全文获取类型
收费全文 | 4562篇 |
免费 | 256篇 |
国内免费 | 395篇 |
专业分类
化学 | 3714篇 |
晶体学 | 79篇 |
力学 | 22篇 |
综合类 | 5篇 |
数学 | 7篇 |
物理学 | 1386篇 |
出版年
2023年 | 21篇 |
2022年 | 24篇 |
2021年 | 53篇 |
2020年 | 72篇 |
2019年 | 63篇 |
2018年 | 57篇 |
2017年 | 44篇 |
2016年 | 124篇 |
2015年 | 132篇 |
2014年 | 147篇 |
2013年 | 345篇 |
2012年 | 217篇 |
2011年 | 195篇 |
2010年 | 210篇 |
2009年 | 265篇 |
2008年 | 265篇 |
2007年 | 342篇 |
2006年 | 239篇 |
2005年 | 275篇 |
2004年 | 279篇 |
2003年 | 283篇 |
2002年 | 221篇 |
2001年 | 114篇 |
2000年 | 157篇 |
1999年 | 137篇 |
1998年 | 119篇 |
1997年 | 98篇 |
1996年 | 114篇 |
1995年 | 131篇 |
1994年 | 111篇 |
1993年 | 63篇 |
1992年 | 84篇 |
1991年 | 36篇 |
1990年 | 27篇 |
1989年 | 24篇 |
1988年 | 22篇 |
1987年 | 20篇 |
1986年 | 14篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1981年 | 6篇 |
1980年 | 10篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1973年 | 9篇 |
1972年 | 1篇 |
排序方式: 共有5213条查询结果,搜索用时 31 毫秒
1.
Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S0 and S1 states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S1 state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications. 相似文献
2.
Impact of the Oxygen Defects and the Hydrogen Concentration on the Surface of Tetragonal and Monoclinic ZrO2 on the Reduction Rates of Stearic Acid on Ni/ZrO2 下载免费PDF全文
Sebastian Foraita Dr. John L. Fulton Zizwe A. Chase Aleksei Vjunov Pinghong Xu Dr. Eszter Baráth Dr. Donald M. Camaioni Dr. Chen Zhao Prof. Dr. Johannes A. Lercher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2423-2434
The role of the specific physicochemical properties of ZrO2 phases on Ni/ZrO2 has been explored with respect to the reduction of stearic acid. Conversion on pure m‐ZrO2 is 1.3 times more active than on t‐ZrO2, whereas Ni/m‐ZrO2 is three times more active than Ni/t‐ZrO2. Although the hydrodeoxygenation of stearic acid can be catalyzed solely by Ni, the synergistic interaction between Ni and the ZrO2 support causes the variations in the reaction rates. Adsorption of the carboxylic acid group on an oxygen vacancy of ZrO2 and the abstraction of the α‐hydrogen atom with the elimination of the oxygen atom to produce a ketene is the key to enhance the overall rate. The hydrogenated intermediate 1‐octadecanol is in turn decarbonylated to heptadecane with identical rates on all catalysts. Decarbonylation of 1‐octadecanol is concluded to be limited by the competitive adsorption of reactants and intermediate. The substantially higher adsorption of propionic acid demonstrated by IR spectroscopy and the higher reactivity to O2 exchange reactions with the more active catalyst indicate that the higher concentration of active oxygen defects on m‐ZrO2 compared to t‐ZrO2 causes the higher activity of Ni/m‐ZrO2. 相似文献
3.
Coordination compounds of Cu (II), Y (III), Zr (IV) and La (III) with the tetradentate Schiff base (H2L) obtained through the condensation of p‐phenylenediamine with salicylaldehyde under reflux conditions. The complexes were characterized by elemental analysis, magnetic susceptibility, molar conductance and also, with various spectroscopic techniques such as 1H NMR, UV–Vis., IR and XRD techniques. Electrolytic nature of complexes was ascertained by molar conductance values. In these four complexes, the ligand chelates act in a tetradentate manner via azomethine nitrogen and oxygen atoms of phenolic groups. Electronic spectroscopic data are in agreement with an octahedral geometrical structure. Thermal degradation analyses in nitrogen gas were used to investigate the number and location of water molecules. The chemical formulae of metal complexes were confirmed by microanalytical data. The activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* were calculated from the DTG curves using Coats Redfern (CR) and Horowitz–Metzeger (HM) methods at n = 1 or n ≠ 1. Nematicidal activities indicate that the ligand exhibit greater activity when compared to its complexes. In addition metal complexes displayed good moderate nematicidal activities. 相似文献
4.
We report extensive computational studies of some novel intermolecular systems and their properties. Recombination of alkali-halide counterions separated by a noncovalently trapped hydrocarbon molecule is prevented by significant potential energy barriers, resulting in unusual metastable insertion complexes. These systems are extremely polar, while the inserted molecule is strongly counter-polarized, leading to significant cooperative nonadditivity effects. The compression and electric field produced by the counterions favours isomerization of the trapped molecule via a significant reduction of the barriers to bond rearrangement, in a field-induced mechanochemical process. The predicted IR intensity spectra clearly reflect (1) formation of the insertion complex, rather than simple attachment of alkali halide, and (2) isomerization of the trapped molecule, thus allowing experimental access to these events. 相似文献
5.
The difference between the swiftlet white edible bird's nest from limestone caves versus house‐farmed ones, especially in response to high temperature and stewing time in water where the latter type would disintegrate readily, has been a puzzle for a long time. We show that edible bird's nests from the limestone caves have calcite deposits on the surface of the nest cement as compared to the house‐farmed nests which are built by swiftlets on timber planks. The micron and sub‐micron calcite particles are seen in SEM‐EDX and further characterized by ATR‐FTIR and Raman microspectroscopy. The calcite deposits make it possible for the cave nest to retain a gelatinous texture under the harsh retort conditions at 121 °C for 20 mins in commercial bottling. We show that house‐farmed nests can be soaked in CaCl2(aq) followed by rinsing with Na2CO3(aq) to grow the same calcite deposits on the nest cement with the same characteristic as cave nests. Therefore, there should no longer be a need to harvest cave nests, and we can better conserve the dwindling population and natural habitats of cave swiftlets. 相似文献
6.
Bifurcated halogen bonds are constructed with FBr and FI as Lewis acids, paired with NH3 and NCH bases. The first type considered places two bases together with a single acid, while the reverse case of two acids sharing a single base constitutes the second type. These bifurcated systems are compared with the analogous H-bonds wherein FH serves as the acid. In most cases, a bifurcated system is energetically inferior to a single linear bond. There is a larger energetic cost to forcing the single σ-hole of an acid to interact with a pair of bases, than the other way around where two acids engage with the lone pair of a single base. In comparison to FBr and FI, the H-bonding FH acid is better able to participate in a bifurcated sharing with two bases. This behavior is traced to the properties of the monomers, in particular the specific shape of the molecular electrostatic potential, the anisotropy of the orbitals of the acid and base that interact directly with one another, and the angular extent of the total electron density of the two molecules. 相似文献
7.
Dr. Andrew M. Turner Dr. Sankhabrata Chandra Prof. Ryan C. Fortenberry Prof. Dr. Ralf I. Kaiser 《Chemphyschem》2021,22(10):985-994
Ices of acetylene (C2H2) and ammonia (NH3) were irradiated with energetic electrons to simulate interstellar ices processed by galactic cosmic rays in order to investigate the formation of C2H3N isomers. Supported by quantum chemical calculations, experiments detected product molecules as they sublime from the ices using photoionization reflectron time-of-flight mass spectrometry (PI-ReTOF-MS). Isotopically-labeled ices confirmed the C2H3N assignments while photon energies of 8.81 eV, 9.80 eV, and 10.49 eV were utilized to discriminate isomers based on their known ionization energies. Results indicate the formation of ethynamine (HCCNH2) and 2H-azirine (c-H2CCHN) in the irradiated C2H2:NH3 ices, and the energetics of their formation mechanisms are discussed. These findings suggest that these two isomers can form in interstellar ices and, upon sublimation during the hot core phase, could be detected using radio astronomy. 相似文献
8.
9.
Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides 下载免费PDF全文
Dr. Abdessamad Benidar Prof. Dr. Didier Bégué Dr. Falk Richter Prof. Dr. Claude Pouchan Prof. Dr. Mohammed Lahcini Dr. Jean‐Claude Guillemin 《Chemphyschem》2015,16(4):848-854
Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides. 相似文献
10.
《Angewandte Chemie (International ed. in English)》2017,56(8):2208-2211
To understand the molecular details of O2‐tolerant hydrogen cycling by a soluble NAD+‐reducing [NiFe] hydrogenase, we herein present the first bioinspired heterobimetallic S‐oxygenated [NiFe] complex as a structural and vibrational spectroscopic model for the oxygen‐inhibited [NiFe] active site. This compound and its non‐S‐oxygenated congener were fully characterized, and their electronic structures were elucidated in a combined experimental and theoretical study with emphasis on the bridging sulfenato moiety. Based on the vibrational spectroscopic properties of these complexes, we also propose novel strategies for exploring S‐oxygenated intermediates in hydrogenases and similar enzymes. 相似文献