Using nanosecond laser pulses to debond the glass-EVA layer from silicon photovoltaic modules.

The active silicon cell of a solar photovoltaic (PV) panel is covered by an ethylenevinylacetate (EVA) adhesive and a protective top glass layer. Separating this glass-EVA layer from the underlying silicon represents a bottleneck for recycling PV panels. Previous work has shown that the EVA-Si bond can be weakened by applying a continuous source of heat to melt the EVA. In this paper, a new method using nanosecond laser pulses is demonstrated to induce transient melting selectively at the EVA-Si interface. This impulsive heating method can cleanly separate the glass-EVA layer from the silicon in both model and commercial multicrystalline PV panels. The dependence of this debonding on parameters like laser pulse fluence (laser pulse energy per area), wavelength, applied pressure, and scan speed were characterized. For model PV panels, the single-pulse laser fluences required for spontaneous separation of the assembly under the force of gravity, were 0.23, 0.32 and 0.78 J/cm2 for 355 nm, 532 nm and 1064 nm, respectively. The use of shorter wavelengths reduces the laser fluence needed for debonding, while higher fluences can compensate for faster laser beam scanning rates. Optical and electron microscopy images of the Si surfaces before and after laser irradiation show that the textured antireflection layer is destroyed but the silver metal grid remains intact. Preliminary experiments using 532 nm pulses showed that the laser debonding method could remove the glass-EVA layer from sections of decommissioned commercial PV panels, even when the top glass layer was densely cracked.

Generating Stable Nitrogen Bubble Layers on Poly(methyl methacrylate) Films by Photolysis of 2-Azidoanthracene.

2-Azidoanthracene (2N3-AN) can act as a photochemical source of N2 gas when dissolved in an optically transparent polymer such as poly(methyl methacrylate) (PMMA). Irradiation at 365 or 405 nm of a 150 µm-thick polymer film submerged in water causes the rapid appearance of a surface layer of bubbles. The rapid appearance of surface bubbles cannot be explained by normal diffusion of N2 through the polymer and likely results from internal gas pressure buildup during the reaction. For an azide concentration of 0.1 M and a light intensity of 140 mW/cm2, the yield of gas bubbles is calculated to be approximately 40%. The dynamics of bubble growth depend on the surface morphology, light intensity, and 2N3-AN concentration. A combination of nanoscale surface roughness, high azide concentration, and high light intensity is required to attain the threshold N2 gas density necessary for rapid, high-yield bubble formation. The N2 bubbles adhered to the PMMA surface and survived for days under water. The ability to generate stable gas bubbles "on demand" using light permits the demonstration of photoinduced flotation and patterned bubble arrays.

Effects of solvent and micellar encapsulation on the photostability of avobenzone.

The photodegradation of avobenzone (AV), the only ultraviolet filter molecule approved by the Food and Drug Administration to absorb UVA radiation, is an important problem in sunscreen formulations. In this paper, the photophysics and photostability of AV in various solvent systems and in aqueous micelles are studied. AV in its keto-enol tautomer functions as an effective UVA protection agent. AV is highly susceptible to photoinduced diketonization in both nonpolar solvents and in aqueous aggregates but is considerably more stable in polar, protic solvents like methanol. By studying its stability in different surfactant solutions, we show that incorporation of AV into sodium dodecylsulfate (SDS) micelles can achieve stability levels comparable to neat methanol. Steady-state spectral shifts, fluorescence anisotropy, and time-resolved fluorescence decay measurements are all consistent with AV experiencing a polar environment after micellar encapsulation. It is proposed that AV is encapsulated in the palisade layer of the SDS micelles, which allows access to water molecules that facilitate the re-formation of the enol form after photon absorption and relaxation. Although the detailed mechanism of AV tautomerization remains unclear, this work suggests that tuning the chemical microenvironment of AV may be a useful strategy for improving sunscreen efficacy.

Correction: Photochemical degradation of the UV filter octyl methoxycinnamate in solution and in aggregates.

Correction for 'Photochemical degradation of the UV filter octyl methoxycinnamate in solution and in aggregates' by Kerry M. Hanson et al., Photochem. Photobiol. Sci., 2015, 14, 1607-1616.

Hybrid Molecule-Nanocrystal Photon Upconversion Across the Visible and Near-Infrared.

The ability to upconvert two low energy photons into one high energy photon has potential applications in solar energy, biological imaging, and data storage. In this Letter, CdSe and PbSe semiconductor nanocrystals are combined with molecular emitters (diphenylanthracene and rubrene) to upconvert photons in both the visible and the near-infrared spectral regions. Absorption of low energy photons by the nanocrystals is followed by energy transfer to the molecular triplet states, which then undergo triplet-triplet annihilation to create high energy singlet states that emit upconverted light. By using conjugated organic ligands on the CdSe nanocrystals to form an energy cascade, the upconversion process could be enhanced by up to 3 orders of magnitude. The use of different combinations of nanocrystals and emitters shows that this platform has great flexibility in the choice of both excitation and emission wavelengths.

Photochemical degradation of the UV filter octyl methoxycinnamate in solution and in aggregates.

The photodegradation of the ultraviolet (UV) filter octyl methoxycinnamate (OMC) is investigated in both dilute solution and in aggregated form. In dilute solution, the ratio of trans and cis isomers achieved at the photostationary state is solvent-dependent because of variations in the isomerization quantum yield. The two isomeric forms at the photostationary state are highly resistant to further photodegradation and no other UVA-absorbing species are formed. Aggregation of OMC, either in a neat film or in aqueous colloidal suspensions, leads to irreversible photodegradation of the molecule and the formation of multiple photoproducts. In addition to previously identified photoproducts like the UVB-absorbing cis and trans isomers and photodimers, we find photoproduct species whose absorption extends into the UVA. Characterization of the photophysical properties of these species indicates that they have long-lived excited-states (τf > 1 ns, 400 nm), unlike the isomeric forms of OMC (τf < 30 ps, 266 nm), and that excitation at 405 nm can sensitize the formation of singlet oxygen. These results show that the environment of OMC affects the photochemistry of the molecule and that the environmental conditions must be taken into account when considering the molecule's stability. In particular, aggregation of OMC molecules results in complex photochemistry that can produce species whose absorption extends into UVA and are capable of generating reactive oxygen species.

Synthesis and photophysical properties of a "face-to-face" stacked tetracene dimer.

A covalently linked tetracene dimer has been prepared and its molecular structure is characterized by (1)H NMR and MALDI-TOF mass spectroscopy, and elemental analysis. The minimized molecular structure reveals that the tetracene subunits in a dimer adopt a "face-to-face" stacked configuration. Its absorption spectrum differs significantly from that of the monomeric counterpart in solution, suggesting the presence of strong interactions between the two tetracene subunits. In solution, the fluorescence spectrum is dominated by a band at around 535 nm, due to an oxidative impurity. In the longer wavelength range, a short-lived lower energy emission can be identified as the intrinsic emission of the dimer. In a polystyrene matrix or at low temperatures, the lifetime of the lower energy emission lengthens and it becomes more prominent. We suggest that the interactions between the two tetracene subunits produce a short-lived, lower energy "excimer-like" state. The fluorescence decays show no observable dependence on an applied magnetic field, and no obvious evidence of significant singlet fission is found in this dimer. This research suggests that even though there are strong electronic interactions between the tetracene subunits in the dimer, singlet fission cannot be achieved efficiently, probably because the formation of "excimer-like" states competes effectively with singlet fission.

Application of nonlinear optical microscopy for imaging skin.

Recent advances in the use of nonlinear optical microscopy (NLOM) in skin microscopy are presented. Nonresonant spectroscopies including second harmonic generation, coherent anti-Stokes Raman and two-photon absorption are described and applications to problems in skin biology are detailed. These nonlinear techniques have several advantages over traditional microscopy methods that rely on one-photon excitation: intrinsic 3D imaging with <1 microm spatial resolution, decreased photodamage to tissue samples and penetration depths up to 1,000 microm with the use of near-infrared lasers. Thanks to these advantages, nonlinear optical spectroscopy has become a powerful tool to study the physical and biochemical properties of the skin. Structural information can be obtained using the response of endogenous chemical species in the skin, such as collagen or lipids, indicating that optical biopsy may replace current invasive, time-consuming traditional histology methods. Insertion of specific probe molecules into the skin provides the opportunity to monitor specific biochemical processes such as skin transport, molecular penetration, barrier homeostasis and ultraviolet radiation-induced reactive oxygen species generation. While the field is quite new, it seems likely that the use of NLOM to probe structure and biochemistry of live skin samples will only continue to grow.

Two-photon standing-wave fluorescence correlation spectroscopy.

A fluorescence correlation spectroscopy experiment that combines two-photon excitation and a standing-wave interference pattern is presented. The experimental correlation function can be analyzed using a simple expression involving (1) an exponential decay with time constant tau(f), which reflects diffusion across the interference fringes, and (2) a longer-lived decay with time constant tau(omega), which reflects diffusion in and out of the focal spot. The diffusion of Rhodamine 110 in water and ethylene glycol is measured using this method. The ability to simultaneously measure diffusion on two different time and lengthscales makes this experiment especially useful in environments where anomalous diffusion is suspected.

Sunscreen enhancement of UV-induced reactive oxygen species in the skin.

The number of UV-induced (20 mJ cm(-2)) reactive oxygen species (ROS) generated in nucleated epidermis is dependent upon the length of time the UV filter octocrylene, octylmethoxycinnamate, or benzophenone-3 remains on the skin surface. Two-photon fluorescence images acquired immediately after application of each formulation (2 mg cm(-2)) to the skin surface show that the number of ROS produced is dramatically reduced relative to the skin-UV filter control. After each UV filter remains on the skin surface for t=20 min, the number of ROS generated increases, although it remains below the number generated in the control. By t=60 min, the filters generate ROS above the control. The data show that when all three of the UV filters penetrate into the nucleated layers, the level of ROS increases above that produced naturally by epidermal chromophores under UV illumination.

Two-photon fluorescence imaging and reactive oxygen species detection within the epidermis.

Two-photon fluorescence microscopy is used to detect ultraviolet-induced reactive oxygen species (ROS) in the epidermis and the dermis of ex vivo human skin and skin equivalents. Skin is incubated with the nonfluorescent ROS probe dihydrorhodamine, which reacts with ROS such as singlet oxygen and hydrogen peroxide to form fluorescent rhodamine-123. Unlike confocal microscopic methods, two-photon excitation provides depth penetration through the epidermis and dermis with little photodamage to the sample. This method also provides submicron spatial resolution such that subcellular areas that generate ROS can be detected. In addition, comparative studies can be made to determine the effect of applied agents (drugs, therapeutics) upon ROS levels at any layer or cellular region within the skin.

Dietary lutein reduces ultraviolet radiation-induced inflammation and immunosuppression.

Ultraviolet radiation (UVR) promotes skin cancer development by mutagenic, immunosuppressive, and oxidative-stress-inducing mechanisms; however, certain antioxidants may counteract and prevent UVR-induced photodamage. Lutein is a xanthophyll carotenoid with potent antioxidant activity. Because reactive oxygen species (ROS) are believed to have a role in UVR-induced skin damage, we investigated whether lutein can modify UVR effects including the tissue swelling response to midrange UVR (280-320 nm, ultraviolet B (UVB) radiation) and UVB suppression of contact hypersensitivity (CHS) in both the local and the systemic models of UV-induced immunosuppression. We found that compared to mice fed the standard laboratory diet, mice fed dietary lutein demonstrated significant inhibition of ear swelling owing to UVB radiation. Mice exposed to 1700 J per m2 UVB radiation four times at daily intervals and then sensitized to dinitrofluorobenzene at the site of irradiation showed a decreased CHS response upon challenge. This suppression by UVB radiation was significantly inhibited by lutein feeding. When UVB radiation was given at a single dose of 10,000 J per m2 to inhibit the induction of CHS at a distant, nonirradiated site, no effect of lutein was seen. Finally, lutein accumulated in the skin of mice following diet supplementation and was shown to decrease ROS generation following UVR exposure. Thus, lutein modulates the skin's response to UVR and may contribute to the defense against some of the deleterious effects of solar radiation.

Neonatal development of the stratum corneum pH gradient: localization and mechanisms leading to emergence of optimal barrier function.

Although basal permeability barrier function is established at birth, the higher risk for infections, dermatitis, and percutaneous absorption of toxic agents may indicate incomplete permeability barrier maturation in the early neonatal period. Since stratum corneum (SC) acidification in adults is required for normal permeability barrier homeostasis, and lipid processing occurs via acidic pH dependent enzymes, we hypothesized that, in parallel with the less acidic surface pH, newborn SC would exhibit signs of incomplete barrier formation. Fluorescence lifetime imaging reveals that neonatal rat SC acidification first becomes evident by postnatal day 3, in extracellular "microdomains" at the SC- stratum granulosum (SG) interface, where pH-sensitive lipid processing is known to occur. This localized acidification correlated temporally with efficient processing of secreted lamellar body contents to mature extracellular lamellar bilayers. Since expression of the key acidifying mechanism NHE1 is maximal just prior to birth, and gradually declines over the first postnatal week, suboptimal SC acidification at birth cannot be attributed to insufficient NHE1 expression, but could instead reflect reduced NHE1 activity. Expression of the key lipid processing enzyme, beta-glucocerebrosidase (beta-GlcCer'ase), develops similar to NHE1, excluding a lack of beta-GlcCer'ase protein as rate limiting for efficient lipid processing. These results define a postnatal development consisting of initial acidification in the lower SC followed by outward progression, which is accompanied by formation of mature extracellular lamellar membranes. Thus, full barrier competence appears to require the extension of acidification in microdomains from the SC/SG interface outward toward the skin surface in the immediate postnatal period.

Bioconvertible vitamin antioxidants improve sunscreen photoprotection against UV-induced reactive oxygen species.

The ability of sunscreens and antioxidants to deactivate highly destructive reactive oxygen species in human skin has remained inconclusive. Two-photon fluorescence imaging microscopy was used to determine the effect of sunscreen/antioxidant combinations upon UV-induced ROS generation in ex vivo human skin. A sunscreen combination containing octylmethoxycinnamate (Parsol MCX) and avobenzone (Parsol 1789) at SPF 8 and SPF 15 was tested for its ability to prevent UV radiation from generating ROS in the viable epidermal strata of ex vivo human skin. A UV dose equivalent to two hours of North American solar UV was used to irradiate the skin. Each sunscreen reduced the amount of ROS induced in the viable strata by a value consistent with the SPF level. UV photons that were not absorbed/scattered by the sunscreen formulations generated ROS within the viable epidermal layers. The addition of the bioconvertible antioxidants vitamin E acetate and sodium ascorbyl phosphate (STAY-C 50) improves photoprotection by converting to vitamins E and C, respectively, within the skin. The bioconversion forms an antioxidant reservoir that deactivates the ROS generated (within the strata granulosum, spinosum, and basale) by the UV photons that the sunscreens do not block in the stratum corneum.

NHE1 regulates the stratum corneum permeability barrier homeostasis. Microenvironment acidification assessed with fluorescence lifetime imaging.

The outermost epidermal layer, the stratum corneum (SC), exhibits an acidic surface pH, whereas the pH at its base approaches neutrality. NHE1 is the only Na(+)/H(+) antiporter isoform in keratinocytes and epidermis, and has been shown to regulate intracellular pH. We now demonstrate a novel function for NHE1, as we find that it also controls acidification of extracellular "microdomains" in the SC that are essential for activation of pH-sensitive enzymes and the formation of the epidermal permeability barrier. NHE1 expression in epidermis is most pronounced in granular cell layers, and although the surface pH of NHE1 knockout mice is only slightly more alkaline than normal using conventional pH measurements, a more sensitive method, fluorescence lifetime imaging, demonstrates that the acidic intercellular domains at the surface and of the lower SC disappear in NHE1 -/- animals. Fluorescence lifetime imaging studies also reveal that SC acidification does not occur through a uniform gradient, but through the progressive accumulation of acidic microdomains. These findings not only visualize the spatial distribution of the SC pH gradient, but also demonstrate a role for NHE1 in the generation of acidic extracellular domains of the lower SC, thus providing the acidification of deep SC interstices necessary for lipid processing and barrier homeostasis.

Two-photon fluorescence lifetime imaging of the skin stratum corneum pH gradient.

Two-photon fluorescence lifetime imaging is used to identify microdomains (1-25 microm) of two distinct pH values within the uppermost layer of the epidermis (stratum corneum). The fluorophore used is 2',7'-bis-(2-carboxyethyl)-5-(and-6)-carboxyfluorescein (BCECF), whose lifetime tau (pH 4.5, tau = 2.75 ns; pH 8.5, tau = 3.90 ns) is pH dependent over the pH range of the stratum corneum (pH 4.5 to pH 7.2). Hairless mice (SKH1-hrBR) are used as a model for human skin. Images (< or =50 microm x 50 microm) are acquired every 1.7 microm from the stratum corneum surface to the first viable layer (stratum granulosum). Acidic microdomains (average pH 6.0) of variable size (~1 microm in diameter with variable length) are detected within the extracellular matrix of the stratum corneum, whereas the intracellular space of the corneocytes in mid-stratum corneum (25 microm diameter) approaches neutrality (average pH 7.0). The surface is acidic. The average pH of the stratum corneum increases with depth because of a decrease in the ratio of acidic to neutral regions within the stratum corneum. The data definitively show that the stratum corneum acid mantle results from the presence of aqueous acidic pockets within the lipid-rich extracellular matrix.

Observation and quantification of ultraviolet-induced reactive oxygen species in ex vivo human skin.

Two-photon fluorescence imaging is used to detect UV-induced reactive oxygen species (ROS) in ex vivo human skin in this study. ROS (potentially H202, singlet oxygen or peroxynitrite [or all]) are detected after reaction with nonfluorescent dihydrorhodamine-123 (DHR) and the consequent formation of fluorescent rhodamine-123 (R123). The cellular regions at each epidermal stratum that generate ROS are identified. R-123 fluorescence is detected predominately in the lipid matrix of the stratum corneum. In contrast, the strongest R123 fluorescence signal is detected in the intracellular cytoplasm of the viable epidermal keratinocytes. A simple bimolecular one-step kinetic model is used for estimating the upper bound of the number of ROS that are generated in the skin and that react with DHR. After ultraviolet-B radiation (280-320 nm) (UVB) equivalent to 2 h of noonday summer North American solar exposure (1600 J m(-2) UVB), the model finds that 14.70 x 10(-3) mol of ROS that react with DHR are generated in the stratum corneum of an average adult-size face (258 cm(-2)). Approximately 10(-4) mol are potentially generated in the lower epidermal strata. The data show that two-photon fluorescence imaging can be used to detect ROS in UV-irradiated skin.