The Impact of Continuous Oxygen Flux in a Thin Film Photopolymerization Reaction with Peroxy‐Mediated Regeneration of Initiator

Eosin, a photosensitizer dye that can exist in multiple oxidation states, has been shown to initiate visible‐light photopolymerizations of acrylates in open air when used in combination with tertiary amines. The exact mechanism behind this reactivity with micromolar concentrations of eosin in aqueous monomer solutions initially containing millimolar concentrations of oxygen has not been conclusively established, although pathways for regeneration of eosin in the presence of oxygen certainly play a role. In this work, a reaction–diffusion model incorporating a peroxy‐mediated eosin‐regeneration mechanism is built to explore the effects of oxygen diffusing into the system as the light‐activated reaction proceeds. An oxygen concentration‐dependent flux boundary condition is used to model the continuous replenishment of oxygen at the surface open to air as it is consumed by reaction. The model predicts the formation of a free radical concentration front that initially forms closer to the open surface and gradually moves toward the closed surface, with polymer film thickness increasing and the time required for polymerization to begin decreasing as the initial eosin concentration is increased. These results suggest that oxygen's dual role as both a free radical inhibitor and a precursor of the oxidizing species required for regeneration of eosin brings about interesting spatial variations when the reaction is carried out in a thin film geometry that is exposed to open air. In this case, an assumption of a well‐mixed system is not appropriate and the kinetics of the reaction and conversion as a function of position are likely to depend on the geometry of the system.

     

Multiwavelength spectrophotometric determination of acid dissociation constants Part IV. Water-insoluble pyridine derivatives

A multiwavelength spectrophotometric (WApH) titration method for determination of acid dissociation constants (pK(a) values) of ionizable compounds developed previously was applied in the case of pyridine derivatives of pharmaceutical interest. Specifically, UV absorption spectra of the drug solution are acquired in the course of a pH-metric titration using an optical device based on a fibre optics dip probe, a light source and a diode array detector. Target factor analysis was applied to deduce the pK(a) values from the spectral data recorded at different pH. Using this technique, the pK(a) values of six pyridine derivatives were determined successfully. It was demonstrated that the WApH technique in this case outperforms conventional pH-metric methods with respect to the measurement of pK(a) values of the sparingly water soluble samples reported in this study.     

Kinetics of styrene homogeneous polymerization to atactic polypropylene

The rate of polymerization of styrene initiated by hydroperoxidized atactic polypropylene in a homogeneous toluene solution has been measured at 60 and 70°C. The reaction is first-order with respect to styrene concentration and independent of the polymeric hydroperoxide concentration above 2 × 10^?5N hydroperoxide. The individual rate constants, length and frequency of the grafted polystyrene chains along the polypropylene backbone have been calculated and their significance discussed. The initiation rate constant compares closely with values reported for the analogous tert-butyl hydroperoxide-initiated polymerization. The rate constant for the chain transfer termination elementary step at 70°C., however, is 18 times the value reported for the tert-butyl hydroperoxide-initiated polymerization of styrene. This high constant accounts for the relatively low rates of polymerization observed and high termination rates. Chain deactivation is presumably accelerated by increased collisions between growing styrene chains and inactive propylene hydroperoxide and polystyrene molecules. Distribution of polystyrene grafts on polypropylene is estimated from knowledge of effects of styrene concentration, polymeric hydroperoxide concentration, and temperature upon the rate of polymerization.     

On the structure of Si(113)

The structure of the (113) face of Si has received a large amount of interest recently because of its high stability, despite having a high index. There remains some controversy about the surface reconstruction, various groups having reported observations of both 3 × 1 and 3 × 2 structures. We have obtained atomically resolved STM images of this surface showing areas of 3 × 1 reconstructed surface, the structure of which matches a modified version of a previously proposed model. In addition we have also obtained CITS images showing the complex underlying reconstruction and spectroscopy measurements which are comparable with a recent ARUPS study of the same surface.     

Effect of V K centers on positron annihilation in KCl and Ag-doped KCl

Positron lifetime spectra have been measured at 77 K for KCl and Ag-doped KCl before and after x-irradiation at 77 K and after annealing at room temperature. Radiation at 77 K reduces the intensity of the intermediate lifetime (τ₂) component. Radiation-induced defects were monitored optically and by ESR. The experiment shows that the changes observed in the positron decay are associated with the presence ofV _K centers. Work support in part by the Research Corporation. Paper C1 presented at 3rd Internat'l Conf. Positron Annihilation, Otaniemi, Finland (August 1973).     

Single Cooper pair pump

We have operated a Cooper pair pump, a linear array of superconducting tunnel junctions in which single Cooper pairs are moved under the influence of ac signals applied to two gate electrodes. The pump is based on the Coulomb blockade of charge tunneling. Because of the small junction capacitance precisely one Cooper pair is transferred per ac cycle. The current-voltage characteristics of this device show current plateaus close to 2ef, wheref is the frequency of the ac voltages. Deviations are explained in terms of Zener tunneling, Cooper pair co-tunneling, and sporadic quasiparticle tunneling.     

Bell inequalities with no quantum violation and unextendable product bases

The strength of classical correlations is subject to certain constraints, commonly known as Bell inequalities. Violation of these inequalities is the manifestation of nonlocality-displayed, in particular, by quantum mechanics, meaning that quantum mechanics can outperform classical physics at tasks associated with such Bell inequalities. Interestingly, however, there exist situations in which this is not the case. We associate an intriguing class of bound entangled states, constructed from unextendable product bases with a wide family of tasks, for which (i) quantum correlations do not outperform the classical ones but (ii) there exist supraquantum nonsignaling correlations that do provide an advantage.     

Investigation of the effect of pressure on retention of small molecules using reversed-phase ultra-high-pressure liquid chromatography

The effect of inlet pressure on the retention of a series of low molecular weight acids, bases and neutrals, was investigated at constant temperature in reversed-phase liquid chromatography using a commercial ultra-high-pressure system (Waters UPLC instrument). For neutral compounds, relatively small increases in retention factor of up to approximately 12% for a pressure increase of 500bar were noted; the largest values were obtained for polar solutes, or solutes of higher molecular weight. Ionisable acids and bases gave much larger increases in retention with pressure, in some cases as high as 50% for a pressure increase of 500bar. Thus, such compounds could show increases in retention factor approaching 100% over the pressure range available in the commercial UPLC instrument. Due to these differential increases, significant selectivity effects can be obtained for mixtures of different types of solute merely by changing the pressure.