Effect of Graphene Characteristics on Morphology and Performance of Composite Noble Metal-Reduced Graphene Oxide SERS Substrate

Graphene/noble metal substrates for surface enhanced RAMAN scattering (SERS) possess synergistically improved performance, due to the strong chemical enhancement mechanism accounted to graphene and the electromagnetic mechanism raised from the metal nanoparticles. However, only the effect of noble metal nanoparticles characteristics on the SERS performance was studied so far. In attempts to bring a light to the effect of quality of graphene, in this work, two different graphene oxides were selected, slightly oxidized GOS (20%) with low aspect ratio (1000) and highly oxidized (50%) GOG with high aspect ratio (14,000). GO and precursors for noble metal nanoparticles (NP) simultaneous were reduced, resulting in rGO decorated with AgNPs and AuNPs. The graphene characteristics affected the size, shape, and packing of nanoparticles. The oxygen functionalities actuated as nucleation sites for AgNPs, thus GOG was decorated with higher number and smaller size AgNPs than GOS. Oppositely, AuNPs preferred bare graphene surface, thus GOS was covered with smaller size, densely packed nanoparticles, resulting in the best SERS performance. Fluorescein in concentration of 10⁻⁷ M was detected with enhancement factor of 82 × 10⁴. This work demonstrates that selection of graphene is additional tool toward powerful SERS substrates.     

Development of Analytical Strategies for the Determination of Olive Fruit Bioactive Compounds Using UPLC-HRMS and HPLC-DAD. Chemical Characterization of Kolovi Lesvos Variety as a Case Study

In this study, an overall survey regarding the determination of several bioactive compounds in olive fruit is presented. Two methodologies were developed, one UPLC-Q-TOF-MS method for the determination of olive fruit phenolic compounds and one HPLC-DAD methodology targeting the determination of pigments (chlorophylls and carotenoids), tocopherols (α-, β, -γ, δ-) and squalene. Target and suspect screening workflows were developed for the thorough fingerprinting of the phenolic fraction of olives. Both methods were validated, presenting excellent performance characteristics, and can be used as reliable tools for the monitoring of bioactive compounds in olive fruit samples. The developed methodologies were utilized to chemical characterize the fruits of the Kolovi olive variety, originating from the island of Lesvos, North Aegean Region, Greece. Twenty-five phenolic compounds were identified and quantified in Kolovi olives with verbascoside, hydroxytyrosol, oleacein and oleomissional found in significantly high concentrations. Moreover, 12 new bioactive compounds were identified in the samples using an in-house suspect database. The results of pigments analysis suggested that Kolovi variety should be characterized as low pigmentation, while the tocopherol and squalene content was relatively high compared to other olive varieties. The characterization of Kolovi olive bioactive content highlighted the high nutritional and possible economic value of the Kolovi olive fruit.     

Visualizing defects and pore connectivity within metal–organic frameworks by X-ray transmission tomography

Metal–Organic Frameworks (MOFs) have the potential to change the landscape of molecular separations in chemical processes owing to their ability of selectively binding molecules. Their molecular sorting properties generally rely on the micro- and meso-pore structure, as well as on the presence of coordinatively unsaturated sites that interact with the different chemical species present in the feed. In this work, we show a first-of-its-kind tomographic imaging of the crystal morphology of a metal–organic framework by means of transmission X-ray microscopy (TXM), including a detailed data reconstruction and processing approach. Corroboration with Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) images shows the potential of this strategy for further (non-destructively) assessing the inner architecture of MOF crystals. By doing this, we have unraveled the presence of large voids in the internal structure of a MIL-47(V) crystal, which are typically thought of as rather homogeneous lattices. This challenges the established opinion that hydrothermal syntheses yield relatively defect-free material and sheds further light on the internal morphology of crystals.

TXM-tomography unraveled large macropore defects within a MIL-47(V) MOF crystal. These pores do not seem to be well connected and they show a preferential orientation.     

Synthesis of 2D Germanane (GeH): a New,Fast, and Facile Approach

Germanane (GeH), a germanium analogue of graphane, has recently attracted considerable interest because its remarkable combination of properties makes it an extremely suitable candidate to be used as 2D material for field effect devices, photovoltaics, and photocatalysis. Up to now, the synthesis of GeH has been conducted by substituting Ca by H in a β‐CaGe₂ layered Zintl phase through topochemical deintercalation in aqueous HCl. This reaction is generally slow and takes place over 6 to 14 days. The new and facile protocol presented here allows to synthesize GeH at room temperature in a significantly shorter time (a few minutes), which renders this method highly attractive for technological applications. The GeH produced with this method is highly pure and has a band gap (E_g) close to 1.4 eV, a lower value than that reported for germanane synthesized using HCl, which is promising for incorporation of GeH in solar cells.     

Natural examples of -complete sets in analysis

The purpose of this paper is to show that given any non-negative real number , the set of entire functions whose order is equal to is -complete, and the set of all sequences of entire functions whose orders converge to is -complete.

     

Sharp Sobolev type inequalities for higher fractional derivativesInégalités optimales de type Sobolev pour les dérivées fractionelles d'ordre supérieur

On $\text{R}{}^{\mathrm{n}}$, n?1 and n≠2, we prove the existence of a sharp constant for Sobolev inequalities with higher fractional derivatives. Let s be a positive real number. For n>2s and $\text{q=}\text{2n}\text{n?2s}$ any function $\text{f∈}\text{H}{}^{\mathrm{s}}\text{(}\text{R}{}^{\mathrm{n}}\text{)}$ satisfies

$\text{6f6}{}^2{}_{\mathrm{q}}\text{?S}{}_{\mathrm{n,s}}\text{(?Δ)}{}^{\mathrm{s/2}}\text{f}{}^2{}_2\text{,}$

where the operator (?Δ)^s in Fourier spaces is defined by $\text{(?Δ)}{}^{\mathrm{s}}\text{f}\text{(k):=(2π|k|)}{}^{\mathrm{2s}}\text{f}\text{(k)}$. To cite this article: A. Cotsiolis, N.C. Tavoularis, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 801–804.     

Elliptic problems with discontinuities

In this paper we prove two existence theorems for elliptic problems with discontinuities. The first one is a noncoercive Dirichlet problem and the second one is a Neumann problem. We do not use the method of upper and lower solutions. For Neumann problems we assume that f is nondecreasing. We use the critical point theory for locally Lipschitz functionals.     

Embeddings of 2-spheres in 4-manifolds

We prove that the action of the orthogonal group of an integral, unimodular lattice whose rank and signature satisfy a certain indefiniteness condition acts transitively on pairs of mutually orthogonal elements with the same isometric invariants.     

The swelling interface number as a criterion for prediction of diffusional solute release mechanisms in swellable polymers

When a glassy polymer containing a uniformly dispersed solute is brought in contact with a penetrant, solute diffusion will be associated with the transport mechanism and penetration velocity of the penetrant in the polymer. Analysis and prediction of mechanisms of diffusional solute release may be obtained through a new dimensionless number, the swelling interface number, Sw, which compares the relative mobilities of the penetrant and the solute in the presence of macromolecular relaxations in the polymer. It is shown that a sufficient and necessary criterion for time-independent diffusional solute release rates from these swellable systems is that the Sw be smaller than 10^?2. The swelling interface number Sw may be related to easily determined structural and thermodynamic parameters of the solute/polymer/penetrant system. Preliminary experimental results of dynamic water swelling of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) and diffusional release of theophylline from initially glassy copolymers show that decreasing values of Sw are related to increased pseudo-case-II transport kinetics of the solute.     

Modelling of drug diffusion through swellable polymeric systems

A drug diffusion model for the case of diffusion of an initially uniformly distributed drug through a polymeric matrix is presented and solved. Drug diffusion from a single surface is analyzed for the case of countercurrent diffusion of a solvent which is thermodynamically compatible with the polymer. Due to swelling, considerable volume expansion is observed leading to a moving-boundary diffusion problem. Drug concentration profiles within the polymer and drug release rates can be determined. The results are in agreement with experimental data obtained for the system of KCl distributed in hydrophilic hydroxypropyl methyl cellulose matrices, in the form of tablets.