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51.
Grzegorz Zajac Agnieszka Kaczor Katarzyna Chruszcz‐Lipska Jan Cz. Dobrowolski Malgorzata Baranska 《Journal of Raman spectroscopy : JRS》2014,45(10):859-862
Raman optical activity (ROA) spectra were calculated for a set of conformers of astaxanthin, which is a non‐rigid molecule exhibiting strong resonance enhancement in the visible range. Single electronic state theory of the Resonance ROA (RROA) predicts the spectrum to be monosigned. For astaxanthin, it appeared that some of the conformers exhibit different sign of the bands than the other conformers. As a result, the conformer population averaged spectrum of astaxanthin can exhibit both signs of the bands, or be monosigned depending on which conformers are dominating, that reflects a departure from the single electronic state approximation. Moreover, use of different basis sets and/or density functional theory (DFT) functionals results in different conformer populations, thus yielding again either monosigned ROA spectrum or with bands of both signs. Consequences of these two findings for the astaxanthin RROA spectrum are discussed. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
52.
Dargiewicz M Biczysko M Improta R Barone V 《Physical chemistry chemical physics : PCCP》2012,14(25):8981-8989
Time-Dependent Density Functional Theory (TD-DFT) computations, with M05-2X and PBE0 functionals, have been employed for a detailed study of the Electron-Driven Proton-Transfer (PT) processes in an Adenine-Thymine Watson-Crick Base Pair in the gas phase and in solution, with the bulk solvent described by the polarizable continuum model. In the gas phase, TD-DFT computations predict that the Adenine → Thymine Charge Transfer (CT) excited state undergoes a barrierless PT reaction, in agreement with CC2 computations (S. Perun, A. Sobolewski, W. Domcke, J. Phys. Chem. A, 2006, 110, 9031.). The good agreement between the TD-DFT approach and CC2 results validates the former for the studies of excited state properties, excited state proton transfer reaction, and deactivation mechanisms in the DNA base pairs. Next, it is shown that inclusion of solvent effects significantly influences the possibility of both barrier-less excited state proton transfer and radiation-less deactivation through conical intersection with the ground state, affecting the energy of the CT excited state in the Franck-Condon region, the energy barrier associated to the PT process and the energy gap with the ground electronic state. These findings clearly indicate that environmental effects, with a special attention to proper treatment of dynamical solvation effects, have to be included for reliable computational analysis of photophysical and photochemical processes occurring in condensed phases. 相似文献
53.
Malgorzata Frik Dr. Josefina Jiménez Ismael Gracia Prof. Larry R. Falvello Sarya Abi‐Habib Karina Suriel Prof. Theodore R. Muth Prof. María Contel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(12):3659-3674
The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au2(mes)2(μ‐LL)] (LL=dppe: 1,2‐bis(diphenylphosphano)ethane 1 a , and water‐soluble dppy: 1,2‐bis(di‐3‐pyridylphosphano)ethane 1 b ) with Ag+ and Cu+ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au2M(μ‐mes)2(μ‐LL)][A] (M=Ag, A=ClO4?, LL=dppe 2 a , dppy 2 b ; M=Ag, A=SO3CF3?, LL=dppe 3 a , dppy 3 b ; M=Cu, A=PF6?, LL=dppe 4 a , dppy 4 b ). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au2(mes)2(μ‐dppy)] ( 1 b ) and [Au2Ag(μ‐mes)2(μ‐dppe)][SO3CF3] ( 3 a ) were determined by a single‐crystal X‐ray diffraction study. 3 a in solid state is not a cyclic trinuclear Au2Ag derivative but it gives an open polymeric structure instead, with the {Au2(μ‐dppe)} fragments “linked” by {Ag(μ‐mes)2} units. The very short distances of 2.7559(6) Å (Au? Ag) and 2.9229(8) Å (Au? Au) are indicative of gold–silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self‐aggregation of [Au2M(μ‐mes)2(μ‐LL)]+ units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au? Au and/or Au? M metallophilic interactions, as that observed for 3 a . In solid state the heterometallic Au2M complexes with dppe ( 2 a – 4 a ) show a shift of emission maxima (from ca. 430 to the range of 520‐540 nm) as compared to the parent dinuclear organometallic product 1 a while the complexes with dppy ( 2 b–4 b ) display a more moderate shift (505 for 1 b to a max of 563 nm for 4 b ). More importantly, compound [Au2Ag(μ‐mes)2(μ‐dppy)]ClO4 ( 2 b ) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au2Cl2(μ‐LL)] (LL dppy 5 b ) was also studied for comparative purposes. The antimicrobial activity of 1–5 and Ag[A] (A=ClO4?, SO3CF3?) against Gram‐positive and Gram‐negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au2M derivatives with dppe ( 2 a – 4 a ) were the more active (minimum inhibitory concentration 10 to 1 μg mL?1). Compounds containing silver were ten times more active to Gram‐negative bacteria than the parent dinuclear compound 1 a or silver salts. Au2Ag compounds with dppy ( 2 b , 3 b ) were also potent against fungi. 相似文献
54.
The effect of mechanical activation on the structure and thermal reactions of glasses has been studied on the example of Na–Al–Fe
phosphate glasses. These glasses are used in nuclear technology for immobilization of radioactive waste. The glasses were
activated by grinding in a planetary mill. Mechanical activation causes a decrease of the T
g temperature as well as of the glass crystallization temperature. The type of crystalline phases formed and the quantitative
proportions between them are changing. Analysis of inter-atomic interactions in the structure of glass was applied to explain
the observed regularities governing the crystallization of the activated glasses. 相似文献
55.
56.
Mieczysaw Korolczuk Malgorzata Grabarczyk 《Fresenius' Journal of Analytical Chemistry》1999,363(4):421-423
A voltammetric determination of Cr(VI) in a flow system is described based on the selective accumulation of the reduction
product of Cr(VI) on an HMDE, its complexation with DTPA and subsequent reduction of the complex in presence of nitrate. The
calibration graphs were linear up to 100 and 5 nmol/L for deposition times 120 and 600 s, respectively. The relative standard
deviation was 2.8% (n = 5) for Cr(VI) concentrations of 5 × 10–8 mol/L. The detection limits (3 σ) for Cr(VI) were 1.0 and 0.12 nmol/L at deposition times of 120 and 600 s, respectively.
Typical interferences derived from real water samples are discussed. The method has been applied for the determination of
Cr(VI) in spiked natural water samples.
Received: 18 June 1998 / Revised: 28 September 1998 / Accepted: 5 October 1998 相似文献
57.
58.
Numerical Algorithms - In a number of our previous papers, we have proposed interval versions of multistep methods (explicit and implicit), including interval predictor-corrector methods, in which... 相似文献
59.
This paper presents an ADBASE-based parallel algorithm forsolving multiple objective linear programs (MOLPs). Job balance,speedup and scalability are of primary interest in evaluatingefficiency of the new algorithm. The scalability of a parallelalgorithm is a measure of its capacity to increase performance withrespect to the number of processors used. Implementation results onIntel iPSC/2 and Paragon multiprocessors show that the algorithmsignificantly speeds up the process of solving MOLPs, which isunderstood as generating all or some efficient extreme points andunbounded efficient edges. The algorithm is shown to be scalable andgives better results for large problems. Motivation andjustification for solving large MOLPs are also included. 相似文献
60.
Zurowski Radoslaw Gluszek Malgorzata Antosik Agnieszka Pietrzak Emilia Rokicki Gabriel Szafran Mikolaj 《Journal of Thermal Analysis and Calorimetry》2018,133(1):453-463
Journal of Thermal Analysis and Calorimetry - To study the effect of ionic liquids (ILs) of the microstructure on the surface of the coal, four ILs ([Emim][BF4], [Bmim][BF4], [Bmim][NO3], and... 相似文献