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81.
Regis Grailhe Fabienne Merola Jacqueline Ridard Stephen Couvignou Chantal Le Poupon Jean-Pierre Changeux Helene Laguitton-Pasquier 《Chemphyschem》2006,7(7):1442-1454
Using fluorescence lifetime microspectroscopy and imaging techniques, we have studied the fluorescence of cyan fluorescent protein (CFP) transiently expressed in HEK-293 cells, in the presence or absence of its fluorescence resonance energy transfer (FRET) partner, yellow fluorescent protein (YFP). When the two proteins are attached through a 27-amino-acid linker, a 33 % average efficiency of intramolecular energy transfer is accurately determined inside the cell. Additionally, we observe a systematic quenching of the CFP fluorescence with increasing levels of protein expression. This quenching cannot be accounted for by formation of the previously described dimer of GFP-related proteins, since its magnitude is unchanged when the fluorescent proteins carry the mutation A206K shown to dissociate this dimer in vitro. Even when the intracellular protein concentration largely exceeds the in vitro dissociation constant of the dimer, self-association remains undetectable, either between free proteins or intramolecularly within the CFP-YFP construct. Instead, the detailed concentration effects are satisfactorily accounted for by a model of intermolecular, concentration-dependent energy transfer, arising from molecular proximity and crowding. In the case of CFP alone, we suggest that self-quenching could result from a pseudo-homo FRET mechanism between different, spectrally shifted emissive forms of the protein. These phenomena require careful consideration in intracellular FRET studies. 相似文献
82.
Laszlo Revesz Chantal Briswalter Richard Heng Albert Leutwiler Rudolf Mueller Hans-Juerg Wuethrich 《Tetrahedron letters》1994,35(52):9693-9696
Improved procedures have been developed for the synthesis of P1 aspartate-based 2,6-dichlorobenzoyloxymethyl ketone 1 and fluoromethyl ketone 2, the prodrugs of two potent ICE-inhibitors. 1 was prepared from (R)-trans-4,5-O-isopropylidene-4,5-dihydroxy-2-pentenecarboxylic acid ethyl ester; 2 was obtained via a nitro-aldol condensation as key step from in situ generated fluoroacetaldehyde. 相似文献
83.
Near the interface between a normal metal and a superconductor, Cooper pairs penetrate into the normal side, giving rise to
the proximity effect. The two electrons of these pairs have entangled spin and orbital degrees of freedom. Nonlocal features
of quantum mechanics can be probed by separating these two electrons. This is achieved with a fork geometry with two normal
leads containing either spin- or energy-selective filters. A signature of entanglement can be detected by measuring the positive
noise cross-correlations in this fork. In the case of energy filters, Bell-inequality checks constitute a definite probe of
entanglement. We formulate Bell-type inequalities in terms of current-current cross-correlations associated with contacts
with varying magnetization orientations. We find maximal violation (as in photons) when a superconductor is the particle source. 相似文献
84.
Cadot E Pouet MJ Robert-Labarre C du Peloux C Marrot J Sécheresse F 《Journal of the American Chemical Society》2004,126(29):9127-9134
Cyclic oxothiomolybdates containing polyphosphate ions were prepared by simple reactions in aqueous medium of the corresponding polyphosphate ions and the cyclic precursor K(2)I(2)Mo(10)S(10)O(10)(OH)(10)(OH(2))(5).15H(2)O. K(5)[Cl(P(2)O(7)]Mo(12)S(12)O(12)(OH)(12)(H(2)O)(4)].22H(2)O (1) was isolated from concentrated chloride solution (2.5 mol.L(-1)). 1 reveals a remarkable complex containing two different substrates encapsulated in a dodecanuclear ring, a H-bonded Cl(-) ion, and a covalently bonded [P(2)O(7)] group. The chloride ion in 1 can be selectively removed for a monohydrogenophosphate group yielding K(6)[(HPO(4))(P(2)O(7))Mo(12)S(12)O(12)(OH)(12)(H(2)O)(2)].19H(2)O (2), a mixed species containing a [P(2)O(7)] and a [HPO(4)] group. The substitution is accompanied by a significant change of the ring, which adopts a "pear-shape" conformation. In the presence of triphosphate ion, the "heart-shaped" decanuclear ring Rb(3)[(H(2)P(3)O(10))Mo(10)S(10)O(10)(OH)(10)].17.5H(2)O (3) is formed containing a linear [P(3)O(10)] group intimately embedded in the inorganic cyclic host. The three compounds were structurally characterized by single-crystal X-ray diffraction. The behaviors of 1, 2, and 3 in solution were studied by (31)P NMR. Variable temperature experiments, supported by a two-dimensional COSY (31)P experiment, revealed that the supramolecular interaction existing between the chloride ion and the ring in solid 1 is maintained in solution. Nevertheless, 1 remains labile, and successive equilibria were evidenced and interpreted as an ion-pair association involving a halide ion (Cl, Br, or I), responsible for the conformational change of the [P(2)O(7)] group within the cavity. The influence of the nature of the halide guest (Cl(-), Br(-), and I(-)) on the successive equilibria was studied, and the thermodynamic constant related to the postulated equilibrium was determined. The stability of the supramolecular association decreases in the order Cl > Br > I. In solution, a phosphate exchange is observed for 2 while for 3 the absence of temperature dependence of the (31)P NMR spectrum confirms the conformation of the host-guest system is blocked. Elemental analysis and infrared characterizations are also supplied. 相似文献
85.
Bock C Paquet C Couillard M Botton GA MacDougall BR 《Journal of the American Chemical Society》2004,126(25):8028-8037
A rapid synthesis method for the preparation of PtRu colloids and their subsequent deposition on high surface area carbons is presented. The reaction mechanism is shown to involve the oxidation of the solvent, ethylene glycol, to mainly glycolic acid or, depending on the pH, its anion, glycolate, while the Pt(+IV) and Ru(+III) precursor salts are reduced. Glycolate acts as a stabilizer for the PtRu colloids and the glycolate concentration, and hence the size of the resulting noble metal colloids is controlled via the pH of the synthesis solution. Carbon-supported PtRu catalysts of controlled size can be prepared within the range of 0.7-4 nm. Slow scan X-ray diffraction and high-resolution transmission electron microscopy show the PtRu catalysts to be crystalline. The Ru is partly dissolved in the face-centered cubic Pt lattice, but the catalysts also consist of a separate, hexagonal Ru phase. The PtRu catalysts appear to be of the same composition independent of the catalyst size in the range of 1.2-4 nm. Particular PtRu catalysts prepared in this work display enhanced activities for the CH(3)OH electro-oxidation reaction when compared to two commercial catalysts. 相似文献
86.
Paquet C Cyr PW Kumacheva E Manners I 《Chemical communications (Cambridge, England)》2004,(2):234-235
The refractive index, molar refraction and Abbe number of polyferrocene derivatives are reported and the values indicate that these materials are very promising for a range of photonics applications. 相似文献
87.
A model coupling differential equations and an optimization problem with equality and inequality constraints is described. The first order optimality conditions are coupled with the differential equations to form a differential-algebraic system. Inequality constraints for the optimization variables induce discontinuities in the first derivatives of the solution in time. Tracking techniques based on sensitivity analysis and second order multistep methods are proposed to locate the discontinuities. Application to the dynamics of organic atmospheric aerosol particles is given to illustrate the detection of the activation of constraints. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
88.
Hao-Jung Chang Mykhailo V. Bondar Dr. Natalia Munera Dr. Sylvain David Dr. Olivier Maury Dr. Gerard Berginc Dr. Boris Le Guennic Dr. Denis Jacquemin Dr. Chantal Andraud Dr. David J. Hagan Dr. Eric W. Van Stryland 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(17):e202104072
The fast relaxation processes in the excited electronic states of functionalized aza-boron-dipyrromethene (aza-BODIPY) derivatives ( 1 – 4 ) were investigated in liquid media at room temperature, including the linear photophysical, photochemical, and nonlinear optical (NLO) properties. Optical gain was revealed for nonfluorescent derivatives 3 and 4 in the near infrared (NIR) spectral range under femtosecond excitation. The values of two-photon absorption (2PA) and excited-state absorption (ESA) cross-sections were obtained for 1–4 in dichloromethane using femtosecond Z-scans, and the role of bromine substituents in the molecular structures of 2 and 4 is discussed. The nature of the excited states involved in electronic transitions of these dyes was investigated using quantum-chemical TD-DFT calculations, and the obtained spectral parameters are in reasonable agreement with the experimental data. Significant 2PA (maxima cross-sections ∼2000 GM), and large ESA cross-sections ∼10−20 m2 of these new aza-BODIPY derivatives 1–4 along with their measured high photostability reveal their potential for photonic applications in general and optical limiting in particular. 相似文献
89.
90.