Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Horizontal and sun-normal spectral biologically effective ultraviolet irradiances

The dependence of the spectral biologically effective solar UV irradiance on the orientation of the receiver with respect to the sun has been determined for relatively cloud-free days at a sub-tropical Southern Hemisphere latitude for the solar zenith angle range 35-64 degrees. For the UV and biologically effective irradiances, the sun-normal to horizontal ratio for the total UV ranges from 1.18 +/- 0.05 to 1.27 +/- 0.06. The sun-normal to horizontal ratio for biologically effective irradiance is dependent on the relative effectiveness of the relevant action spectrum in the UV-A waveband. In contrast to the total UV, the diffuse UV and diffuse biologically effective irradiances are reduced in a sun-normal compared with a horizontal orientation by a factor ranging from 0.70 +/- 0.05 to 0.76 +/- 0.03.     

Validation of Sun Exposure Reported Annually Against Interim Self‐report and Daily Sun Diaries

Data on personal sun exposure over a period exceeding the immediate past days or weeks are typically self‐reported in brief questionnaire items. The validity of such self‐reporting of longer term personal sun exposure, for example over a year, including detail on variation across seasons, has not previously been investigated. In a volunteer sample (n = 331) of Australian adults aged 18 years and over, we assessed the 12‐month reliability of sun exposure reported separately for each season, and its accuracy compared to a daily sun diary in the same season. Seasonal time outdoors displayed fair‐to‐good reliability between baseline and end of study (12 months), with responses showing higher agreement at lower levels of time outdoors. There was good agreement for ranking of individuals' time outdoors with the daily sun diary data, although the actual diary time outdoors was typically considerably lower than the self‐reported questionnaire data. Place of residence, education, being a smoker, day of the week (i.e. working day vs nonworking day) and working mainly outdoors were significant predictors of agreement. While participants overestimated their actual time outdoors, the self‐report questionnaire provided a valid ranking of long‐term sun exposure against others in the study that was reliable over time.     

Location and vitamin D synthesis: is the hypothesis validated by geophysical data?

The literature reports strong correlations between UV exposure and latitude gradients of diseases. Evidence is emerging about the protective effects of UV exposure for cancer (breast, colo-rectal, prostate), autoimmune diseases (multiple sclerosis, type II diabetes) and even mental disorders, such as schizophrenia. For the first time, the available levels of vitamin D producing UV or "vitamin D UV" (determined from the previtamin D action spectrum) and erythemal (sunburning) UV from throughout the USA are measured and compared, using measurements from seven locations in the USA are measured and compared, using measurements from seven locations in the US EPA's high accuracy Brewer Spectrophotometer network. The data contest longstanding beliefs on the location-dependence and latitude gradients of vitamin D UV. During eight months of the year centered around summer (March-October), for all sites (from 18 degrees N to 44 degrees N latitude) the level of vitamin D UV relative to erythemal UV was equal (within the 95% confidence interval of the mean level). Therefore, there was no measured latitude gradient of vitamin D UV during the majority of the year across the USA. During the four cooler months (November-February), latitude strongly determines vitamin D UV. As latitude increases, the amount of vitamin D UV decreases dramatically, which may inhibit vitamin D synthesis in humans. Therefore, a larger dose of UV relative to erythemal UV is required to produce the same amount of vitamin D in a high latitude location. However, the data shows that at lower latitude locations (<25 degrees N), wintertime vitamin D UV levels are equal to summertime levels, and the message of increasing UV exposure during winter is irrelevant and may lead to excessive exposure. All results were confirmed by computer modeling, which was also used to generalize the conclusions for latitudes from 0 degrees to 70 degrees N. The results of this paper will impact on research into latitudinal gradients of diseases. In particular, it may no longer be correct to assume vitamin D levels in populations follow significant latitude gradients for a large proportion of the year.     

Does a high UV environment ensure adequate vitamin D status?

This study assesses the Vitamin D status of 126 healthy free-living adults aged 18-87 years, in southeast Queensland, Australia (27 degrees S) at the end of the 2006 winter. Participants provided blood samples for analysis of 25(OH)D (the measure of an individual's Vitamin D status), PTH, Calcium, Phosphate, and Albumin, completed a questionnaire on sun-protective/sun-exposure behaviours, and were assessed for phenotypic characteristics such as skin/hair/eye colour and BMI. We found that 10.2% of the participants had serum 25(OH)D levels below 25 nmol/l (considered deficient) and a further 32.3% had levels between 25 nmol/l and 50 nmol/l (considered insufficient). Our results show that low levels of 25(OH)D can occur in a substantial proportion of the population at the end of winter, even in a sunny climate. 25(OH)D levels were higher amongst those who spent more time in the sun and lower among obese participants (BMI>30) than those who were not obese (BMI<30). 25(OH)D levels were also lower in participants who had black hair, dark/olive skin, or brown eyes, when compared with participants who had brown or fair hair, fair skin, or blue/green eyes. No associations were found between 25(OH)D status and age, gender, smoking status, or the use of sunscreen.     

Personal solar UV exposure measurements employing modified polysulphone with an extended dynamic range

Polysulphone dosimeters using a simple to use filter have been developed and tested to provide an extended dynamic measurement range of personal solar UV exposures over an extended period (3 to 6 days). At a Southern Hemisphere subtropical site (27.6 degrees S, 151.9 degrees E), the dynamic range of the filtered polysulphone allowed measurements of erythemal exposures to approximately 100 minimum erythemal dose (MED) for a change in optical absorbance at 330 nm (deltaA330) of 0.35. In comparison, unfiltered polysulphone dosimeters were exposed to approximately 8 MED for the same deltaA330. The error associated with the use of the filtered polysulphone dosimeters is of the order of +/-15%, compared with +/-10% of the unfiltered variety. The developed filtered polysulphone dosimeter system allowed the measurement of erythemal UV exposures over 3 to 6 days at a subtropical site without the need to replace the dosimeters because of saturation. The results show that longer-term measurement programs of personal solar UV have been made more feasible with the use of these polysulphone dosimeters with an extended dynamic range compared with unfiltered polysulphone dosimeters.     

Applications of 95Mo NMR. 5—substituent effects in the 95Mo and 13C NMR spectra of benzyltricarbonyl(η5-cyclopentadienyl)molybdenum(II) derivatives

A systematic study has been made of the effects of substituent induced chemical shifts in [(η⁵-C₅H₅)(CO)₃Mo(CH₂C₆H₄R)] compounds. Both ⁹⁵Mo and ¹³C NMR shifts in the aromatic ring are reported. The (η⁵-C₅H₅)(CO)₃MoCH₂? group is a reasonably strong resonance donor (σ_R° = ?0.21) and weak inductive donor (σ_I = ?0.07). The molybdenum chemical shifts are extremely sensitive to the effects of distant substituents (range c. 40 ppm). Since the shift correlates well with substituent constants in this series, it is suggested that the chemical shift is controlled by the paramagnetic term for this spin 5/2 nucleus.     

In Vitro Investigations on the Effect of Dermal Fibroblasts on Keratinocyte Responses to Ultraviolet B Radiation

Exposure to ultraviolet radiation is closely linked to the development of skin cancers in humans. The ultraviolet B (UVB) radiation wavelength (280–320 nm), in particular, causes DNA damage in epidermal keratinocytes, which are linked to the generation of signature premalignant mutations. Interactions between dermal fibroblasts and keratinocytes play a role in epidermal repair and regeneration after UVB‐induced damage. To investigate these processes, established two and three‐dimensional culture models were utilized to study the impact of fibroblast–keratinocyte crosstalk during the acute UVB response. Using a coculture system it was observed that fibroblasts enhanced keratinocyte survival and the repair of cyclobutane pyrimidine dimers (CPDs) after UVB radiation exposure. These findings were also mirrored in irradiated human skin coculture models employed in this study. Fibroblast coculture was shown to play a role in the expression and activation of members of the apoptotic cascade, including caspase‐3 and Bad. Interestingly, the expression and phosphorylation of p53, a key player in the regulation of keratinocyte cell fate postirradiation, was also shown to be influenced by fibroblast‐produced factors. This study highlights the importance of synergistic interactions between fibroblasts and keratinocytes in maintaining a functional epidermis while promoting repair and regeneration following UVB radiation‐induced damage.