putative H2S/HS. environment, are characterized using computational chemistry. A bio‐inspired mechanistic cycle involving a keto intermediate and HSSH production is found to be potentially viable. An alternative pathway, proceeding through an enol intermediate is found to exhibit similar energetic requirements. Non‐cyclical pathways, in which HSS. is generated in the final step instead of HS., show a markedly increased thermodynamic driving force (ca. 70 kJ mol?1) and thus warrant serious consideration in the context of the prebiotic ribonucleotide reduction. 相似文献
8.
Yunshan Liu Haojie Zhang Wanqing Zhang Prof. Bernard P. Binks Prof. Zhenggang Cui Prof. Jianzhong Jiang 《Angewandte Chemie (International ed. in English)》2023,62(5):e202210050
A ferrocene surfactant can be switched between single and double head form (FcN+C12/Fc+N+C12) triggered by redox reaction. FcN+C12 can neither stabilize an O/W emulsion alone nor an oil-in-dispersion emulsion in combination with alumina nanoparticles due to the steric hindrance of the ferrocene group. However, such steric hindrance can be overcome by increasing the charge density in Fc+N+C12, so that oil-in-dispersion emulsions can be co-stabilized by Fc+N+C12 and alumina nanoparticles at very low concentrations (1×10−7 M (≈50 ppb) and 0.001 wt %, respectively). Not only can reversible formation/destabilization of oil-in-dispersion emulsions be achieved by redox reaction, but also reversible transformation between oil-in-dispersion emulsions and Pickering emulsions can be obtained through reversing the charge of alumina particles by adjusting the pH. The results provide a new protocol for the design of surfactants for stabilization of smart oil-in-dispersion emulsions. 相似文献
9.
ortho‐, meta‐, and para‐Dihydroindenofluorene Derivatives as Host Materials for Phosphorescent OLEDs 下载免费PDF全文
Maxime Romain Sébastien Thiery Anna Shirinskaya Dr. Céline Declairieux Dr. Denis Tondelier Bernard Geffroy Dr. Olivier Jeannin Dr. Joëlle Rault‐Berthelot Dr. Rémi Métivier Dr. Cyril Poriel 《Angewandte Chemie (International ed. in English)》2015,54(4):1176-1180
This work reports the first structure–properties relationship study of ortho [2,1‐c]‐, meta [1,2‐a]‐, and para [1,2‐b]dihydroindenofluorenes, highlighting the influence of bridge rigidification on the electronic properties. This study has made it possible to devise an extended π‐conjugated molecule with both a high triplet state energy level and excellent thermal and morphological stability. As a proof of concept, dihydroindenofluorenes were used as the host in sky‐blue phosphorescent organic light‐emitting diodes (PhOLEDs) w ith high performance. 相似文献
10.
Sonja Kracht Dr. Matthias Messerer Dr. Matthieu Lang Dr. Sonja Eckhardt Dr. Miriam Lauz Prof. Bernard Grobéty Prof. Katharina M. Fromm Prof. Bernd Giese 《Angewandte Chemie (International ed. in English)》2015,54(10):2912-2916
Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag+ ions bound by peptides with histidine as the Ag+‐binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100 nm Ag@AgCl/peptide nanocomposites which are cleaved into 15 nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time‐resolved UV/Vis spectra which exhibit an isosbestic point. 相似文献