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161.
Ove Alexander Høgmoen Åstrand Lars Peter Engeset Austdal Ragnhild E. Paulsen Trond Vidar Hansen Pål Rongved 《Tetrahedron》2013
Herein the synthesis and characterization of new, lipophilic highly Zn2+-selective fluorescent probes are reported. High affinity for zinc (Kd 1.1–8.0 nM) over other biologically relevant metals and mixtures of metals was observed. Excitation at 360 nm afforded an emission spectrum with maximum at 530 nm for the zinc bound complex. The linear relationship between fluorescence intensity and zinc concentration indicates that FZnA-probes can be used for quantification. The probes have been synthesized in 28–45% overall yield and the feasibility for further functionalization with biologically relevant side chains has been demonstrated. In vitro studies using PC12 cells and 10 μM of one of the novel probes (FZnA-Ada) visualized endogenous labile Zn2+ after 45 min incubation time. 相似文献
162.
163.
Poul Erik Hansen Fadhil S. Kamounah Diana Zhiryakova Yana Manolova Liudmil Antonov 《Tetrahedron letters》2014
It has recently been suggested that 1,1′,1′′-(2,4,6-trihydroxybenzene-1,3,5-triyl)triethanone may be tautomeric. Using 13C NMR chemical shifts and deuterium isotope effects on 13C chemical shifts, it is demonstrated that this is not the case. This compound occurs as a strongly hydrogen bonded benzene structure with hydrogen bonds between OH groups and the acetyl groups in both non-polar and hydrogen donating solvents. Quantum-chemical calculations using MP2 and M06-2X methods show substantial preference for the phenol structure in both the gas phase, and in cyclohexane and methanol. In addition, conventional UV–vis spectroscopy data suggest not tautomeric, but aggregation behaviour of the molecule in methanol and acetonitrile. 相似文献
164.
Helene?Bonkerud?Dugstad Nickolaj?Jacob?PetersenEmail author Henrik?Jensen Charlotte?Gabel-Jensen Steen?Honoré?Hansen Stig?Pedersen-Bjergaard 《Analytical and bioanalytical chemistry》2014,406(2):421-429
A small and very simple electromembrane extraction probe (EME-probe) was developed and coupled directly to electrospray ionization mass spectrometry (ESI-MS), and this system was used to monitor in real time in vitro metabolism by rat liver microsomes of drug substances from a small reaction (incubation) chamber (37 °C). The drug-related substances were continuously extracted from the 1.0 mL metabolic reaction mixture and into the EME-probe by an electrical potential of 2.5 V. The extraction probe consisted of a 1-mm long and 350-μm ID thin supported liquid membrane (SLM) of 2-nitrophenyl octyl ether. The drugs and formed metabolites where extracted through the SLM and directly into a 3 μL min?1 flow of 60 mM HCOOH inside the probe serving as the acceptor solution. The acceptor solution was directed into the ESI-MS-system, and the MS continuously monitored the drug-related substances extracted by the EME-probe. The extraction efficiency of the EME-probe was dependant on the applied electrical potential and the length of the SLM, and these parameters as well as the volume of the reaction chamber were set to the values mentioned above to avoid serious depletion from the reaction chamber (soft extraction). Soft extraction was mandatory in order not to affect the reaction kinetics by sample composition changes induced by the EME-probe. The EME-probe/MS-system was used to establish kinetic profiles for the in vitro metabolism of promethazine, amitriptyline and imipramine as model substances. 相似文献
165.
David Moe Almenningen Brita Susanne Haga Henrik Erring Hansen Dr. Audun Formo Buene Prof. Dr. Bård Helge Hoff Prof. Dr. Odd Reidar Gautun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202201726
Designing and evaluating novel dye concepts is crucial for the development of the field of dye-sensitized solar cells (DSSCs). In our recent report, the novel concept of tethering the anti-aggregation additive chenodeoxycholic acid (CDCA) to dyes for DSSC was introduced. Based on the performance improvements seen for this modification, the aim of this study is to see if a simplified anti-aggregation unit could achieve similar results. The following study reports the synthesis and photovoltaic characterization of two novel dyes decorated with the steric ethyladamantyl moiety on the π-spacer, and on the triarylamine donor. This modification is demonstrated to be successful in increasing the photovoltages in devices employing copper-based electrolytes compared to the non-modified reference dye. The best photovoltaic performance is achieved by a device prepared with the adamantyl decorated donor dye and CDCA, this device achieves a power conversion efficiency of 6.1 % (Short-circuit current=8.3 mA cm−2, Open-circuit voltage=1054 mV, Fill factor=0.69). The improved photovoltaic performance seen for the adamantyl decorated donor demonstrate the potential of ethyladamantyl side chains as a tool to ensure surface protection of TiO2. 相似文献
166.
Dr. Thomas Hansen Dr. Alba Nin-Hill Prof. Dr. Jeroen D. C. Codée Dr. Trevor A. Hamlin Prof. Dr. Carme Rovira 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201649
The development of small-molecule covalent inhibitors and probes continuously pushes the rapidly evolving field of chemical biology forward. A key element in these molecular tool compounds is the “electrophilic trap” that allows a covalent linkage with the target enzyme. The reactivity of this entity needs to be well balanced to effectively trap the desired enzyme, while not being attacked by off-target nucleophiles. Here we investigate the intrinsic reactivity of substrates containing a class of widely used electrophilic traps, the three-membered heterocycles with a nitrogen (aziridine), phosphorus (phosphirane), oxygen (epoxide) or sulfur atom (thiirane) as heteroatom. Using quantum chemical approaches, we studied the conformational flexibility and nucleophilic ring opening of a series of model substrates, in which these electrophilic traps are mounted on a cyclohexene scaffold (C6H10Y with Y=NH, PH, O, S). It was revealed that the activation energy of the ring opening does not necessarily follow the trend that is expected from C−Y leaving-group bond strength, but steeply decreases from Y=NH, to PH, to O, to S. We illustrate that the HOMONu–LUMOSubstrate interaction is an all-important factor for the observed reactivity. In addition, we show that the activation energy of aziridines and phosphiranes can be tuned far below that of the corresponding epoxides and thiiranes by the addition of proper electron-withdrawing ring substituents. Our results provide mechanistic insights to rationally tune the reactivity of this class of popular electrophilic traps and can guide the experimental design of covalent inhibitors and probes for enzymatic activity. 相似文献
167.
Intramolecular NH…O,S,N interactions in non-tautomeric systems are reviewed in a broad range of compounds covering a variety of NH donors and hydrogen bond acceptors. 1H chemical shifts of NH donors are good tools to study intramolecular hydrogen bonding. However in some cases they have to be corrected for ring current effects. Deuterium isotope effects on 13C and 15N chemical shifts and primary isotope effects are usually used to judge the strength of hydrogen bonds. Primary isotope effects are investigated in a new range of magnitudes. Isotope ratios of NH stretching frequencies, νNH/ND, are revisited. Hydrogen bond energies are reviewed and two-bond deuterium isotope effects on 13C chemical shifts are investigated as a possible means of estimating hydrogen bond energies. 相似文献
168.
Jiang X Arrington J Benmokhtar F Camsonne A Chen JP Choi S Chudakov E Cusanno F Deur A Dutta D Garibaldi F Gaskell D Gayou O Gilman R Glashauser C Hamilton D Hansen O Higinbotham DW Holt RJ de Jager CW Jones MK Kaufman LJ Kinney ER Kramer K Lagamba L de Leo R Lerose J Lhuillier D Lindgren R Liyanage N McCormick K Meziani ZE Michaels R Moffit B Monaghan P Nanda S Paschke KD Perdrisat CF Punjabi V Qattan IA Ransome RD Reimer PE Reitz B Saha A Schulte EC Sheyor R Slifer K Solvignon P Sulkosky V 《Physical review letters》2007,98(18):182302
We measured the angular dependence of the three recoil-proton polarization components in two-body photodisintegration of the deuteron at a photon energy of 2 GeV. These new data provide a benchmark for calculations based on quantum chromodynamics. Two of the five existing models have made predictions of polarization observables. Both explain the longitudinal polarization transfer satisfactorily. Transverse polarizations are not well described, but suggest isovector dominance. 相似文献
169.
Iodice M Cusanno F Acha A Ambrozewicz P Aniol KA Baturin P Bertin PY Benaoum H Blomqvist KI Boeglin WU Breuer H Brindza P Bydzovský P Camsonne A Chang CC Chen JP Choi S Chudakov EA Cisbani E Colilli S Coman L Craver BJ De Cataldo G de Jager CW De Leo R Deur AP Ferdi C Feuerbach RJ Folts E Fratoni R Frullani S Garibaldi F Gayou O Giulani F Gomez J Gricia M Hansen JO Hayes D Higinbotham DW Holmstrom TK Hyde CE Ibrahim HF Jiang X Kaufman LJ Kino K Kross B Lagamba L LeRose JJ Lindgren RA 《Physical review letters》2007,99(5):052501
An experiment measuring electroproduction of hypernuclei has been performed in hall A at Jefferson Lab on a 12C target. In order to increase counting rates and provide unambiguous kaon identification two superconducting septum magnets and a ring imaging Cherenkov detector were added to the hall A standard equipment. An unprecedented energy resolution of less than 700 keV FWHM has been achieved. Thus, the observed (Lambda)(12)B spectrum shows for the first time identifiable strength in the core-excited region between the ground-state s-wave Lambda peak and the 11 MeV p-wave Lambda peak. 相似文献
170.
Total Synthesis of the Anti‐inflammatory and Pro‐resolving Lipid Mediator MaR1n−3 DPA Utilizing an sp3–sp3 Negishi Cross‐Coupling Reaction
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Jørn Eivind Tungen Dr. Marius Aursnes Dr. Jesmond Dalli Dr. Hildur Arnardottir Prof. Dr. Charles Nicholas Serhan Prof. Dr. Trond Vidar Hansen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14575-14578
The first total synthesis of the lipid mediator MaR1n?3 DPA ( 5 ) has been achieved in 12 % overall yield over 11 steps. The stereoselective preparation of 5 was based on a Pd‐catalyzed sp3–sp3 Negishi cross‐coupling reaction and a stereocontrolled Evans–Nagao acetate aldol reaction. LC‐MS/MS results with synthetic material matched the biologically produced 5 . This novel lipid mediator displayed potent pro‐resolving properties stimulating macrophage efferocytosis of apoptotic neutrophils. 相似文献