Drivers for Sun Protection in Black South Africans

Sun protection behavior studies are almost exclusively carried out in populations with fair skin for the obvious reason that people with unpigmented skin are more susceptible to the health impacts of excess solar ultraviolet radiation exposure. In a dataset of 1271 Black South Africans, we analyzed factors related to sun protection applied when spending time outdoors including awareness of skin cancer, gender, age and Living Standards Measure (LSM) where 1–4 equate to the lowest, 5–7 intermediate and 8–10 the highest LSM status. The most important driver for Black South Africans to use sun protection was whether they were aware of skin cancer (OR: 2.6 for those who were aware versus those who were not, P < 0.0001). Sunscreen was preferred by respondents in LSM 8-10 whereas people in the lowest group (LSM 1-4) favored shade, umbrellas and hats. One in two respondents claimed to use some form of sun protection, which appears to be higher than deeply pigmented populations in other countries.     

Serial Cross-Sectional Observations of Sun-Protective Behaviors at an Annual Outdoor Motorsport Event in Tropical Queensland,Australia

Skin cancer, the most prevalent cancer in Caucasians residing at low latitudes, can primarily be prevented by avoiding overexposure to sunlight. Serial cross-sectional observations were conducted at an outdoor motorsport event held in Townsville, Queensland each July (Southern winter) to determine whether sun-protection habits changed over time. Most (71.1%) of the 1337 attendees observed (97.6% lightly pigmented skin, 64.0% male) wore a hat (any style shading the face), while few (18.5%) wore three-quarter or full-length sleeves. While hat-wearing rates (any style) were similar in 2009 (326, 72.6%) and 2013 (625, 70.4%), the use of sun-protective styles (wide-brimmed/bucket/legionnaires) decreased from 29.2% to 18.6% over the same period, primarily because the use of sun-protective hats halved (from 28.7% to 14.0%) among females, while decreasing from 29.4% to 21.1% in males. Although relatively few individuals wore sun-protective (three-quarter-length or full-length) sleeves regardless of year (OR = 0.117, P < 0.0001), encouragingly, the use of sun-protective sleeves more than doubled between 2009 (10.5%) and 2013 (22.5%). Interestingly females, albeit the minority, at this sporting event were less likely to wear a hat (OR = 0.473, P < 0.0001) than males. These findings highlight the need for continued momentum toward skin cancer primary prevention through sun protection with a dedicated focus on outdoor sporting settings.     

Sun protection Provided by Regulation School Uniforms in Australian Schools: An Opportunity to Improve Personal Sun protection During Childhood

Childhood sun exposure is linked to excessive pigmented mole development and melanoma risk. Clothing provides a physical barrier, protecting skin from ultraviolet radiation (UVR). Extending sleeves to elbow length and shorts to knee length has been shown to significantly reduce mole acquisition in preschoolers from tropical Queensland. We used publicly available uniform images and guidelines from primary schools in Townsville (latitude 19.25°S, n = 43 schools), Cairns (16.87°S, n = 46) and the Atherton Tablelands (17.26°S, n = 23) in tropical Australia to objectively determine the body surface proportion covered by regulation school uniforms. Uniforms of nongovernment, large (≥800 students), urban, educationally advantaged schools with comprehensive sun protection policies covered more skin than those of government schools (63.2% vs 62.0%; P < 0.001), smaller schools (63.4% vs 62.3%; P = 0.009), rural (62.7% vs 61.9%; P = 0.002) and educationally disadvantaged schools (62.8% vs 62.3%; P < 0.001) with underdeveloped sun protection policies (62.8% vs 62.2%; P = 0.002). Overall, SunSmart and non‐SunSmart school uniforms covered identical body surface proportions (62.4%, P = 0.084). Although wearing regulation school uniforms is mandatory at most Australian primary schools, this opportunity to improve children's sun protection is largely overlooked. Recent evidence suggests that even encouraging minor alterations to school uniforms (e.g. slightly longer sleeves/dresses/skirts/shorts) to increase skin coverage may reduce mole acquisition and melanoma risk, especially in high‐risk populations.     

Diffuse Reflectance Spectroscopy Versus Mexameter® MX18 Measurements of Melanin and Erythema in an African Population

Melanin provides protection against excess exposure to solar ultraviolet radiation (UVR) and related adverse health effects. Diffuse reflectance spectroscopy (DRS) can be used to calculate cutaneous melanin and erythema, but this is complex and has been mostly used for light‐to‐medium pigmented skin. Handheld reflectance spectrophotometers, such as the Mexameter^® MX18, can also be used. We compared DRS‐calculated melanin and erythema values with Mexameter melanin and erythema index values to understand how these techniques/measurements correlate in an African population of predominantly deeply pigmented skin. Five hundred and three participants comprised 68.5% self‐identified Black African, 9.9% Indian/Asian, 18.4% White and 2.9% Colored. The majority of Black African (45%), Indian/Asian (34%) and Colored (53%) participants self‐identified their skin as being “brown.” Measured melanin levels increased with darker self‐reported skin color. DRS‐calculated and Mexameter melanin values demonstrated a positive correlation (Spearman rho = 0.87, P < 0.001). The results from both instruments showed erythema values were strongly correlated with their own melanin values. This finding is considered spurious and may result from the complexity of separating brown and red pigment when using narrowband reflectance techniques. Further work is needed to understand melanin, erythema and color in Black skin given sun‐related health risks in vulnerable groups in Africa.     

On the Formation of Thymine Photodimers in Thymine Single Strands and Calf Thymus DNA

Solar light leads to thymine dimers that are mutagenic and primary cause of skin cancer. Here, we report absorption and synchrotron radiation circular dichroism (CD) spectra of T_n single strands with different number n of bases (n = 2–7, 10, 11) recorded after various 254 nm irradiation times. From a principal component analysis of the CD spectra, we extract fingerprint spectra of both the cyclobutane pyrimidine dimer (CPD) and the pyrimidine (6‐4) pyrimidone photoadduct (64PP). Extending the CD measurements to the vacuum ultraviolet region in combination with systematic examinations of size effects is a new approach to gain insight on the dimeric photoproducts. We find a simple linear correlation between n and average number of dimers formed after 1 h of irradiation. The probability for a thymine to engage in a dimer increases from 32% for n = 2 to 41% for n = 11, which implies limited effects of terminal thymines, i.e., the reaction does not occur preferentially at the extremities of the single strands as previously stated. It is even possible to form two dimers with only two bridging thymines. Finally, experiments conducted on calf thymus DNA provided a similar signature of the photodimer, but differences are also evident.     

Acute Ultraviolet Radiation Perturbs Epithelialization but not the Biomechanical Strength of Full‐thickness Cutaneous Wounds

We hypothesized that priming of the skin with ultraviolet radiation (UVR) before being injured would enhance wound healing. Four groups, each comprising 20 immunocompetent hairless mice, were exposed to simulated solar irradiation in escalating UVR doses; 0 standard erythema dose (SED) = control, 1 SED, 3 SED and 5 SED. Twenty‐four hours after UV irradiation, inflammation was quantified by skin reflectance (erythema) and myeloperoxidase (MPO) tissue levels, and two 6 mm full‐thickness excisional wounds and one 3 cm incisional wound were inflicted. Epidermal hyperplasia was assessed by quantitative histology. Five days after wounding, wound coverage by neoepithelium and wound width of the excisional wounds was quantified in hematoxylin–eosin sections, and breaking strength was measured in strips from incisional wounds. Erythema (P < 0.001), MPO levels (P < 0.0005) and epidermal cell layers (P < 0.001) increased dose‐dependently by UV exposure of dorsal skin. In the excisional wounds, epithelial coverage decreased (P = 0.024) by increasing the UVR dose, whereas there was no significant difference (P = 0.765) in wound MPO levels. Neither wound width (P = 0.850) nor breaking strength (P = 0.320) differed among the groups. Solar‐simulated UVR 24 h before wounding impaired epithelialization but was not detrimental for surgical incisional wound healing.     

The pressure effect study on the burning rate of ammonium nitrate-HTPB-based propellant with the influence catalysts

The burning rate of AN–HTPB-based propellant catalysed with chromium salt has been studied using conventional strand burner under the various pressure range, i.e. from atmospheric pressure to 6.897 MPa and verified with Piobert law, i.e. r = aP ⁿ . At atmospheric pressure, the burning rate AN–HTPB propellant was being accelerated with the chromium-based catalysts used. In case of lead chromate-catalysed system, burning rate was observed 2.655 times higher than burning rate (r = 0.200 mm s⁻¹) of virgin AN–HTPB propellant sample. However, the Copper chromate-catalysed propellant burned with slower rate (r = 0.160 mm s⁻¹) than the virgin AN–HTPB propellant sample. The burning rate of all catalysed propellant samples are found to be the pressure sensitive and accelerated higher with rise of pressure. The highest burning rate (r = 2.422 mm s⁻¹) was recorded with ammonium dichromate and lowest (r = 1.40 mm s⁻¹) with lead chromate-catalysed propellant sample with the rise of pressure up to 6.897 MPa at different pressures. A linear relationship was observed between the burning rate and pressure rise which followed the Piobert law, i.e. r = aP ⁿ . The pressure index (n) values of AN–HTPB-based samples were calculated higher when catalysed with ammonium dichromate, Copper Chromate, Cr₂O₃, Potassium dichromate (n = 0.525, 0.555, 0.429, and 0.408 respectively) and lower (n = 0.226) with lead chromate compared to virgin sample (n = 0.405). Higher value indicates the positive effect on accelerating the burning rate with catalyst at higher pressure ranges.     

Combined DFT with NBO and QTAIM studies on the hydrogen bonds in (CH<Subscript>3</Subscript>OH)<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 2–8) clusters

The (CH₃OH) _n (n = 2–8) clusters formed via hydrogen bond (H-bonds) interactions have been studied systemically by density functional theory (DFT). The relevant geometries, energies, and IR characteristics of the intermolecular OH···O H-bonds have been investigated. The quantum theory of atoms in molecule (QTAIM) and natural bond orbital (NBO) analysis have also been applied to understand the nature of the hydrogen bonding interactions in clusters. The results show that both the strength of H-bonds and the deformation are important factors for the stability of (CH₃OH) _n clusters. The weakest H-bond was found in the dimer. The strengths of H-bonds in clusters increase from n = 2 to 8, moreover, the strengths of H-bonds in (CH₃OH) _n (n = 4–8) clusters are remarkably stronger than those in (CH₃OH) _n (n = 2, 3) clusters. The small differences of the strengths of H-bonds among (CH₃OH) _n (n = 6–8) clusters indicate that a partial covalent character is attributed to the H-bonds in these clusters. The linear relationships between the electron density of BCP (ρ_b) and the H···O bond length of H-bonds as well as the second-perturbation energies E(2) have also been investigated and used to study the nature of H-bonds, respectively.     

Spectroscopic study of molecular structures of novel Schiff base derived from o-phthaldehyde and 2-aminophenol and its coordination compounds together with their biological activity

New Schiff base (H₂L) ligand is prepared via condensation of o-phthaldehyde and 2-aminophenol. The metal complexes of Cr(III), Mn(II), Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) with the ligand are prepared in good yield from the reaction of the ligand with the corresponding metal salts. They are characterized based on elemental analyses, IR, solid reflectance, magnetic moment, electron spin resonance (ESR), molar conductance, ¹H NMR and thermal analysis (TGA). From the elemental analyses data, the complexes are proposed to have the general formulae [M(L)(H₂O)n]·yH₂O (where M = Mn(II) (n = 0, y = 1), Fe(II) (n = y = 0), Co(II) (n = 2, y = 0), Ni(II) (n = y = 2), Cu(II) (n = 0, y = 2) and Zn(II) (n = y = 0), and [MCl(L)(H₂O)]·yH₂O (where M = Cr(III) and Fe(III), y = 1–2). The molar conductance data reveal that all the metal chelates are non-electrolytes. IR spectra show that H₂L is coordinated to the metal ions in a bi-negatively tetradentate manner with ONNO donor sites of the azomethine N and deprotonated phenolic-OH. This is supported by the ¹H NMR and ESR data. From the magnetic and solid reflectance spectra, it is found that the geometrical structures of these complexes are octahedral (Cr(III), Fe(III), Co(II) and Ni(II) complexes), tetrahedral (Mn(II), Fe(II) and Zn(II) complexes) and square planar (Cu(II) complex). The thermal behaviour of these chelates is studied and the activation thermodynamic parameters, such as, E*, ΔH*, ΔS* and ΔG* are calculated from the DrTGA curves using Coats-Redfern method. The parent Schiff base and its eight metal complexes are assayed against two fungal and two bacterial species. With respect to antifungal activity, the parent Schiff base and four metal complexes inhibited the growth of the tested fungi at different rates. Ni(II) complex is the most inhibitory metal complex, followed by Cr(III) complex, parent Schiff base then Co(II) complex. With regard to bacteria, only two of the tested metal complexes (Mn(II) and Fe(II)) weakly inhibit the growth of the two tested bacteria.     

Measurements of the thermal neutron cross-sections and resonance integrals for 186W (n,γ) 187W and 98Mo (n,γ) 99Mo reactions

The thermal neutron cross-sections and resonance integrals of the ¹⁸⁶W (n,γ) ¹⁸⁷W and ⁹⁸Mo (n,γ) ⁹⁹Mo reactions in the thermal and 1/E regions, respectively, of a thermal reactor neutron spectrum have been experimentally determined by the activation method using ¹⁹⁷Au (n,γ) ¹⁹⁸Au reaction as a single comparator. The high purity natural W, Mo, and Zr foils; and Au wire diluted in aluminum, were irradiated without Cd shield in two neutron irradiation sites, characterized with different values for the thermal-to-epithermal flux ratios, f at the Second Egyptian Research Reactor (ETRR-2). The induced activities in the samples were measured by high-resolution γ-ray spectrometry with a calibrated germanium detector. Thermal neutron cross-sections for 2200 m/s neutrons and resonance integrals for the ¹⁸⁶W (n,γ) ¹⁸⁷W and ⁹⁸Mo (n,γ) ⁹⁹Mo reactions have been obtained relative to the reference values, σ₀ = 98.65 ± 0.09 b and I ₀ = 1500 ± 28 b for the ¹⁹⁷Au (n,γ) ¹⁹⁸Au reaction. The necessary correction factors for thermal neutron and resonance neutron self-shielding effects, and the epithermal flux index (α) were taken into account in the determinations. The results obtained were: σ₀ = 38.43 ± 0.4 b and I ₀ = 502 ± 65 b for ¹⁸⁶W (n,γ) ¹⁸⁷W, and σ₀ = 0.137 ± 0.014 band I ₀ = 6.47 ± 0.8 for ⁹⁸Mo (n,γ) ⁹⁹Mo. These results are discussed and compared with previous measurements and evaluated data in literature. The traditional method of determining thermal cross-sections and resonance integrals via neutron irradiation with and without Cd shield in one irradiation position was avoided in this work by neutron irradiation without Cd shield in at least two different neutron irradiation positions. This method provides alternative way for determining thermal cross-sections and resonance integrals simultaneously.     

Growth Pattern, Electronic Structures and Magnetic Moments of Small Lutetium Clusters

The lowest-energy configurations, electronic structures and magnetic moments of small Lu _n (n = 2–20) clusters have been investigated within the framework of density functional theory. The results show that Lu _n (n = 4, 8, 13, and 18) clusters are more stable than their respective neighbors, and structural transformation reveals at n = 16. As the number of atoms increases, the magnetic moments increase in an alternating fashion until they reach a maximum of 4.00 μ_B for Lu₈ clusters, followed by even–odd oscillation between 0.00 and 1.00 μ_B over the range n = 9–20.     

Thermal decomposition of some biologically active complexes of ruthenium (III) with quinolone derivatives

A series of new complexes with mixed ligands of the type RuL₂(DMSO) _m Cl₃·nH₂O ((1) L: norfloxacin (nf), m = 1, n = 1; (2) L: ciprofloxacin (cp), m = 2, n = 2; (3) L: ofloxacin (of), m = 1, n = 1; (4) L: enrofloxacin (enro), m = 0.5, n = 4; DMSO: dimethylsulfoxide) were synthesised and characterised by chemical analysis and IR data. In all complexes both fluoroquinolone derivative and DMSO act as unidentate. The thermal behaviour steps were investigated in synthetic air flow. The thermal transformations are complex processes according to TG and DTG curves including dehydration, quinolone derivative and DMSO degradation respectively. The final product of decomposition is ruthenium (IV) oxide.     

Sun exposure and Protection Behavior of Danish Farm Children: Parental Influence on Their Children

Healthy sun habits acquired in childhood could reduce skin cancer incidence. We examined the sun exposure and protection behavior of an expected high‐exposure group of children, and the association to their parents. Open, prospective cohort study. One hundred and thirty nine participants (40 families) kept daily sun behavior diaries (sun exposure, sunscreen use, sunburns) over a 4‐month summer period (15 985 diary days). The Pigment Protection Factor (PPF), an objective measure of sun exposure, was measured at two body sites, before and after summer. All participants presented data from the same 115 days. Risk behavior (sun exposure of upper body) took place on 9.5 days (boys) and 15.6 days (girls). Sunburn and sunscreen use were infrequent. Boys’ sun exposure resulted in an increased photo protection over the study period of 1.7 SED (upper arm) and 0.8 SED (shoulder) to elicit erythema. Corresponding values for girls were as follows: 0.9 SED (upper arm) and 0.5 SED (shoulder). Boys’ sunscreen use correlated to their mothers’ (r = 0.523, P = 0.02). Girls’ number of risk days (r = 0.552, P = 0.005) and sun exposure (upper arm: r = 0.621, P < 0.001) correlated to their mothers’. The children's sun exposure was substantial. Only mothers influenced children's sun behavior and exposure. This may be of relevance in future sun protection campaigns.     

Thermal study of some new quinolone ruthenium(III) complexes with potential cytostatic activity

A series of new complexes with mixed ligands of the type RuL _m (DMSO) _n Cl₃·xH₂O ((1) L: oxolinic acid (oxo), m = 1, n = 0, x = 4; (2) L: pipemidic acid (pip), m = 2, n = 1, x = 2; (3) L: enoxacin (enx), m = 2, n = 1, x = 0; (4) L: levofloxacin (levofx), m = 2, n = 2, x = 8; DMSO: dimethylsulfoxide) were synthesized and characterized by chemical analysis, IR and electronic data. Except oxolinic acid that behaves as bidentate, the other ligands (quinolone derivatives and DMSO) act as unidentate. Electronic spectra are in accordance with an octahedral stereochemistry. The thermal analysis (TG, DTA) in synthetic air flow elucidated the composition and also the number and nature of both water and DMSO molecules. The TG curves show 3–5 well-separated thermal steps. The first corresponds to the water and/or DMSO loss at lower temperatures followed either by quinolone thermal decomposition or pyrolisys at higher temperatures. The final product is ruthenium(IV) oxide.     

New sol–gel precursors for binary oxides of antimony,Sb<Subscript>2</Subscript>O<Subscript>3</Subscript> (senarmonite) and α-Sb<Subscript>2</Subscript>O<Subscript>4</Subscript>: synthesis and characterization of some ketoximate modified antimony(III) alkoxides

Hydrolysis of pure Sb(OPrⁱ)₃ by sol–gel method followed by sintering at 500 °C yields microcrystallites of Sb₂O₃ (senarmonite phase). Under similar conditions bimetallic alkoxide, [NaSb(OPrⁱ)₄], yields a mixture of binary oxides Sb₂O₃ and Sb₂O₄. Chemical modification of Sb(OPrⁱ)₃ with oximes forms monomeric products of the type [Sb(OPrⁱ)_3−n {ON=C(CH₃)R} _n ] {where R = CH₃, n = 1 [1]; n = 2 [2]; n = 3 [3]; R = 2-C₅H₄N, n = 1 [4]; n = 2 [5]; n = 3 [6]; R = 2-C₄H₃O, n = 1 [7]; n = 2 [8]; n = 3 [9]; R = 2-C₄H₃S, n = 1 [10]; n = 2 [11]; n = 3 [12]}. The liquid products [1–3, 7 & 10] were purified by distillation while the solids by recrystallization. All these products were characterized by elemental analyses, IR, NMR (¹H and ¹³C{¹H}) and representative derivatives [1], [2] and [3] by FAB mass studies. On the basis of these studies, a distorted pyramidal structure for all the derivatives may be assumed in the solution state containing an end-on coordination of oximes with the metal atom. Hydrolysis of the distilled precursors [1], [2] and [3] under sol–gel conditions yields pure nano-sized α-Sb₂O₄. All the oxides were characterized by XRD, SEM and EDX analysis exhibiting minimum particle size for the oxide obtained from the precursor [3].     

Coordination polymers with adamantanediacetate bridges: syntheses, structures, and magnetic properties

Abstract  Two new coordination polymers, [CoL(bpp)] _n (1) and [MnL(bipy)] _n ·0.25nH₂L·0.5nH₂O (2) (H₂L = 1,3-adamantanediacetic acid, bpp = 1,3-bis(4-pyridyl)propane, bipy = 4,4′-bipyridine), were synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, and thermal analysis. Complex 1 is an one-dimensional (1D) chain structure of Co(II) bridged by L²⁻ as well as bpp. Complex 2 consists of a two-dimensional (2D) (3,6)-connected topology layer structure. Variable temperature magnetic susceptibility measurements in the range of 2–300 K reveal the existence of weak antiferromagnetic interactions in two complexes with J = −1.74 cm⁻¹, g = 2.26 for 1 and J = −0.10 cm⁻¹, g = 1.67 for 2. Index abstract  Two mental-organic frameworks, namely [CoL(bpp)] _n (1) and [MnL(bipy)] _n ·0.25nH₂L·0.5nH₂O (2) (H₂L = 1,3-adamantanediacetic acid, bpp = 1,3-bis(4-pyridyl)propane, bipy = 4,4′-bipyridine), have been synthesized based on 1,3-adamantanediacetic acid and N-donor coligand with metal ions Co(II) and Mn(II). The magnetic measurement of the two polymers reveals typical antiferromagnetism exchange. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Dismantlement of ammonia upon interaction with Ben (n ≤ 10) clusters

The interaction of ammonia with Be_n (n < 1–10) clusters has been investigated by density functional theory and ab initio calculations. The main conclusion is that, regardless of the size of the Be cluster, neither the structure of ammonia nor that of the Be clusters are preserved due to a systematic dissociation of its N H bonds and a spontaneous H-shift toward the available Be atoms. This H migration not only leads to rather stable Be H bonds, but dramatically enhances the strength of the Be N bonds as well. Accordingly, the maximum stability is found for the interaction with the beryllium trimer, leading to a complex with three N Be and three Be H bonds. Another maximum in stability, although lower than that reached for n = 3, is found for the Be heptamer, since from n = 6, a new N Be bond is formed, so that complexes from n = 6 to n = 10 are characterized by the formation of a NBe₄ moiety, whose stability reaches a maximum at n = 7. The bonding characteristics of the different species formed are analyzed by means of AIM, NBO, ELF and AdNDP approaches.     

Electrospray Ionization Based Methods for the Generation of Polynuclear Oxo- and Hydroxo Group 6 Anions in the Gas-Phase

Electrospray ionization (ESI) of the Lindqvist (n-Bu₄N)₂[M₆O₁₉] (M = Mo, W) polyoxometalates provides a straightforward entry for the generation of an assortment of oxo- and hydroxo anions in the gas-phase. In particular, the series of oxo dianions of general formula [(MO₃) _n O]²⁻ (n = 2–6; M = Mo, W), monoanions, namely [(MO₃) _n O]⁻ (n = 1, 2) and [(MO₃) _n ]⁻ (n = 1, 2), and the hydroxo [(MO₃) _n (OH)]⁻ (n = 1–6) species can be readily generated in the gas-phase upon varying the solvent composition as well as the ionisation conditions (typically the U_c cone voltage). Complementary tandem mass experiments (collision induced dissociation and ion–molecule reactions) are also used aimed to investigate the consecutive dissociation of these species and their intrinsic gas-phase reactivity towards methanol. Special emphasis is paid to some of the key factors of these group 6 anions related to the gas-phase activation of methanol, such as molecular composition, open vs closed shell electronic nature and cluster size.