UV Index on tilted surfaces

Solar ultraviolet erythemal irradiance (UVER) has been studied on inclined planes with different orientations in Valencia, Spain. To do this a platform was designed that could turn through 90 degrees on its own axis. The radiometers were inclined at an angle close to the latitude of Valencia (39.5 degrees N). Using two timers the platform could be turned through 90 degrees every 5 min. On clear or partially cloudy days, including those with different turbidity values, it was observed that the UVER showed a maximum at 1200 h GMT, very close to solar noon, in the north and south positions, while the maximum for east and west orientations was found at approximately one hour before and one hour after midday respectively. It was also observed how the irradiance for the south orientation was greater and for the north was less than for the horizontal plane, as well as the opposite performances of the east and west orientations, for four days close to the summer and winter solstices and each equinox. Some experimental results were also compared with the results from the SMARTS2.9 model for the same conditions. It was found that the model frequently overestimated the experimental data. With respect to the maximum calculated UV Index in the different planes this was always higher for the south orientation than for the north, while it was similar for east and west orientations throughout the year. Finally the accumulated erythemal dosage for the considered period was obtained as a function of phototype and orientation, confirming that the accumulated erythemal dosage decreased by around 37% in the north orientation compared to the horizontal value, while in the south position it was only 6% less and some 20% and 15% less in the east and west positions, respectively.     

Spectral shade ratios on horizontal and sun normal surfaces for single trees and relatively cloud free sky.

Spectral shade ratios, defined as the ratios of the spectral irradiances on horizontal and sun normal planes in the tree shade to those on a horizontal plane in sunlight, were calculated. These planes were in the shade of an isolated medium canopy density tree and a sparse canopy density tree at the tree shade sites of the centre, edge and trunk. The sun normal plane was employed as there are some activities that have exposures to parts of the body that are orientated in a sun normal plane. The horizontal plane shade ratios for the medium density canopy dropped by 47-56% from the ratios in the range 301 to 310 nm to the ratios in the range 391 to 400 nm. In absolute terms, the largest change in the shade ratio of 0.28 was for the centre and edge sites compared to 0.07 for the trunk. Similarly, for the sun normal plane, the ratio dropped by 40-49% with an absolute reduction of 0.19 for the edge and 0.04 for the trunk. For the sparse density canopy, the decrease in the shade ratios over the same wavelength range was a drop by 37-42% on a horizontal plane or, in absolute terms, a reduction by 0.22 for the edge and 0.13 for the trunk. Similarly, the decrease was 34-39% on the sun normal plane or, in absolute terms, a reduction by 0.19 for the edge and 0.12 for the trunk.     

UV cross-linking of unmodified DNA on glass surfaces

The performance of DNA microarrays strongly depends on their surface properties. Furthermore, the immobilization method of the capture molecules is of importance for the efficiency of the microarray in terms of sensitivity and specificity. This work describes the immobilization of single-stranded capture oligonucleotides by UV cross-linking on silanated (amino and epoxy) glass surfaces. Thereby we used amino (NH₂) and poly thymine/poly cytosine modifications of the capture sequences as well as unmodified capture molecules. The results were compared to UV cross-linking of the same DNA oligonucleotides on unmodified glass surfaces. Immobilization and hybridization efficiency was demonstrated by fluorescence and enzyme-induced deposition of silver nanoparticles. We found out that single-stranded DNA molecules do not require a special modification to immobilize them by UV cross-linking on epoxy- or amino-modified glass surfaces. However, higher binding rates can be achieved when using amino-modified oligonucleotides on an epoxy surface. The limit of detection for the used settings was 5 pM.     

On the maximum spreading diameter of impacting droplets on well-prepared solid surfaces

This paper presents a systematic study of liquid droplet impact on three polymer surfaces: poly(methyl methacrylate), poly(methyl methacrylate/n-butyl methacrylate), and poly(n-butyl methacrylate). Changing from one surface to the next represents an incremental variation in solid surface tensions of 5-6 mJ/m2. These surfaces were prepared through careful experimental procedures that were used for the determination of solid surface tensions from contact angles. Our data for the maximum spreading diameter of water and formamide impacting on these surfaces were compared with those predicted from literature models. Of the models selected, we modified the model of Pasandideh-Fard et al. [Phys. Fluids 1996, 8, 650] and the results yielded a least error of only 5.09 +/- 5.05% in the determination of the maximum spreading diameter. The improved model was also compared with literature data, and good agreement was found. Of course, any such comparisons would rely on accurate experimental impact dynamics data on carefully prepared surfaces.     

Routine measurement of erythemally effective UV irradiance on inclined surfaces

Measurements of erythemally weighted UV radiation are usually related to a horizontal surface. The radiation is weighted with the sensitivity of the human skin, but the surface of the human body has only few horizontal surfaces. Therefore the UV radiation on inclined surfaces has to be quantified to investigate UV effects on humans. To fulfill this task three fully automatic measuring systems were built to measure the erythemally weighted UV radiation in 27 directions within 2 min. This system measures routinely during the whole day and has now been in operation for nearly three years (in total 2000 measurement days) under any kind of meteorological conditions. The measurements provide the informations needed for further investigations concerning the UV effects on humans. The calibration of the erythemally weighting radiometers was performed in a way to provide reliable UV index measurements for all directions. The results of four exemplary measurement days in summer and winter for clear sky and overcast conditions are presented.     

Spectral UV irradiance on vertical surfaces: a case study

The UV spectral irradiance on horizontal and vertically oriented surfaces was measured throughout a cloudless day (18 July 1995) at Izana station, Tenerife, using a Bentham DTM300 spectroradiometer scanning from 290 to 500 nm in steps of 5 nm. Results show that irradiance measured on a horizontal surface is not proportional to irradiance on a vertical surface. The relation between the two depends upon orientation of the vertical surface, zenith angle and wavelength. At short UVB wavelengths surfaces directed toward the solar azimuth received their maximum irradiances much closer to solar noon than the maxima for longer wavelengths. Some vertical surfaces also received significantly more irradiance than the horizontal surface at long wavelengths during all but the central hours of the day, while at short wavelengths all vertical irradiances were less than the horizontal except for the measurements at the extreme ends of the day. Erythemally effective radiation followed the diurnal pattern of irradiations for short UVB wavelengths.     

Clean coupling of unfunctionalized porphyrins at surfaces to give highly oriented organometallic oligomers

The direct coupling of complex, functional organic molecules at a surface is one of the outstanding challenges in the road map to future molecular devices. Equally demanding is to meet this challenge without recourse to additional functionalization of the molecular building blocks and via clean surface reactions that leave no surface contamination. Here, we demonstrate the directional coupling of unfunctionalized porphyrin molecules--large aromatic multifunctional building blocks--on a single crystal copper surface, which generates highly oriented one-dimensional organometallic macromolecular nanostructures (wires) in a reaction which generates gaseous hydrogen as the only byproduct. In situ scanning tunneling microscopy and temperature programmed desorption, supported by theoretical modeling, reveal that the process is driven by C-H bond scission and the incorporation of copper atoms in between the organic components to form a very stable organocopper oligomer comprising organometallic edge-to-edge porphyrin-Cu-porphyrin connections on the surface that are unprecedented in solution chemistry. The hydrogen generated during the reaction leaves the surface and, therefore, produces no surface contamination. A remarkable feature of the wires is their stability at high temperatures (up to 670 K) and their preference for 1D growth along a prescribed crystallographic direction of the surface. The on-surface formation of directional organometallic wires that link highly functional porphyrin cores via direct C-Cu-C bonds in a single-step synthesis is a new development in surface-based molecular systems and provides a versatile approach to create functional organic nanostructures at surfaces.     

Self-assembly of normal alkanes on the Au (111) surfaces

The self-assembled monolayers (SAMs) of normal alkanes (n-C(n)H(2n+2)) with different carbon chain lengths (n=14-38) in the interfaces between alkane solutions (or liquids), and the reconstructed Au (111) surfaces have been systematically studied by means of scanning tunneling microscopy (STM). In contrast to previous studies, which concluded that some n-alkanes (n=18-26) can not form well-ordered structures on Au (111) surfaces, we observed SAM formations for all these n-alkanes without any exceptions. We find that gold reconstruction plays a critical role in the SAM formation. The alkane monolayers adopt a lamellar structure in which the alkane molecules are packed side-by-side, to form commensurate structures with respect to the reconstructed Au (111) surfaces. The carbon skeletons are found to lie flat on the surfaces, which is consistent with the infrared spectroscopic studies. Interestingly, we find that two-dimensional chiral lamellar structures form for alkanes with an even carbon number due to the specific packing of alkane molecules in a tilted lamella. Furthermore, we find that the orientation of alkane molecules deviates from the exact [011] direction, because of the intermolecular interactions among the terminal methyl groups of neighboring lamellae; this results in differences of molecular orientation between mirror structures of adjacent zigzag alkane lamellae. Structural models have been proposed, that shed new light on monolayer formation.     

Reversible oriented immobilization of histidine-tagged proteins on gold surfaces using a chelator thioalkane

The reversible oriented immobilization of proteins on solid surfaces is a prerequisite for the investigation of molecular interactions at interfaces or the construction of supramolecular assemblies. We demonstrate a generally applicable method using a synthetic chelator thioalkane which can self-assemble on a gold surface via its thiol group. It exposes its nitrilotriacetic acid group which serves as a chelator for transition metal ions. Reversible binding of a F_ab fragment modified with a C-terminal hexahistidine extension was monitored in situ using surface plasmon resonance. The directed immobilization of proteins on surfaces opens new ways for structural investigations of proteins and the development of biosensors.     

Intrinsic crazing and anisotropy of maximum recoverable extension in oriented glassy polycarbonate

The critical draw ratio for initiation of intrinsic crazing in polycarbonate below the glass transition temperature has been determined after preorientation in the melt. Even when referred to the isotropic state, this ratio is found to depend not only on the extent of preorientation but also to be distinctly anisotropic. Under the assumption that intrinsic crazing occurs at the maximum extension of the entanglement network, these results are incompatible with a strain dependent but homogeneous breakdown of the entanglement network, but can be interpreted in terms of departure from affine transformation of the radius of gyration of an entangled length.     

A general route to transform normal hydrophilic cloths into superhydrophobic surfaces

Herein, we describe a simple and inexpensive method for forming superhydrophobic cloths with the highest water contact angle of close to 180 degrees , in which normal commercial cloths serving as pristine materials are modified with suitable gold micro/nanostructures.     

Assembly of oriented zeolite monolayers and thin films on polymeric surfaces via hydrogen bonding

The b-oriented monolayers of microsized silicalite-1 crystals have been manually assembled on glass plate supported poly(ethylene oxide) (PEO), poly(vinyl alcohol) (PVA), chitosan, and poly(methyl methacrylate) (PMMA) thin films via hydrogen bonding with much enhanced binding strength and satisfactory degrees of coverage and close packing. The exerted pressure and rubbing time in the manual assembly do not affect the binding strength of the silicalite-1 monolayer on the glass plate supported polymeric film. This manual assembly has been further applied to fabricate zeolite monolayers on commercially available Plexiglas surfaces and b-oriented multilayered films of silicalite-1 crystals on glass plates. The assembly method established in this study provides a feasible way to produce zeolite monolayers on polymer-modified solid substrates and Plexiglas and to fabricate zeolite-polymer composite membranes by means of the layer-by-layer technique.     

Masterless soft lithography: patterning UV/ozone-induced adhesion on poly(dimethylsiloxane) surfaces

A novel microreactor-based photomask capable of effecting high resolution, large area patterning of UV/ozone (UVO) treatments of poly(dimethylsiloxane) (PDMS) surfaces is described. This tool forms the basis of two new soft lithographic patterning techniques that significantly extend the design rules of decal transfer lithography (DTL). The first technique, photodefined cohesive mechanical failure, fuses the design rules of photolithography with the contact-based adhesive transfer of PDMS in DTL. In a second powerful variation, the UVO masks described in this work enable a masterless soft lithographic patterning process. This latter method, UVO-patterned adhesive transfer, allows the direct transfer of PDMS-based polymer microstructures from a slab of polymer to silicon and other material surfaces. Both methods exploit the improved process qualities that result from the use of a deuterium discharge lamp to affect the UVO treatment to pattern complex, large area PDMS patterns with limiting feature sizes extending well below 1 microm (> or = 0.3 microm). The use of these structures as resists is demonstrated for the patterning of metal thin films. A time-of-flight secondary ion mass spectroscopy study of the process provides new insights into the mechanisms that contribute to the chemistry responsible for the interfacial adhesion of DTL transfers.     

Effect of pH and hydration on the normal and lateral interaction forces between alumina surfaces

Interaction forces between alumina surfaces were measured using an AFM-colloid probe method at different pHs. For an alpha-alumina-sapphire system at acidic pH, the force curve exhibited a well-defined repulsive barrier and an attractive minimum. At basic pH, the interactive force was repulsive at all separations with no primary minimum. Lateral force measurements under the same conditions showed that frictional forces were nearly an order of magnitude smaller at basic pH than those observed at acidic pH. This behavior was attributed to the hydration of the alumina surface. Normal and lateral force measurements with the strongly hydrated rho-alumina surfaces supported these findings.     

Using a family of dividing surfaces normal to the minimum energy path for quantum instanton rate constants

One of the outstanding issues in the quantum instanton (QI) theory (or any transition-state-type theory) for thermal rate constants of chemical reactions is the choice of an appropriate "dividing surface" (DS) that separates reactants and products. (In the general version of the QI theory, there are actually two dividing surfaces involved.) This paper shows one simple and general way for choosing DSs for use in QI theory, namely, using the family of (hyper) planes normal to the minimum energy path on the potential energy surface at various distances s along it. Here the reaction coordinate is not one of the dynamical coordinates of the system (which will in general be the Cartesian coordinates of the atoms), but rather simply a parameter which specifies the DS. It is also shown how this idea can be implemented for an N atom system in three-dimensional space in a way that preserves overall translational and rotational invariance. Numerical application to a simple system (the collinear H+H(2) reaction) is presented to illustrate the procedure.     

Molecular responses to stress induced in normal human caucasian melanocytes in culture by exposure to simulated solar UV

Melanocytes play a central role in the response of skin to sunlight exposure. They are directly involved in UV-induced pigmentation as a defense mechanism. However, their alteration can lead to melanoma, a process where the role of sun overexposure is highly probable. The transformation process whereby UV damage may result in melanoma initiation is poorly understood, especially in terms of UV-induced genotoxicity in pigmented cells, where melanin can act either as a sunscreen or as a photosensitizer. The aim of this study was to analyze the behavior of melanocytes from fair skin under irradiation mimicking environmental sunlight in terms of spectral power distribution. To do this, normal human Caucasian melanocytes in culture were exposed to simulated solar UV (SSUV, 300-400 nm). Even at relatively high doses (until 20 min exposure, corresponding to 12 kJ/m2 UV-B and 110 kJ/m2 UV-A), cell death was limited, as shown by cell viability and low occurrence of apoptosis (caspase-3 activation). Moreover, p53 accumulation was three times lower in melanocytes than in unpigmented cells such as fibroblasts after SSUV exposure. However, an important fraction of melanocyte population was arrested in G2-M phase, and this correlated well with a high induction level of the gene GADD45, 4 h after exposure. Among the genes involved in DNA repair, gene XPC was the most inducible because its expression increased more than two-fold 15 h after a 20 min exposure, whereas expression of P48 was only slightly increased. In addition, an early induction of Heme Oxygenase 1 (HO1) gene, a typical response to oxidative stress, was also observed for the first time in melanocytes. Interestingly, this induction remained significant when melanocytes were exposed to UV-A radiation only (320-400 nm), and stimulation of melanogenesis before irradiation further increased HO1 induction. These results were obtained with normal human cells after exposure to SSUV radiation, which mimicked natural sunlight. They provide new data related to gene expression and suggest that melanin in light skin could contribute to sunlight-induced genotoxicity and maybe to melanocyte transformation.     

Extracting maximum information from polarized surface vibrational spectra: application to etched, H-terminated Si(110) surfaces

A general method to maximize the information extracted from polarized surface absorption spectra is developed and applied to the study of etched Si(110) surfaces. In essence, this technique transforms spectra from the experimental reference frame, which is defined by the direction of the surface electric field during irradiation by s- and p-polarized light, into a more appropriate Cartesian reference frame defined by the surface normal and the plane of incidence. If the Cartesian reference frame is aligned with high symmetry directions of the system, significant spectral simplification can result. This analysis relies on the well-known boundary conditions on interfacial electric fields and is independent of any adsorbate screening or the effective dielectric constant of the adsorbate layer. The validity of this analysis is demonstrated on the spectra of NH4F-etched, H-terminated Si(110). The transition dipole moments of the symmetric and antisymmetric Si[Single Bond]H stretch modes associated with flat terraces are polarized along the [110] and [001] directions, respectively. Two additional modes with transition dipoles polarized along the [001] and [110] directions are assigned to defect species associated with microfaceting and other surface roughness. Data taken in two different experimental geometries are shown to be in excellent quantitative agreement, confirming the validity of the technique. Additionally, the measured adsorbate layer dielectric constant is in good agreement with previously reported values for hydrogen-terminated silicon surfaces.     

Interaction of rotationally aligned and of oriented molecules in gas phase and at surfaces

Recent developments concerning the generation of molecular beams containing oriented/aligned molecules will be reviewed and applications of such tools to the study of elementary processes occurring both in homogeneous and heterogeneous phases will be presented. First we will discuss the case of symmetric top molecules oriented by hexapoles. Here the molecular polarization is obtained by the use of an external field and allows to control which end of the molecular projectile is going to collide with the target. Then we will review the so-called collisional alignment, a molecular polarization phenomenon occurring in supersonic expansions of gaseous mixtures. The key feature, in this case, is the velocity dependence of the alignment degree, which allows the use of mechanical devices to filter out of the beam the molecules having either a random (statistical) or a preferential (non-statistical) spatial distribution of their rotational angular momentum J with respect to the molecular beam axis. The physical mechanisms underlying the collisional alignment will be resumed and some relevant gas-phase experiments demonstrating its occurrence will be illustrated. Application of such methodologies to the investigation of the stereodynamics of elementary processes occurring in gas-surface interaction will be presented and discussed for both weakly and strongly interacting systems.     

Evidence of the interaction of evaporated Pt nanoparticles with variously treated surfaces of highly oriented pyrolytic graphite

The interactions of Pt nanoparticles, deposited by evaporation onto highly oriented pyrolytic graphite surfaces modified by kiloelectronvolt Ar+ beam treatment, have been studied by X-ray photoelectron spectroscopy core-level line shape analysis. The C1s and Pt4f7/2 peaks were each considered to be composed of one asymmetric peak, and changes in their asymmetry parameters were used to study their interfacial interactions. In addition to these changes, strong signal intensity changes with time were found for both the C1s and Pt4f peaks, indicating an initial crystalline orientational instability of the Pt nanoparticles, which is supported by time-dependent high-resolution electron microscopy studies at elevated temperatures.