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121.
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122.
Garza AJ Nag M Carroll WR Goddard WA Roberts JD 《Journal of the American Chemical Society》2012,134(36):14772-14780
The populations of diaxial (aa) and diequatorial (ee) conformers of trans-1,2- and cis-1,3-cyclohexanedicarboxylic acids (CDCAs; 1 and 2, respectively) and their salts were determined in water and dimethyl sulfoxide (DMSO) solutions from vicinal proton-proton NMR J couplings ((3)J(HH)). Optimized geometries and free energies for these compounds were obtained at the M06-2X/cc-pVTZ(-f)++ level. Although carboxylic acid groups in cyclohexane rings are generally believed to be far more stable (~2 kcal/mol) in equatorial than axial positions, this investigation demonstrated that an aa conformation (normally assumed to be completely insignificant for these compounds) can be favored depending on the medium and ionization state: strong ee preferences (>90%) were observed in water and DMSO for both diacids and their salts, except for the dianion of 1 in DMSO, which was found to be substantially aa (~57%). The possibility of intramolecular hydrogen bonding (H-bonding) was also investigated; the ratios of the ionization constants (K(1)/K(2)) indicated an absence of intramolecular H-bonding because K(1)/K(2) ? 10(4) (a standard criterion for non-H-bonding in dicarboxylic acids) for both 1 and 2 in water and also for 2 in DMSO. For 1, K(1)/K(2) increased drastically in DMSO (K(1)/K(2) = 4 × 10(6)), where (3)J(HH) and the ratio K(1)/K(E) = 10, K(E) being the acidity constant of the monomethyl ester of 1, indicated the formation of an intramolecular H-bond for the monoanion in this solvent. An explanation for the observation of compact dianions in solution in terms of the generalized Born equation is also provided. 相似文献
123.
Shilpi Agarwal Tapas K. Das Rukmini Dey Sankhasubhra Nag 《General Relativity and Gravitation》2012,44(7):1637-1655
We apply the theory of algebraic polynomials to analytically study the transonic properties of general relativistic hydrodynamic axisymmetric accretion onto non-rotating astrophysical black holes. For such accretion phenomena, the conserved specific energy of the flow, which turns out to be one of the two first integrals of motion in the system studied, can be expressed as a 8th degree polynomial of the critical point of the flow configuration. We then construct the corresponding Sturm’s chain algorithm to calculate the number of real roots lying within the astrophysically relevant domain of \mathbbR{\mathbb{R}}. This allows, for the first time in literature, to analytically find out the maximum number of physically acceptable solution an accretion flow with certain geometric configuration, space-time metric, and equation of state can have, and thus to investigate its multi-critical properties completely analytically, for accretion flow in which the location of the critical points can not be computed without taking recourse to the numerical scheme. This work can further be generalized to analytically calculate the maximal number of equilibrium points certain autonomous dynamical system can have in general. We also demonstrate how the transition from a mono-critical to multi-critical (or vice versa) flow configuration can be realized through the saddle-centre bifurcation phenomena using certain techniques of the catastrophe theory. 相似文献
124.
Joby E. Joy Eric Atamanik Rohini Mani Abanti Nag R.M. Tiwari V. Thangadurai J. Gopalakrishnan 《Solid State Sciences》2010,12(12):1970-1976
We describe the synthesis, structures and dielectric properties of new perovskite oxides of the formula, Ba3MIIITiMVO9, for MIII = Fe, Ga, Y, Lu and MV = Nb, Ta, Sb. While MV = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where MIII/Ti/MV metal-oxygen octahedra are corner-connected, the MV = Sb oxides show a distinct preference for the 6H structure, where SbV/TiIV metal-oxygen octahedra share a common face forming (Sb,Ti)O9 dimers that are corner-connected to the MIIIO6 octahedra. The preference of antimony oxides (SbV:4d10) for the 6H structure – which arises from a special SbV–O chemical bonding that tends to avoid linear Sb–O–Sb linkages unlike NbV/TaV:d0 atoms which prefer ~180° Nb/Ta–O–Nb/Ta linkages – is consistent with the crystal chemistry of MV–O oxides in general. The dielectric properties reveal a significant difference among MIII members. All the oxides with the 3C structure excepting those with MIII = Fe show a normal low loss dielectric behaviour with ε = 20–60 in the temperature range 50–400 °C; the MIII = Fe members with this structure (MV = Nb, Ta) display a relaxor-like ferroelectric behaviour with large ε values at frequencies ≤1 MHz (50–500 °C). 相似文献
125.
Kang M Nag OK Hwang S Kim I Yang H Kyhm K Woo HY 《Physical chemistry chemical physics : PCCP》2010,12(47):15482-15489
The solvent effects were studied in fluorescence resonance energy transfer (FRET) from a cationic polyfluorene copolymer (FHQ, FPQ) to a fluorescein (Fl)-labelled oligonucleotide (ssDNA-Fl). Upon addition of dimethyl sulfoxide (DMSO), the optical properties of polymers and the probe dye were substantially modified and the FRET-induced PL signal was enhanced 3.8-37 times, relative to that in phosphate buffer solution (PBS). The hydrophobic interaction between polymers and ssDNA-Fl is expected to decrease in the presence of DMSO, which induces the weaker polymer/ssDNA-Fl complexation with longer intermolecular donor-acceptor separation and perturbs the competition between the FRET and PL quenching processes such as photo-induced charge transfer. The gradual decrease in Fl PL quenching with increasing the DMSO content was investigated by measuring the Stern-Volmer quenching constants (3.3-4.2 × 10(6) M(-1) in PBS, 0.56-1.1 × 10(6) M(-1) in 80 vol% DMSO) and PL lifetime of the excited Fl* in polymer/ssDNA-Fl (600 ps in PBS and 2120 ps in 80 vol% DMSO for FHQ/ssDNA-Fl) in PBS/DMSO mixtures. The substantially reduced PL quenching would amplify the resulting FRET Fl signal. The signal amplification in real DNA detection was also demonstrated with fluorescein-labelled PNA (probe PNA) in the presence of a complementary target DNA and noncomplementary DNA in aqueous DMSO solutions. This approach suggests a simple way of modifying the fine-structure of polymer/ssDNA-Fl and improving the detection sensitivity in conjugated polymer-based FRET bioassays. 相似文献
126.
Kalyan Raidongia Angshuman Nag Dr. K. P. S. S. Hembram Dr. Umesh V. Waghmare Prof. Dr. Ranjan Datta Dr. C. N. R. Rao Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(1):149-157
A new analogue of graphene containing boron, carbon and nitrogen (BCN) has been obtained by the reaction of high‐surface‐area activated charcoal with a mixture of boric acid and urea at 900 °C. X‐ray photoelectron spectroscopy and electron energy‐loss spectroscopy reveal the composition to be close to BCN. The X‐ray diffraction pattern, high‐resolution electron microscopy images and Raman spectrum indicate the presence of graphite‐type layers with low sheet‐to‐sheet registry. Atomic force microscopy reveals the sample to consist of two to three layers of BCN, as in a few‐layer graphene. BCN exhibits more electrical resistivity than graphene, but weaker magnetic features. BCN exhibits a surface area of 2911 m2 g?1, which is the highest value known for a BxCyNz composition. It exhibits high propensity for adsorbing CO2 (≈100 wt %) at 195 K and a hydrogen uptake of 2.6 wt % at 77 K. A first‐principles pseudopotential‐based DFT study shows the stable structure to consist of BN3 and NB3 motifs. The calculations also suggest the strongest CO2 adsorption to occur with a binding energy of 3.7 kJ mol?1 compared with 2.0 kJ mol?1 on graphene. 相似文献
127.
Choudhury Dibyasree Lahiri Susanta Nag Taraknath Sodaye Suparna Bombard Aude 《Journal of Radioanalytical and Nuclear Chemistry》2020,323(2):897-902
Journal of Radioanalytical and Nuclear Chemistry - Poly (vinyl alcohol)-ethylene glycol (PVA-EG) composites were geared up using casting method. The PVA-EG composite films have been irradiated at... 相似文献
128.
Using atom probe tomography, the partitioning of alloying elements between α and β in the alloy Ti metal-5553 (Ti–5Al–5Mo–5V–3Cr–0.5Fe) has been investigated as a function of heat-treatment. It has been shown that β-solutionizing followed by step-quenching to a higher temperature (700°C) or slow-cooling leads to substantial partitioning of the alloying elements, including an enrichment of slow-diffusing Mo at the α/β interfaces. In contrast, it was found that the combination of β-solutionizing, quenching to room temperature and aging at 400°C leads to rather limited partitioning of these alloying elements. 相似文献
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