253 research outputs found

    Spontaneous formation of optically induced surface relief gratings

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    A model based on Fick's law of diffusion as a phenomenological description of the molecular motion, and on the coupled mode theory, is developped to describe single-beam surface relief grating formation in azopolymers thin films. It allows to explain the mechanism of spontaneous patterning, and self-organization. It allows also to compute the surface relief profile and its evolution in time with good agreement with experiments

    Microbubble PhoXonic resonators: Chaos transition and transfer

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    We report the activation of optomechanical chaotic oscillations in microbubble resonators (MBRs) through a blue-side excitation of its optical resonances. We confirm the sequence of quasi-periodical oscillation, spectral continuum and aperiodic motion; as well as the transition to chaos without external feedback or modulation of the laser source. In particular, quasi periodic transitions and a spectral continuum are reported for MBRs with diameters up to 600 μm, whereas only an abrupt transition into a spectral con- tinuum is observed for larger microbubbles

    Nonlinear optical effects and optomechanical oscillations in hollow Whispering Gallery Mode microresonators: coexistence, suppression, amplification and route to chaos

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    Whispering Gallery Mode (WGM) hollow microcavities turn out to be the site of an extremely rich and complex phenomenological scenario when pumped with a continuous-wave laser source. The coexistence of numerous non-linear and optomechanical effects have been reviewed in this paper. In our previous works we have investigated and described non-linear emissions as the stimulated Brillouin and Raman scattering, the degenerated and non-degenerated Kerr effects, such as four wave mixing (FWM). These effects happened concomitantly to parametric optomechanical oscillations which are the consequence of the radiation pressure. We have confirmed the regenerative oscillation of acoustic eigenmodes of the cavity leading to parametric instabilities and the activation of optomechanical chaotic oscillations. Finally, we have demonstrated that the blue-side excitation of WGM resonances lead to the chaos transition with a spectral evolution depending on the cavity size

    Sigma-electrons responsible for cooperativity and ring equalization in hydrogen-bonded supramolecular polymers

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    We have quantum chemically analyzed the cooperative effects and structural deformations of hydrogen-bonded urea, deltamide, and squaramide linear chains using dispersion-corrected density functional theory at BLYP-D3(BJ)/TZ2P level of theory. Our purpose is twofold: (i) reveal the bonding mechanism of the studied systems that lead to their self-assembly in linear chains; and (ii) rationalize the C-C bond equalization in the ring moieties of deltamide and squaramide upon polymerization. Our energy decomposition and Kohn-Sham molecular orbital analyses reveal cooperativity in all studied systems, stemming from the charge separation within the sigma-electronic system by charge transfer from the carbonyl oxygen lone pair donor orbital of one monomer towards the sigma* N-H antibonding acceptor orbital of the neighboring monomer. This key orbital interaction causes the C=O bonds to elongate, which, in turn, results in the contraction of the adjacent C-C single bonds that, ultimately, makes the ring moieties of deltamide and squaramide to become more regular. Notably, the pi-electron delocalization plays a much smaller role in the total interaction between the monomers in the chain.Theoretical Chemistr

    Analytical approaches to RNA profiling data for the identification of genes enriched in specific cells

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    We have recently developed a novel method for the affinity purification of the complete suite of translating mRNA from genetically labeled cell populations. This method permits comprehensive quantitative comparisons of the genes employed by each specific cell type. We provide a detailed description of tools for analysis of data generated with this and related methodologies. An essential question that arises from these data is how to identify those genes that are enriched in each cell type relative to all others. Genes relatively specifically employed by a cell type may contribute to the unique functions of that cell, and thus may become useful targets for development of pharmacological tools for cell-specific manipulations. We describe here a novel statistic, the specificity index, which can be used for comparative quantitative analysis to identify genes enriched in specific cell populations across a large number of profiles. This measure correctly predicts in situ hybridization patterns for many cell types. We apply this measure to a large survey of CNS cell-specific microarray data to identify those genes that are significantly enriched in each population Data and algorithms are available online (www.bactrap.org)

    Diquat Derivatives: Highly Active, Two-Dimensional Nonlinear Optical Chromophores with Potential Redox Switchability

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    In this article, we present a detailed study of structure−activity relationships in diquaternized 2,2′-bipyridyl (diquat) derivatives. Sixteen new chromophores have been synthesized, with variations in the amino electron donor substituents, π-conjugated bridge, and alkyl diquaternizing unit. Our aim is to combine very large, two-dimensional (2D) quadratic nonlinear optical (NLO) responses with reversible redox chemistry. The chromophores have been characterized as their PF_6^− salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Their visible absorption spectra are dominated by intense π → π^* intramolecular charge-transfer (ICT) bands, and all show two reversible diquat-based reductions. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering with an 800 nm laser, and Stark spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β_0. The directly and indirectly derived β values are large and increase with the extent of π-conjugation and electron donor strength. Extending the quaternizing alkyl linkage always increases the ICT energy and decreases the E_(1/2) values for diquat reduction, but a compensating increase in the ICT intensity prevents significant decreases in Stark-based β_0 responses. Nine single-crystal X-ray structures have also been obtained. Time-dependent density functional theory clarifies the molecular electronic/optical properties, and finite field calculations agree with polarized HRS data in that the NLO responses of the disubstituted species are dominated by ‘off-diagonal’ β_(zyy) components. The most significant findings of these studies are: (i) β_0 values as much as 6 times that of the chromophore in the technologically important material (E)-4′-(dimethylamino)-N-methyl-4-stilbazolium tosylate; (ii) reversible electrochemistry that offers potential for redox-switching of optical properties over multiple states; (iii) strongly 2D NLO responses that may be exploited for novel practical applications; (iv) a new polar material, suitable for bulk NLO behavior

    Parametrical optomechanical oscillations in phoxonic whispering gallery mode resonators

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    We report on the experimental and theoretical analysis of parametrical optomechanical oscillations in hollow spherical phoxonic whispering gallery mode resonators due to radiation pressure. The optically excited acoustic eigenmodes of the phoxonic cavity oscillate regeneratively leading to parametric oscillation instabilities

    Parathyroidectomy and survival in a cohort of Italian dialysis patients: results of a multicenter, observational, prospective study

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    Background: Severe secondary hyperparathyroidism (SHPT) is associated with mortality in end stage kidney disease (ESKD). Parathyroidectomy (PTX) becomes necessary when medical therapy fails, thus highlighting the interest to compare biochemical and clinical outcomes of patients receiving either medical treatment or surgery. Methods: We aimed to compare overall survival and biochemical control of hemodialysis patients with severe hyperparathyroidism, treated by surgery or medical therapy followed-up for 36 months. Inclusion criteria were age older than 18 years, renal failure requiring dialysis treatment (hemodialysis or peritoneal dialysis) and ability to sign the consent form. A control group of 418 patients treated in the same centers, who did not undergo parathyroidectomy was selected after matching for age, sex, and dialysis vintage. Results: From 82 Dialysis units in Italy, we prospectively collected data of 257 prevalent patients who underwent parathyroidectomy (age 58.2 ± 12.8 years; M/F: 44%/56%, dialysis vintage: 15.5 ± 8.4 years) and of 418 control patients who did not undergo parathyroidectomy (age 60.3 ± 14.4 years; M/F 44%/56%; dialysis vintage 11.2 ± 7.6 y). The survival rate was higher in the group that underwent parathyroidectomy (Kaplan–Meier log rank test = 0.002). Univariable analysis (HR 0.556, CI: 0.387–0.800, p = 0.002) and multivariable analysis (HR 0.671, CI:0.465–0.970, p = 0.034), identified parathyroidectomy as a protective factor of overall survival. The prevalence of patients at KDOQI targets for PTH was lower in patients who underwent parathyroidectomy compared to controls (PTX vs non-PTX: PTH < 150 pg/ml: 59% vs 21%, p = 0.001; PTH at target: 18% vs 37% p = 0.001; PTH > 300 pg/ml 23% vs 42% p = 0.001). The control group received more intensive medical treatment with higher prevalence of vitamin D (65% vs 41%, p = 0.0001), calcimimetics (34% vs 14%, p = 0.0001) and phosphate binders (77% vs 66%, p = 0.002). Conclusions: Our data suggest that parathyroidectomy is associated with survival rate at 36 months, independently of biochemical control. Lower exposure to high PTH levels could represent an advantage in the long term. Graphical abstract: [Figure not available: see fulltext.]
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