Thermal, thermomechanical, and caloric properties of commercial orthodontic wires (produced by Natural Orthodontics Corp., USA) with cylindrical and rectangular geometry were studied. Depending on the applied forces, there were identified the range of elasticity, the elasticity–viscoelasticity coexistence domain and the domain in which a maximum force of 18 N is applied, for the orthodontic wires. When increasing the thickness of orthodontic wires, deformation decreases. The Controlled Force Module, in the tension mode, was used for the determination of the orthodontic wires elongation at application of the stretching forces from 0 to 13 N, at 35 °C, maintaining each static force value for 3 min. The increase in the cross-sectional area of the orthodontic wires disfavors the process of elongation of the sample, at the same applied static force. Using the Multi-Frequency–Strain–Stress modulus, in the tension mode, DMA cyclic heating–cooling measurements were performed. The measured physical quantities for orthodontic wires were Storage Modulus, Loss Modulus, Tanδ and Stiffness, at heating and cooling. Thus, the characteristic temperatures of the phase transitions (As, Af, Ms, Mf), of all the studied orthodontic wires were identified. Also, the values of the elasticity modulus (Young’s Modulus) of the orthodontic wires were calculated at 35 °C. With the DSC Q200 device, using temperature-modulated differential scanning calorimetry method, a multi-step temperature variation program, was applied to a rectangular wire, in three stages (cooling–heating–cooling). Through the interpretation of heat fluxes (reversible, irreversible and total), the phase transitions in the formation of martensite, austenite, but also of the rombohedral phase (R-phase), were identified. Formations of austenite and martensite were also evidenced by the classical DSC method, but the classical DSC method also enabled the R-phase identification. The adherence of some food dyes on the orthodontic wires, as well as the modification of the surface roughness of the orthodontic wire after the deposition of the food dye, was also studied. By magnetic measurements, it was established that the orthodontic wires had paramagnetic properties at room temperature, and nitinol was a mixture of 49.2% austenite and 50.8% martensite.
Asymmetric conjugate addition of arylboronic acids to 2-nitroacrylamide in the presence of cationic palladium–Chiraphos complex proceeds with high yield and enantioselectivity (73–89% ee) using as low as 0.05–0.25 mol % of the catalyst. The adducts can be smoothly transformed into the corresponding β2-homophenylglycines in two simple steps. 相似文献
The scope of the enantioselective Mukaiyama–Michael reactions catalyzed by trans‐2,5‐diphenylpyrrolidine has been expanded to include both α‐ and β‐substituted enals. However, the rationalization of the observed enantioselectivity is far from obvious since the catalyst is not very sterically hindered. DFT calculations were carried out to rationalize the observed stereoselectivities. Transition states of the C?C bond formation between iminium intermediates and silyloxyfurans were located and their relative energies were used to estimate the stereoselectivity data. We find excellent agreement between the predicted and observed stereoselectivities. The analysis of intermolecular forces reveals that the enantioselectivity is mostly due to stabilizing noncovalent interactions between the reacting partners, not due to steric hindrance. The role of attractive noncovalent interactions in enantioselective catalysis may be underappreciated. 相似文献
similar to thep-Laplacian, that tend to ∞ on a given closed set ofp-capacity zero. Moreover, we show that everyGδ-set of vanishingp-capacity is the infinity set of someA-superharmonic function.
The research is financed by the Academy of Finland (Project #8597). 相似文献
Photosensitive cholesteric polysiloxanes, which contain an azo dye, were irradiated with linearly polarized light. The cholesteric samples were oriented in the Grandjean texture. Before irradiation they reflected circularly polarized light in the near infrared region. For perpendicular incidence, only one order of reflection was observed. Upon irradiation with linearly polarized light, which is absorbed by the azo dye, additional reflection bands appeared in the visible part of the spectrum. It turned out that the additional reflection is caused by a new Bragg type grating which shows higher reflection orders. The formation of the grating is based on the periodic deformation of the helical ordering of the molecules. The deformation is periodic, as due to photoselection, only dye molecules in equidistant layers with a suitable orientation absorb radiation. For low exposure, the grating reflects linearly polarized light. After continued irradiation, the reflection bands disappear almost completely. High birefringence, strongly dichroic dye absorption and the loss of the reflecting properties prove that a planar nematic texture has developed. The formation of this texture from the Grandjean texture is a new example for photoinduced rotational diffusion. 相似文献
Cholesteric polysiloxanes containing an azo dye were irradiated with linearly or circularly polarized laser light or with the unpolarized light from a HgXe lamp. Photoinduced rotational diffusion was observed leading to new textures with a completely different orientational distribution of the chromophoric and the mesogenic side chains. A broad variety of new structures was detected depending on the polarization state of the light, the helical arrangement of the azo dye and the optional application of an electrical d.c. field. The new structures were characterized by spectroscopy with polarized light. Co-operative reorientation of chromophoric and mesogenic side chains was proven. The formation of a Bragg grating upon short term irradiation with linearly polarized light was observed. Continued irradiation leads in most cases to a strongly birefringent texture with a high dichroic ratio of the azo dye resembling a planar nematic texture. With circularly polarized light or with unpolarized light, a uniaxial homeotropic texture appeared predominantly. The formation of the new textures occurred in the glassy state of the samples leading to new structures with good optical quality and an exceptionally good long-term stability. 相似文献
A new pulse sequence, long-range CPMG-adjusted heteronuclear single quantum coherence (LR-CAHSQC), is proposed for the determination of long-range JCH coupling constants from a long-range 1H-13C correlation experiment. The long-range heteronuclear coupling constants can be directly extracted from COSY-type antiphase peak patterns. The current approach utilizes CPMG-sequences for polarization transfer, and thus avoids the evolution of homonuclear JHH couplings, which normally may introduce abnormalities into the cross peak pattern. The differences between LR-CAHSQC and normal LR-HSQC are discussed. 相似文献
The kinetics of the i-C4H5 (buta-1,3-dien-2-yl) radical reaction with molecular oxygen has been measured over a wide temperature range (275–852 K) at low pressures (0.8–3 Torr) in direct, time-resolved experiments. The measurements were performed using a laminar flow reactor coupled to photoionization mass spectrometer (PIMS), and laser photolysis of either chloroprene (2-chlorobuta-1,3-diene) or isoprene was used to produce the resonantly stabilized i-C4H5 radical. Under the experimental conditions, the measured bimolecular rate coefficient of i-C4H5 + O2 reaction is independent of bath gas density and exhibits weak, negative temperature dependency, and can be described by the expression k3 = (1.45 ± 0.05) × 10?12 × (T/298 K)?(0.13±0.05) cm3 s?1. The measured bimolecular rate coefficient is surprisingly fast for a resonantly stabilized radical. Under combustion conditions, the reactions of i-C4H5 radical with ethylene and acetylene are believed to play an important role in forming the first aromatic ring. However, the current measurements show that i-C4H5 + O2 reaction is significantly faster under combustion conditions than previous estimations suggest and, consequently, inhibits the soot forming propensity of i-C4H5 radicals. The bimolecular rate coefficient estimates used for the i-C4H5 + O2 reaction in recent combustion simulations show significant variation and are up to two orders of magnitude slower than the current, measured value. All estimates, in contrast to our measurements, predict a positive temperature dependency. The observed products for the i-C4H5 + O2 reaction were formaldehyde and ketene. This is in agreement with the one theoretical study available for i-C4H5 + O2 reaction, which predicts the main bimolecular product channels to be H2CO + C2H3 + CO and H2CCO + CH2CHO. 相似文献