Radical Formation in the Gas‐Phase Ozonolysis of Deprotonated Cysteine

Although the deleterious effects of ozone on the human respiratory system are well‐known, many of the precise chemical mechanisms that both cause damage and afford protection in the pulmonary epithelial lining fluid are poorly understood. As a key first step to elucidating the intrinsic reactivity of ozone with proteins, its reactions with deprotonated cysteine [Cys?H]^? are examined in the gas phase. Reaction proceeds at near the collision limit to give a rich set of products including 1) sequential oxygen atom abstraction reactions to yield cysteine sulfenate, sulfinate and sulfonate anions, and significantly 2) sulfenate radical anions formed by ejection of a hydroperoxy radical. The free‐radical pathway occurs only when both thiol and carboxylate moieties are available, implicating electron‐transfer as a key step in this reaction. This novel and facile reaction is also observed in small cys‐containing peptides indicating a possible role for this chemistry in protein ozonolysis.     

The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation

The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa)₄]?CH₂Cl₂ (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4‐methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf₂] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect.     

Synthesis,Structure, and Properties of SrC(NH)3, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif

Strontium guanidinate, SrC(NH)₃, the first compound with a doubly deprotonated guanidine unit, was synthesized from strontium and guanidine in liquid ammonia and characterized by X‐ray and neutron diffraction, IR spectroscopy, and density‐functional theory including harmonic phonon calculations. The compound crystallizes in the hexagonal space group P6₃/m, constitutes the nitrogen analogue of strontium carbonate, SrCO₃, and its structure follows a layered motif between Sr²⁺ ions and complex anions of the type C(NH)₃^2?; the anions adopt the peculiar trinacria shape. A comparison of theoretical phonons with experimental IR bands as well as quantum‐chemical bonding analyses yield a first insight into bonding and packing of the formerly unknown anion in the crystal.     

Analysis methodology for 3C-PIV data of rotary wing vortices

3C-PIV data from tip vortices of either fixed-wing or rotating wing experiments are challenging from an analysis point of view. Model motion, vortex wander, spurious vectors, periodic and aperiodic effects, turbulence, and other disturbing effects are all present in the data. In most cases the vortices are not measured perpendicular to their axis as well. Engineers need time-averaged properties from the vortex in the vortex axis system for a proper modelization within simulation codes. This article describes the methods needed to deal with all the mentioned problem areas, including the conditional averaging and rotation into the vortex axis system. The methods are validated by using numerically generated vortex vector fields, and finally applied to experimental data from a hover condition of a model rotor.     

Heat transfer during dry spinning of fibers

Summary Heat transfer to fibers formed in dry spinning has been subjected to fundamental analysis. Solutions of the equation of energy have been derived and tested with experimental data. Results were deemed satisfactory in view of the accuracy of the experimental data. The present work is believed to yield a good representation of the heat transfer in the dry spinning process.Nomenclature h heat transfer coefficient, cal/cm² °C sec - k thermal conductivity, cal/cm °C sec - r radial distance, cm - t time, sec - Z axial distance, cm - A surface area, cm² - A _n or n-th root of - A ₀ energy required for solvent evaporation, cal/sec cm³ - C _p specific heat cal/gm °C - J ₀ Bessel function of first kind, order zero - J ₁ Bessel function of first kind, order one - J ₂ Bessel function of first kind, order two - N k/(R ² C _p V) - Q volumetric flow rate cm³/sec - R outside radius, cm - T point temperature, °C - T _S surface temperature °C - T ₀ initial fiber temperature °C - T ambient air temperature, °C - average fiber temperature, °C - ₁ average fiber temperature of preceding segment, °C - V average fiber velocity relative to air strean, cm/sec - V _r radial velocity component, cm/sec - V _z axial velocity components, cm/sec - V direction velocity component cm/sec - W weight of solvent evaporated in a given fiber segment, gms - _n a solution of the equation J ₀(X)=0 - heat of vaporization of solvent, cal/gm - dimension - r/R - density, gms/cc     

Fatigue and static strength of notched and unnotched aluminum-alloy and steel specimens

This paper describes a method of presentation of fatigue data on three commonly used aircraft materials, 2024-T3 and 7075-T6 aluminum alloys and normalized SAE 4130 steel, such that variations in fatigue strength with stress-concentration factor can be shown. Comparisons of the fatigue strengths of 2024-T3 and 7075-T6 aluminum are made for the most useful range of stress-concentration factors. Static-strength results of notched and unnotched specimens of the three materials are presented to show how the strength varies with some parameters of the stress concentration. Comparison of the data with one theory for the strength of cracked specimens was made.     

Well-posedness of the fundamental boundary value problems for constrained anisotropic elastic materials

We consider the equations of linear homogeneous anisotropic elasticity admitting the possibility that the material is internally constrained, and formulate a simple necessary and sufficient condition for the fundamental boundary value problems to be well-posed. For materials fulfilling the condition, we establish continuous dependence of the displacement and stress on the elastic moduli and ellipticity of the elasticity system. As an application we determine the orthotropic materials for which the fundamental problems are well-posed in terms of their Young's moduli, shear moduli, and Poisson ratios. Finally, we derive a reformulation of the elasticity system that is valid for both constrained and unconstrained materials and involves only one scalar unknown in addition to the displacements. For a two-dimensional constrained material a further reduction to a single scalar equation is outlined.This paper is dedicated to Professor Joachim Nitsche on the occasion of his sixtieth birthday     

The annular twist mapping of the restricted three-body problem

This paper presents a new derivation of the twist mapping in the planar restricted problem. It differs from other treatments in the use of a novel canonical transformation which allows for the utilization of symplectic reduction techniques.     

Axisymmetric stagnation point flow and mass transfer for power-law fluids

The boundary-layer equations for axisymmetric stagnation point flow of a power-law fluid are solved by a similarity transformation, and values of the wall shear rate are obtained. Theoretical expressions for local and average Sherwood numbers are derived from the convective diffusion equation for systems with high Schmidt numbers. The results can be used to predict diffusion coefficients of dilute species in fluids with specified power-law characteristics.     

Social-support moderated stress: a nonlinear dynamical model and the stress-buffering hypothesis

Health psychology has studied the cross-sectional, stationary relationships linking stress, social support, and health. Levels of stress-related illness are generally modeled by including a nonlinear multiplicative or 'buffering' effect, corresponding to the interaction of stressor levels with social support from family and friends. The motivation of the present research is to extend an iterative, dynamic model of this well-investigated psychological process using a dynamical systems model expressed as a set of continuous, nonlinear differential equations similar to those of the 'Oregonator,' a model of a nonlinear dynamic chemical system. This model of the behavior of an individual is amenable to numerical investigation of its stationary-state stability properties, temporal evolution, and cause-effect relationships. The continuous variables in this new approach refer to varying states of an individual; they are Perceived stress (X), Symptoms (Y), and Social support (Z). It is expected that poor health in this model, represented by Symptoms (Y), is directly related to Perceived stress, as well as being tied in more complicated ways to Social support. A number of such models may be envisioned, some including a multiplicative, 'buffering' (- X x Z) effect of social support dependent on stress levels. We explore the behavior of this model over ranges of parameter values and initial conditions and relate these results to how an individual reacts to environmental challenges at various levels of stressors and social-support recruitment. Data generated by the model are in turn analyzed with a traditional cross-sectional statistical technique. Similarities and differences between chemical and psychological systems are discussed.