Seasonal Variation in Measured Solar Ultraviolet Radiation Exposure of Adults in Subtropical Australia

Generating accurate population-specific public health messages regarding sun protection requires knowledge about seasonal variation in sun exposure in different environments. To address this issue for a subtropical area of Australia, we used polysulphone badges to measure UVR for the township of Nambour (26° latitude) and personal UVR exposure among Nambour residents who were taking part in a skin cancer prevention trial. Badges were worn by participants for two winter and two summer days. The ambient UVR was approximately three times as high in summer as in winter. However, participants received more than twice the proportion of available UVR in winter as in summer (6.5%vs 2.7%, P < 0.05), resulting in an average ratio of summer to winter personal UVR exposure of 1.35. The average absolute difference in daily dose between summer and winter was only one-seventh of a minimal erythemal dose. Extrapolating from our data, we estimate that ca. 42% of the total exposure received in the 6 months of winter (June–August) and summer (December–February) is received during the three winter months. Our data show that in Queensland a substantial proportion of people’s annual UVR dose is obtained in winter, underscoring the need for dissemination of sun protection messages throughout the year in subtropical and tropical climates.     

First biosynthetic evidence on the phenyl-containing polyketides of the marine mollusc Scaphander lignarius

The biosynthesis of lignarenones 1 and 2, the major polyketides of the Mediterranean mollusc Scaphander lignarius is described. The process is primed by benzoic acid and requires acetate and propionate as extender units. The labeling pattern suggests PKS-like synthesis of an unusual E,Z,E-triene chain and origin of the benzoate unit from phenylalanine. 13C-13C NMR COSY has been used to establish the labeling positions due to incorporation of 13C2-acetate.     

Shape memory epoxies based on networks with chemical and physical crosslinks

Epoxies are an important family of shape memory polymers (SMP) due to their excellent stability and thermo-mechanical endurance and the high values of shape fixity and shape recovery. Actuators based on these materials can be designed for large tensile elongations (e.g., 75% or higher) or large recovered stresses (e.g., 3 MPa or higher). However, meeting these requirements simultaneously is a difficult task because changes in the crosslink density affect both variables in opposite ways. We show that an SMP based on an epoxy network with both chemical and physical crosslinks could be strained up to 75% in four repeated shape memory cycles with tensile stresses close to 3 MPa. Shape fixity and shape recovery values were close to 98% and 96%, respectively, for everyone of the cycles, without any significant change between the first and subsequent cycles.     

Self‐Assembled Triple‐Stranded Lanthanide Dimetallic Helicates with a Ditopic Ligand Derived from Bis(benzimidazole)pyridine and Featuring an (4‐Isothiocyanatophenyl)ethynyl Substituent

Bis(2‐{6‐(diethylcarbamoyl)‐4‐[(4‐isothiocyanatophenyl)ethynyl]pyridin‐2′‐yl}‐1‐ethylbenzimidazol‐5‐yl)methane ( L ^G ) reacts with trivalent lanthanide ions in acetonitrile to yield triple‐stranded dimetallic helicates [Ln₂( L ^G )₃]⁶⁺. ¹H‐NMR Data point to the helicates being the only species formed under stoichiometric conditions and having a time‐averaged D₃ symmetry on the NMR time scale. The photophysical properties of L ^G and its helicates are discussed with respect to the closely related ligands L ^B , L ^E , and their complexes, two ligands devoid of the isothiocyanatophenylethynyl substituent. The quantum yield of the ligand fluorescence is three times smaller compared to L ^E , while that of the Eu^III‐centered luminescence (1.1%) is three times larger. On the other hand, the luminescence of Tb^III is not sensitized by L ^G . This is explained in terms of energy differences between the singlet and triplet states on one hand, and between the 0‐phonon transition of the triplet state and the excited metal ion states on the other. This work demonstrates that bulky substituents in the 4‐position of the pyridine ring do not prevent the formation of triple‐stranded helicates, opening the way for luminescent probes that can easily be coupled to biological materials.     

Complexes of platinum(II) containing neutral and deprotonated 9-methyladenine. Synthesis, x-ray structures, and NMR studies on the cyclic trimer cis-[L2Pt[9-MeAd([bond]H)]]3(NO3)3 and the Dinuclear cis-[L2Pt(ONO2)[9-MeAd([bond]H)]PtL2](NO3)2 (L = PMePh2)

The dinuclear hydroxo complex cis-[L(2)Pt(mu-OH)](2)(NO(3))(2) (L = PMePh(2), 1), in CH(2)Cl(2), CH(3)CN, or DMF solution, deprotonates the NH(2) group of 9-methyladenine (9-MeAd) to give the complex cis-[L(2)Pt[9-MeAd(-H)]](3)(NO(3))(3), 2, which was isolated in good yield. The X-ray structure shows that the nucleobase binds symmetrically the metal centers through the N(1),N(6) atoms forming a cyclic trimer with Pt...Pt distances in the range 5.202(1)-5.382(1) A. Dissolution of 2 in DMSO or DMF determines the partial (or total) dissociation of the cyclic structure to form several fragments. A multinuclear NMR analysis of the resulting mixture supports the presence of the mononuclear species cis-[L(2)Pt[9-MeAd(-H)]](+), 3, in which the deprotonated nucleobase chelates the metal center with the N(6),N(7) atoms. Addition of a stoichiometric amount of the nitrato complex cis-[L(2)Pt(ONO(2))(2)] (L = PMePh(2), 4) to a DMSO or DMF solution of 2 affords quantitatively the diplatinated compound cis-[L(2)Pt(ONO(2))[9-MeAd(-H)]PtL(2)](NO(3))(2), 5. The single-crystal X-ray analysis shows that the adenine behaves as a tridentate ligand bridging two cis-L(2)Pt units at the N(1) and N(6),N(7) sites, respectively [Pt(1)-N(1) = 2.109(5) A, Pt(2)-N(6) = 2.095(7) A, Pt(2)-N(7) = 2.126(7) A]. The N(1)-bonded metal center completes the coordination sphere through an oxygen atom of a nitrate group, and its coordination plane is arranged orthogonally with respect the second one. The Pt-O distance [2.109(5) A] is similar to those found in the nitrato complex 4 [2.110 A, average]. The related complex cis-[[L(2)Pt(ONO(2))](2)(9-MeAd)](NO(3))(2), 6, containing the neutral adenine platinated at the N(1),N(7) atoms, was isolated and its stability in solution investigated by NMR spectroscopy. In DMSO, 6 undergoes decomposition forming a mixture of the species 4, 5, and the adenine mono- and bis-adducts cis-[L(2)Pt(9-MeAd)(DMSO)](2+), 7, and cis-[L(2)Pt(9-MeAd)(2)](2+), 8, respectively. This last complex, quantitatively formed upon addition of 9-MeAd (Pt/adenine = 1:2) to the mixture, was also isolated and characterized.     

Silica-supported metallocenes: stereochemical comparison between homogeneous and heterogeneous catalysis

Propylene was polymerized in the presence of the isospecific Et(Ind)₂ZrCl₂ (Et: ethylene, Ind: indenyl) and the aspecific (Ind)₂ZrCl₂ complexes in solution and anchored to SiO₂ and SiO₂/MAO (MAO: methylaluminoxane) supports. From the stereochemical analysis of the polypropene samples obtained it can be deduced that (i) the same active species is formed when a metallocene is in solution and when it is anchored to the SiO₂/MAO support and (ii) a completely different active species is formed when the metallocene is anchored to the silica. The fact that both systems Et(Ind)₂ZrCl₂ SiO₂ and (Ind)₂ZrCl₂ SiO₂ produce the same prevailingly isospecific polymer suggests that only isospecific centers are formed in this case, independently of the metallocene stereochemical structure.     

Susceptibility to basal cell carcinoma is associated with high dermal mast cell prevalence in non-sun-exposed skin for an Australian populations

In a Danish population, basal cell carcinoma (BCC) patients have a higher dermal mast cell prevalence in buttock skin than controls. This finding was supported by a functional link in mice between histamine-staining dermal mast cells and the extent of susceptibility to UV-B-induced systemic immunomodulation. It was important to confirm that this association was maintained in an Australian population with very different ancestry and sun exposure patterns. Australian BCC patients (n = 26) had significantly higher densities of mast cells in the dermis of buttock skin than control subjects (n = 25) (P = 0.0003, Mann-Whitney U-test). However, this correlation was lost at the sun-exposed site of the hand (P = 0.547, Mann-Whitney U-test). To further evaluate whether a relationship exists between dermal mast cell prevalence in sun-exposed skin and incidence of BCC in a larger study, biopsies of dorsal hand skin were obtained from an age-stratified random sample of 166 Queensland subjects, together with the 51 South Australian subjects, and dermal mast cell prevalence was quantified. Older subjects (over the median age of 42 years) had a greater incidence of BCC development (P = 0.0001, chi-square test) and significantly higher mast cell densities in hand skin (P = 0.0001, chi-square test) than younger subjects. However, mast cell density in sun-exposed hand skin was not significantly associated with BCC incidence. Finally, cellular expression of c-kit correlated with mast cell prevalence in non-sun-exposed skin, thereby implicating the stem cell factor-c-kit axis in the intrinsic mechanisms that regulate prevalence. These results show that high prevalence of dermal mast cells in buttock skin but not hand is associated with BCC development in an Australian population.     

Effects of chlorinated aliphatic hydrocarbons on the fidelity of cell division in human CYP2E1 expressing cells

Chlorinated organic chemicals are widely used in industry and are present in the environment. Five chlorinated aliphatic hydrocarbons, namely 1-2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, 2,3-dichlorobutane and 1-chlorohexane were investigated to determine their influence upon the fidelity of cell division in cultured mammalian cells. In order to determine the influence of these chemical compounds upon the fidelity of cell division, a technique known as differential staining of chromosomes and spindle was performed with one genetically engineered cell line and its parental cell line. The genetically engineered cell line used in this study expressed a human P450 enzyme, CYP2E1. Four chemicals, 1-2-dichloroethane, trichloroethylene, 2,3-dichlorobutane and 1-chlorohexane required metabolic bioactivations in order to induce spindle damage in cultured mammalian cells whereas 1,1,2-trichloroethane was a direct-acting spindle poison.