全文获取类型
收费全文 | 17724篇 |
免费 | 2775篇 |
国内免费 | 377篇 |
专业分类
化学 | 10874篇 |
晶体学 | 120篇 |
力学 | 2688篇 |
综合类 | 83篇 |
数学 | 1787篇 |
物理学 | 5324篇 |
出版年
2024年 | 34篇 |
2023年 | 225篇 |
2022年 | 414篇 |
2021年 | 491篇 |
2020年 | 661篇 |
2019年 | 576篇 |
2018年 | 398篇 |
2017年 | 420篇 |
2016年 | 822篇 |
2015年 | 847篇 |
2014年 | 868篇 |
2013年 | 1203篇 |
2012年 | 1012篇 |
2011年 | 1086篇 |
2010年 | 905篇 |
2009年 | 1090篇 |
2008年 | 1129篇 |
2007年 | 1293篇 |
2006年 | 1223篇 |
2005年 | 952篇 |
2004年 | 801篇 |
2003年 | 820篇 |
2002年 | 509篇 |
2001年 | 482篇 |
2000年 | 407篇 |
1999年 | 382篇 |
1998年 | 321篇 |
1997年 | 269篇 |
1996年 | 226篇 |
1995年 | 175篇 |
1994年 | 147篇 |
1993年 | 98篇 |
1992年 | 94篇 |
1991年 | 68篇 |
1990年 | 62篇 |
1989年 | 35篇 |
1988年 | 31篇 |
1987年 | 40篇 |
1986年 | 39篇 |
1985年 | 37篇 |
1984年 | 33篇 |
1983年 | 14篇 |
1982年 | 24篇 |
1981年 | 15篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 21篇 |
1977年 | 15篇 |
1976年 | 17篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
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
992.
We apply the first-principles approach to study the structural stability, Vickers hardness, and elastic modulus of ReB12 and RuB12. In particular, we further investigate the influence of high pressure on the structural stability and mechanical properties of ReB12 and RuB12. The calculated results show that ReB12 and RuB12 are thermodynamic stability under high pressure. Here, ReB12 is more thermodynamic stability than that of the RuB12. The calculated Vickers hardness of ReB12 and RuB12 is 16.25 and 16.55 GPa, respectively. It is found that the calculated elastic constants and elastic modulus of ReB12 and RuB12 increase with increasing pressure. In particular, the calculated elastic constants and elastic modulus of ReB12 are larger than that of the RuB12. The calculated electronic structure shows that the high hardness and elastic modulus of ReB12 and RuB12 are attributed to the 3D network B-B covalent bonds. 相似文献
993.
Waro Nakanishi Satoko Hayashi Taro Nishide Shota Otsuki 《International journal of quantum chemistry》2020,120(4):e26073
A method to elucidate the dynamic and static natures of the activated interactions in transition states (TSs) is proposed using quantum theory of atoms-in-molecules (QTAIM) dual functional analysis (QTAIM-DFA). The natures are determined for the ligand exchange at the N of sulfonylimino-λ3-bromanes, RBr-*-N(SO2CF3)-*-X′R′ (R, R′ = Me or Ph, X′ = Br′ or I′). Asterisks (*) emphasize the presence of bond critical points within the interactions in question. While data from the optimized structures of TSs correspond to the static nature, those from the perturbed and optimized structures represent the dynamic nature. The nature of the interactions in Br-*-N-*-X′ calculated with QTAIM-DFA, using the perturbed structures generated using the normal coordinates for the imaginary frequencies (NIV), was very similar to that in trigonal bipyramidal adduct formation through charge transfer. The results with NIV were precisely the same as those obtained based on intrinsic reaction coordinate (IRC). The high applicability of QTAIM-DFA is demonstrated when analyzing the activated interactions in TSs. 相似文献
994.
Eugene A. Kotomin Yuri A. Mastrikov Rotraut Merkle Joachim Maier 《Current Opinion in Electrochemistry》2020
The efficiency of solid oxide fuel cells (SOFC) depends critically on materials, in particular for the cathode where the oxygen reduction reaction (ORR) occurs. Typically, mixed conducting perovskite ABO3-type materials are used for this purpose. The dominating surface terminations are (001) AO and BO2, with the relative fractions depending on materials composition and ambient conditions.Here, results of recent large-scale first principles (ab initio) calculations for the two alternative polar (La,Sr)O and MnO2 (001) terminations of (La,Sr)MnO3 cathode materials are discussed. The surface oxygen vacancy concentration for the (La,Sr)O termination is more than 5 orders of magnitude smaller compared to MnO2, which leads to drastically decreased estimated ORR rates. Thus, it is predicted for prototypical SOFC cathode materials that the BO2 termination largely determines the ORR kinetics, although with Sr surface segregation (long-term degradation) its fraction of the total surface area decreases, which slows down cathode kinetics. 相似文献
995.
Gerui Pei Dr. Pei Zhao Song Xu Xintian Zhao Prof. Chuncai Kong Prof. Zhimao Yang Prof. Masahiro Ehara Prof. Tao Yang 《ChemistryOpen》2020,9(11):1195-1201
The coordination of 10-electron diatomic ligands (BF, CO N2) to iron complexes Fe(CO)2(CNArTripp2)2 [ArTripp2=2,6-(2,4,6-(iso-propyl)3C6H2)2C6H3] have been realized in experiments very recently (Science, 2019 , 363, 1203–1205). Herein, the stability, electronic structures, and bonding properties of (E1E2)Fe-(CO)2(CNArTripp2)2 (E1E2=BF, CO, N2, CN−, NO+) were studied using density functional (DFT) calculations. The ground state of all those molecules is singlet and the calculated geometries are in excellent agreement with the experimental values. The natural bond orbital analysis revealed that Fe is negatively charged while E1 possesses positive charges. By employing the energy decomposition analysis, the bonding nature of the E2E1–Fe(CO)2(CNArTripp2)2 bond was disclosed to be the classic dative bond E2E1→Fe(CO)2(CNArTripp2)2 rather than the electron-sharing double bond. More interestingly, the bonding strength between BF and Fe(CO)2(CNArTripp2)2 is much stronger than that between CO (or N2) and Fe(CO)2(CNArTripp2)2, which is ascribed to the better σ-donation and π back-donations. However, the orbital interactions in CN−→Fe(CO)2(CNArTripp2)2 and NO+→Fe(CO)2(CNArTripp2)2 mainly come from σ-donation and π back-donation, respectively. The different contributions from σ donation and π donation for different ligands can be well explained by using the energy levels of E1E2 and Fe(CO)2(CNArTripp2)2 fragments. 相似文献
996.
SARS-CoV-2, or severe acute respiratory syndrome coronavirus 2, represents a new strain of Coronaviridae. In the closing 2019 to early 2020 months, the virus caused a global pandemic of COVID-19 disease. We performed a virtual screening study in order to identify potential inhibitors of the SARS-CoV-2 main viral protease (3CLpro or Mpro). For this purpose, we developed a novel approach using ensemble docking high-throughput virtual screening directly coupled with subsequent Linear Interaction Energy (LIE) calculations to maximize the conformational space sampling and to assess the binding affinity of identified inhibitors. A large database of small commercial compounds was prepared, and top-scoring hits were identified with two compounds singled out, namely 1-[(R)-2-(1,3-benzimidazol-2-yl)-1-pyrrolidinyl]-2-(4-methyl-1,4-diazepan-1-yl)-1-ethanone and [({(S)-1-[(1H-indol-2-yl)methyl]-3-pyrrolidinyl}methyl)amino](5-methyl-2H-pyrazol-3-yl)formaldehyde. Moreover, we obtained a favorable binding free energy of the identified compounds, and using contact analysis we confirmed their stable binding modes in the 3CLpro active site. These compounds will facilitate further 3CLpro inhibitor design. 相似文献
997.
Jilai Li Caiyun Geng Thomas Weiske Helmut Schwarz 《Angewandte Chemie (International ed. in English)》2020,59(30):12308-12314
[V2O]+ remains “invisible” in the thermal gas‐phase reaction of bare [V2]+ with CO2 giving rise to [V2O2]+; this is because the [V2O]+ intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V2O]+ and its involvement in the [V2]+ → [V2O2]+ chemistry are demonstrated by a cross‐over labeling experiment with a 1:1 mixture of C16O2/C18O2, generating the product ions [V216O2]+, [V216O18O]+, and [V218O2]+ in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V2]+ versus [V2O]+ towards CO2. 相似文献
998.
Erik Barwa Tobias F. Pascher Milan On
k Christian van der Linde Martin K. Beyer 《Angewandte Chemie (International ed. in English)》2020,59(19):7467-7471
We investigate activation of carbon dioxide by singly charged hydrated magnesium cations Mg .+(H2O)n, through infrared multiple photon dissociation (IRMPD) spectroscopy combined with quantum chemical calculations. The spectra of [MgCO2(H2O)n].+ in the 1250–4000 cm?1 region show a sharp transition from n=2 to n=3 for the position of the CO2 antisymmetric stretching mode. This is evidence for the activation of CO2 via charge transfer from Mg .+ to CO2 for n≥3, while smaller clusters feature linear CO2 coordinated end‐on to the metal center. Starting with n=5, we see a further conformational change, with CO2.? coordination to Mg2+ gradually shifting from bidentate to monodentate, consistent with preferential hexa‐coordination of Mg2+. Our results reveal in detail how hydration promotes CO2 activation by charge transfer at metal centers. 相似文献
999.
Duan Bortk Daniel Pecher Daniel Vgh Martin Breza Peter Miku Viktor Milata 《Journal of mass spectrometry : JMS》2020,55(10)
Twenty‐one pentafluorphenylhydrazones have been analyzed by means of tandem mass spectrometry (ESI MS/MS) conditions to compare their fragmentations with those ones obtained from quantum‐chemical calculations of the hydrazone moiety depending on the substitution from the aldehyde site. The hydrazone N–N bond is disrupted under such conditions, and these results are in accordance with the facts that an electron‐rich particle, such as an anion and or radical in a solution, can cause this disruption and simultaneous defluorination in para‐position of the hydrazone part of the molecule. 相似文献
1000.
《Journal of Saudi Chemical Society》2020,24(12):942-954
Novel 4-vinyl guaiacol based thioether derivatives were synthesized in a three-step reaction procedure by thiol-ene coupling as the key step. The synthesized compounds were characterised by spectroscopic techniques and evaluated for their tribological and antioxidant properties in two different base oils namely epoxy2-ethylhexyl esters of karanja fatty acids (EKE) and dioctyl sebacate (DOS). It was found that the synthesized products were exhibited superior antioxidant performance compared to butylated hydroxytoluene (BHT). All the three synthesized additives were improved the tribological properties of the base oil EKE and DOS. Dithio derivative at 0.75 wt% reduced the wear scar diameter by 36% and at 1 wt% improved the weld point by 33% of base oil EKE. Surface and elemental analysis result suggests that in the tribochemical process the synthesized thioether derivatives decompose and form an effective tribofilms on interacting surfaces. X-ray Photoelectron Spectroscopy (XPS) of the surface lubricated with base oil containing DMFD was evidence for the formation of tribofilm with FeS, FeSO4 and Fe2O3. The antiwear behaviour of the additives was well correlated with quantum chemical calculations. Overall the dithio derivative is more effective as antiwear, extreme pressure and antioxidant bio lubricant additive than other thioether derivatives. 相似文献