DISTRIBUTIONS OF FREE RADICALS AMONG AMINO ACIDS FROM LYOPHILIZED ULTRAVIOLET-IRRADIATED PROTEINS

Abstract— The effects of u.v.-irradiation at 254 nm upon lyophilized ribonuclease, lysozyme, insulin, and chymotrypsinogen have been investigated by electron spin resonance (ESR). enzymatic assay, and labeling of free radical sites with tritiated hydrogen sulfide (HST). The ESR signal of the irradiated protein diminishes on exposure to HST, and tritium becomes covalently bound to carbon. The distribution of tritium among the amino acids of each protein. studied as an indicator of the carbon free radical distribution, differs markedly from those observed previously to result from exposure to gamma radiation, electrical discharge. or hydrogen atoms. However, the earlier observation that the tritium distribution is influenced by protein conformation holds true as well for u.v.-irradiation. Moreover, the distributions of tritium among the amino acids of u.v.-irradiated proteins indicate a broad scattering of free radicals. Tyrosine and phenylalanine, residues that absorb light energy in the region of the wavelength employed, are not particularly important as radical carriers. Thus, for ribonuclease, these residues incorporated 3.8 and 1.5 per cent of the total tritium, but they absorb 51 and 12 per cent of the light, respectively. These results, together with the observed low recoveries of methionine, an amino acid that does not absorb at 254 nm, add weight to the concept that a migration of energy ensues after the initial absorption of light energy and that photolytic damage may thus be due to destruction of amino acids other than those initially absorbing the u.v.-radiation.     

A Type Calculus for Executable Modelling Languages

There is considerable current interest in the design and constructionof directly executable modelling languages for mathematicalprogramming. The present research extends contemporary modellinglanguages by specifying a type calculus for an extended dimensionalsystem that determines if the model is well formed in the sensethat the objective function and constraints consist of homogeneouscomponents. Each variable, coefficient, constant, function,constraint, input, and output of the model is assigned a typethat consists of its concepts, quantities, and units of measurementwith optional scale factors. In checking the composition offunctions and constraints, the system can do automatic unitconversions and apply user-supplied conversions. The systemallows a hierarchy of concepts that provides inheritance ofquantities and automatic concept conversion. In addition, eachset in a model is typed so the system can check the validityof operations on indices.     

The flat-maximum effect and generic linear scoring models: a test

Received on 1 July 1991. Predicting human behaviour patterns with linear correlationmodels has absorbed researchers for the past five decades. Althoughmost observers generally concede that humans are inferior tosuch models in combining information, linear scoring modelsare unfortunately, plagued by the flat-maximum effect or the‘curse of insensitivity’. As Lovie & Lovie(1986)observe: ‘The predictive ability of linear models is insensitiveto large variations in the size of regression weights and tothe number of predictors.’ In essence, seemingly differentscoringmodels tend to produce indistinguishable predictive outcomes. Since its demonstration by Dawes & Corrigan (1974), observershave cast the flat maximum in a decidedly negative light. Incontrast, Lovie & Lovie (1986) present a provocatively contrarianview of the flat maximum‘s positive potential. In thissame vein, we examine the predictive power of a generic credit-scoringmodel versus individual empirically derived systems. If, asWainer (1976) noted in regard to the flat maximum, ’itdon‘t make no nevermind’, generic credit-scoringmodels could provide cheaper alternatives to individual empiricallyderived models. During the period 1984–8, a series of linear credit-scoringmodels were developed for ten Southeastern U.S. credit unions.For each credit union, stepwise multiple regression was employedto select a subset of explanatory variables to be used in adiscriminant analysis. A generic credit-scoring equation wasdeveloped from the resulting discriminant analyses using weightedaverage coefficients from five systems. The predictive powerof the generic model was compared to the predictive power ofholdout sample of the five remaining credit-scoring models. In all cases, the generic model's performance was very closeto that of the empirically derived models. Thus, our findingssupport Lovie & Lovie's (1986) challenge to the conventionalwisdom that the flat maximum casts a pall on the successfulmodelling of judgement processes. Indeed, the flat maximum impliesa positive role for simpler, and hence cheaper, generic models.Although further research is needed, it should be possible todevelop hybrid models with generic cores that perform as wellas empirically derived linear models.     

Review of Chemometrics Applied to Spectroscopy: 1985-95, Part 2

INTRODUCTION

Before beginning Part 2 of this review, a caveat noted by Deming and Palasota is brought to the reader's attention: [1] “Press et al. [2] have emphasized that data ‘consist of numbers, of course. But these numbers are fed into the computer, not produced by it. These are numbers to be treated with considerable respect, never to be tampered with, nor subjected to a numerical process whose character you do not completely understand. You are well advised to acquire reverence for data that is rather diferent fiom the “sporty” attitude which is sometimes allowable, or even commendable, in other numerical tasks.’ Yet by and large within chemometrics, preprocessing often seems to be carried out with little understanding of its fundamental efect on the structure of the data.”     

Very Low Frequency Far-Infrared Spectra of Mixtures of Dioxan with the Halogens and Related Molecules

Abstract

There has been considerable interest recently in the study of the submillimetre (or very far-infrared) absorption shown by both polar^1–4 and non-polar molecules.^2,5–8 Such absorption, in the ～5–100 cm^?1 region, for non-polar molecules is thought^2,6 to be caused by fluctuating dipoles associated with classical quadrupole-induced dipole interactions (in general multipole-induced dipole interactions). These effects are said to be “collision-induced” and can be thought of as being due to “collision” complexes in the liquid phase. For polar molecules the absorption is now thought^1–4 to be due to libration of the dipole in a “cage” of surrounding molecules (either molecules of the same species or of solvent). This so-called Poley-Hill model^9,10 is not inconsistent with the idea^1,2 of a residual rotation of the molecular dipole in the liquid phase. This similarity is underlined by the fact that some simple polar molecules^11,12 have a liquid phase Poley-Hill absorption the general shape and position of which follow quite closely that of the pressure broadened, gas phase spectrum. Our interest in the far-infrared region stems from our studies on halogen complexes with various n and bπ donors.^13,14 The pyridine-I₂ system (in cyclohexane) for example shows two bands in the far in frared not present in either component. The band at -183 cm is thought to be the stretching mode of the iodine, perturbed in the complex. The band at ～96 cm to the v(1-I) band, has so far been interpreted molecular″ stretching modebetween donor and acceptor, v(D-A).     

Graphene electrochemistry: an overview of potential applications

Graphene, a 2D nanomaterial that possesses spectacular physical, chemical and thermal properties, has caused immense excitement amongst scientists since its freestanding form was isolated in 2004. With research into graphene rife, it promises enhancements and vast applicability within many industrial aspects. Furthermore, graphene possesses a vast array of unique and highly desirable electrochemical properties, and it is this application that offers the most enthralling and spectacular journey. We present a review of the current literature concerning the electrochemical applications and advancements of graphene, starting with its use as a sensor substrate through to applications in energy production and storage, depicting the truly remarkable journey of a material that has just come of age.