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
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.
We consider two impact mappings, the Brach impact mapping and an energetic impact mapping, for rigid-body mechanisms with impacts and friction. The two impact mappings represent the opposite end of the spectrum from basic to advanced impact mappings. Both impact mappings are briefly derived and described. For the Brach impact mapping we will introduce the concept of impulse ratio and discuss how the kinetic energy changes during an impact as the impulse ratio is varied. This analysis is used to further extend the Brach impact mapping to cover situations that were previously omitted. Finally, we make comparisons between the two impact mappings and show how the Painlevé paradox appears in the two impact mappings. The conclusion of the comparisons is that while the basic impact mapping seems easy to implement in a computer simulator it may in the end be more complex and also introduce unnecessary complications that are completely artificial. 相似文献
Living materials are created through the embedding of live, whole cells into a matrix that can house and sustain the viability of the encapsulated cells. Through the immobilization of these cells, their bioactivity can be harnessed for applications such as bioreactors for the production of high‐value chemicals. While the interest in living materials is growing, many existing materials lack robust structure and are difficult to pattern. Furthermore, many living materials employ only one type of microorganism, or microbial consortia with little control over the arrangement of the various cell types. In this work, a Pluronic F127‐based hydrogel system is characterized for the encapsulation of algae, yeast, and bacteria to create living materials. This hydrogel system is also demonstrated to be an excellent material for additive manufacturing in the form of direct write 3D‐printing to spatially arrange the cells within a single printed construct. These living materials allow for the development of incredibly complex, immobilized consortia, and the results detailed herein further enhance the understanding of how cells behave within living material matrices. The utilization of these materials allows for interesting applications of multikingdom microbial cultures in immobilized bioreactor or biosensing technologies. 相似文献
Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of 1H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties. 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
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
Waxes and wax emulsions are one of the most important solutions for non-biocidal wood protection. Wax treated wood is designed for outdoor use, therefore it is of considerable importance to elucidate the influence of weathering on the photodegradation processes. It is presumed, that wax treatment will reduce water uptake and thus reduce or slow down photodegradation processes. In order to test this hypothesis, three types of wax emulsions at two different concentrations were vacuum impregnated into Norway spruce wood specimens: an emulsion of montan wax (LGE), an emulsion of polyethylene (WE1) and an emulsion of oxidized polyethylene (WE6) wax. The samples were exposed to artificial accelerated weathering (AAW) for 500 cycles. Before and after AAW colour, the contact angle of water and moisture content were determined. Chemical and morphological changes at exposed surfaces were also investigated with FTIR spectroscopy and SEM. In parallel, the uptake of wax emulsions and water into the axial surfaces of samples was determined with a tensiometer. The moisture content measurements showed that the best hydrophobic effect was achieved with LGE treated wood, where the lowest colour and FTIR changes were observed as well. These results were supported by tensiometer measurements as well. Presented data clearly showed that high loadings of waxes reduce or at least slow down weathering. Among tested waxes, montan wax was found the most effective. 相似文献
We investigate a family of polytopes introduced by E.M. Feichtner, A. Postnikov and B. Sturmfels, which were named nestohedra. The vertices of these polytopes may intuitively be understood as constructions of hypergraphs. Limit cases in this family of polytopes are, on the one end, simplices, and, on the other end, permutohedra. In between, as notable members one finds associahedra and cyclohedra. The polytopes in this family are investigated here both as abstract polytopes and as realized in Euclidean spaces of all finite dimensions. The later realizations are inspired by J.D. Stasheff ?s and S. Shnider?s realizations of associahedra. In these realizations, passing from simplices to permutohedra, via associahedra, cyclohedra and other interesting polytopes, involves truncating vertices, edges and other faces. The results presented here reformulate, systematize and extend previously obtained results, and in particular those concerning polytopes based on constructions of graphs, which were introduced by M. Carr and S.L. Devadoss. 相似文献