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231.
Maliarik M Nagle JK Ilyukhin A Murashova E Mink J Skripkin M Glaser J Kovacs M Horváth A 《Inorganic chemistry》2007,46(11):4642-4653
The new crystalline compounds Tl2Ni(CN)4 and Tl2Pd(CN)4 were synthesized by several procedures. The structures of the compounds were determined by single-crystal X-ray diffraction. The compounds are isostructural with the previously reported platinum analogue, Tl2Pt(CN)4. A new synthetic route to the latter compound is also suggested. In contrast to the usual infinite columnar stacking of [M(CN)4]2- ions with short intrachain M-M separations, characteristic of salts of tetracyanometalates of NiII, PdII, and PtII, the structure of the thallium compounds is noncolumnar with the two TlI ions occupying axial vertices of a distorted pseudo-octahedron of the transition metal, [MTl2C4]. The Tl-M distances in the compounds are 3.0560(6), 3.1733(7), and 3.140(1) A for NiII, PdII, and PtII, respectively. The short Tl-Ni distance in Tl2Ni(CN)4 is the first example of metal-metal bonding between these two metals. The strength of the metal-metal bonds in this series of compounds was assessed by means of vibrational spectroscopy. Rigorous calculations, performed on the molecules in D4h point group symmetry, provide force constants for the Tl-M stretching vibration constants of 146.2, 139.6, and 156.2 N/m for the NiII, PdII, and PtII compounds, respectively, showing the strongest metal-metal bonding in the case of the Tl-Pt compound. Amsterdam density-functional calculations for isolated Tl2M(CN)4 molecules give Tl-M geometry-optimized distances of 2.67, 2.80, and 2.84 A for M = NiII, PdII, and PtII, respectively. These distances are all substantially shorter than the experimental values, most likely because of intermolecular Tl-N interactions in the solid compounds. Time-dependent density-functional theory calculations reveal a low-energy, allowed transition in all three compounds that involves excitation from an a1g orbital of mixed Tl 6pz-M ndz2 character to an a2u orbital of dominant Tl 6pz character. 相似文献
232.
In a recent paper, we suggested that the acid- or base-catalyzed dehydration of a hydrated carbonyl compound provides a suitable foundation for an organic-based pH oscillator. Here we present the first experimental example of such an oscillator in a flow reactor, utilizing the base-catalyzed dehydration of methylene glycol as a source of positive feedback (OH- autocatalysis) coupled with the base-catalyzed hydrolysis of gluconolactone for negative feedback (H+ production). The large amplitude oscillations (between pH 7 and 10) are reproduced in a kinetic model of the reaction. Such experiments present new possibilities in the design of pH oscillators. 相似文献
233.
McIntee JW Sundararajan C Donovan AC Kovacs MS Capretta A Valliant JF 《The Journal of organic chemistry》2008,73(21):8236-8243
A convenient method for the preparation of fluorous aryl stannanes was developed as a means of expanding the general utility of the fluorous labeling strategy (FLS). Following the synthesis of a novel fluorous distannane, a palladium-catalyzed cross-coupling reaction was used to prepare the target compounds from aryl halides. The scope of the reaction was investigated by preparing a small library of model compounds where the reaction yields were similar to those reported for the analogous procedures employing hexamethyl- or hexabutyldistannanes. The utility of the reported methodology was demonstrated through the successful synthesis of fluorous precursors to two established molecular imaging and therapy agents (FIAU, IUdR). These were radiolabeled with iodine-125 and the desired products isolated in high yield and effective specific activity. 相似文献
234.
Optimization of TRPV6 Calcium Channel Inhibitors Using a 3D Ligand‐Based Virtual Screening Method 下载免费PDF全文
Dr. Céline Simonin Dr. Mahendra Awale Michael Brand Dr. Ruud van Deursen Dr. Julian Schwartz Dr. Michael Fine Dr. Gergely Kovacs Pascal Häfliger Dr. Gergely Gyimesi Abilashan Sithampari Prof. Dr. Roch‐Philippe Charles Prof. Dr. Matthias A. Hediger Prof. Dr. Jean‐Louis Reymond 《Angewandte Chemie (International ed. in English)》2015,54(49):14748-14752
Herein, we report the discovery of the first potent and selective inhibitor of TRPV6, a calcium channel overexpressed in breast and prostate cancer, and its use to test the effect of blocking TRPV6‐mediated Ca2+‐influx on cell growth. The inhibitor was discovered through a computational method, xLOS, a 3D‐shape and pharmacophore similarity algorithm, a type of ligand‐based virtual screening (LBVS) method described briefly here. Starting with a single weakly active seed molecule, two successive rounds of LBVS followed by optimization by chemical synthesis led to a selective molecule with 0.3 μM inhibition of TRPV6. The ability of xLOS to identify different scaffolds early in LBVS was essential to success. The xLOS method may be generally useful to develop tool compounds for poorly characterized targets. 相似文献
235.
236.
Jozsef Garai 《Solid State Communications》2010,150(35-36):1710-1714
It is suggested that at the melting temperature the wavelength of the average thermal phonon vibration is equal to or is a harmonic of the distance separating the atomic layers in the crystal. This resonance between the phonon and lattice vibrations equals out the energy of the vibrating atoms in the surface layer. If this “uniform” energy is higher than the energy corresponding to the metastable transition state then all the surface atoms lose its position stability. In order to make the jump to the next potential well energy is required to overcome on the viscous resistance of the liquid. If this energy, latent heat of fusion, is supplied then the atomic/molecular sheet or platelets from the surface are detached and melting occurs. The proposed model is consistent with all of the characteristic features of melting and freezing. Equations calculating the average phonon wavelength and the corresponding lattice distance at the melting temperature are derived from fundamental thermodynamic relationships. The required thermodynamic parameters are determined from experiments of the nine selected highly symmetrical solids. The calculated wavelengths of the phonon vibration are equal to or is a harmonic of the -spacing of the atomic/molecular layers in agreement with theory. 相似文献
237.
Ulam asked in 1945 if there is an everywhere dense rational set, i.e., 1 a point set in the plane with all its pairwise distances rational. Erdős conjectured that if a set S has a dense rational subset, then S should be very special. The only known types of examples of sets with dense (or even just infinite) rational subsets are
lines and circles. In this paper we prove Erdős’ conjecture for algebraic curves by showing that no irreducible algebraic
curve other than a line or a circle contains an infinite rational set. 相似文献
238.
2H/1H measurements of amphiboles and nominally anhydrous minerals (clinopyroxene,garnet and diamond) using high‐temperature continuous flow elemental analyser/pyrolysis/isotope ratio mass spectrometry 下载免费PDF全文
239.
The Relationship between NMR Chemical Shifts of Thermally Polarized and Hyperpolarized 89Y Complexes and Their Solution Structures 下载免费PDF全文
Dr. Yixun Xing Dr. Ashish K. Jindal Dr. Martín Regueiro‐Figueroa Dr. Mariane Le Fur Nelly Kervarec Piyu Zhao Dr. Zoltan Kovacs Dr. Laura Valencia Dr. Paulo Pérez‐Lourido Prof. Raphaël Tripier Dr. David Esteban‐Gómez Dr. Carlos Platas‐Iglesias Prof. A. Dean Sherry 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16657-16667
Recently developed dynamic nuclear polarization (DNP) technology offers the potential of increasing the NMR sensitivity of even rare nuclei for biological imaging applications. Hyperpolarized 89Y is an ideal candidate because of its narrow NMR linewidth, favorable spin quantum number (I= ), and long longitudinal relaxation times (T1). Strong NMR signals were detected in hyperpolarized 89Y samples of a variety of yttrium complexes. A dataset of 89Y NMR data composed of 23 complexes with polyaminocarboxylate ligands was obtained using hyperpolarized 89Y measurements or 1H,89Y‐HMQC spectroscopy. These data were used to derive an empirical equation that describes the correlation between the 89Y chemical shift and the chemical structure of the complexes. This empirical correlation serves as a guide for the design of 89Y sensors. Relativistic (DKH2) DFT calculations were found to predict the experimental 89Y chemical shifts to a rather good accuracy. 相似文献
240.