Kinetic study of early stages of heterophase polymerization of vinyl chloride initiated by radiation

The kinetics of the radiation-induced bulk polymerization of vinyl chloride in the early stages was determined in the temperature range of ?30 to 50°C and dose rates varying from 0.6 to 17 rad/sec by the dilatometric method. Some runs of polymerization of vinyl chloride added with different percentages of tetrahydrofuran were also carried out. The results were found to agree with those previously obtained with polymerizations carried out to high conversions. The results are discussed on the assumption of a decrease in the extent of swelling of the polymer by monomer with decreasing polymerization temperature. By comparison with the data of other precipitating polymerization systems the possibility of a generalized interpretation for the heterophase polymerization is examined.     

Studies of pectin/polyvinylpyrrolidone blends exposed to ultraviolet radiation

The new biodegradable blends composed of natural pectin and synthetic polymer: polyvinylpyrrolidone were obtained by casting from aqueous solutions. The molecular interactions between components have been studied by FTIR. The blends were exposed to UV-irradiation and the changes in chemical structure were investigated using absorption spectroscopy (FTIR and UV-Vis). The morphology of sample surfaces before and after exposure to UV was observed by atomic force microscopy. Insoluble gel, formed as a result of photocrosslinking, was appointed gravimetrically. The relation between the blend composition and the efficiency of observed photoreactions has been considered.     

Diurnal variation of ocular exposure to solar ultraviolet radiation based on data from a manikin head

Measurements were conducted at San Ya, China (18.4°N, 109.7°E, altitude 18 m) to investigate the diurnal variation of ocular exposure to ultraviolet (UV) radiation. The experimental apparatus was composed of a manikin and a dual-detector spectrometer to simultaneously measure ocular and ambient UV data. The experimental apparatus was rotated clockwise to simulate three different types of exposure. When the manikin was facing into the sun, the ocular exposure to UV radiation on a summer day was bimodally distributed. The maximum ocular UV irradiance occurred at solar elevations of around 40° and 50° for UVA and UVB respectively. The spectral irradiances were measured at specific wavelength to obtain the ocular biologically effective UV (UV(BE) ) irradiances for photokeratitis, photoconjunctivitis and cataract, and the UV index (UVI) was calculated at the same time point for comparison. When the manikin faced the sun, the maximal ocular UV(BE) irradiance values were obtained at the solar elevation where the UVI value was 8. The results of this study showed that protection against ocular overexposure during outdoor activities should be taken not only at noon but also at other times.     

Simulating the experimental vacuum ultraviolet radiation of rare-gases plasma

Experimental excimer continua emitted by electric discharge plasma of krypton and xenon were interpreted as the ¹ Σ _u ⁺ → ¹ Σ _g ⁺ bound-free transitions. The relative populations of the lower vibrational levels of the ¹ Σ _u ⁺ state were derived fitting experimental spectra with the theoretical ones.     

Depletion of cutaneous glutathione by ultraviolet radiation

Supplemental antioxidants may have a role in ameliorating or preventing the actinic damage that can lead to cutaneous disorders such as skin cancer, hyperpigmentation, and premature aging. Glutathione is an important endogenous antioxidant and fulfills various protective functions in the skin. Irradiation of hairless mice with short (UVB) or long (UVA) wavelength ultraviolet radiation or with UVA combined with a photosensitizing psoralen (PUVA) can deplete skin glutathione levels. Ultraviolet B irradiation causes rapid transient fluctuations in the epidermal glutathione level and the relative amount present as the oxidized form. Ultraviolet A irradiation can deplete epidermal and dermal glutathione for several hours but requires much higher doses than UVB. PUVA treatments may lead to extensive and prolonged depletions of epidermal and dermal glutathione, the severity of which is dependent on the psoralen dose and may last for several days. These transient depletions, oxidations, and sometimes rapid recoveries of cutaneous glutathione levels are compatible with a role for glutathione as an endogenous photoprotective agent in the skin. Experimental evidence supports such a role: for example severe skin edema develops in mice only after about 50% of the glutathione has been depleted by PUVA treatment. Although different mechanisms are involved in each case, glutathione depletion may contribute to the production of phototoxicity by UVB, UVA, and by PUVA. Understanding the depletion mechanisms may allow the development of strategies aimed at preventing loss of cutaneous glutathione, and at reinforcing the natural protective functions of this critical cell component.     

Sensitivity of the retina to radiation damage as a function of wavelength.

Abstract—Exposure of the retina of the rhesus monkey to visible and infrared radiation from CW optical sources like the Sun, xenon lamps, etc. produces small lesions or scotomata which may be classified as thermal or photochemical, depending on the wavelength and duration of exposure. The action spectrum for the production of retinal lesions has been determined for eight monochromatic laser wavelengths extending from 1064 to 441 nm. The corneal power required to produce a lesion decreases by three orders of magnitude in going from 1064 to 441 nm. Exposure to 1064 nm radiation for 1000 s produces a typical thermal lesion at elevated retinal temperatures. whereas a 1000 s exposure to 441 nm light produces a photochemical lesion at power levels too low to raise the retinal temperature by an appreciable amount (<0.1°). The two types of lesion have entirely different characteristics as will be discussed in some detail. The photopathology of thc photochemical lesion has been studied at postexposure times ranging from 1 h to 90 days and will be demonstrated in a number of histological slides. Moreover, this photopathology correlates well with monocular visual acuity tests in the rhesus monkey as defined by the Landolt ring technique. To further elucidate the differential effects on the retina of short vs long wavelength CW radiation, we have divided a simulated solar spectrum at sea level into two spectral bands. 400–800 nm and 700–1400 nm, and determined the radiant exposures required to produce very mild lcsions on the rhesus retina for exposure times of 1, 10, 100 and 1000 s. To correlate our data with solar retinitis and eclipse blindness the image diameter or spot size on the retina was 159 μm, corresponding to the image size of the Sun on the human retina. Exposure to the 400–800 nm spectrum for durations of 10 s or greater required approximately 400 J/cm² to produce a mild photochemical lesion. Reciprocity is maintained over the exposure range 10–1000 s. Radiant exposure to the 700–1400 nm spectrum, on the other hand, required roughly 69,100 J/cm² for a 1000 s exposure. This was a mild thermal lesion. We were unable to produce a lesion for exposure times less than 1000 s. We interpret these data to mean that solar retinitis and eclipse blindness are primarily photochemical events produced by the short wavelength component of the solar spectrum, and that the infrared component of the solar spectrum plays only a minor role in these retinal pathologies.     

A behavioral model for estimating population exposure to solar ultraviolet radiation

Determining the variability of solar UV exposure of different members of a population by direct measurement demands high compliance over an extended period of time by a large number of people. An alternative approach is to model the variables that affect personal exposure and this is the basis of the method reported here, which uses a random sampling technique to explore variability of exposure at different times of the year by habitués. It is shown that there are large variations in daily personal erythemal exposure, more so for indoor workers living in northern Europe than those resident in Florida, which are due not only to seasonal changes in ambient, but just as importantly to seasonal variation in behavior. Not surprisingly, holiday and summer weekend exposure account for the largest daily UV doses. Northern Europeans who take their summer vacation in Florida can double their exposure during this period compared with holidaying at home and this illustrates just how important sun protection measures should be during recreational exposure in areas of high insolation if the annual UV burden is to be sensibly controlled.     

Daily and circadian variation in survival from ultraviolet radiation in Chlamydomonas reinhardtii

The survival of organisms depends on their ability to adapt to their environment, one important aspect of which is the daily cycle of day and night. During the day, organisms use a variety of strategies to protect themselves from deleterious ultraviolet (UV) wavelengths of sunlight. Among those strategies could be timing of UV-sensitive cellular processes to occur at night to avoid UV-induced damage. We tested whether the unicellular alga Chlamydomonas reinhardtii uses this strategy by measuring the survival of cells following exposure to UV radiation at different phases of the day. Chlamydomonas cells displayed a rhythm of survival from UV radiation where the most sensitive phases occurred during the end of the day and at the beginning of the night. This phase of sensitivity corresponds to the time of nuclear division. The rhythm continues in constant light indicating control by a circadian clock. The results presented here suggest a hypothesis of how circadian clocks may have evolved; a temporal program whereby light-sensitive processes are timed to avoid sunlight-induced damage would be advantageous and therefore selected.     

Effects of cycloheximide on liquid-holding recovery from ultraviolet radiation damage in yeast cells

Abstract. The role of protein synthesis in liquid-holding recovery from ultra-violet radiation damage in synchronized Saccharomyces cerevisiae cells has been studied using cycloheximide as a specific inhibitor of cytoplasmic protein synthesis. Liquid-holding recovery from UV-induced budding delay is completed within a few hours and is not inhibited by the presence of cycloheximide. Liquid-holding recovery from lethal UV damage is unaffected by cycloheximide for liquid-holding times less than about 12 h. For longer times recovery is inhibited, with survival enhancement eliminated after about 48 h. Periods greater than 48 h of liquid-holding in the presence of cycloheximide result in survival less than that obtained with immediate plating, but the same concentration of cycloheximide is not toxic to unirradiated cells.     

Sensitive luminescence techniques to study the early stages of polymer oxidation

This paper describes recent developments in the use of chemiluminescence (CL) and profluorescent nitroxides (PFNs) in probing the “induction period” of polymer oxidation. CL measures the instantaneous rate of reaction of hydroperoxides responsible for initiating degradation and the spreading of oxidation, while PFNs can be used to measure the concentration of alkyl radicals produced in oxidation events and thus provide an integrating sensor for the extent of cumulative damage. The PFN additive acts as an oxidation retarder by competing with oxygen to scavenge the alkyl radicals that generate chain carrying peroxy radicals and so mirrors the performance of hindered amine stabilisers (HAS) in one part of their stabilisation cycle. Using the example of polypropylene (PP) and cis-polyisoprene (PIP) as substrates which can rapidly spread oxidative damage, the factors controlling the reaction of PFNs can be determined from CL and fluorescence as well as infra-red (IR) spectroscopy through the detection of oxidation products as measured by the carbonyl index. Matrix effects on the reactivity are demonstrated using a polyethylene-norbornene copolymer (TOPAS) as carrier for both PIP and the PFN and it is seen that the PFN is a radical scavenger only above T_g of the carrier. When PIP alone is oxidized, the PFN is an integrating sensor for free radical production under ambient conditions for up to twelve months while also stabilizing the polymer. Critically, it is thus able to determine the underlying rate of radical production in the oxidation induction period.     

Effects of ultraviolet radiation on aqueous polyelectrolyte solutions

The effects of ultraviolet radiation on dilute aqueous solutions of poly(acrylic acid) and of other polyelectrolytes were studied by viscosity measurements in connection with the effects of ionizing radiation. It was found that ultraviolet light of wavelength below about 2300 Å brought about degradation of polymer chains mainly by indirect action via water, while light of wavelength above 2300 Å caused degradation by direct action in some polymers. It was deduced from the experiments that the protective effect of NaCl could be largely attributed to a decrease in the indirect action. It was also found that a low concentration of methanol was effective in preventing degradation by direct action, although methanol promoted degradation when present in high concentration. Since the promotive effect was not observed when light of wavelength below 3700 Å was eliminated by a filter, this effect was attributed to active products of the irradiation of methanol.     

Determination of ultraviolet radiation intensity using polysulphone film

The use of a polysulphone film as a physical standard for measuring light dosage in accelerated weathering tests is described. Tables are given of equivalent dose at 305 nm and correction factors for temperature of exposure. Examples of application are outlined showing effect of lamp and filter age on UV intensity and comparison of different light sources.     

Nanoconfinement as a tool to study early stages of polymer crystallization

This article promotes the idea that crystallization experiments under confinement can be an interesting tool to learn more about the early stages of polymer crystallization in bulk systems. Based on various results from the recent literature, it is demonstrated that crystalline forms that are metastable, transient, or inaccessible in bulk samples can be easily obtained and studied in nanoscopic compartments. This is interesting in the light of the recent discussion about thermodynamic reasons for the temporary occurrence of a mesophase at the growth front of crystals in bulk polymers, in particular, about a hexagonally packed mesophase in polyethylene. The experimental findings for nanoconfined methylene sequences seem to support indirectly thermodynamic approaches explaining the occurrence of a mesophase based on the small thickness of the crystal at the growth front. A first estimate for the critical crystal thickness d_mc defining the transition from hexagonal to orthorhombic packing in case of confined methylene sequences is provided based on results for side chain polymers. Further perspectives of crystallization experiments on confined systems are discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1556–1561, 2008     

Impact of ultraviolet radiation on the performance of polymer electrolyte membrane

Journal of Solid State Electrochemistry - The effect of ultraviolet (UV) radiation, with wide range of wavelengths, on Nafion 112 membrane was studied at different UV exposure times up to...     

The early stages of the sol-gel processing of TEOS

The reactivity of tetraethoxysilane (TEOS) used in many sol-gel syntheses can be increased by prehydrolysis. In contrast to one-step prehydrolysis acidic two-step prehydrolysis causes an increase of the reactivity of the low molecular species provided the total water/TEOS ratios are the same in both cases. By choice of the processing conditions of the hydrolysis—shown on variation of water content, hydrolysis steps and heat treatment—the degree of condensation, the ratio of hydrolyzable (-OC₂H₅) and hydrolyzed groups (-OH) and the structure of the low molecular species (short chains, 3-membered and 4-membered rings) can be influenced systematically. The development of the building units formed in the early reaction stages is ascertained by molybdate method and ²⁹Si NMR measurements.     

Butyltins biomagnification from macroalgae to green sea urchin: a field assessment

Biomagnification of butyltins (BTs) was examined in a simple food web including seawater, macroalgae (Alaria esculenta, Laminaria longicruris, Ulvaria obscura) and green urchin (Strongylocentrotus droebachiensis). The study was conducted in shallow waters of the St Lawrence Estuary (Canada) adjacent to two areas potentially contaminated by BTs. Levels of tri‐ (TBT), di‐ (DBT) and mono‐BT (MBT) were determined in seawater, green urchin (including faecal matter after sampling) and macroalgae surrounding the urchins at each sampling site. The concentrations of TBT in seawater from all stations were relatively low (3–7 ngSn l^?1), and both the TBT and the total BTs (∑BT = MBT + DBT + TBT) concentrations decreased with increase in distance from the BT sources. The concentrations of TBT in algae were 0.35 ngSn g^?1 dry weight (DW) in A. esculenta, 0.40 ngSn g^?1 DW in L. longicruris and 3.58 ngSn g^?1 DW in U. obscura. Following their location, green urchins feeding mainly on these algae accumulated BTs at levels ranging from 4 to 85 ngSn g^?1 DW in gonads and from 35 to 334 ngSn g^?1 DW in gut. The mean bioconcentration factor (BCF) calculated from seawater to algae ranged from 17 in A. esculenta to 151 in U. obscura, whereas the biomagnification factor (BMF) from algae to urchins ranged from 2 to 17 in gonads and from 10 to 67 in gut. The overall bioaccumulation factor of TBT between seawater and internal organs of urchins reached an average value of 1.2 × 10³. These results are the first to illustrate high BT BCFs and BMFs in human‐edible macroalgae and urchins sampled from northern coastal areas with a low TBT contamination level. Copyright © 2003 John Wiley & Sons, Ltd.     

Overview of the inactivation by 254 nm ultraviolet radiation of bacteria with particular relevance to biodefense

Abstract Our goal was to ultimately predict the sensitivity of untested bacteria (including those of biodefense interest) to ultraviolet (UV) radiation. In this study, we present an overview and analysis of the relevant 254 nm data previously reported and available in the literature. The amount of variability in this data prevented us from determining an "average" response for any bacterium. Therefore, we developed particular selection criteria to include the data in our analysis and suggested future guidelines for reporting UV sensitivity results. We then compiled a table of the sensitivity to 254 nm UV for 38 bacteria and three bacterial spores. The UV sensitivity was quite similar (within 10%) among the spores of Bacillus anthracis (strains Vollum 1B and Sterne), Bacillus subtilis, and Bacillus megaterium. These data indicate that spores of B. subtilis and B. megaterium could be adequate simulants of B. anthracis spores in UVC experiments. Spores of B. anthracis, B. subtilis and B. megaterium were 5-10 times more resistant to UV than were their corresponding vegetative cells. The vegetative cells of B. anthracis showed similar UV sensitivity to those of Burkholderia pseudomallei, Shigella sonnei, and a wild-type strain of Escherichia coli. Yersinia enterocolitica and Vibrio cholerae appeared more sensitive to UV and Salmonella typhi slightly more resistant to UV than E. coli. The sensitivity (at 254 nm) of all vegetative bacteria ranged from 11 to 80 Jm(2) for a 1 Log(10) kill and from 25-200 Jm(2) for 4 Log(10) kill.