Atom-specific identification of adsorbed chiral molecules by photoemission

The study of chiral adsorbed molecules is important for an analysis of enantioselectivity in heterogeneous catalysis. Here we show that such molecules can be identified through circular dichroism in core-level photoemission arising from the chiral carbon atoms in stereoisomers of 2,3-butanediol molecules adsorbed on Si(100), using circularly polarized x rays. The asymmetry in the carbon 1s intensity excited by right and left circularly polarized light is readily observed, and changes sign with the helicity of the radiation or handedness of the enantiomers; it is absent in the achiral form of the molecule. This observation demonstrates the possibility of determining molecular chirality in the adsorbed phase

Oxygen vacancy clusters in bulk cerium oxide and the impact of gold atoms

Ceria is important for catalysis due to its ability to form and utilize oxygen vacancies during redox reactions. Understanding the dynamic formation of the oxygen vacancies has contributed to the development of efficient catalytic processes. Here, we demonstrate the presence of oxygen vacancy clusters in the bulk of ceria and gold/ceria catalysts upon anaerobic carbon monoxide oxidation and describe their interplay with the orbital hybridization of Ce3+ 4f and 5d states. Observations are made using in situ X-ray Raman scattering spectroscopy at O K-and Ce N4,5-edges and in situ X-ray diffraction. These, combined with multiplet calculations, allow detection of the formation of Ce3+ in gold/ceria upon low temperature carbon monoxide oxidation. The modifications observed at the O K-edge reflect the rearrangement of the bulk oxygen sublattice. Density-functional theory calculations show vacancy ordering in the bulk, and explain modifications at the O K-edge, involving the hybridization of the Ce 4f and 5d and O 2p orbitals

The biocompatibility of titanium in a buffer solution: compared effects of a thin film of TiO2 deposited by MOCVD and of collagen deposited from a gel

This study aims at evaluating the biocompatibility of titanium surfaces modified according two different ways: (i) deposition of a bio-inert, thin film of rutile TiO2 by chemical vapour deposition (MOCVD), and (ii) biochemical treatment with collagen gel, in order to obtain a bio-interactive coating. Behind the comparison is the idea that either the bio-inert or the bio-active coating has specific advantages when applied to implant treatment, such as the low price of the collagen treatment for instance. The stability in buffer solution was evaluated by open circuit potential (OCP) for medium time and cyclic voltametry. The OCP stabilized after 5104 min for all the specimens except the collagen treated sample which presented a stable OCP from the first minutes. MOCVD treated samples stabilized to more electropositive values. Numeric results were statistically analysed to obtain the regression equations for long time predictable evolution. The corrosion parameters determined from cyclic curves revealed that the MOCVD treatment is an efficient way to improve corrosion resistance. Human dermal fibroblasts were selected for cell culture tests, taking into account that these cells are present in all bio-interfaces, being the main cellular type of connective tissue. The cells grew on either type of surface without phenotype modification. From the reduction of yellow, water-soluble 3-(4,5-dimethyldiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT cytotoxicity test), MOCVD treated samples offer better viability than mechanically polished Ti and collagen treated samples as well. Cell spreading, as evaluated from microscope images processed by the program Sigma Scan, showed also enhancement upon surface modification. Depending on the experimental conditions, MOCVD deposited TiO2 exhibits different nanostructures that may influence biological behaviour. The results demonstrate the capacity of integration in simulated physiologic liquids for an implant pretreated by either method

Large-area polycrystalline α-MoO3 thin films for IR photonics

In recent years, the excitation of surface phonon polaritons (SPhPs) in van der Waals materials received wide attention from the nanophotonics community. Alpha-phase Molybdenum trioxide (α-MoO3), a naturally occurring biaxial hyperbolic crystal, emerged as a promising polaritonic material due to its ability to support SPhPs for three orthogonal directions at different wavelength bands (range 10–20 µm). Here, we report on the fabrication, structural, morphological, and optical IR characterization of large-area (over 1 cm2 size) α-MoO3 polycrystalline film deposited on fused silica substrates by pulsed laser deposition. Due to the random grain distribution, the thin film does not display any optical anisotropy at normal incidence. However, the proposed fabrication method allows us to achieve a single α-phase, preserving the typical strong dispersion related to the phononic response of α-MoO3 flakes. Remarkable spectral properties of interest for IR photonics applications are reported. For instance, a polarization-tunable reflection peak at 1006 cm−1 with a dynamic range of ∆R = 0.3 and a resonance Q-factor as high as 53 is observed at 45◦ angle of incidence. Additionally, we report the fulfillment of an impedance matching condition with the SiO2 substrate leading to a polarization-independent almost perfect absorption condition (R < 0.01) at 972 cm−1 which is maintained for a broad angle of incidence. In this framework our findings appear extremely promising for the further development of mid-IR lithography-free, scalable films, for efficient and large-scale sensors, filters, thermal emitters, and label-free biochemical sensing devices operating in the free space, using far-field detection setups

Large-area polycrystalline α\alpha-MoO3 thin films for IR photonics

In recent years, excitation of surface phonon polaritons (SPhPs) in van der Waals materials received wide attention from the nanophotonics community. Alpha-phase Molybdenum trioxide ($\alpha$-MoO3), a naturally occurring biaxial hyperbolic crystal, emerged as a promising polaritonic material due to its ability to support SPhPs for three orthogonal directions at different wavelength bands (range 10-20 $\mu$m). Here, we report on the fabrication and IR characterization of large-area (over 1 cm$^2$ size) $\alpha$-MoO3 polycrystalline films deposited on fused silica substrates by pulsed laser deposition. Single alpha-phase MoO3 films exhibiting a polarization-dependent reflection peak at 1006 cm$^{-1}$ with a resonance Q-factor as high as 53 were achieved. Reflection can be tuned via changing incident polarization with a dynamic range of $\Delta$R=0.3 at 45 deg. incidence angle. We also report a polarization-independent almost perfect absorption condition (R<0.01) at 972 cm$^{-1}$ which is preserved for a broad angle of incidence. The development of a low-cost polaritonic platform with high-Q resonances in the mid-infrared (mid-IR) range is crucial for a wide number of functionalities including sensors, filters, thermal emitters, and label-free biochemical sensing devices. In this framework our findings appear extremely promising for the further development of lithography-free, scalable films, for efficient and large-scale devices operating in the free space, using far-field detection setups.Comment: 17 pages, 12 figure

Tripartite Relationship Among Synaptic, Amyloid, and Tau Proteins: An In Vivo and Postmortem Study

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Increases in a Pro-inflammatory Chemokine, MCP-1, Are Related to Decreases in Memory Over Time

Objective: To determine the longitudinal relationship between monocyte chemotactic protein 1 (MCP-1)/CCL2 and memory function in older adults.Methods: We examined longitudinal plasma MCP-1/CCL2 levels and a longitudinal verbal memory measure (CVLT-II 20’ recall) in a sample of 399 asymptomatic older adults (mean age = 72.1). Total visits ranged from 1 to 8, with an average time of 2.1 years between each visit, yielding 932 total observations. In order to isolate change over time, we decomposed MCP-1/CCL2 into subject-specific means and longitudinal deviations from the mean. The decomposed MCP-1/CCL2 variables were entered as predictors in linear mixed effects models, with age at baseline, sex, and education entered as covariates and recall as the longitudinal outcome. In follow-up analyses, we controlled for global cognition and APOE genotype, as well as baseline vascular risk factors. We also examined the specificity of findings by examining the longitudinal association between the MCP-1/CCL2 variables and non-memory cognitive tests.Results: Within-subject increases in MCP-1/CCL2 levels were associated with decreases in delayed recall (t = −2.65; p = 0.01) over time. Results were independent of global cognitive function and APOE status (t = −2.30, p = 0.02), and effects remained when controlling for baseline vascular risk factors (t = −1.92, p = 0.05). No associations were noted between within-subject increases in MCP-1/CCL2 levels and other cognitive domains.Conclusions: In an asymptomatic aging adult cohort, longitudinal increases in MCP-1/CCL2 levels were associated with longitudinal decline in memory. Results suggest that “healthy aging” is typified by early remodeling of the immune system, and that the chemokine, MCP-1/CCL2, may be associated with negative memory outcomes

“Liquid Biopsy” of White Matter Hyperintensity in Functionally Normal Elders

Background and Objective: In the aging brain, increased blood-brain barrier (BBB) leakage and white matter hyperintensity (WMH) on MRI are frequently presumed secondary to cerebral small vessel disease (cSVD) or endotheliopathy. We investigate this association in vivo by quantifying protein cargo from endothelial-derived exosomes (EDE), and comparing levels between two groups of functionally normal elders with and without WMH. In addition, we study associations of EDE proteins with upstream and downstream factors, such as inflammation and neurodegenerative changes, respectively.Methods: Twenty six neurologically normal older adults completed general health questionnaires, neuropsychological and physical examinations, and brain MRI. WMH was visually graded with modified Fazekas score of 2 or greater used to classify 11 subjects as cases, and 15 without WMH as controls. Plasma total exosomes were precipitated and EDEs enriched by sequential immuno-precipitations. In addition, we quantified three inflammatory cytokines from plasma and imaging variables on MRI. Group means were compared, the discriminant functions of biomarkers calculated, and the association of EDE biomarkers with plasma inflammatory markers, cognition, and imaging outcomes assessed via regression modeling.Results: Plasma levels of EDE cargo proteins GLUT1, LAT1, P-GP, and NOSTRIN were significantly higher in subjects with WMH in comparison to those without. In contrast, EDE levels of the marker with low expression in brain (VCAM1) were equal between groups. The effect sizes for each of the brain-expressed cargo proteins (GLUT1, LAT1, and P-GP) were such that age-adjusted logistic regressions revealed areas under the curve (AUC) with range of 0.82–0.89, differentiating subjects with WMH from those without. VCAM1 poorly discriminated between groups (AUC:0.55). Higher levels of all brain-expressed EDE proteins were also associated with lower cognitive function, unrelated to burden of WMH. Levels of LAT1 and P-GP were significantly inversely associated with global gray matter volumes, and EDE GLUT1, LAT-1, and P-GP concentrations were significantly associated with systemic IL-6 levels.Conclusion: In a case control study of clinically normal adults with and without WMH, concentrations of EDE proteins were significantly higher in subjects with WMH in comparison to controls. This work is a first step toward in vivo dissection of molecular changes in endothelia of functionally normal subjects with radiographic evidence of age-associated white matter disease

Minimalism in Radiation Synthesis of Biomedical Functional Nanogels

A scalable, single-step, synthetic approach for the manufacture of biocompatible, functionalized micro- and nanogels is presented. In particular, poly(N-vinyl pyrrolidone)-grafted-(aminopropyl)methacrylamide microgels and nanogels were generated through e-beam irradiation of PVP aqueous solutions in the presence of a primary amino-group-carrying monomer. Particles with different hydrodynamic diameters and surface charge densities were obtained at the variance of the irradiation conditions. Chemical structure was investigated by different spectroscopic techniques. Fluorescent variants were generated through fluorescein isothiocyanate attachment to the primary amino groups grafted to PVP, to both quantify the available functional groups for bioconjugation and follow nanogels localization in cell cultures. Finally, a model protein, bovine serum albumin, was conjugated to the nanogels to demonstrate the attachment of biologically relevant molecules for targeting purposes in drug delivery. The described approach provides a novel strategy to fabricate biohybrid nanogels with a very promising potential in nanomedicine