SEASONAL TRENDS IN ERYTHEMAL and CARCINOGENIC ULTRAVIOLET RADIATION AT MID-SOUTHERN LATITUDES1989–1991

A network of solar carcinogenic/erythemal ultraviolet radiometers has been established in New Zealand. Daily integrated irradiances of this biologically harmful ultraviolet radiation for 1989, 1990 and 1991 are reported from radiometers located at Wellington (41°S) and Christchurch (43.5°S) and for 1990 and 1991 from the Auckland (37°S) radiometer. Although the monitoring program has not been running sufficiently long to discern any long-term changes in levels of solar ultraviolet radiation, shorter term trends are apparent, which are attributed to a seasonal cycle in levels of ozone at midlatitudes and changes in atmospheric aerosols.     

PHOTOSENSITIZATION WITH BACTERIOCHLORINS

Abstract— Biophysical and photobiological properties of a group of bacteriochlorins were compared with efficacy of these products for photodynamic therapy of murine tumors. Predictive factors for selective photosensitization in vivo include affinity binding to lipoproteins greater than albumin, extinction coefficient at the wavelength of irradiation and tumor/skin distribution. Efficacy was correlated with circulating plasma levels of the different sensitizers but not with the photodynamic therapy response in cell culture.     

Investigation into the GC separation of enantiomers on a trifluoroacetylated cyclodextrin. Part II: Effect of derivatization on stereoselectivity towards alcohols

Two acyl and three fluoroacyl derivatives of 32 chiral alcohols have been chromatographed on a GC column coated with octakis(2,6-di-O-n-pentyl-3-O-trifluoroacetyl)- γ-cyclodextrin. Significant differences were observed between the stereoselectivity obtained for the derivatives and that for the underivatized alcohols. Of the derivatives, only the fluoroacylated compounds were separated into enantiomers. Derivatization with fluoroacyl groups reversed the elution order for at least some of the analytes. Stereoselectivity towards simple 2- and 3-hydroxy alkanes and their fluoroacyl derivatives was highest for those alcohols with a four-carbon chain attached to the stereogenic center. For longer-chain fluoroacyl derivative groups stereoselectivity was higher for the 2- and 3-hydroxy alkanes. Differences in stereoselectivity towards alcohols with a methyl-branched alkane chain and their fluoroacyl derivatives was related to the distance between the methyl group and the hydroxyl or fluoroacyl groups. Different degrees of saturation in the carbon chain resulted in differences in stereoselectivity. Thermodynamic data calculated for a number of analytes suggest that the alcohols and trifluoroacetate derivatives are interacting with the stationary phase by similar mechanisms. The stereospecific interaction appears to have a hydrogen bonding or dipole–dipole contribution and some form of steric component, depending upon the shape and/or size of the solute.     

Mass spectrometric investigation of polyfluorinated C60. Evidence for the existence of C60F2n (n = 0–30)

Electron-capture negative ion chemical ionization (EC-NICI) and field desorption (FD) mass spectrometric techniques were utilized to examine polyfluorinated C₆₀. Two different samples from the same preparation, one prior to sublimation and the other sublimed material, were investigated. From the raw non-sublimed product in EC-NCI six series of ions corresponding to different numbers of attached oxygen atoms were obtained, which are represented by the formula [C₆₀F_2nO_m]^?, where n ranged from 0 to 30 and m from 0 to 5. The sublimed material in EC-NICI produced the same six series of ions with up to 48 fluorine atoms attached to C₆₀. The field desorption of the same sample produced similar results, but the signal-to-noise ratios of the spectra were low. Both samples, in the two different techniques examined, yielded C₆₀F₆₀ ions with only an even number of fluorine atoms attached. The present investigation, for the first time, provides direct experimental evidence for the existence of higher fluorinated C₆₀ up to C₆₀F₆₀ and multiple oxides of polyfluoro-C₆₀ with up to five oxygen atoms attached.     

Impedance study of Ni–Co electro-deposition on Fe powder particles in fluidised bed systems

The electrochemical impedance method was applied during the electrochemical deposition of a binary Ni–Co coating on iron powder in a fluidised bed electrode system. The influence of the suspension density on the charge transfer in the course of the electro-deposition process was studied. At a potential of −900 mV (vs. Ag/AgCl/3 M KCl), when the binary Ni–Co layer was formed, the impedance data were characterised by two semicircles with the semicircle at high frequencies being larger in magnitude. A contribution of the diffusion process to the overall current was observed. The optimal suspension density for the charge transfer in the bed was 10×10⁻³–15×10⁻³ (i.e., 4–6 g of iron powder in 50 ml of electrolyte). The most probable mechanism of the charge transfer for the studied concentrations of powder particles is the convective mechanism. The iron particles dispersed in the electrolyte were considered to act as either a depolariser or an additional working electrode depending on the applied electrode potential and on the suspension density.     

Mesoscale simulation of polymer reaction equilibrium: combining dissipative particle dynamics with reaction ensemble Monte Carlo. I. Polydispersed polymer systems

We present a mesoscale simulation technique, called the reaction ensemble dissipative particle dynamics (RxDPD) method, for studying reaction equilibrium of polymer systems. The RxDPD method combines elements of dissipative particle dynamics (DPD) and reaction ensemble Monte Carlo (RxMC), allowing for the determination of both static and dynamical properties of a polymer system. The RxDPD method is demonstrated by considering several simple polydispersed homopolymer systems. RxDPD can be used to predict the polydispersity due to various effects, including solvents, additives, temperature, pressure, shear, and confinement. Extensions of the method to other polymer systems are straightforward, including grafted, cross-linked polymers, and block copolymers. To simulate polydispersity, the system contains full polymer chains and a single fractional polymer chain, i.e., a polymer chain with a single fractional DPD particle. The fractional particle is coupled to the system via a coupling parameter that varies between zero (no interaction between the fractional particle and the other particles in the system) and one (full interaction between the fractional particle and the other particles in the system). The time evolution of the system is governed by the DPD equations of motion, accompanied by changes in the coupling parameter. The coupling-parameter changes are either accepted with a probability derived from the grand canonical partition function or governed by an equation of motion derived from the extended Lagrangian. The coupling-parameter changes mimic forward and reverse reaction steps, as in RxMC simulations.     

Rationalizing the diverse reactivity of [1.1.1]propellane through σ–π-delocalization

[1.1.1]Propellane is the ubiquitous precursor to bicyclo[1.1.1]pentanes (BCPs), motifs of high value in pharmaceutical and materials research. The classical Lewis representation of this molecule places an inter-bridgehead C–C bond along its central axis; ‘strain relief’-driven cleavage of this bond is commonly thought to enable reactions with nucleophiles, radicals and electrophiles. We propose that this broad reactivity profile instead derives from σ–π-delocalization of electron density in [1.1.1]propellane. Using ab initio and DFT calculations, we show that its reactions with anions and radicals are facilitated by increased delocalization of electron density over the propellane cage during addition, while reactions with cations involve charge transfer that relieves repulsion inside the cage. These results provide a unified framework to rationalize experimental observations of propellane reactivity, opening up opportunities for the exploration of new chemistry of [1.1.1]propellane and related strained systems that are useful building blocks in organic synthesis.

A unified framework that explains the reactivity of [1.1.1]propellane through electron delocalization.     

Et3SiH + KOtBu provide multiple reactive intermediates that compete in the reactions and rearrangements of benzylnitriles and indolenines

The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to one of the intermediates, but we now highlight the interplay and competition between them.

The combination of potassium tert-butoxide and triethylsilane provides simultaneous access to multiple reactive intermediates, radicals, H-atom donors, hydride donors and electron donors, giving scope for unprecedented reaction outcomes.     

A Dual Threat: Redox-Activity and Electronic Structures of Well-Defined Donor–Acceptor Fulleretic Covalent-Organic Materials

The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.