Atomistic origins of the phase transition mechanism in Ge(2)Sb(2)Te(5)

The fast and reversible phase transition mechanism between crystalline and amorphous phases of Ge(2)Sb(2)Te(5) has been in debate for several years. Through employing first-principles density functional theory calculations, we identify a direct structural link between the metastable crystalline and amorphous phases. The phase transition is driven by the displacement of Ge atoms along the rocksalt [111] direction from stable octahedron to high energy unstable tetrahedron sites close to the intrinsic vacancy regions, which generates a high energy intermediate phase between metastable and amorphous phases. Due to the instability of Ge at the tetrahedron sites, the Ge atoms naturally shift away from those sites, giving rise to the formation of local-ordered fourfold motifs and the long-range structural disorder. Intrinsic vacancies, which originate from Sb(2)Te(3), lower the energy barrier for Ge displacements, and hence, their distribution plays an important role in the phase transition. The high energy intermediate configuration can be obtained experimentally by applying an intense laser beam, which overcomes the thermodynamic barrier from the octahedron to tetrahedron sites. The high figure of merit of Ge(2)Sb(2)Te(5) is achieved from the optimal combination of intrinsic vacancies provided by Sb(2)Te(3) and the instability of the tetrahedron sites provided by GeTe.

Magneto-optical rotation of heavy-metal oxide glasses

Magneto-optical rotation was measured at room temperature for glasses containing Bi2O3-CdO-GeO2 (BCG), and Bi2O3-PbO-GeO2-B2O3 (BPGP). A pulsed magnetic field between 50 and 80 KG was used to measure Faraday rotation at 632.8 nm as a function of the concentration of Bi and Cd for BCG and Bi and Pb for BPGB. Verdet constant as high as 0.162 min G-1 cm-1 at 632.8 nm for the BPGB sample with the highest concentrations of Bi and Cd was found. Verdet constant increases linearly with the heavy-metal concentration for the BPGB whereas it reaches some saturation for the BCG system. Measurements of the magneto-optical rotation at other wavelengths in the visible and the refractive index at 632.8 nm are also reported. © 1998 Elsevier Science B.V. All rights reserved.

Tm3+ and Tm3+-Ho3+ doped fluorogermanate glasses for S-band amplifiers

Two series of glasses with composition (mol%) 70PbGeO3- 15PbF2-15CdF2, the first one with different Tm 3+ contents (0.2, 0.4, 0.6 and 0.8 mol%) and the second one with 0.2 mol% Tm3+ and different Ho3+ contents (0.1, 0.5, 1.0 and 1.5 mol%), have been prepared and some of their spectroscopic properties studied. Absorption in the visible-near infrared and emission in the near infrared region of the electromagnetic spectrum have been obtained. Concerning emission at the 1.4-1.5 μm region, optimization of rare earth ions content leads to 0.2 and 0.5 mol% for Tm3+ and Ho3+, respectively. We discuss potential application of these compositions. © 2005 Elsevier B.V. All rights reserved.

Effects in the population inversion of3H4 level in Tm, Tm-Tb and Tm-Eu doped germanate glasses for amplifiers applications

The population inversion of the Tm3+ in GLKZ glass involved in the 1470 nm emission (3H4 → 3F 4) as a function of Tb (or Eu) concentration was calculated by computational simulation for a CW laser pumping at 792 nm. These calculations were performed using the experimental Tm→Tb an Tm→Eu transfer rates and the spectroscopic parameters of the Tm (0.1 mol %) system. The result shows that 0.2 mol % (Tb3+) and 0.4 mol % of Eu3+ ions propitiate best population inversion of Tm3+ (0.1 mol %) maximizing the amplification coefficient of germanate (GLKZ) glass when operating as laser intensity amplification at 1470 nm. Besides the effective deactivation of the 3F4 level, the presence of Tb3+ or Eu 3+ ions introduce a depopulation of the 3H4 emitting level by means of a cross relaxation process with Tm3+ ions. In spite of this, the whole effect is verified to be benefic for using Tm-doped GLKZ glass codoped with Tb3+ or Eu3+ as a suitable material for confectioning optical amplifiers that operates in the S-band for telecommunication.

Tunable plasmon resonance modes on gold nanoparticles in Er 3 +-doped germanium-tellurite glass

Relative to the Er3 +:gold-nanoparticle (Er3 +:Au-NP) axis, the polarization of the gold nanoparticle can be longitudinal (electric dipole parallel to the Er3 +:Au-NP axis) or transverse (electric dipole perpendicular to the Er3 +:Au-NP axis). For longitudinal polarization, the plasmon resonance modes of gold nanoparticles embedded in Er3 +-doped germanium-tellurite glass are activated using laser lines at 808 and 488 nm in resonance with radiative transitions of Er3 + ions. The gold nanoparticles were grown within the host glass by thermal annealing over various lengths of time, achieving diameters lower than 1.6 nm. The resonance wavelengths, determined theoretically and experimentally, are 770 and 800 nm. The absorption wavelength of nanoparticles was determined by using the Frohlich condition. Gold nanoparticles provide tunable emission resulting in a large enhancement for the 2H11/2 → 4I13/2 (emission at 805 nm) and 4S 3/2 → 4I13/2 (emission at 840 nm) electronic transitions of Er3 + ions; this is associated with the quantum yield of the energy transfer process. The excitation pathways, up-conversion and luminescence spectra of Er3 + ions are described through simplified energy level diagrams. We observed that up-conversion is favored by the excited-state absorption due to the presence of the gold nanoparticles coupled with the Er3 + ions within the glass matrix. © 2013 Elsevier B.V.

Synthesis, characterization and study of physical properties of novel M(n+1)AX(n) compounds

Mn+1AXn compounds, the ternary layered nanolaminates have gathered momentum in the last decade since its advent because of their unusual but exciting properties. These technologically important compounds combine some of the best properties of metals and ceramics. Like ceramics they are refractory, oxidation resistant, elastically stiff and relatively light. They also exhibit metallic properties like excellent machinability, thermal and electrical conductivity. This dissertation concentrates on the synthesis of germanium-based 211 Mn+1AXn compounds. The main objective of the research was to synthesize predominantly single phase samples of Cr2GeC, V2GeC and Ti2GeC. Another goal was to study the effect of solid substitutions on the M-site of Mn+1AXn compounds with Ge as an A-element. This study is in itself the first to demonstrate the synthesis of (Cr0.5V0.5)2GeC a novel Mn+1AXn compound. Scanning electron microscopy coupled with energy dispersive spectroscopy, x-ray diffraction and electron probe microanalysis were employed to confirm the presence of predominantly single phase samples of M2GeC compounds where M = Ti, V, Cr and (Cr 0.5V0.5). A large part of the dissertation also focuses on the effect of the compressibility on the Ge-based 211 Mn+1AXn compounds with the aid of diamond anvil cell and high energy synchrotron radiation. This study also concentrates on the stability of these compounds at high temperature and thereby determines its suitability as high temperature structural materials. In order to better understand the effect of substitutions on A-site of 211 Mn+1 AXn compounds under high pressure and high temperature, a comparison is made with previously reported 211 Mn+1AXn compounds with Al, Ga and S as A-site elements.

Doehlert Design-desirability Function Multi-criteria Optimal Separation Of 17 Phenolic Compounds From Extra-virgin Olive Oil By Capillary Zone Electrophoresis.

In Brazil, the consumption of extra-virgin olive oil (EVOO) is increasing annually, but there are no experimental studies concerning the phenolic compound contents of commercial EVOO. The aim of this work was to optimise the separation of 17 phenolic compounds already detected in EVOO. A Doehlert matrix experimental design was used, evaluating the effects of pH and electrolyte concentration. Resolution, runtime and migration time relative standard deviation values were evaluated. Derringer's desirability function was used to simultaneously optimise all 37 responses. The 17 peaks were separated in 19min using a fused-silica capillary (50μm internal diameter, 72cm of effective length) with an extended light path and 101.3mmolL(-1) of boric acid electrolyte (pH 9.15, 30kV). The method was validated and applied to 15 EVOO samples found in Brazilian supermarkets.

Intensification Of Bioactive Compounds Extraction From Medicinal Plants Using Ultrasonic Irradiation.

Extraction processes are largely used in many chemical, biotechnological and pharmaceutical industries for recovery of bioactive compounds from medicinal plants. To replace the conventional extraction techniques, new techniques as high-pressure extraction processes that use environment friendly solvents have been developed. However, these techniques, sometimes, are associated with low extraction rate. The ultrasound can be effectively used to improve the extraction rate by the increasing the mass transfer and possible rupture of cell wall due the formation of microcavities leading to higher product yields with reduced processing time and solvent consumption. This review presents a brief survey about the mechanism and aspects that affecting the ultrasound assisted extraction focusing on the use of ultrasound irradiation for high-pressure extraction processes intensification.

One-dimensional Silicon And Germanium Nanostructures With No Carbon Analogues.

In this work we report new silicon and germanium tubular nanostructures with no corresponding stable carbon analogues. The electronic and mechanical properties of these new tubes were investigated through ab initio methods. Our results show that these structures have lower energy than their corresponding nanoribbon structures and are stable up to high temperatures (500 and 1000 K, for silicon and germanium tubes, respectively). Both tubes are semiconducting with small indirect band gaps, which can be significantly altered by both compressive and tensile strains. Large bandgap variations of almost 50% were observed for strain rates as small as 3%, suggesting their possible applications in sensor devices. They also present high Young's modulus values (0.25 and 0.15 TPa, respectively). TEM images were simulated to help in the identification of these new structures.

Influence Of The Stage Of Ripeness On The Composition Of Iridoids And Phenolic Compounds In Genipap (genipa Americana L.).

Genipap fruits, native to the Amazon region, were classified in relation to their stage of ripeness according to firmness and peel color. The influence of the part of the genipap fruit and ripeness stage on the iridoid and phenolic compound profiles was evaluated by HPLC-DAD-MS(n), and a total of 17 compounds were identified. Geniposide was the major compound in both parts of the unripe genipap fruits, representing >70% of the total iridoids, whereas 5-caffeoylquinic acid was the major phenolic compound. In ripe fruits, genipin gentiobioside was the major compound in the endocarp (38%) and no phenolic compounds were detected. During ripening, the total iridoid content decreased by >90%, which could explain the absence of blue pigment formation in the ripe fruits after their injury. This is the first time that the phenolic compound composition and iridoid contents of genipap fruits have been reported in the literature.

Anthocyanin And Other Phenolic Compounds In Ceylon Gooseberry (dovyalis Hebecarpa) Fruits.

Ceylon gooseberry is a deep-purple exotic berry that is being produced in Brazil with great market potential. This work aimed to determine major phenolic compounds in this specie by HPLC-PDA-ESI/MS. Samples were collected in two different seasons. Pulp and skin were analyzed separately. Non-acylated rutinoside derivatives of delphinidin (∼60-63%) and cyanidin (∼17-21%) were major anthocyanins tentatively identified. All anthocyanins had higher concentration in skin than in pulp (64-82 and 646-534mg of cyaniding-3-glucoside equivalents/100g skin and pulp, respectively). Moreover, anthocyanin profile changed between sampling dates (p<0.05). Mainly for delphinidin-3-rutinoside which could be a result of season variation. In this specie, non-anthocyanin polyphenols represent less than 35% of total extracted polyphenols. The tentative identification proposed a flavonol and three ellagitannins as major compounds of the non-anthocyanin phenolics fraction. Finally, anthocyanin is the major phenolic class in this fruit and its composition and content are significantly affected by season.

Sorghum Flour Fractions: Correlations Among Polysaccharides, Phenolic Compounds, Antioxidant Activity And Glycemic Index.

Nutrients composition, phenolic compounds, antioxidant activity and estimated glycemic index (EGI) were evaluated in sorghum bran (SB) and decorticated sorghum flour (DSF), obtained by a rice-polisher, as well as whole sorghum flour (WSF). Correlation between EGI and the studied parameters were determined. SB presented the highest protein, lipid, ash, β-glucan, total and insoluble dietary fiber contents; and the lowest non-resistant and total starch contents. The highest carbohydrate and resistant starch contents were in DSF and WSF, respectively. Phenolic compounds and antioxidant activities were concentrated in SB. The EGI values were: DSF 84.5±0.41; WSF 77.2±0.33; and SB 60.3±0.78. Phenolic compounds, specific flavonoids and antioxidant activities, as well as total, insoluble and soluble dietary fiber and β-glucans of sorghum flour samples were all negatively correlated to EGI. RS content was not correlated to EGI.

Nature-inspired Enzymatic Cascades To Build Valuable Compounds.

Biocatalysis currently is focusing on enzymatic and multi-enzymatic cascade processes instead of single steps imbedded into chemical pathways. Alongside this scientific revolution, this review provides an overview on multi-enzymatic cascades that are responsible for the biosynthesis of some terpenes, alkaloids and polyethers, which are important classes of natural products. Herein, we illustrate the development of studies inspired by multi- and chemo-enzymatic approaches to build the core moieties of polyethers, polypeptide alkaloids, piperidines and pyrrolidines promoted by the joint action of oxidoreductases, hydrolases, cyclases, transaminases and imine reductases.

Profile Of Phenolic Compounds Of Brazilian Virgin Olive Oils By Rapid Resolution Liquid Chromatography Coupled To Electrospray Ionisation Time-of-flight Mass Spectrometry (rrlc-esi-tof-ms).

In recent years, agronomical researchers began to cultivate several olive varieties in different regions of Brazil to produce virgin olive oil (VOO). Because there has been no reported data regarding the phenolic profile of the first Brazilian VOO, the aim of this work was to determine phenolic contents of these samples using rapid-resolution liquid chromatography coupled to electrospray ionisation time-of-flight mass spectrometry. 25 VOO samples from Arbequina, Koroneiki, Arbosana, Grappolo, Manzanilla, Coratina, Frantoio and MGS Mariense varieties from three different Brazilian states and two crops were analysed. It was possible to quantify 19 phenolic compounds belonging to different classes. The results indicated that Brazilian VOOs have high total phenolic content because the values were comparable with those from high-quality VOOs produced in other countries. VOOs from Coratina, Arbosana and Grappolo presented the highest total phenolic content. These data will be useful in the development and improvement of Brazilian VOO.