Measurement of UV radiation using suspensions of microorganisms

The measurement of solar UV radiation is usually performed using physical devices like photodiodes or photomultipliers or with chemical substances (actinometry). The application of biological material such as microorganisms for this purpose has gained increasing importance in the last few years. The microorganisms may be dried and spread on a flat surface or they may be in aqueous suspensions contained in UV-transparent vessels. If the measurements are done on flat surfaces, the irradiance weighted by the action spectrum of the dried microorganism used is the result of the measurement. If aqueous suspensions of microorganisms are used, contained for instance in spherical vessels, the fluence weighted by the action spectrum of the microorganisms in the aqueous suspension is the result. A problem of this method of measurement can be that inside the vessel the distribution of UV radiation is usually not homogeneous, causing distributions of fluences among the irradiated microorganisms, which may result in variation of the results depending on the mixing characteristics of the suspension during irradiation.     

UV angle-resolved photoelectron spectra of mixed methylene dihalides using synchrotron radiation

Photoelectron spectra for the dihalomethanes CH₂BrCl, CH₂ClI and CH₂Br₂ have been recorded with photons in the energy range 19–115 eV using Daresbury Laboratory Synchroton Radiation Source. Ionization energies have been measured for all valence falling within this energy including Br 3d and I 4d orbitals. Asymmetry parameters have been measured for all intense ionization processes and characteristic Cooper minima observed for halogen lone pair orbitals. For CH₂ClI lone pair orbital β spectra show strong evidence of mixed halogen character although a similar situation is not observed for CH₂BrCl. Partial photoionization cross sections are tabulated for the observed ionization processes. Detailed spectra are presented for the molecule CH₂ClI since this appears to be the first photoelectron study of this molecule.     

Effects of UV radiation of cells

UV radiation interacts with mammalian cells in a very complex manner, although DNA appears to be the main chromophore. Recent literature within this field is reviewed. The review is concentrated on the following main topics: Chromophores for UV action, photoproducts in DNA, repair of UV-induced DNA damage, wavelength interactions, inactivation, mutagenesis, transformation and protection mechanisms against UV damage.     

The Titanium Dioxide Sensitised Photo-Oxidation of Sulphides

Titanium dioxide has been shown to photosensitise the oxidation of sulphides to give sulphoxides and sulphones. Evidence is presented against the involvement of singlet oxygen and in favour of the sulphide radical cations as being intermediates.     

High-energy ionising radiation initiated decomposition of acetovanillone

Hydroxyl radical, hydrated electron and hydrogen atom intermediates of water radiolysis react with acetovanillone with rate coefficients of (1.05±0.1)×10¹⁰, (3.5±0.5)×10⁹ and (1.7±0.2)×10¹⁰mol^?1 dm³ s^?1. Hydroxyl radical and hydrogen atom attach to the ring forming cyclohexadienyl type radicals. The hydroxyl–cyclohexadienyl radical formed in hydroxyl radical reaction in dissolved oxygen free solution partly transforms to phenoxyl radical. In the presence of O₂ phenoxyl radical formation and ring destruction are observed. Hydrated electron in O₂ free solution attaches to the carbonyl oxygen and undergoes protonation yielding benzyl type radical. In air saturated 0.5 mmol dm^?3 solution using 15 kGy dose most part of acetovanillone is degraded, for complete mineralisation five times higher dose is required. The experiments clearly show that acetovanillone can be efficiently removed from water by applying irradiation technology.     

UV radiation: balancing risks and benefits

We use action spectra published by the International Commission on Illumination to examine diurnal, seasonal and latitudinal variations in erythemally weighted (sunburning) UV-a health risk, and vitamin D-weighted UV-a health benefit. Vitamin D-weighted UV is more strongly dependent on ozone and solar zenith angle. Consequently, its diurnal, seasonal and geographic variability is more pronounced than for erythemally weighted UV. We then investigate relationships between the two quantities. An algorithm is developed and used to relate vitamin D production to the widely used UV index, to help the public to optimize their exposure to UV radiation. In the summer at noon, there should at mid-latitudes be sufficient UV to photosynthesize optimal vitamin D in approximately 1 min for full body exposure, whereas skin damage occurs after approximately 15 min. Further, while it should be possible to photosynthesize vitamin D in the winter at mid-latitudes, the amount of skin that must be exposed is larger than from the hands and face alone. This raises the question of whether the action spectrum for vitamin D production is correct, since studies have reported that production of vitamin D is not possible in the winter at mid-latitudes.     

UV radiation and skin cancer in Norway

A distinct increase in skin cancer incidences is observed since the registration started in Norway in the 1950s. As UV radiation is assumed to be the main risk factor for skin cancer, hourly values of the UV irradiance were reconstructed for the period 1957–2005 for 17 of the Norwegian counties (58–70°N). For reconstruction, a radiation transfer model is run with total ozone amount and cloud information as meteorological input. Reconstructed hourly erythemally weighted UV irradiances for about 5 years are compared to measurements at four stations, two stations representing the north–south extension of Norway, and two stations at about 60°N representing the eastern inland – Western coastal contrasts. The agreement between reconstructed and measured UV varies between 0% for the northernmost site to 10–15% overestimation for the other locations. For clear sky, a reasonable agreement between reconstructed and measured data was found for all stations, while for overcast, an overestimation of 10–20% was found for all but the northernmost station. Both the cancer incidences and the reconstructed UV values have a distinct north–south increase. The UV increase towards south is mostly due to increasing solar elevation. The west to east increase is much smaller, and differences in UV are due to differences in both cloud optical thickness and total cloud amount. One additional outcome from this work is that long-term UV-data are reconstructed for Norway, data that can be used in further biological and medical studies related to UV effects.     

Fabrication of paper-based analytical device by silanisation of filter cellulose using alkyltrimethoxysilane coupled with UV radiation

A method was developed for the fabrication of microfluidic paper-based analytical devices (μPAD). This method was based on the silanisation of cellulose in filter paper using alkyltrimethoxysilane coupled with UV radiation. The filter paper sheet was hydrophobised by immersion in an octadecyltrimethoxysilane/heptane (OTMS/heptane) solution (0.25 vol. %) containing 5 vol. % of ethyl acetate (EtOAc). The hydrophobic-hydrophilic contrast was generated on the filter paper after the hydrophobised paper sheet was exposed to UV light with a metal mask creating the desired pattern on the sheet. The exposed area was oxidised to create a hydrophilic area, while the hydrophobic area was protected by the metal mask. The optimal conditions for the fabrication of μPAD were studied; these included ethyl acetate concentration (C_EtOAc), immersion time, octadecyltrimethoxysilane concentration (C_OTMS) and exposure time. This method is cost-effective and simple. In addition, different functional groups could be further grafted for various assay purposes. To demonstrate the feasibility of the μPAD in analytical applications, a flower-shaped μPAD with eight channels and eight detection units was fabricated and used to determine the nitrite content in pickled vegetables. The nitrite content (124 µg g^?1) in the sample determined by this method compared favourably with that measured using a standard method (137 µg g^?1).     

The influence of UV radiation on silk fibroin

An investigation into the influence of UV-irradiation on regenerated silk fibroin dissolved in water was carried out using UV-Vis and fluorescence spectroscopy. It was found that the absorption of regenerated silk fibroin in solution increased during UV-irradiation of the sample, most notably between 250 and 400 nm. Moreover, after UV-irradiation a wide peak emerged between 290 and 340 nm with maximum at about 305 nm. The new peak suggests that new photoproducts are formed during UV-irradiation of regenerated silk fibroin.The fluorescence of regenerated silk fibroin was observed at 305 nm, at 480 nm and at 601 nm after excitation at 275 nm. UV-irradiation caused fluorescence fading at 305 nm and at 601 nm. The increase of fluorescence was observed at 480 nm, probably due to formation of new photoproducts. After excitation at 305 nm the fluorescence of regenerated silk fibroin was observed at 340 nm and at 400 nm. UV-irradiation caused fluorescence fading at 340 nm. FTIR spectroscopy showed that primary structure of regenerated silk fibroin was not significantly affected by UV radiation. SDS-PAGE chromatography showed alterations of molecular weight of silk after UV exposure.     

Influence of UV radiation on four freshwater invertebrates

Laboratory tests confirmed a negative and variable response of the following four species to artificial UV radiation: Cypridopsis vidua, an ostracode; Chironomus riparius, a midge larvae; Hyalella azteca, an amphipod; and Daphnia magna, a daphnid. Severe damage occurred at UV-B irradiance ranging from 50 to 80% of incident summer values. Under constant exposure to UV and photosynthetically active radiation (PAR) the acute lethal response was recorded at 0.3, 0.8, 0.8 and 4.9 W m-2 UV-B for D. magna, H. azteca, C. riparius and C. vidua, respectively. Sublethal UV-B damage to invertebrates included impaired movement, partial paralysis, changes in pigmentation and altered water balance (bloating). A series of UV-B, UV-A and PAR treatments, applied separately and in combination, revealed a positive role for both UV-A and PAR in slowing down UV-B damage. Mean lethal concentration values of the species typically more tolerant to UV and PAR (Cypridopsis, Chironomus) decreased conspicuously when both UV-A and PAR were eliminated. For UV-B-sensitive species (Hyalella, Daphnia) these differences were notably smaller. We suggest that this gradation of sensitivity among the tested species demonstrates potential differences in repairing mechanisms which seem to work more efficiently for ostracodes and chironomids than for amphipods and daphnids. Manipulations with a cellulose acetate filter showed that lower range UV-B (280-290 nm), produced by FS-40 lamps, may cause excessive UV damage to invertebrates.     

UV index forecasts and measurements of health-effective radiation

While erythemal irradiance as a potentially damaging effect to the skin has been extensively studied and short-term forecasts have been issued to the public to reduce detrimental immediate and long-term effects such as sunburn and skin cancer by overexposure, beneficial effects to human health such as vitamin D(3) production by UV radiation and melatonin suppression by blue visible light have attained more and more attention, though both of them have not become part of forecasting yet. Using 4years of solar radiation data measured at the mid-latitude site Lindenberg (52°N), and forecast daily maximum UV index values, an overall good correspondence has been found. The data base of solar UV radiation and illuminance has also been used to analyze effects of clouds and aerosols on the effective irradiance. Optically thick clouds can strongly modify the ratios between erythemal and vitamin D(3) effective irradiance such that direct radiative transfer modeling of the latter in future UV forecasts should be preferably used. If parameterizations of vitamin D(3) effective irradiance from erythemal irradiance are used instead, the optical cloud depth would have to be taken into account to avoid an overestimation of vitamin D(3) with parameterizations neglecting cloud optical depth. Particular emphasis for the beneficial effects has been laid in our study on low exposure. Daily doses of solar irradiation for both vitamin D(3) and melatonin suppression do not reach minimum threshold doses even with clear sky and unobstructed horizon during the winter months.     

Degradation of ROMP-based bio-renewable polymers by UV radiation

The degradation of a bio-renewable polymer under UV exposure was studied using various methods. Degradation of the bio-renewable polymer increased with increasing exposure time. Enhanced cross-link density in the early stage of degradation was confirmed by Soxhlet extraction. Tensile testing showed a transition from ductile failure to brittle fracture. Surface cracks and embrittlement were primary reasons for most reductions in mechanical properties, such as tensile strength and breaking strain. The effects of degradation were confined to the surface of thick bio-based polymer specimens, confirmed by both SEM and PAS-FTIR. Depth profile studies of degraded samples showed that the concentration of oxidation products, such as hydroxyl and carbonyl groups, varied with depth depending on the diffusion of oxygen.     

负载型双金属铁钯纳米催化降解微囊藻毒素-LR

探讨膨润土负载双金属铁钯(B-Fe/Pd)纳米材料催化降解微囊藻毒素-LR(MC-LR)的效果和机理.结果表明,在5mgL-1的MC-LR溶液中加入0.1g的纳米B-Fe/Pd,初始pH为6.86,振荡速度为250rmin-1,温度为298K的条件下,经过180min后对MC-LR的降解效率达96.86%.降解溶液的UV-vis和HPLC结果表明,MC-LR在238nm的特征峰消失.通过SEM-EDS、XRD、FTIR和XPS技术对B-Fe/Pd降解前后的样品进行表征,结果显示,降解后纳米B-Fe/Pd中的Fe形成了Fe的氧化物与氢氧化物.降解过程的动力学拟合结果显示,B-Fe/Pd降解MC-LR符合伪一级动力学,活化能为12.77kJmol-1.根据降解、表征和动力学结果分析其反应机理,推断是MC-LR首先吸附在B-Fe/Pd颗粒表面,接着纳米铁与水反应产生的氢气在Pd的催化作用下产生大量的氢自由基,并与MC-LR发生链式还原反应,使得MC-LR中最具毒性的共轭双键断开而降解.     

Label-free immunosensing of microcystin-LR using a gold electrode modified with gold nanoparticles

The hepatotoxic microcystins, especially microcystin?CLR (MC?CLR), are causing serious problems to public health and fisheries. We describe here a label-free amperometric immunosensor for rapid determination of MC?CLR in water sample. The sensor was prepared by immobilizing antibody on a gold electrode coated with L-cysteine-modified gold nanoparticles. The stepwise self-assembly of the immunosensor was monitored and characterized by means of electrochemical impedance spectroscopy and differential pulse voltammetry. A 0.60?mmol L^?1 solution of hydroquinone was used as the electron mediator. The immunosensor was incubated with MC?CLR at 25?°C for 20?min, upon which the differential pulse voltammetric current changed linearly over the concentration range from 0.05 to 15.00???g L^?1, with a detection limit of 20?ng L^?1. The developed biosensor was used to determine MC?CLR in spiked crude algae samples. The recovery was in the range from 95.6 to 105%. This method is simple, economical and efficient, this making it potentially suitable for field analysis of MC-LR in crude algae and water samples.

PVC-laponite nanocomposites: Enhanced resistance to UV radiation

Laponite, a clay mineral, was treated by intercalation of two different phthalocyanine amide polymers based on aliphatic amine (MF-PcAl) as well as an aromatic one (MF-PcAr). The intercalation of the amide polymers was followed by X-ray diffraction (XRD). The different forms of laponite even in its untreated form were incorporated into poly(vinyl chloride) (PVC) formulations via melt blending method to produce PVC-laponite nanocomposites of exfoliated type which was confirmed by XRD. The stabilization mode of the incorporated laponites against UV radiation is discussed based on scanning electron microscopy (SEM), XRD, UV-vis absorption and transmission spectra, electron paramagnetic resonance (EPR), differential scanning calorimetry (DSC) and mechanical properties. Improved resistance to the UV degradative effect was explained on the light of the ability of the clay to scatter the light and to trap any growing radicals as well in addition to the sacrificing role of phthalocyanines by absorbing the incident light on the expense of the PVC and transmitting the rest of the light in another non-harmful form such as heat.     

Photo-degradation of PADC by UV radiation at various wavelengths

The effects of ultraviolet (UV) photons at different wavelengths (namely UVA, UVA + B and UVC) on PADC (polyallyl diglycol carbonate) were investigated in this study. The chemical modifications were studied by Fourier Transform Infrared (FTIR) spectrometry and the corresponding nano-mechanical properties were also determined. The scission process could be revealed by the decreasing net absorbance at particular wavelengths in the infrared (IR) spectra. On the other hand, the cross-linking was indicated by the increased hardness and reduced modulus determined with a nanoindenter. UVA caused no chemical modifications as most of the UV photons in this range were not absorbed by PADC. Both UVA + B and UVC irradiation caused scission of the chemical bonds, which was also manifested by the faster chemical etching rates. The bulk etch rate increased from 1.37 to 5.73 μm/h for 60 h of UVA + B exposure for 3 h of chemical etching, and increased to 5.13 μm/h for 60 h of UVC exposure. For 3 h of etching, the bulk etch rate remained unchanged for UVC exposures longer than 20 h. The saturation of the bulk etch rate was due to formation of cross-linked structures on the surface of the PADC samples. It was also observed that a UVC exposure caused a comparatively higher bulk etch rate at the beginning of etching. However, the bulk etch rate decreased with the depth of the PADC sample due to the lower rate of oxygen diffusion into deeper regions.     

Stereoselective Triplet‐Sensitised Radical Reactions of Furanone Derivatives

The stereo‐ and regioselectivity of triplet‐sensitised radical reactions of furanone derivatives have been investigated. Furanones 7 a , b were excited to the ³ππ* state by triplet energy transfer from acetone. Intramolecular hydrogen abstraction then occurred such that hydrogen was transferred from the tetrahydropyran to the β position of the furanone moiety. Radical combination of the tetrahydropyranyl and the oxoallyl radicals led to the final products 8 a , b . In the intramolecular reaction, overall, a pyranyl group adds to the α position of the furanone. The effect of conformation was first investigated with compounds 9 a , b carrying an additional substituent on the tether between the furanone and pyranyl moiety. Further information on the effect of conformation and the relative configuration at the pyranyl anomeric centre and the furanone moiety was obtained from the transformations of the glucose derivatives 12 , 14 , 17 and 18 . Radical abstraction occurred at the anomeric centre and at the 5′‐position of the glucosyl moiety. Computational studies of the hydrogen‐abstraction step were carried out with model structures. The activation barriers of this step for different stereoisomers and the abstraction at the anomeric centre and at the 6‘‐position of the tetrahydropyranyl moiety were calculated. The results of this investigation are in accordance with experimental observations. Furthermore, they reveal that the reactivity and regioselectivity are mainly determined in the hydrogen‐abstraction step. Intramolecular hydrogen abstraction (almost simultaneous electron and proton transfer) in ³ππ* excited furanones only takes place under restricted structural conditions in a limited number of conformations that are defined by the relative configuration of the substrates. It is observed that in the biradical intermediate, back‐hydrogen transfer occurs leading to the starting compound. In the case of glucose derivatives, this reaction led to epimerisation at the anomeric centre.     

Sensitised near-infrared emission from lanthanides using a covalently-attached Pt(II) fragment as an antenna group

In a series of heterodinuclear complexes in which a Pt(PPh3)2(catecholate) chromophore is covalently linked to a lanthanide tris(diketonate) unit, sensitised near-IR emission from Yb(III), Nd(III) and Er(III) occurs on excitation of the Pt(II) chromophore at 520 nm.     

XPS analysis of PTFE decomposition due to ionizing radiation

X-ray induced photoelectron spectroscopy (XPS) in combination with depth profiling has been used to investigate the structure and the degradation mechanism of PTFE bonded gas diffusion electrodes (GDE). The XP-spectra of these electrodes show distinctly separated binding states of the C1s electrons at E_b=292 eV and E_b=286 eV. These binding states are related to the carbon in the (CF₂)_n configuration (C1s_CF2) and the graphite (C1s_graphite), respectively. The C1s_CF2 signal decreases are induced by both X-ray exposure and ion etching. Simultaneously a decrease of the F1s signal has been approved. The intensity ratio of F1s to C1s_CF2 has increased during the experiment. These results indicate a decomposition of PTFE which creates CF fractions, leading to an excess intensity in the energetic range between the C1s binding states of the PTFE and the graphite. Although both the F1s and the C1s spectra are strongly modified by ionizing radiation, samples are comparable, when exposition doses are equal.