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101.
Konstantin E. Komolov Mònica Aguilà Darwin Toledo Joan Manyosa Pere Garriga Karl-Wilhelm Koch 《Analytical and bioanalytical chemistry》2010,397(7):2967-2976
Surface plasmon resonance spectroscopy allows the study of protein interaction dynamics in real-time. Application of this
technique to G-protein coupled receptors, the largest family of receptors involved in signal transduction, has been complicated
by their low level of expression and the critical dependence of their native conformation on the hydrophobic transmembrane
lipid environment. Here, we investigate and compare three different strategies to immobilize rhodopsin, a prototypical G-protein
coupled receptor on a sensor chip surface using antibodies and a lectin for receptor capturing. By further probing of different
experimental conditions (pH, detergent type) we identified the optimal factors to maintain rhodopsin in a functional conformation
and extended this approach to recombinant rhodopsin that was heterologously expressed in COS cells. Functional operation of
rhodopsin on the sensor chip surface was proven by its activation and subsequent light-stimulated G-protein coupling. The
influence of these experimental parameters on the association and dissociation kinetics of G-protein receptor coupling was
determined. Thereby, we found that the kinetics of Gt interaction were not changed by the strategy of immobilization or the type of detergent. Regeneration of opsin directly on
a chip allowed recycling of the immobilized native and recombinant receptor. Thus, the approach provides an experimental framework
for choosing the most suitable conditions for the solubilization, immobilization, and for functional tests of rhodopsin on
a biosensor surface. 相似文献
102.
Laia Vilà‐Nadal José Pedro Sarasa Dr. Antonio Rodríguez‐Fortea Dr. Joan Igual Dr. Leonid P. Kazansky Dr. Josep M. Poblet Prof. Dr. 《化学:亚洲杂志》2010,5(1):97-104
DFT calculations were carried out to study 183W NMR chemical shifts in the family of the Keggin anions with formula α‐[XW12O40]q? (X=B, Al, Si, P, Ga, Ge, As, Zn), in the β‐ and γ‐[SiW12O40]4? geometric isomers, in the derivative Dawson anion [P2W18O62]6?, and in the most symmetrical Lindqvist [W6O19]2? anion and its derivative [W10O32]4?. In this article, we show that the geometry employed in the calculation of NMR chemical shifts in polyoxotungstates is extremely important if we want to be quantitative. Using very large basis sets of QZ4P quality and taking into account the conductor‐like screening model (COSMO) to account for solvent effects (aqueous and organic solutions), good geometries were found for the polyoxoanions. From these optimal geometries the 183W NMR chemical shifts were computed with the more standard basis sets of TZP quality and including spin–orbit corrections inside the zero‐order regular approximation (ZORA) to describe the relativistic effects of the internal electrons. With this strategy the mean absolute error between experimental and theoretical values was found to be less than 10 ppm, which is similar to the experimental error. We also discuss how the geometry of the polyoxoanion influences on the shielding. 相似文献
103.
Carolina Lourencetti Pilar Fernández Celia Prado Joan O. Grimalt 《Analytica chimica acta》2010,662(1):23-30
A method for the estimation of the human intake of trihalomethanes (THMs), namely chloroform, bromodichloromethane, dibromochloromethane and bromoform, during showering and bathing is reported. The method is based on the determination of these compounds in exhaled breath that is collected by solid adsorption on Tenax using a device specifically designed for this purpose. Instrumental measurements were performed by automatic thermal desorption coupled to gas chromatography with electron capture detection. THMs in exhaled breath samples were determined during showering and swimming pool attendance. The levels of these compounds in indoor air and water were also determined as reference for interpretation of the exhaled breath results. The THM concentrations in exhaled breath of the volunteers measured before the exposure experiments showed a close correspondence with the THMs levels in indoor air where the sampler was located. Limits of detection in exhaled breath were dependent on THM analytes and experimental sites. They ranged between 170 and 710 ng m−3 in the swimming pool studies and between 97 and 460 ng m−3 in the showering studies. Application of this method to THMs determination during showering and swimming pool activities revealed statistically significant increases in THMs concentrations when comparing exhaled breath before and after exposure. 相似文献
104.
Joan A. Vaccaro 《Foundations of Physics》2011,41(10):1569-1596
An increasing number of experiments at the Belle, BNL, CERN, DAΦNE and SLAC accelerators are confirming the violation of time
reversal invariance (T). The violation signifies a fundamental asymmetry between the past and future and calls for a major
shift in the way we think about time. Here we show that processes which violate T symmetry induce destructive interference
between different paths that the universe can take through time. The interference eliminates all paths except for two that
represent continuously forwards and continuously backwards time evolution. Evidence from the accelerator experiments indicates
which path the universe is effectively following. This work may provide fresh insight into the long-standing problem of modeling
the dynamics of T violation processes. It suggests that T violation has previously unknown, large-scale physical effects and
that these effects underlie the origin of the unidirectionality of time. It may have implications for the Wheeler-DeWitt equation
of canonical quantum gravity. Finally it provides a view of the quantum nature of time itself. 相似文献
105.
Joan Boulanger Olivier Balima 《Journal of Quantitative Spectroscopy & Radiative Transfer》2011,112(7):1222-1228
We present the first reconstruction algorithm for refractive index imaging, which is based on the radiative transfer equation (RTE). An objective function is iteratively minimized to find a solution to the problem of inversion of the refractive index field. The function describes the discrepancies of the emerging light measurements on the surface of the sample to be probed with predicted data from the corresponding numerical model. The unknown refractive index field is updated within each reconstruction iteration according to a search direction on the index distribution given by the adjoint model to the RTE. In this paper, emphasis is placed on the theoretical aspects. Preliminary tests are demonstrated on generic phantoms. 相似文献
106.
Rand DA Shaw SE Ochoa JR Ripin DJ Taylor A Fan TY Martin H Hawes S Zhang J Sarkisyan S Wilson E Lundquist P 《Optics letters》2011,36(3):340-342
A cryogenic Yb amplifier using two laser materials, Gd3Sc2Al3O12 and Y3Al5O12 (YAG), has been used to obtain 70 W average power at 5 kHz pulse repetition frequency; the output was compressed to 1.6 ps, compared with an input compressible to 1.4 ps. The gain broadening obtained by combining two media enables shorter pulses than using Yb:YAG alone but retains the power-scaling advantages of cryogenic Yb:YAG. 相似文献
107.
Sergey V. Gonchenko Ivan I. Ovsyannikov Joan C. Tatjer 《Regular and Chaotic Dynamics》2014,19(4):495-505
It was established in [1] that bifurcations of three-dimensional diffeomorphisms with a homoclinic tangency to a saddle-focus fixed point with the Jacobian equal to 1 can lead to Lorenz-like strange attractors. In the present paper we prove an analogous result for three-dimensional diffeomorphisms with a homoclinic tangency to a saddle fixed point with the Jacobian equal to 1, provided the quadratic homoclinic tangency under consideration is nonsimple. 相似文献
108.
Lan-Ying Qin Andrew G. Cole Marc-Raleigh Brescia Joan J. Zhang James R. Wareing Juerg Zimmermann John J. Baldwin 《Tetrahedron letters》2010,51(34):4486-4489
A facile synthesis of novel 2-amino-6-arylmethyl-7-carboxamido-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-ones is described. The synthesis was developed on solid phase and was applied to provide a series of analogs in good yield. The key reactions are acylation of a cysteine derivative with 2,4-dichloropyrimidine-5-carbonyl chloride followed by cyclization to generate a 6-arylmethyl-7-carboxamido-2-chloro-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-one, which is further derivatized with an amine to give the desired 2-amino-6-arylmethyl-7-carboxamido-7,8-dihydropyrimido[5,4-f][1,4]thiazepin-5-one. 相似文献
109.
Carmen Coll Elena Aznar Ramón Martínez‐Máñez Prof. M. Dolores Marcos Dr. Félix Sancenón Dr. Juan Soto Dr. Pedro Amorós Joan Cano Dr. Eliseo Ruiz Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(33):10048-10061
We report the preparation of a MCM‐41 mesoporous material that contains the dye [Ru(bipy)3]Cl2 (bipy=bipyridine) inside the mesopores and functionalised with suitable binding groups at the entrance of the pores. Solids S1 – S3 were obtained by the reaction of the mesoporous material with N‐methyl‐N′‐propyltrimethoxysilylimidazolium chloride, N‐phenyl‐N′‐[3‐(trimethoxysilyl)propyl]thiourea, or N‐phenyl‐N′‐[3‐(trimethoxysilyl)propyl]urea, respectively. A study of the dye delivery of these systems in buffered water (pH 7.0, 2‐[4‐(2‐hydroxyethyl)piperazin‐1‐yl]ethanesulfonic acid (HEPES), 10?3 mol dm?3) in the presence of a family of carboxylate ions was carried out. In the interaction of the anions with the surface of the solids, the response depends on the characteristics of the binding groups (i.e., imidazolium, urea and thiourea) at the pore outlets and their specific interaction with the corresponding anion. The interaction of long‐chain carboxylate ions with the binding sites at the surface of the solids resulted in a remarkable inhibition of the delivery of the dye. This inhibition was observed clearly for the dodecanoate anion, whereas the octanoate, decanoate, cholate, deoxycholate, glycodeoxycholate and taurocholate anions induced a certain pore blockage that varied according to the solid studied. The interaction of smaller anions, such as acetate, butanoate, hexanoate and octanoate, with the solids had no effect on the dye release process. The possible use of the gating system for the chromo‐fluorogenic detection of anionic surfactants through selective dye delivery inhibition was also explored. Molecular dynamic simulations that use force‐field methods have been made to theoretically study the capping carboxylate mechanism. The calculations are in agreement with the experimental results, thus allowing a representation of the dye delivery inhibition in the presence of long‐chain carboxylate ions. 相似文献