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141.
Fluorogenic analogues of α‐tocopherol developed by our group have been instrumental in monitoring reactive oxygen species (ROS) within lipid membranes. Prepared as two‐segment trap‐reporter (chromanol‐BODIPY) probes, photoinduced electron transfer (PeT) was utilized to provide these probes with an off/on switch mechanism warranting the necessary sensitivity. Herein, we rationalize within the context of Marcus theory of electron transfer how substituents on the BODIPY core and linker length joining the trap and reporter segments, tune PeT efficiency. DFT and electrochemical studies were used to estimate the thermodynamic driving force of PeT in our constructs. By tuning the redox potential over a 400 mV range, we observed over an order of magnitude increase in PeT efficiency. Increasing the linker length between the chromanol and BODIPY by 2.8 angstroms, in turn, decreased PeT efficiency 2.7‐fold. Our results illustrate how substituent and linker choice enable “darkening” the off state of fluorogenic probes based on BODIPY fluorophores, by favoring PeT over radiative emission from the singlet excited state manifold. Ultimately, our work brings light to the sensitivity ceiling one may achieve in developing fluorogenic antioxidant analogues of α‐tocopherol. The work provides general guidelines applicable to those developing fluorogenic probes based on PeT. 相似文献
142.
Enrique Gil de Montes Dr. Alena Istrate Dr. Claudio D. Navo Dr. Ester Jiménez-Moreno Emily A. Hoyt Dr. Francisco Corzana Prof. Inmaculada Robina Dr. Gonzalo Jiménez-Osés Dr. Antonio J. Moreno-Vargas Dr. Gonçalo J. L. Bernardes 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6255-6259
An azanorbornadiene bromovinyl sulfone reagent for cysteine-selective bioconjugation has been developed. Subsequent reaction with dipyridyl tetrazine leads to bond cleavage and formation of a pyrrole-linked conjugate. The latter involves ligation of the tetrazine to the azanorbornadiene-tagged protein through inverse electron demand Diels–Alder cycloaddition with subsequent double retro-Diels–Alder reactions to form a stable pyrrole linkage. The sequence of site-selective bioconjugation followed by bioorthogonal bond cleavage was efficiently employed for the labelling of three different proteins. This method benefits from easy preparation of these reagents, selectivity for cysteine, and stability after reaction with a commercial tetrazine, which has potential for the routine preparation of protein conjugates for chemical biology studies. 相似文献
143.
Gonzalo García-Reyes 《General Relativity and Gravitation》2018,50(4):45
We construct relativistic models of charged dust thick disks for a particular conformastatic spacetime through a Miyamoto–Nagai transformation used in Newtonian gravity to model disk like galaxies. Two simple families of thick disk models and a family of thick annular disks based on the field of an extreme Reissner–Nordström black hole and a Morgan–Morgan-like metric are considered. The electrogeodesic motion of test particles around the structures are analyzed. Also the stability of the particles against radial perturbation is studied using an extension of the Rayleigh criteria of stability of a fluid in rest in a gravitational field. The models built satisfy all the energy conditions. 相似文献
144.
145.
Dr. Karl P. J. Gustafson Dr. Tamás Görbe Dr. Gonzalo de Gonzalo-Calvo Ning Yuan Cynthia L. Schreiber Dr. Andrey Shchukarev Dr. Cheuk-Wai Tai Prof. Dr. Ingmar Persson Prof. Dr. Xiaodong Zou Prof. Dr. Jan-E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(39):9174-9179
Herein, we report on the use a biohybrid catalyst consisting of palladium nanoparticles immobilized on cross-linked enzyme aggregates of lipase B of Candida antarctica (CalB CLEA) for the dynamic kinetic resolution (DKR) of benzylic amines. A set of amines were demonstrated to undergo an efficient DKR and the recyclability of the catalysts was studied. Extensive efforts to further elucidate the structure of the catalyst are presented. 相似文献
146.
147.
Gonzalo Angulo Dr. Daniel R. Kattnig Dr. Arnulf Rosspeintner Dr. Günter Grampp Prof. Eric Vauthey Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(7):2291-2299
In a previous article we showed how to perform and analyze steady‐state and nanosecond time‐resolved experiments on fluorescence quenching by electron transfer in a coherent manner. Now, by making use of a superior time resolution, we explore the first stages of this kind of reaction. The novel information gained enables us to merge the results on the viscosity and the driving‐force dependencies of the reaction rate. A unique set of parameters for a single reaction channel suffices to describe all the results in the frame of differential encounter theory for diffusion‐influenced, bimolecular, remote electron‐transfer reactions. The inclusion of the solvent structure is crucial for the understanding of the reaction kinetics. To the authors’ best knowledge, this is the first time that such a comprehensive set of data has been successfully and jointly explained in the field, with physically sound parameters for electron‐transfer reactions. 相似文献
148.
Juan C. del Valle Enrique Camarillo Julio A. Gonzalo Carmen Aragó Manuel Marqués 《哲学杂志》2015,95(7):683-690
Recently, the paraelectric response of water was investigated in the range 0–100 °C. It showed an almost perfect Curie–Weiss behaviour up to 60 °C, but a slight change in slope of 1/εd versus T at 60 °C was overlooked. In this work, we report optical extinction measurements on metallic (gold and silver) nanoparticles dispersed in water, annealed at various temperatures in the range from 20 to 90 °C. An anomalous response at 60 °C is clearly detectable, which we associate to a subtle structural transformation in the water molecules at that temperature. This water anomaly is also manifested by means of a blue shift in the longitudinal surface plasmon resonance of the metallic nanoparticles for the solutions annealed at temperatures higher than about 60 °C. A reanalysis of 1/εd (T) for water in the whole temperature range leads us to conclude that the water molecule undergoes a subtle transformation from a low temperature (0–60 °C) configuration with a dipole moment μ1 = 2.18 D (close to the molecular dipole moment of ice) to a high temperature (60–100 °C) configuration with μ2 = 1.87 D (identical to the molecular dipole moment in water vapour). 相似文献
149.
150.
Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez Edith Miranda Cruz Javier Domínguez‐Álvarez Jesús Hernández‐Méndez 《Journal of separation science》2009,32(4):575-584
In the present work we address the development of a simple and effective method for the determination of triazine herbicide residues in horticultural products by CE in nonaqueous media (NACE). Potato samples were selected as a representative matrix of such foods with a nonfatty content. Isolation of the analytes from the sample matrix was accomplished by extraction with organic solvents, assisted by ultrasound; a clean‐up step of the organic extracts was carried out with SPE, using an Oasis MCX® sorbent to retain the analytes directly from the organic medium. The detection limits achieved in spiked potatoes (1.7–4.0 μg/kg) were lower than the default value of maximum residue level (MRL) established by current EU legislation for pesticide residues in foodstuffs. The results obtained were compared with HPLC in order to evaluate the performance of the NACE procedure. 相似文献