Raman scattering of InSb quantum dots grown on InP substrates

In this paper we present the Raman scattering of self-assembled InSb dots grown on (001) oriented InP substrates. The samples were grown by pulsed molecular beam epitaxy mode. Two types of samples have been investigated. In one type the InSb dots were capped with 200 monolayers of InP; in the other type no capping was deposited after the InSb dot formation. We observe two peaks in the Raman spectra of the uncapped dot, while only one peak is observed in the Raman spectra of the capped dots. In the case of the uncapped dots the peaks are attributed to LO-like and TO-like vibration of completely relaxed InSb dots, in agreement with high resolution transmission electron microscopy photographs. The Raman spectra of the capped dot suggest a different strain state in the dot due to the capping layer.

Design and construction of precision heat fluxmeters

InAlAs/InGaAs/InP based high electron mobility transistor devices have been structurally and electrically characterized, using transmission electron microscopy and Raman spectroscopy and measuring Hall mobilities. The InGaAs lattice matched channels, with an In molar fraction of 53%, grown at temperatures lower than 530¿°C exhibit alloy decomposition driving an anisotropic InGaAs surface roughness oriented along [1math0]. Conversely, lattice mismatched channels with an In molar fraction of 75% do not present this lateral decomposition but a strain induced roughness, with higher strength as the channel growth temperature increases beyond 490¿°C. In both cases the presence of the roughness implies low and anisotropic Hall mobilities of the two dimensional electron gas.

Effects of Nb doping on the TiO2 anatase-to-rutile phase transition

We study the influence of Nb doping on the TiO2 anatase-to-rutile phase transition, using combined transmission electron microscopy, Raman spectroscopy, x-ray diffraction and selected area electron diffraction analysis. This approach enabled anatase-to-rutile phase transition hindering to be clearly observed for low Nb-doped TiO2 samples. Moreover, there was clear grain growth inhibition in the samples containing Nb. The use of high resolution transmission electron microscopy with our samples provides an innovative perspective compared with previous research on this issue. Our analysis shows that niobium is segregated from the anatase structure before and during the phase transformation, leading to the formation of NbO nanoclusters on the surface of the TiO2 rutile nanoparticles.

Influence of premetallization surface treatment on the formation of Schottky Au-nGaN contacts

The influence of premetallization surface preparation on the structural, chemical, and electrical properties of Au-nGaN interfaces has been investigated by x-ray photoemission spectroscopy (XPS), current-voltage measurement (I-V) and cross-section transmission electron microscopy (TEM). XPS analysis showed that the three GaN substrate treatments investigated i.e., ex situ hydrofluoric acid etch, in situ anneal in ultrahigh-vacuum (UHV), and in situ Ga reflux cleaning in UHV result in surfaces increasingly free of oxygen contamination. XPS and TEM characterization of Au-nGaN formed after the three premetallization surface treatments show that HF etching and UHV annealing produce abrupt, well-defined interfaces. Conversely, GaN substrate cleaning in a Ga flux results in Au/GaN intermixing. I-V characterization of Au¿nGaN contacts yields a Schottky barrier height of 1.25 eV with a very low-ideality factor and very good contact uniformity for the premetallization UHV anneal, while the Ga reflux cleaning results in a much lower barrier (0.85 eV), with poor ideality and uniformity. I-V and XPS results suggest a high density of acceptor states at the surface, which is further enhanced by UHV annealing. These results are discussed in the context of current models of Schottky barrier formation.

Identification and isolation of two ascomycete fungi from spores of the arbuscular mycorrhizal fungus Scutellospora castanea.

Two filamentous fungi with different phenotypes were isolated from crushed healthy spores or perforated dead spores of the arbuscular mycorrhizal fungus (AMF) Scutellospora castanea. Based on comparative sequence analysis of 5.8S ribosomal DNA and internal transcribed spacer fragments, one isolate, obtained from perforated dead spores only, was assigned to the genus Nectria, and the second, obtained from both healthy and dead spores, was assigned to Leptosphaeria, a genus that also contains pathogens of plants in the Brassicaceae. PCR and randomly amplified polymorphic DNA-PCR analyses, however, did not indicate similarities between pathogens and the isolate. The presence of the two isolates in both healthy spores and perforated dead spores of S. castanea was finally confirmed by transmission electron microscopy by using distinctive characteristics of the isolates and S. castanea. The role of this fungus in S. castanea spores remains unclear, but the results serve as a strong warning that sequences obtained from apparently healthy AMF spores cannot be presumed to be of glomalean origin and that this could present problems for studies on AMF genes.

Are the light-harvesting I complexes from Rhodospirillum rubrum arranged around the reaction centre in a square geometry?

The basic photosynthetic unit containing the reaction centre and the light-harvesting I complex (RC-LHI) of the purple non-sulphur bacterium Rhodospirillum rubrum was purified and reconstituted into two-dimensional (2D) membrane crystals. Transmission electron microscopy using conventional techniques and cryoelectron microscopy of the purified single particles and of 2D crystals yielded a projection of the RC-LHI complex at a resolution of at least 1.6 nm. In this projection the LHI ring appears to have a square symmetry and packs in a square crystal lattice. The square geometry of the LHI ring was observed also in images of single isolated particles of the RC-LHI complex. However, although the LHI units are packed identically within the crystal lattice, a new rotational analysis developed here showed that the reaction centres take up one of four possible orientations within the ring. This fourfold disorder supports our interpretation of a square ring symmetry and suggests that a hitherto undetected component may be present within the photosynthetic unit.

Evaluation of uptake and transport of cationic and anionic ultrasmall iron oxide nanoparticles by human colon cells.

Nanoparticles (NPs) are in clinical use or under development for therapeutic imaging and drug delivery. However, relatively little information exists concerning the uptake and transport of NPs across human colon cell layers, or their potential to invade three-dimensional models of human colon cells that better mimic the tissue structures of normal and tumoral colon. In order to gain such information, the interactions of biocompatible ultrasmall superparamagnetic iron oxide nanoparticles (USPIO NPs) (iron oxide core 9-10 nm) coated with either cationic polyvinylamine (aminoPVA) or anionic oleic acid with human HT-29 and Caco-2 colon cells was determined. The uptake of the cationic USPIO NPs was much higher than the uptake of the anionic USPIO NPs. The intracellular localization of aminoPVA USPIO NPs was confirmed in HT-29 cells by transmission electron microscopy that detected the iron oxide core. AminoPVA USPIO NPs invaded three-dimensional spheroids of both HT-29 and Caco-2 cells, whereas oleic acid-coated USPIO NPs could only invade Caco-2 spheroids. Neither cationic aminoPVA USPIO NPs nor anionic oleic acid-coated USPIO NPs were transported at detectable levels across the tight CacoReady? intestinal barrier model or the more permeable mucus-secreting CacoGoblet? model.

Magnetization versus heat treatment in rapidly solidified NdFeB alloys

NdFeB melt-spun amorphous or partially amorphous alloys of four compositions were prepared. Their crystallization kinetics induced by thermal treatment was studied by differential scanning calorimetry and scanning and transmission electron microscopy. Scanning electron microscopy demonstrated that heterogeneous nucleation occurs preferentially at the ribbon surface which was in contact with the wheel. The explicit form of the kinetic equation that best describes the first stage of crystallization under high undercooling conditions was obtained for each alloy. From the crystallization results, the lower part of the experimental time-temperature-transformation curves was deduced for each alloy and extrapolated up to the high-temperature limit of their validity. Microstructural observations showed a typical size of the microcrystals obtained by heat treatment of ~100 nm. From the magnetic properties measured with a vibrating sample magnetometer, the same magnetic behavior of partially crystallized alloys is observed regardless of the temperature of annealing provided the same crystallization fraction, x, is achieved, at least for small values of x (typically ~10%).

Molecular mechanisms of action of herbal antifungal alkaloid berberine, in Candida albicans.

Candida albicans causes superficial to systemic infections in immuno-compromised individuals. The concomitant use of fungistatic drugs and the lack of cidal drugs frequently result in strains that could withstand commonly used antifungals, and display multidrug resistance (MDR). In search of novel fungicidals, in this study, we have explored a plant alkaloid berberine (BER) for its antifungal potential. For this, we screened an in-house transcription factor (TF) mutant library of C. albicans strains towards their susceptibility to BER. Our screen of TF mutant strains identified a heat shock factor (HSF1), which has a central role in thermal adaptation, to be most responsive to BER treatment. Interestingly, HSF1 mutant was not only highly susceptible to BER but also displayed collateral susceptibility towards drugs targeting cell wall (CW) and ergosterol biosynthesis. Notably, BER treatment alone could affect the CW integrity as was evident from the growth retardation of MAP kinase and calcineurin pathway null mutant strains and transmission electron microscopy. However, unlike BER, HSF1 effect on CW appeared to be independent of MAP kinase and Calcineurin pathway genes. Additionally, unlike hsf1 null strain, BER treatment of Candida cells resulted in dysfunctional mitochondria, which was evident from its slow growth in non-fermentative carbon source and poor labeling with mitochondrial membrane potential sensitive probe. This phenotype was reinforced with an enhanced ROS levels coinciding with the up-regulated oxidative stress genes in BER-treated cells. Together, our study not only describes the molecular mechanism of BER fungicidal activity but also unravels a new role of evolutionary conserved HSF1, in MDR of Candida.

Interactions between cells and functionalized nanoparticles

In this present thesis Superparamagnetic Iron Oxide Nanoparticles (SPIONs) with 9 nm in diameter were selected as nanocarriers in order to study their potential application as drug delivery systems. Therefore the aim of the study was to demonstrate the proof of concept by establishing an efficient system of drug delivery, which would be a valuable tool in biomedical applications, such as the treatement of cancer, by reducing the side effects due to administration of a high concentration of therapeutic agents. As demonstrated in a previous study, the uptake of SPIONs by tumoral human cells was enhanced by the presence of amino groups on their surface. The stabilization of SPIONs were then performed and optimized by the coating of poly(vinylalcohol) and poly(vinylalcohol/vinylamine). Such nanoparticles were known as aminoPVA-SPIONs. The toxicity and the inflammatory reaction of aminoPVA-SPIONs were evaluated in order to establish their potentiel use in the human body. The results demonstrated that the human cells were able to invaginate aminoPVA-SPIONS without revealing any toxicity and inflammatory reaction. The analysis by transmission electron microscopy (TEM), scanning electron microscopy (SEM), cryo-TEM, confocal microscopy and histological staining (i.e. Prussian Blue) showed that the iron oxide core of SPIONs were located in the cytoplasm of cells and concentrated in vesicles. The evaluation of the mechanism of uptake of aminoPVA-SPIONs revealed that their uptake by monolayer cell culture was performed via an active mechanism, which was achieved by a clathrin-mediated endocytosis. Consequently, it was suggested that aminoPVA-SPIONs were good candidates as nanocarriers in drug delivery systems, which were able to reach the cytoplasm of cells. Their incubation with three-dimensional models mimicing tissues, such as differentiated rat brain cell-derived aggregates and spheroids, revealed that aminoPVA-SPIONs were able to invade into deep cell layers according to the stage of growth of these models. In the view of these promising results, drug-SPIONs were prepared by the functionalization of aminoPVA-SPIONs via a biological labile chemical bond by one of these three antineoplastic agents, which are widely used in clinical practice: 5-fluorourdine (Fur) (an antimetabolite), or camptothecin (CPT) (a topoisomerase inhibitor) or doxorubicin (DOX) (an anthracycline which interfere with DNA). The results shown that drug-SPIONs were internalized by human melanoma cells, as it was expected due the previous results with aminoPVA-SPIONs, and in addition they were active as anticancer agents, suggesting the efficient release of the drug from the drug-SPIONs. The results with CPT-SPIONs were the most promising, whereas DOX- SPIONs did not demonstrate a prononced activity of DOX. In conclusion, the results demonstrated that functionalized iron oxide nanoparticles are a promising tool in order to deliver therapeutic agents. - Dans le cadre de ce travail de thèse, les nanoparticules superparamagnétiques d'oxyde de fer (SPIONs) ayant un diamètre de 9 nm ont été choisies, afin d'étudier leur éventuelle utilisation dans un système de délivrance d'agents thérapeutiques. Ainsi le but de la thèse est de démontrer la faisabilité de fabriquer un système efficace de délivrance d'agents thérapeutiques, qui serait un outil intéressant dans le cadre d'une utilisation biomédicale, par exemple lors du traitement du cancer, qui pourrait réduire les effets secondaires provoqués par le dosage trop élevé de médicaments. Comme il a été démontré dans une précédente étude, l'invagination des SPIONs par des cellules humaines cancéreuses est améliorée par la présence de groupes fonctionnels amino à leur surface. La stabilisation des SPIONs est ainsi effectuée et optimisée par l'enrobage de poly(vinylalcool) et de (poly(vinylalcool/vinylamine), qui sont connues sous le nom de aminoPVA-SPIONs. La toxicité et la réaction inflammatoire des aminoPVA-SPIONs ont été évaluées dans le but de déterminer leur potentielle utilisation dans le corps humain. Les résultats démontrèrent que les cellules humaines sont capables d'invaginer les aminoPVAS-SPIONs sans induire une réaction toxique ou inflammatoire. L'analyse par la microscopie électronique en transmission électronique (TEM), la microscopie électronique à balayage (SEM), le cryo-microscopie électronique (SEM), la microscopie confocale et la coloration histologique (par ex, le bleu de Prusse) a montré que l'oxyde de fer des SPIONs est localisé dans le cytoplasme des cellules et est concentré dans des vesicules. L'évaluation du méchanisme d'invagination des aminoPVA-SPIONs ont révélé que leur invagination par des monocultures de cellules est effectué par un méchanisme actif, contrôlé par une endocytose induite par les clathrins. Par conséquent, les aminoPVA-SPIONs sont de bons candidats en tant que transporteurs (nanocamers) dans un système de délivrance d'agents thérapeuthique, capable d'atteindre le cytoplasme des cellules. Leur incubation avec des modèles tridimenstionnels imitant les tissues, tels que les aggrégats de cellules de cerveau différenciées et les sphéroïdes, a montré que les aminoPVA-SPIONs sont capable de pénétrer dans les couches profondes des modèles, selon l'état d'avancement de leur croissance. En vue de ces résultats prometteurs, les drug-SPIONs ont été préparés en fonctionalisant les aminoPVA-SPIONs par le biai d'une liaison chimique labile par un des trois agents thérapeutiques, déjà utilisé en pratique : 5-fluorourdine (Fur) (un antimétabolite), or camptothecin (CPT) (un inhibiteur de la topoisomerase) or doxorubicin (DOX) (un anthracycline qui interfère avec le DNA). Les résultats ont montré que les drug-SPIONs sont capable d'être internalisés par les mélanomes, comme il a été attendu d'après les résultats obtenus précédemment avec les aminoPVA-SPIONs, et de plus, les drug-SPIONs sont actifs, ce qui suggère un relargage efficace de l'agent thérapeutique du drug-SPIONs. Les résultats obtenus avec les CPT-SPIONs sont les plus prometteurs, tandis que ceux avec les DOX-SPIONs, ce n'est pas le cas, dont l'activité thérapeutique de DOX n'a pas été aussi efficace. En conclusion, les résultats ont pu démontrer que les nanoparticules d'oxyde de fer fonctionnalisées sont un outil prometteur dans la délivrance d'agents thérapeutiques.

An ultra-sensitive impedimetric immunosensor for detection of the serum oncomarker CA-125 in ovarian cancer patients.

Effective treatment of ovarian cancer depends upon the early detection of the malignancy. Here, we report on the development of a new nanostructured immunosensor for early detection of cancer antigen 125 (CA-125). A gold electrode was modified with mercaptopropionic acid (MPA), and then consecutively conjugated with silica coated gold nanoparticles (AuNP@SiO2), CdSe quantum dots (QDs) and anti-CA-125 monoclonal antibody (mAb). The engineered MPA|AuNP@SiO2|QD|mAb immunosensor was characterised using transmission electron microscopy (TEM), atomic force microscopy (AFM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Successive conjugation of AuNP@SiO2, CdSe QD and anti-CA-125 mAb onto the gold electrode resulted in sensitive detection of CA-125 with a limit of detection (LOD) of 0.0016 U mL(-1) and a linear detection range (LDR) of 0-0.1 U mL(-1). Based on the high sensitivity and specificity of the immunosensor, we propose this highly stable and reproducible biosensor for the early detection of CA-125.

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved. The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10 - 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.

Effect of the nanoparticles on the structure and crystallization of amorphous silicon thin films produced by rf glow discharge

Thin films of nanostructured silicon (ns-Si:H) were deposited by plasma-enhanced chemical vapor deposition in the presence of silicon nanoparticles at 100 C substrate temperature using silane and hydrogen gas mixture under continuous wave (cw) plasma conditions. The nanostructure of the films has been demonstrated by diverse ways: transmission electron microscopy, Raman spectroscopy and x-ray diffraction, which have shown the presence of ordered silicon clusters (1!=2 nm) embedded in an amorphous silicon matrix. Due to the presence of these ordered domains, the films crystallize faster than standard hydrogenated amorphous silicon samples, as evidenced by electrical measurements during the thermal annealing.

Graphoepitaxy of CeO2 on MgO and its application to the fabrication of 45° grain boundary Josephson junctions of YBa2Cu3O7-x

We communicate a detailed study of the epitaxial growth of CeO2 on MgO. The key feature of the growth is the dependence of the in¿plane orientation of the CeO2 epitaxial layer on the MgO surface morphology. Atomic force microscopic (AFM) measurements, x¿ray analyses, as well as high¿resolution transmission electron microscopy (HRTEM) investigations reveal that on rough substrates a cube¿on¿cube growth of CeO2 on MgO occurs while on smooth substrates the CeO2 unit cell is rotated around the surface normal by 45° with respect to the MgO unit cell when the deposition rate is low (~0.3 Å/s) during the first stages of growth. This growth mechanism can be used for a defined fabrication of 45° grain boundaries in the CeO2 layer by controlling the surface roughness of the MgO substrate. This report demonstrates that these 45° grain boundaries may be used to fabricate YBa2Cu3O7¿x Josephson junctions.

Plasma-enhanced chemical vapor deposition of boron nitride thin films from B2H6-H2-NH3 and B2H6-N2 gas mixtures

Highly transparent and stoichiometric boron nitride (BN) films were deposited on both electrodes (anode and cathode) of a radio-frequency parallel-plate plasma reactor by the glow discharge decomposition of two gas mixtures: B2H6-H2-NH3 and B2H6-N2. The chemical, optical, and structural properties of the films, as well as their stability under long exposition to humid atmosphere, were analyzed by x-ray photoelectron, infrared, and Raman spectroscopies; scanning and transmission electron microscopies; and optical transmittance spectrophotometry. It was found that the BN films grown on the anode using the B2H6-H2-NH3 mixture were smooth, dense, adhered well to substrates, and had a textured hexagonal structure with the basal planes perpendicular to the film surface. These films were chemically stable to moisture, even after an exposition period of two years. In contrast, the films grown on the anode from the B2H6-N2 mixture showed tensile stress failure and were very unstable in the presence of moisture. However, the films grown on the cathode from B2H6-H2-NH3 gases suffered from compressive stress failure on exposure to air; whereas with B2H6-N2 gases, adherent and stable cathodic BN films were obtained with the same crystallographic texture as anodic films prepared from the B2H6-H2-NH3 mixture. These results are discussed in terms of the origin of film stress, the effects of ion bombardment on the growing films, and the surface chemical effects of hydrogen atoms present in the gas discharge.