Free radical-mediated vinyl amination: a mild, general pyrrolidinyl enamine synthesis

The complete scope of free radical-mediated vinyl amination is described, using 5-exo-trig cyclizations of vinyl radicals to the nitrogen of azomethines. The focus is primarily on N,N-dialkyl enamines since their nucleophilicity renders them the most challenging enamines to synthesize using redox conditions. These studies establish several encouraging precedents for the broader application of this strategy.     

An Experimental Investigation into the Acoustic Characteristics of Fluid-filled Porous Structures—A Simplified Model of the Human Skull Cancellous Structure

In nature, shape and structure evolve from the struggle for better performance. Often, biological structures combine multiple beneficial properties, making research into mimicking them very complex. Presented here is a summary of observations from a series of experiments performed on a material that closely resembles the human skull bone’s cancellous structure under acoustic loads. Transmission loss through flat and curved open-cell polyurethane foam samples is observed using air and water as the two interstitial fluids. Reduction in strength and stiffness caused by porosity can be recovered partially by filling the interstitial pores with a fluid. The test findings demonstrate the influence of the interstitial fluid on the mechanical characteristics of a porous structure in a quantitative manner. It is also demonstrated that the transmission loss does not depend only on the mass per unit area of the structure as predicted by acoustic mass law. Current tests also demonstrate that the transmission loss is more sensitive to the interstitial fluid than the shape and support conditions of the structures. Test observations thus support the concepts of “moisture-sensitivity of biological design” and the “law of hierarchy in natural design”.     

Structural and dynamic properties of polyoxyethylene sorbitan monooleate micelle in water dispersion studied by pulsed field gradient NMR

The diffusion phenomenon of a nonionic surfactant, polyoxyethylene sorbitan monooleate (POE-SMO), micelle in aqueous solution was investigated by pulsed field gradient nuclear magnetic resonance (PFG NMR) with a high gradient strength of 17.4 T/m at the diffusion timet _d varied from 3 to 300 ms. This high gradient strength allowed us to measure the slow self-diffusion coefficient of POE-SMO micelle, and the short diffusion time below 10 ms showed the restricted diffusion of the micelle. At the shortt _d the self-diffusion of the micelle was restricted and the restricted sizes were 1.8, 1.5, and 0.8 μm for the POE-SMO concentration of 100, 200 and 300 mM, respectively, and 0.6 μm for the POE-SMO only. The possible reason of this restriction was assumed to be the formation of a spatial network or a micellar clustering. Furthermore, a proton exchange between water molecule and surfactant OH group on the micelle surface was proposed. With respect to this proposal, the residence time of the proton at the micelle surface and the thickness of the surface were investigated from proton self-diffusion coefficients by PFG NMR.     

InAs/GaAs quantum dot infrared photodetectors with different growth temperatures

InAs/GaAs quantum dot infrared photodetectors were fabricated with quantum dots grown at three different temperatures. Large detection wavelength shift (5–14.5 μm) was demonstrated by changing 40 degrees of the epitaxy temperature. The smaller quantum dots grown at lower temperature generate 14.5 μm responses. The detectivity of the normal incident 15 μm QDIP at 77 K is 3 × 10⁸ cm Hz^1/2/W. A three-color detector was also demonstrated with quantum dots grown at medium temperature. The three-color detection comes from two groups of different sizes of dots within one QD layer. This new type of multicolor detector shows unique temperature tuning behavior that was never reported before.     

A new VOF‐based numerical scheme for the simulation of fluid flow with free surface. Part II: application to the cavity filling and sloshing problems

Finite element analysis of fluid flow with moving free surface has been performed in 2‐D and 3‐D. The new VOF‐based numerical algorithm that has been proposed by the present authors (Int. J. Numer. Meth. Fluids, submitted) was applied to several 2‐D and 3‐D free surface flow problems. The proposed free surface tracking scheme is based on two numerical tools; the orientation vector to represent the free surface orientation in each cell and the baby‐cell to determine the fluid volume flux at each cell boundary. The proposed numerical algorithm has been applied to 2‐D and 3‐D cavity filling and sloshing problems in order to demonstrate the versatility and effectiveness of the scheme. The proposed numerical algorithm resolved successfully the free surfaces interacting with each other. The simulated results demonstrated applicability of the proposed numerical algorithm to the practical problems of large free surface motion. It has been also demonstrated that the proposed free surface tracking scheme can be easily implemented in any irregular non‐uniform grid systems and can be extended to 3‐D free surface flow problems without additional efforts. Copyright © 2003 John Wiley & Sons, Ltd.     

Infine Functions, Nonsmooth Alternative Theorems and Vector Optimization Problems

In this paper we introduce a new notion of infine nonsmooth functions and give several characterizations of infineness property. We prove alternative theorems with mixed constraints (i.e., inequality and equality constraints) being described by invex-infine nonsmooth functions. We establish a necessary and sufficient condition for a solution of a vector optimization problem involving mixed constraints to be a properly efficient solution.     

Second Dissociation Constant of Bis-[(2-hydroxyethyl)amino]acetic Acid (BICINE) and pH of Its Buffer Solutions from 5 to 55 °C

The values of the second dissociation constant, K ₂, and related thermodynamic quantities of the ampholyte bis[(2-hydroxyethyl)amino]acetic acid (BICINE) have been determined at temperatures from 5 to 55 ^∘C. The pH values of six equimolal buffer solutions, and four buffer solutions having ionic strengths (I = 0.16 mol⋅kg⁻¹) similar to those in blood plasma, have been evaluated at 12 temperatures from 5 to 55 ^∘C using the Bates–Guggenheim convention. The liquid junction potentials (E _j ) between the buffer solutions of BICINE and saturated KCl solution of the calomel electrode at 25 and 37 ^∘C have been estimated by measurement with a flowing junction cell. These values of E _j have been used to ascertain the operational pH values at 25 and 37 ^∘C. The pK ₂ values at 25 and 37 ^∘C are 8.333 and 8.156, respectively. The thermodynamic quantities associated with the second acid dissociation have been calculated from the values of pK ₂ as a function of temperature. The zwitterionic buffer BICINE was shown to be useful as a pH standard in the region close to that of blood serum.     

Temperature anomaly of the Cd hyperfine field in a trivacancy complex in Ni

The temperature dependence of the Cd hyperfine field in a trivacancy complex in Ni between 25 and300 K is reported. It was found that, unlike the Cd substitutional field in Ni which follows the temperature dependence of the magnetization, the Cd hyperfine field in a trivacancy complex is essentially temperature independent. This temperature anomaly is compared with other temperature anomaly of impurity hyperfine fields in ferromagnetic hosts.