Photoluminescence spectroscopy of CdSe nanoparticles embedded in transparent glass

In this paper we present photoluminescence measurements of CdSe nanoparticles embedded in transparent glass. Sample is prepared using an original technique, which combines both heat treatment and ultraviolet laser irradiation. Photoluminescence spectra displayed one main emission band at 2.14 eV. We identify this bands energy as basic interband transition in CdSe nanoparticle. We calculated energy of basic (1s_h–1s_e) transition in spherical CdSe quantum dot (QD), within infinite potential barrier, in effective-mass approximation. On the basis of this model, average radius of synthesized CdSe QDs is about 3 nm, which is in consistence with AFM measurements and UV–VIS absorption measurements.     

A Rapid HPLC-UV Protocol Coupled to Chemometric Analysis for the Determination of the Major Phenolic Constituents and Tocopherol Content in Almonds and the Discrimination of the Geographical Origin

Reversed phase-high-pressure liquid chromatographic methodologies equipped with UV detector (RP-HPLC-UV) were developed for the determination of phenolic compounds and tocopherols in almonds. Nineteen samples of Texas almonds originating from USA and Greece were analyzed and 7 phenolic acids, 7 flavonoids, and tocopherols (−α, −β + γ) were determined. The analytical methodologies were validated and presented excellent linearity (r² > 0.99), high recoveries over the range between 83.1 (syringic acid) to 95.5% (ferulic acid) for within-day assay (n = 6), and between 90.2 (diosmin) to 103.4% (rosmarinic acid) for between-day assay (n = 3 × 3), for phenolic compounds, and between 95.1 and 100.4% for within-day assay (n = 6), and between 93.2–96.2% for between-day assay (n = 3 × 3) for tocopherols. The analytes were further quantified, and the results were analyzed by principal component analysis (PCA), and agglomerative hierarchical clustering (AHC) to investigate potential differences between the bioactive content of almonds and the geographical origin. A decision tree (DT) was developed for the prediction of the geographical origin of almonds proposing a characteristic marker with a concentration threshold, proving to be a promising and reliable tool for the guarantee of the authenticity of the almonds.     

Characterization of the Phenolic Fingerprint of Kolovi Extra Virgin Olive Oils from Lesvos with Regard to Altitude and Farming System Analyzed by UHPLC-QTOF-MS

Extra virgin olive oil (EVOO) is recognized for its nutritional virtues and the beneficial health effects deriving from its hydrophilic fraction (phenolic acids, phenolic alcohols, flavonoids, and secoiridoids). The phenolic compounds of EVOOs possess multiple biological properties such as antioxidant, antimicrobial, anticarcinogenic, and anti-inflammatory properties, among others. Considering that EVOOs produced in Greece are recognized as high-quality products due to their rich phenolic content, it is imperative to characterize Greek monovarietal EVOOs and ensure that their uniqueness is closely linked to their botanical and territorial origin. In this work, an ultra-high-performance liquid chromatography–quadrupole time-of-flight tandem mass spectrometry (UHPLC-QTOF-MS) analytical method combined with target and suspect screening was used to characterize monovarietal EVOOs of the Kolovi variety from Lesvos, and thereby establish their phenolic fingerprint. Overall, 25 phenols were determined, and the total quantification and semi-quantification results ranged between 251 and 1230 mg/kg, highlighting the high phenolic content of the Kolovi variety from the island of Lesvos in the North Aegean.     

Staleya guttiformis attachment on poly(tert-butylmethacrylate) polymeric surfaces

The attachment behaviour of Staleya guttiformis DSM 11458^T on poly(tert-butyl methacrylate) (P(tBMA)) polymeric surfaces has been studied. The electrostatic charge of the S. guttiformis cell surface (measured as zeta potential via microelectrophoresis) was −43.18 mV. S. guttiformis cells appeared weakly hydrophilic as the water contact angle measured on lawns of bacterial cells was found to be 55 ± 4.9°. It was found that while attaching on P(tBMA) surfaces, S. guttiformis cells produced extracellular polymeric substances (EPS) as observed from atomic force microscopy (AFM) and scanning electron microscopy (SEM) analysis. The AFM high resolution imaging revealed the nano-topography of the ‘free’ (the EPS that is produced by the bacterial cells, but no longer directly attached to the cells) EPS associated on the cell surface and also found on P(tBMA) surface. The ‘free’ EPS exhibited granular structure with lateral dimensions of 30–50 nm and a vertical nano-roughness of 7–10 nm. Another type of the EPS secreted by S. guttiformis cells appeared as a hydogel substance, presumably polysaccharide that formed a biopolymer network that facilitated bacterial attachment.     

Rapid-freeze-quench magnetic circular dichroism of intermediate X in ribonucleotide reductase: new structural insight

To elucidate the electronic structure of intermediate X in the oxygen activation reaction of the R2 subunit of ribonucleotide reductase, a protocol has been developed to perform magnetic circular dichroism (MCD) on a rapid-freeze-quench, strain free optical sample. RFQ-MCD data have been collected on intermediate X in the double mutant of R2, Y122/Y356F. While X has been reported to exhibit a broad absorption band at 365 nm, there are at least 10 electronic transitions observed at low-temperature MCD. From C0/D0 ratios, the transitions of X can be divided into three regions: 16 000-22 000 cm-1 region involving spin-allowed ligand field transitions of the Fe(IV), 23 000-24 000 cm-1 region of spin-forbidden, spin-flip transitions on the Fe(IV), and the charge transfer (CT) region from 26 000 to 32 000 cm-1. The C0/D0 ratios from d --> d and CT transitions strongly support significant Fe(IV) character coupled into the paramagnetic center. Ligand field (spin-allowed d --> d region) analysis allows the bis-mu-oxo and mu-oxo plus other monoanionic bridge possibilities for the structure of intermediate X to be distinguished, providing new insight into the molecular mechanism of the cluster formation in R2.     

A Spectroscopic and Molecular Modelling Study of the Nature of the Association Complexes of Nile Red with Cyclodextrins

The polarity-sensitive fluorescent dye Nile Red forms association complexes with various cyclodextrins in aqueous solution. The formation of such association complexes has a significant effect on the Nile Red fluorescence, with the largest effect being observed in -cyclodextrin solution. When -cyclodextrin is used to increase the Nile Red concentration in solution, the absorption spectrum shows a large blue shift indicating the formation of an inclusion complex, but surprisingly the Nile Red fluorescence is strongly suppressed. A proposed explanation for this observation involves the formation of 1:2 host:guest complexes, in which the Nile Red guests are included as relatively non-fluorescent dimers. When the solutions were prepared by adding -cyclodextrinto a near-saturated aqueous solution of Nile Red (so that 1:1 or 2:1 complexation shouldbe favoured), significant fluorescence enhancement was observed. Analysis of thefluorescence enhancement as a function of host concentration indicated the formationof 2:1 host:guest complexes in these solutions. However, electrospray mass spectroscopic studies show no evidence for the formation of any such inclusion complexes. Furthermore, molecular modelling shows that the formation of a complex involving full insertion of Nile Red in the -cyclodextrin cavity is not stable, and will quickly eject the Nile Red guest molecule. These modelling results suggest that an association complex involving capping (via the association of Nile Red parallel to the cavity opening, or by partial insertion into the cavity) of the -cyclodextrin cavity by one or two Nile Red molecules is much more likely.     

Comparison of Numerical Simulation Models for Open Loop Flight Simulations in the Human Centrifuge

To achieve predefined Gz load profile in high G training in human centrifuge, it is necessary to determine angular velocity and acceleration of a planetary axis (centrifuge arm). Initial value problem that can not be solved in closed form was obtained. Several discretization methods for calculating angular velocity of centrifuge arm driven by DC servo motor are presented. Simulations are performed for different positive and negative values of Gz onset. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

On Gradient Ricci Solitons

In the first part of the paper we derive integral curvature estimates for complete gradient shrinking Ricci solitons. Our results and the recent work in M. Fernandez-Lopez and E. Garcia-Rio, Rigidity of shrinking Ricci solitons in Math. Z. (2011) classify complete gradient shrinking Ricci solitons with harmonic Weyl tensor. In the second part of the paper we address the issue of existence of harmonic functions on gradient shrinking Kähler and gradient steady Ricci solitons. Consequences to the structure of shrinking and steady solitons at infinity are also discussed.     

Modulated structures in bent-core liquid crystals: two faces of one phase

The Landau-de Gennes type continuous model is used to describe the 2D modulated structures made of bent-core liquid crystals. It is shown that modulation is a direct consequence of the chiral symmetry breaking. Structures with synclinic and anticlinic layer tilt are found to coexist in the polarization modulated and layer undulated (PM-LU) liquid crystal phase. The synclinic PM-LU structure corresponds to the columnar B(1RevTilted) phase. Experimentally obtained electron density maps are included, which support theoretical findings.     

Kinetic determination of morphine by means of Bray-Liebhafsky oscillatory reaction system using analyte pulse perturbation technique

A novel kinetic method for micro-quantitative determinations of morphine (MH) is proposed and validated. The method is based on the potentiometric monitoring of the concentration perturbations of the oscillatory reaction system being in a stable non-equilibrium stationary state close to the bifurcation point between stable and oscillatory state. The response of the Bray-Liebhafsky (BL) oscillatory reaction as a matrix system, to the perturbations by different concentrations of morphine, is followed by a Pt-electrode. The proposed method relies on the linear relationship between maximal potential shift, ΔE_m, and the logarithm of the added morphine amounts in the range of 0.004-0.18 μmol. Under optimum conditions, the sensitivity of the proposed method (as the limit of detection) is 0.001 μmol and the method is featured by good precision (R.S.D. = 1.6%) as well as the excellent sample throughput (45 samples h⁻¹). In addition to standard solution analysis, this approach was successfully applied for quantitative determination of morphine in a typical pharmaceutical dosage form. Some aspects of the possible mechanism of morphine action on the BL oscillating chemical system are discussed in detail.