Histopathological Analysis of UVB and IR Interaction in Rat Skin

To determine the chronic skin effects caused by the interaction of infrared and ultraviolet B radiations, male Rattus norvegicus (Wistar) (2 months old) were exposed for 15 days to infrared radiation (600–1500 nm, with a peak at 1000 nm, n = 12) for 30 min (1080 J cm^?2) (IRo); to ultraviolet B radiation (peak emission at 313 nm, n = 9) for 90 min (55.08 J cm^?2) (UVB); to infrared radiation followed after 90 min by ultraviolet B (n = 6) (IRUVB) and to ultraviolet B followed after 90 min by infrared radiation (n = 9) (UVBIR). Skin samples were collected and histopathological analysis showed the presence of acanthosis, parakeratotic and orthokeratotic hyperkeratosis, intraepidermal pustules, keratin pearls, detachment of epidermis, collagen necrosis, inflammatory infiltrate, vasodilation, basal cell vacuolization and superficial dermis degeneration both in UVB and UVBIR treatments. IRUVB animals showed the same characteristics as above except for parakeratotic hyperkeratosis, keratin pearls and superficial dermis degeneration. To conclude, infrared radiation exposure after ultraviolet B irradiation increases skin damage without protecting the tissue, while infrared radiation exposure before ultraviolet B irradiation showed a protective effect against ultraviolet skin damage.     

Nonvisual Opsins and the Regulation of Peripheral Clocks by Light and Hormones

The molecular clock machinery is conserved throughout evolution. However, how environmental cues are perceived has evolved in such a way that peripheral clocks in mammals require a variety of signals, including hormones. On the other hand, in nonmammalian cells able to directly detect light, light seems to play a major role in the synchronization of the clock. The interaction between perception of circadian light by nonvisual opsins and hormones will be discussed under the perspective of clock synchronization at the molecular level.     

Surface composition of PdCuAu ternary alloys: a combined LEIS and XPS study

PdCuAu ternary alloy samples with different composition were synthesized on top of ZrO₂‐modified porous stainless steel disks by the sequential electroless deposition technique. The structure, morphology and bulk composition of the samples were characterized by X‐ray diffraction (XRD), scanning electron microscopy and energy dispersive X‐ray spectroscopy (EDX). Complete alloy formation with a pure fcc phase for the Pd₇₁Cu₂₆Au₃, Pd₇₀Cu₂₅Au₅ and Pd₆₇Cu₂₄Au₉ samples and a bcc structure for the Pd₆₂Cu₃₆Au₂ and Pd₆₀Cu₃₇Au₃ samples were obtained upon annealing at 500 °C for 120 h as revealed by XRD. A combination of low‐energy ion scattering (LEIS) and X‐ray photoelectron spectroscopy (XPS) was used to investigate the surface properties of the PdCuAu alloys. XPS results confirmed alloy formation under the annealing conditions. XPS analysis also revealed that the near‐surface regions of the alloys became enriched in Pd with respect to the bulk composition determined by EDX. In contrast, LEIS and angle‐resolved XPS analyses showed that the top‐most surface layers in all samples were copper‐rich compared with the bulk composition. This high Cu surface concentration could impart resistance to bulk sulfide formation to the PdCuAu alloy membranes. Copyright © 2015 John Wiley & Sons, Ltd.     

Optimal design of experiments applied to headspace solid phase microextraction for the quantification of vicinal diketones in beer through gas chromatography-mass spectrometric detection

Vicinal diketones, namely diacetyl (DC) and pentanedione (PN), are compounds naturally found in beer that play a key role in the definition of its aroma. In lager beer, they are responsible for off-flavors (buttery flavor) and therefore their presence and quantification is of paramount importance to beer producers. Aiming at developing an accurate quantitative monitoring scheme to follow these off-flavor compounds during beer production and in the final product, the head space solid-phase microextraction (HS-SPME) analytical procedure was tuned through experiments planned in an optimal way and the final settings were fully validated. Optimal design of experiments (O-DOE) is a computational, statistically-oriented approach for designing experiences that are most informative according to a well-defined criterion. This methodology was applied for HS-SPME optimization, leading to the following optimal extraction conditions for the quantification of VDK: use a CAR/PDMS fiber, 5 ml of samples in 20 ml vial, 5 min of pre-incubation time followed by 25 min of extraction at 30 °C, with agitation. The validation of the final analytical methodology was performed using a matrix-matched calibration, in order to minimize matrix effects. The following key features were obtained: linearity (R² > 0.999, both for diacetyl and 2,3-pentanedione), high sensitivity (LOD of 0.92 μg L⁻¹ and 2.80 μg L⁻¹, and LOQ of 3.30 μg L⁻¹ and 10.01 μg L⁻¹, for diacetyl and 2,3-pentanedione, respectively), recoveries of approximately 100% and suitable precision (repeatability and reproducibility lower than 3% and 7.5%, respectively). The applicability of the methodology was fully confirmed through an independent analysis of several beer samples, with analyte concentrations ranging from 4 to 200 g L⁻¹.     

Luminescent Di‐ and Trinuclear Boron Complexes Based on Aromatic Iminopyrrolyl Spacer Ligands: Synthesis,Characterization, and Application in OLEDs

New bis‐ and tris(iminopyrrole)‐functionalized linear (1,2‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 2 ), 1,3‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 3 ), 1,4‐(HNC₄H₃‐C(H)?N)₂‐C₆H₄ ( 4 ), 4,4′‐(HNC₄H₃‐C(H)?N)₂‐(C₆H₄‐C₆H₄) ( 5 ), 1,5‐(HNC₄H₃C‐(H)?N)₂‐C₁₀H₆ ( 6 ), 2,6‐(HNC₄H₃C‐(H)?N)₂‐C₁₀H₆ ( 7 ), 2,6‐(HNC₄H₃C‐(H)?N)₂‐C₁₄H₈ ( 8 )) and star‐shaped (1,3,5‐(HNC₄H₃‐C(H)?N‐1,4‐C₆H₄)₃‐C₆H₃ ( 9 )) π‐conjugated molecules were synthesized by the condensation reactions of 2‐formylpyrrole ( 1 ) with several aromatic di‐ and triamines. The corresponding linear diboron chelate complexes (Ph₂B[1,3‐bis(iminopyrrolyl)‐phenyl]BPh₂ ( 10 ), Ph₂B[1,4‐bis(iminopyrrolyl)‐phenyl]BPh₂ ( 11 ), Ph₂B[4,4′‐bis(iminopyrrolyl)‐biphenyl]BPh₂ ( 12 ), Ph₂B[1,5‐bis(iminopyrrolyl)‐naphthyl]BPh₂ ( 13 ), Ph₂B[2,6‐bis(iminopyrrolyl)‐naphthyl]BPh₂ ( 14 ), Ph₂B[2,6‐bis(iminopyrrolyl)‐anthracenyl]BPh₂ ( 15 )) and the star‐shaped triboron complex ([4′,4′′,4′′′‐tris(iminopyrrolyl)‐1,3,5‐triphenylbenzene](BPh₂)₃ ( 16 )) were obtained in moderate to good yields, by the treatment of 3 – 9 with B(C₆H₅)₃. The ligand precursors are non‐emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π‐conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time‐dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13 , in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples ( 11 , 12 , 14 , and 15 ), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO–LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π‐system, to afford green to yellow emissions. Organic light‐emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m^?2, for single layer devices, increasing to 4400 cd m^?2 when a hole‐transporting layer is used.     

3D Study of the Morphology and Dynamics of Zeolite Nucleation

The principle aspects and constraints of the dynamics and kinetics of zeolite nucleation in hydrogel systems are analyzed on the basis of a model Na‐rich aluminosilicate system. A detailed time‐series EMT‐type zeolite crystallization study in the model hydrogel system was performed to elucidate the topological and temporal aspects of zeolite nucleation. A comprehensive set of analytical tools and methods was employed to analyze the gel evolution and complement the primary methods of transmission electron microscopy (TEM) and nuclear magnetic resonance (NMR) spectroscopy. TEM tomography reveals that the initial gel particles exhibit a core–shell structure. Zeolite nucleation is topologically limited to this shell structure and the kinetics of nucleation is controlled by the shell integrity. The induction period extends to the moment when the shell is consumed and the bulk solution can react with the core of the gel particles. These new findings, in particular the importance of the gel particle shell in zeolite nucleation, can be used to control the growth process and properties of zeolites formed in hydrogels.     

Surface‐Functionalized Nanoparticles by Olefin Metathesis: A Chemoselective Approach for In Vivo Characterization of Atherosclerosis Plaque

The use of click chemistry reactions for the functionalization of nanoparticles is particularly useful to modify the surface in a well‐defined manner and to enhance the targeting properties, thus facilitating clinical translation. Here it is demonstrated that olefin metathesis can be used for the chemoselective functionalization of iron oxide nanoparticles with three different examples. This approach enables, in one step, the synthesis and functionalization of different water‐stable magnetite‐based particles from oleic acid‐coated counterparts. The surface of the nanoparticles was completely characterized showing how the metathesis approach introduces a large number of hydrophilic molecules on their coating layer. As an example of the possible applications of these new nanocomposites, a focus was taken on atherosclerosis plaques. It is also demonstrated how the in vitro properties of one of the probes, particularly its Ca²⁺‐binding properties, mediate their final in vivo use; that is, the selective accumulation in atherosclerotic plaques. This opens promising new applications to detect possible microcalcifications associated with plaque vulnerability. The accumulation of the new imaging tracers is demonstrated by in vivo magnetic resonance imaging of carotids and aorta in the ApoE^?/? mouse model and the results were confirmed by histology.