EXTRUSION OF SULPHUR DIOXIDE FROM CYCLIC SULPHUR COMPOUNDS

Abstract

The fragmentation of cyclic sulphur compounds such as (1) to (4) by photolysis and flash vacuum thermolysis will be discussed. Many of these reactions have been shown to be synthetically useful. The mechanisms of some of these reactions have been studied in some detail. The use of novel thermolytic and photochemical apparatus will be demonstrated.     

Interstitial fluorescence spectroscopy in the human prostate during motexafin lutetium-mediated photodynamic therapy

The in vivo fluorescence emission from human prostates was measured before and after motexafin lutetium (MLu)-mediated photodynamic therapy (PDT). A single side-firing optical fiber was used for both the delivery of 465 nm light-emitting diode excitation light and the collection of emitted fluorescence. It was placed interstitially within the prostate via a closed transparent plastic catheter. Fitting of the collected fluorescence emission spectra using the known fluorescence spectrum of 1 mg/kg MLu in an intralipid phantom yields a quantitative measure of the local MLu concentration. We found that an additional correction factor is needed to account for the reduction of the MLu fluorescence intensity measured in vivo due to strong optical absorption in the prostate. We have adopted an empirical correction formula given by C = (3.1 cm(-1)/micro's) exp (microeff x 0.97 cm), which ranges from approximately 3 to 16, with a mean of 9.3 +/-4.8. Using a computer-controlled step motor to move the probe incrementally along parallel tracks within the prostate we can determine one-dimensional profiles of the MLu concentration. The absolute MLu concentration and the shape of its distribution are confirmed by ex vivo assay and by diffuse absorption measurements, respectively. We find significant heterogeneity in photosensitizer concentration within and among five patients. These variations occur over large enough spatial scales compared with the sampling volume of the fluorescence emission that mapping the distribution in three dimensions is possible.     

Towards profitability: a utility approach to the credit scoring problem

Since credit scoring was first applied in the 1940s the standard methodology has been to treat consumer lending decisions as binary classification problems, where the goal has been to make the best possible ‘good/bad’ classification of accounts on the basis of their eventual delinquency status. However, the real goal of commercial lending organizations is to forecast continuous financial measures such as contribution to profit, but there has been little research in this area. In this paper, continuous models of customer worth are compared to binary models of customer repayment behaviour. Empirical results show that while models of customer worth do not perform well in terms of classifying accounts by their good/bad status, they significantly outperform standard classification methodologies when ranking accounts based on their financial worth to lenders.     

Minimally adhesive polymer surfaces prepared from star oligosiloxanes and star oligofluorosiloxanes

The effects of the surface energy, storage modulus (G′), and glass‐transition temperature (T_g) on the biofouling behavior of siloxane and fluorosiloxane polymer surfaces (films) were studied. Irregular Si? H‐terminated tetrabranched star oligosiloxanes and star oligofluorosiloxanes were prepared by the acid‐catalyzed equilibration of octamethylcyclotetrasiloxane or 1,3,5‐trimethyl‐1,3,5‐tris(3′,3′,3′‐trifluoropropyl)cyclotrisiloxane with tetrakis(dimethylsiloxy)silane, respectively. Terminal epoxy groups were introduced via Pt‐catalyzed hydrosilylation with allyl glycidyl ether to yield compounds that were subsequently crosslinked with α,ω‐bis(3‐aminopropyl)poly(dimethylsiloxane). The resulting films were characterized by goniometry, dynamic mechanical thermal analysis, and thermogravimetric analysis. The foul‐release behavior was studied by the measurement of how strongly sporelings (young plants) of the green seaweed Ulva adhered. The corrosion protection of aluminum was evaluated by electrochemical impedance spectroscopy. Fluorosiloxane films displayed higher G′ and T_g values, decreased contact angles (with water), and more effectively released Ulva sporelings in comparison with siloxane films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2551–2566, 2006     

Reactive Oxygen Species Explicit Dosimetry for Photofrin-mediated Pleural Photodynamic Therapy

Explicit dosimetry of treatment light fluence and implicit dosimetry of photosensitizer photobleaching are commonly used methods to guide dose delivery during clinical PDT. Tissue oxygen, however, is not routinely monitored intraoperatively even though it is one of the three major components of treatment. Quantitative information about in vivo tissue oxygenation during PDT is desirable, because it enables reactive oxygen species explicit dosimetry (ROSED) for prediction of treatment outcome based on PDT-induced changes in tumor oxygen level. Here, we demonstrate ROSED in a clinical setting, Photofrin-mediated pleural photodynamic therapy, by utilizing tumor blood flow information measured by diffuse correlation spectroscopy (DCS). A DCS contact probe was sutured to the pleural cavity wall after surgical resection of pleural mesothelioma tumor to monitor tissue blood flow (blood flow index) during intraoperative PDT treatment. Isotropic detectors were used to measure treatment light fluence and photosensitizer concentration. Blood-flow-derived tumor oxygen concentration, estimated by applying a preclinically determined conversion factor of 1.5 × 10⁹ μMs cm⁻² to the blood flow index, was used in the ROSED model to calculate the total reacted reactive oxygen species [ROS]rx. Seven patients and 12 different pleural sites were assessed and large inter- and intrapatient heterogeneities in [ROS]rx were observed although an identical light dose of 60 J cm⁻² was prescribed to all patients.     

Practical Synthesis of Sugar Monophosphonucleotides

A reliable procedure for the preparation of sugar nucleoside monophosphates is presented, which involves condensation of an activated glycosyl‐1‐H‐phosphonate with an appropriately protected nucleoside and simple end‐product isolation via lithium perchlorate–induced precipitation. The utility of these methods is demonstrated by the preparation of a number of purine‐ and pyrimidine‐based sugar nucleoside monophosphate derivatives.     

Predictive models of expenditure and over-indebtedness for assessing the affordability of new consumer credit applications

Lenders are under increasing pressure to consider measures of affordability and indebtedness as well as risk, when assessing consumer credit applications. In order to evaluate the affordability of a new credit product, a lender needs information about the applicant's income and outgoings. However, while most lenders obtain information about income and credit commitments many do not have much, if any, pertaining to other expenditure. Therefore, they are not well positioned to determine an individual's ability to fund new borrowing. This paper demonstrates that using only data captured on a typical application form, combined with data from a credit bureau, it is possible to develop good predictive models of expenditure and over-indebtedness that can be used in conjunction with measures of risk to reject applications from individuals who are likely to already be over-indebted, or to restrict the volume of credit advanced to that which the applicant can afford.