Nonlinear optical waveguides fabricated in Mg-doped LiNbO3 by swift heavy ion irradiation: anomalous photorefractive damage behavior

Using swift heavy fluorine ion irradiation, we have successfully fabricated optical waveguides in Mg-doped LiNbO₃ substrates. A systematic characterization of these structures has been carried out including refractive index profiles, propagation losses, nonlinear coefficients, and, specially, photorefractive optical damage. Step-like refractive index profiles with Δn _e ≈ 0.1 and Δn _o ≈ 0.2, propagation losses lower than 0.5 dB/cm and high nonlinear optical coefficients similar to those of the substrate have been obtained. Unexpectedly, the photorefractive damage is only moderately reduced with regard to the one presented in congruent LiNbO₃ waveguides. Specifically, light intensity damage thresholds I _th are only a factor 2 higher at RT and a factor 4 at 90 °C with regard to undoped waveguides. At this latter temperature, a remarkably high I _th = 30.000 W/cm² is reached. A final discussion on the observed anomalous optical damage behavior induced by swift heavy ion irradiation is also included.     

Gold-catalyzed direct cycloketalization of acetonide-tethered alkynes in the presence of water

A methodology for the direct preparation of bridged acetals from acetonide-tethered alkynes under gold catalysis in the presence of water has been developed. The bicyclic ring structures bearing a bridged five-membered ring arise from the regioselective bis-oxycyclization by initial attack of the oxygen atom to the internal alkyne carbon.     

Gold-catalyzed bis-cyclization of 1,2-diol- or acetonide-tethered alkynes. Synthesis of β-lactam-bridged acetals: a combined experimental and theoretical study

2-Azetidinone-tethered alkyn-1,2-diols or alkynyl acetonides, readily prepared from imines of (R)-2,3-O-isopropylideneglyceraldehyde, were used as starting materials for the regio- and diastereospecific catalytic bis-oxycyclization reaction in the presence of a gold/acid binary system. Interestingly, in contrast to the gold-catalyzed reactions of N-tethered terminal alkynes, which lead to the corresponding 6,8-dioxabicyclo[3.2.1]octane derivatives (proximal adduct), the reactions of substituted alkynic diols and acetonides under identical conditions gave the 7,9-dioxabicyclo[4.2.1]nonane derivatives (distal adducts) as the sole products, through exclusive 7-endo/5-exo bis-oxycyclizations by initial attack of the oxygen atom to the external alkyne carbon. Moreover, the mildness of the method allowed the incorporation of a 1,3-diyne moiety as reactive partner, displaying exquisite chemoselectivity toward the internal alkynic moiety. In order to confirm the mechanistic proposal, labeling studies with deuterium oxide have been performed. Besides, density functional calculations were performed to gain insight into the mechanisms of the bis-oxycyclization reactions.     

Real‐Time Operation of Photovoltaic Optoelectronic Tweezers: New Strategies for Massive Nano‐object Manipulation and Reconfigurable Patterning

Optical and optoelectronic techniques for micro‐ and nano‐object manipulation are becoming essential tools in nano‐ and biotechnology. Among optoelectronic manipulation platforms, photovoltaic optoelectronic tweezers (PVOTs) are an emergent technique that are particularly successful at producing permanent nanoparticle microstructures. New strategies to enhance the capabilities of PVOT, based on real‐time operation, are investigated. This optoelectronic platform uses z‐cut LiNbO₃:Fe substrates under excitation by a Gaussian light beam. Unexpected results show that during illumination, metallic particles previously deposited on the substrate are ejected from the light spot region. This behavior differs from the trapping phenomenon observed in previous work on PVOT operation, using a sequential method in which illumination is prior to particle manipulation. To discuss the results, a novel mechanism of charge exchange between particles and the ferroelectric substrate is proposed. Applications of this repulsion behavior are investigated. On the one hand, either particle repulsion or trapping in the illuminated region can be obtained by simply light switching on/off. On the other hand, by moving the light spot, different kinds of arbitrarily shaped tracks along the light path, either empty or filled with particles, are obtained. The results demonstrate new key capabilities of PVOT, such as pattern drawing, erasure, and reconfiguration.     

Photorefractive response and optical damage of LiNbO<Subscript>3</Subscript> optical waveguides produced by swift heavy ion irradiation

The photorefractive behaviour of a novel type of optical waveguides fabricated in LiNbO₃ by swift heavy ion irradiation is investigated. First, the electro-optic coefficient r ₃₃ of these guides that is crucial in the photorefractive effect is measured. Second, two complementary aspects of the photorefractive response are studied: (i) recording and light-induced and dark erasure of holographic gratings; (ii) optical beam degradation in single-beam configuration. The main photorefractive parameters, recording and erasing time constants, maximum refractive-index change and optical damage thresholds are determined.     

Nonlinear optical waveguides generated in lithium niobate by swift-ion irradiation at ultralow fluences

A novel method to produce optical waveguides is demonstrated for lithium niobate (LiNbO(3)). It is based on electronic excitation damage by swift ions, i.e., with energies at approximately 1 MeV/amu or above. The new technique uses high-energy medium-mass ions, such as Cl, with electronic stopping powers above the threshold value for amorphization (5-6 keV/nm), reaching the maximum value a few micrometers inside the crystal. At the ultralow fluence regime (10(12)-10(13) cm(-2)) an effective nanostructured medium is obtained that behaves as an optical waveguide where light propagates transversally to the amorphous nanotracks created by every single impact. The method implies a reduction of 4 orders of magnitude with respect to He implantation. The optical waveguides present reasonable losses (~10 dB/cm) and significant second-harmonic generation (SHG) and electro-optic (EO) responses (>50% bulk) for the lowest fluences.     

Development of insulin resistance during aging: involvement of central processes and role of adipokines

Aging in mammals associates with the development of peripheral insulin resistance. Additionally, adiposity usually increases with aging and this could play a relevant role in the gradual impairment of insulin action. In fact, fat accretion leads to changes in the expression and circulating concentrations of factors originated in adipose tissue like leptin, resistin and inflammatory cytokines which have been shown to modulate insulin signaling in insulin target tissues acting both, directly or through the central nervous system. Even insulin action on peripheral target tissues has been recently demonstrated to be partially mediated by its central action, suggesting that a decrease in central insulin action could be involved in the development of peripheral insulin resistance. In the present review we analyze the available research data on aging-associated insulin resistance making emphasis in the following aspects: 1) The time-course of development of overall insulin resistance and the evolution of changes in circulating adipokines; 2) The effect of caloric restriction and the decrease of adiposity in insulin action; 3) The influence of changes in the central action of factors like leptin or insulin in the development and maintenance of insulin resistance during aging.     

A Versatile Synthesis of β‐Lactam‐Fused Oxacycles through the Palladium‐Catalyzed Chemo‐, Regio‐, and Diastereoselective Cyclization of Allenic Diols

Chemo‐, regio‐ and stereocontrolled palladium‐catalyzed preparations of enantiopure morpholines, oxocines, and dioxonines have been developed starting from 2‐azetidinone‐tethered γ,δ‐, δ,ε‐, and ε,ζ‐allendiols. The palladium‐catalyzed cyclizative coupling reaction of γ,δ‐allendiols 2 with allyl bromide or lithium bromide was effective as 8‐endo cyclization by attack of the primary hydroxy group to the terminal allene carbon to afford enantiopure functionalized oxocines; whereas the palladium‐catalyzed cyclizative coupling reaction of 2‐azetidinone‐tethered ε,ζ‐allendiols 4 furnished dioxonines 16 through a totally chemo‐ and regioselective 9‐endo oxycyclization. By contrast, the palladium‐catalyzed cyclizative coupling reaction of 2‐azetidinone‐tethered δ,ε‐allendiols 3 with aryl and alkenyl halides exclusively generated six‐membered‐ring compounds 14 a and 15 a . These results could be explained through a 6‐exo cyclization by chemo‐ and regiospecific attack of the secondary hydroxy group to the internal allene carbon. Chemo‐ and regiocontrol issues are mainly influenced by the length of the tether rather than by the nature of the metal catalysts and substituents. This reactivity can be rationalized by means of density functional theory calculations.     

Elastic properties of the Ta–V system: bcc Ta0.33V0.67 and C15 TaV2

Resonant ultrasound spectroscopy was used to measure the elastic constants of bcc Ta_0.33V_0.67 over the temperature range 3.5–300?K; the results were compared to earlier measurements on C15 TaV₂. The temperature dependence of the polycrystalline shear modulus is completely different in the two phases; that of the bcc phase decreases with temperature whereas that of the C15 phases increases in an anomalous fashion. This difference is consistent with a model involving doubly-degenerate levels at the X point of the Brillouin zone in the C15 phase with the Fermi level lying near the doubly degenerate level. This model accounted for the unusual behaviour of the C15 phase. Debye temperatures were determined from the ultrasonic measurements: 295?K for the C15 phase and 315?K for the bcc phase.