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101.
Frabetti PL Cheung HW Cumalat JP Dallapiccola C Ginkel JF Greene SV Johns WE Nehring MS Butler JN Cihangir S Gaines I Garbincius PH Garren L Gourlay SA Harding DJ Kasper P Kreymer A Lebrun P Shukla S Bianco S Fabbri FL Sarwar S Zallo A Culbertson R Gardner RW Greene R Wiss J Alimonti G Bellini G Caccianiga B Cinquini L Di Corato M Giammarchi M Inzani P Leveraro F Malvezzi S Menasce D Meroni E Moroni L Pedrini D Perasso L Sala A Sala S Torretta D Vittone M Buchholz D Claes D Gobbi B O'Reilly B 《Physical review letters》1994,72(7):961-964
102.
Indirect photometric detection in capillary electrophoresis (CE) has been predominantly performed in the UV region, in part due to a lack of suitable high-intensity and low-noise light sources in the visible spectral region. A new photometric detector based on light-emitting diodes (LEDs) as light sources and compatible with a commercially available CE instrument has been designed and constructed and its performance evaluated. The utility of this detector was successfully demonstrated by the indirect photometric detection of anions using a dye as probe and absorbance measured in the visible region. The detector exhibited very low baseline noise (around 0.03 mAU), stable output, and improved upper limit of detection linearity (502 mAU) compared with previously used LED detectors. The detector was tested for indirect detection of anions separated with an electrolyte containing 4 mM Orange G as the indirect detection probe, 10 mM histidine as an isoelectric buffer, and 0.05% hydroxypropylmethylcellulose to suppress the electroosmotic flow. Extremely low detection limits were obtained ranging from 0.16-0.36 microM (excluding chloride 0.56 microM), with separation efficiencies in the range of 154,000-274,000 theoretical plates. 相似文献
103.
Sensitive indirect photometric detection of inorganic and small organic anions by capillary electrophoresis using Orange G as a probe ion 总被引:2,自引:0,他引:2
This study addresses the two major problems in the use of dyes as highly absorbing probes for indirect photometric detection in capillary electrophoresis (CE). First, effective electroosmotic flow (EOF) modification or suppression to allow separation and detection of a wide mobility range of analytes is not straightforward when electrolytes containing increased dye concentrations are used. The suppression of EOF to less than + 5x10(-9) m(2)V(-1)s(-1) was achieved with a combination of a poly(ethylenimine) (PEI)-coated capillary and the addition of the neutral polymer hydroxypropylmethylcellulose (HPMC) to the background electrolyte. Second, the deterioration of baselines due to adsorption of the dye probe to the capillary wall is generally a problem. In this work, baseline quality at higher probe concentrations was significantly improved by a rather unusual but highly effective combination of a simultaneous application of a slight overpressure (25 mbar) at the injection end during the separation, and the use of a relatively narrow capillary of 50 microm inner diameter. Both measures would appear to be counterproductive. Optimisation of the probe concentration with regard to signal-to-noise ratio resulted in an electrolyte of 4 mM Orange G, 0.05% HPMC buffered at pH 7.7 by the addition of 10.0 mM histidine isoelectric buffer. Very high separation efficiencies of 128 000-297 000 plates were made possible by the relatively high probe concentration. Combined with excellent detection sensitivity, even with the introduction of hydrodynamic flow and a reduced optical path length, these measures resulted in limits of detection ranging from 0.216 to 0.912 microM with a deuterium lamp light source (248 nm) and from 0.147 to 0.834 microM with a 476 nm blue light-emitting diode (LED) light source. Reproducibility over 30 consecutive runs without changing the electrolyte was excellent, with relative standard deviation (RSD) values of 0.14-0.80% for migration time, 1.27-3.36% for peak area and 0.88-5.12% for peak heights. The optimised electrolyte was used for the analysis of inorganic anions in air filter samples, providing good agreement with results obtained by ion chromatography. 相似文献
104.
Abstract— Ultraviolet irradiation of 14 C-uracil in aqueous solution results in the formation of hydrate and dimer photoproducts. The rate of dimerization increases with increasing uracil concentration, and decreases with increasing concentration of oxygen in solution. The kinetics are in agreement with a model previously proposed to account for the reactions, in which dimerization occurs by a reaction involving the triplet state of uracil, but hydration occurs from an excited singlet state. Oxygen reduces dimer formation by quenching the triplet. The quantum yield for intersystem crossing (ISC) to the triplet depends on the irradiation wavelength, increasing from 0.0014 at 280 nm to 0.016 at 230 nm. The ratio of rate constants for reaction of the triplet with oxygen and for dimerization is 1.1; the ratio of rate constants for triplet decay and for dimerization is 5.9 × 10-5 M. The increase in ISC with photon energy suggests that ISC is favoured from excited vibrational levels. The quantum yield for hydration is about 0.002 at pH 4.5 for all wavelengths, but increases as the pH is decreased. 相似文献
105.
106.
Olsen RA Liu L Ghaderi N Johns A Hatcher ME Mueller LJ 《Journal of the American Chemical Society》2003,125(33):10125-10132
Pyridine carboxamides are a class of medicinal agents with activity that includes the reduction of iron-induced renal damage, the regulation of nicotinamidase activity, and radio- and chemosensitization. Such pharmacological activities, and the prevalence of the carboxamide moiety and the importance of amide rotations in biology, motivate detailed investigation of energetics in these systems. In this study, we report the use of dynamic nuclear magnetic resonance to measure the amide rotational barriers in the pyridine carboxamides picolinamide and nicotinamide. The activation enthalpies and entropies of DeltaH++ = 12.9 +/- 0.3 kcal/mol and DeltaS++ = -7.7 +/- 0.9 cal/mol K for nicotinamide and DeltaH++ = 18.3 +/- 0.4 kcal/mol and DeltaS++ = +1.3 +/- 1.0 cal/mol K for picolinamide report a substantial energetic difference for these regioisomers. Ab initio calculations of the rotational barriers are in good agreement with the experimentally determined values and help partition the 5.4 kcal/mol enthalpy difference into its major contributions. Of principal importance are the variations in steric interactions in the ground states of picolinamide and nicotinamide, superior pi electron donation from the pyridine ring in the transition state of nicotinamide, and an intramolecular hydrogen bond in the ground state of picolinamide. 相似文献
107.
Kenneth C. Johns 《International Journal of Non》1974,9(1):1-21
A two-degree of freedom structural system with both buckling loads equal or nearly so is examined, allowing for the presence of small imperfections specified by the values of two general imperfection parameters. A discrete generalized coordinates energy method is used, and the system considered is non-symmetric in the two modes of deflection. Conclusions regarding the types of behaviour possible are obtained by examination of all possible equilibrium path shapes. Comparison is made to behaviour of idealized systems. Change in buckling load value with imperfection size, or imperfection sensitivity, is established and imperfection sensitivity surface forms are sketched. 相似文献
108.
Gary Chartrand Garry L. Johns Songlin Tian Steven J. Winters 《Journal of Graph Theory》1993,17(4):509-521
The directed distance dD(u, v) from a vertex u to a vertex v in a strong digraph D is the length of a shortest (directed) u - v path in D. The eccentricity of a vertex v in D is the directed distance from v to a vertex furthest from v. The distance of a vertex v in D is the sum of the directed distances from v to the vertices of D. The center C(D) of D is the subdigraph induced by those vertices of minimum eccentricity, while the median M(D) of D is the subdigraph induced by those vertices of minimum distance. It is shown that for every two asymmetric digraphs D1 and D2, there exists a strong asymmetric digraph H such that C(H) ? D1 and M(H) ? D2, and where the directed distance from C(H) to M(H) and from M(H) to C(H) can be arbitrarily prescribed. Furthermore, if K is a nonempty asymmetric digraph isomorphic to an induced subdigraph of both D1 and D2, then there exists a strong asymmetric digraph F such that C(F) ? D1, M(F) ? D2 and C(F) ∩ M(F) ? K. © 1993 John Wiley & Sons, Inc. 相似文献
109.
A synthesis of the phosphotripeptide Glu-PSer-Leu is reported via the stepwise incorporation of the protected phosphoamino acid Nα-tert-butoxycarbonyl-o-dibenzylphosphono-L-serine. 相似文献
110.
Stuart Johns 《The Journal of the Operational Research Society》1996,47(8):1077-1077