Funtional Near Infrared Spectroscopy Study of Language, Joint Attention and Motor Skills

Near infrared spectroscopy (NIRS) is an emerging non-invasive optical neuro imaging technique that monitors the hemodynamic response to brain activation with ms-scale temporal resolution and sub-cm spatial resolution. The overall goal of my dissertation was to develop and apply NIRS towards investigation of neurological response to language, joint attention and planning and execution of motor skills in healthy adults. Language studies were performed to investigate the hemodynamic response, synchrony and dominance feature of the frontal and fronto-temporal cortex of healthy adults in response to language reception and expression. The mathematical model developed based on granger causality explicated the directional flow of information during the processing of language stimuli by the fronto-temporal cortex. Joint attention and planning/ execution of motor skill studies were performed to investigate the hemodynamic response, synchrony and dominance feature of the frontal cortex of healthy adults and in children (5-8 years old) with autism (for joint attention studies) and individuals with cerebral palsy (for planning/execution of motor skills studies). The joint attention studies on healthy adults showed differences in activation as well as intensity and phase dependent connectivity in the frontal cortex during joint attention in comparison to rest. The joint attention studies on typically developing children showed differences in frontal cortical activation in comparison to that in children with autism. The planning and execution of motor skills studies on healthy adults and individuals with cerebral palsy (CP) showed difference in the frontal cortical dominance, that is, bilateral and ipsilateral dominance, respectively. The planning and execution of motor skills studies also demonstrated the plastic and learning behavior of brain wherein correlation was found between the relative change in total hemoglobin in the frontal cortex and the kinematics of the activity performed by the participants. Thus, during my dissertation the NIRS neuroimaging technique was successfully implemented to investigate the neurological response of language, joint attention and planning and execution of motor skills in healthy adults as well as preliminarily on children with autism and individuals with cerebral palsy. These NIRS studies have long-term potential for the design of early stage interventions in children with autism and customized rehabilitation in individuals with cerebral palsy.

QUANTIFICATION OF CALCIUM IN SPARKLING WINES BY INFRARED SPECTROSCOPY

Markets are increasingly competitive and the companies feel the urge to improve their manufacturing processes. Blending that with a larger control of quality and safety it was created a need to develop new methods of analysis each time more accurate, faster and with lower costs. Alentejo is a region with a wide variety of soils, most of them are rich in calcium and potassium. In the production of sparkling wine many wineries use encapsulated yeast in alginate beads, instead of the traditional method, champenoise. The first method is faster, allowing a more versatile production, reducing the risk of contamination and features organoleptic characteristics similar to the traditional method (yeast free). However, encapsulated yeast spheres should be only used if the base wine matches a number of features, among them calcium content. In this study the calcium content in the wine was determined by atomic absorption spectroscopy (AAS) and by near-infrared spectroscopy. The AAS is a high sensitivity method clearly produces a reliable result, however it is very time consuming and produces great quantities of environmental waste, therefore the possibility of using near-infrared spectroscopy as a method was studied to be a fast, simple and clean alternative to the AAS. It was obtained a calibration model with a variation coefficient higher than 0.80 which indicates that the near-infrared spectroscopy as an adequately alternative the ASS.

Mechanism of dehydroxylation temperature decrease and high temperature phase transition of coal-bearing strata kaolinite intercalated by potassium acetate

The thermal decomposition and dehydroxylation process of coal-bearing strata kaolinite–potassium acetate intercalation complex (CSKK) has been studied using X-ray diffraction (XRD), infrared spectroscopy (IR), thermal analysis, mass spectrometric analysis and infrared emission spectroscopy. The XRD results showed that the potassium acetate (KAc) have been successfully intercalated into coal-bearing strata kaolinite with an obvious basal distance increase of the first basal peak, and the positive correlation was found between the concentration of intercalation regent KAc and the degree of intercalation. As the temperature of the system is raised, the formation of KHCO3, KCO3 and KAlSiO4, which is derived from the thermal decomposition or phase transition of CSKK, is observed in sequence. The IR results showed that new bands appeared, the position and intensities shift can also be found when the concentration of intercalation agent is raised. The thermal analysis and mass spectrometric analysis results revealed that CSKK is stable below 300 °C, and the thermal decomposition products (H2O and CO2) were further proved by the mass spectrometric analysis. A comparison of thermal analysis results of original coal-bearing strata kaolinite and its intercalation complex gives new discovery that not only a new mass loss peak is observed at 285 °C, but also the temperature of dehydroxylation and dehydration of coal bearing strata kaolinite is decreased about 100 °C. This is explained on the basis of the interlayer space of the kaolinite increased obviously after being intercalated by KAc, which led to the interlayer hydrogen bonds weakened, enables the dehydroxylation from kaolinite surface more easily. Furthermore, the possible structural model for CSKK has been proposed, with further analysis required in order to prove the most possible structures.

Stichtite : a review

Stichtite is a naturally occurring layered double hydroxide (LDH) with the ideal chemical formula Mg6Cr2CO3(OH)16·4H2O. It has received less attention in the literature than other LDHs and is often described as a rare mineral; however, abundant deposits of the mineral do exist. In this article we aim to review a number of significant publications concerning the mineral stichtite, including papers covering the discovery, geological origin, synthesis and characterizsation of stichtite. Characterization techniques reviewed include powder X-ray diffraction (XRD), infrared spectroscopy (IR), near infrared spectroscopy (NIR), Raman spectroscopy (Raman), thermogravimetry (TG) and electron microprobe analysis.

A novel method for purification of low grade diatomite powders in centrifugal fields

This study presented a novel method for purification of three different grades of diatomite from China by scrubbing technique using sodiumhexametaphosphate (SHMP) as dispersant combinedwith centrifugation. Effects of pH value and dispersant amount on the grade of purified diatomitewere studied and the optimumexperimental conditions were obtained. The characterizations of original diatomite and derived products after purification were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared spectroscopy (IR) and specific surface area analyzer (BET). The results indicated that the pore size distribution, impurity content and bulk density of purified diatomite were improved significantly. The dispersive effect of pH and SHMP on the separation of diatomite from clay minerals was discussed systematically through zeta potential test. Additionally, a possible purification mechanism was proposed in the light of the obtained experimental results.

Preventing industrial scale using bauxite refinery residues

An Australian green power (AGP) company produces energy from burning biomass from the sugar industry and recycled wood waste, however alkali in biomass is released into a recirculating stream that forms a scale as it becomes more concentrated. This investigation has shown that the addition of Bayer liquor (alumina waste residue) successfully removes scale-forming species from the recirculating stream and thus has the potential to reduce the rate of scaling. Characterisation of the scale and Bayer precipitates has been performed using X-ray diffraction (XRD), infrared spectroscopy (IR) and inductively coupled plasma optical emission spectroscopy (ICP-OES).

New insights into the molecular structure of kaolinite–methanol intercalation complexes

A series of kaolinite–methanol complexes with different basal spacings were synthesized using guest displacement reactions of the intercalation precursors kaolinite–N-methyformamide (Kaol–NMF), kaolinite–urea (Kaol–U), or kaolinite–dimethylsulfoxide (Kaol–DMSO), with methanol (Me). The interaction of methanol with kaolinite was examined using X-ray diffraction (XRD), infrared spectroscopy (IR), and nuclear magnetic resonance (NMR). Kaolinite (Kaol) initially intercalated with N-methyformamide (NMF), urea (U), or dimethylsulfoxide (DMSO) before subsequent reaction with Me formed final kaolinite–methanol (Kaol–Me) complexes characterized by basal spacing ranging between 8.6 Å and 9.6 Å, depending on the pre-intercalated reagent. Based on a comparative analysis of the three Kaol–Me displacement intercalation complexes, three types of Me intercalation products were suggested to have been present in the interlayer space of Kaol: (1) molecules grafted onto a kaolinite octahedral sheet in the form of a methoxy group (Al-O-C bond); (2) mobile Me and/or water molecules kept in the interlayer space via hydrogen bonds that could be partially removed during drying; and (3) a mixture of types 1 and 2, with the methoxy group (Al-O-C bond) grafted onto the Kaol sheet and mobile Me and/or water molecules coexisted in the system after the displacement reaction by Me. Various structural models that reflected four possible complexes of Kaol–Me were constructed for use in a complimentary computational study. Results from the calculation of the methanol kaolinite interaction indicate that the hydroxyl oxygen atom of methanol plays the dominant role in the stabilization and localization of the molecule intercalated in the interlayer space, and that water existing in the intercalated Kaol layer is inevitable.

Electrical, structural and magnetic properties of polyaniline/pTSA-TiO2 nanocomposites

Polyaniline (PANI)/para-toluene sulfonic acid (pTSA) and PANI/pTSA-TiO2 composites were prepared using chemical method and characterized by infrared spectroscopy (IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The electrical conductivity and magnetic properties were also measured. In corroboration with XRD, the micrographs of SEM indicated the homogeneous dispersion of TiO nanoparticles in bulk PANI/pTSA matrix. Conductivity of the PANI/pTSA-TiO2 was higher than the PAN[/pTSA, and the maximum conductivity obtained was 9.48 (S/cm) at 5 wt% of TiO2. Using SQUID magnetometer, it was found that PANI/pTSA was either paramagnetic or weakly ferromagnetic from 300 K down to 5 K with H-C approximate to 30 Oe and M-r approximate to 0.015 emu/g. On the other hand,PANI/pTSA-TiO2 was diamagnetic from 300 K down to about 50 K and below which it was weakly ferromagnetic. Furthermore, a nearly temperature-independent magnetization was observed in both the cases down to 50 K and below which the magnetization increased rapidly (a Curie like susceptibility was observed). The Pauli susceptibility (chi(pauli)) was calculated to be about 4.8 X 10(-5) and 1.6 x 10(-5)emug(-1) Oe(-1) K for PANI/pTSA and PANI/pTSA-TiO2, respectively.

Composite cyclodextrin-calcium carbonate porous microparticles and modified multilayer capsules: novel carriers for encapsulation of hydrophobic drugs

Novel composite cyclodextrin (CD)-CaCO3 spherical porous microparticles have been synthesized through Ca2+-CD complex formation, which influences the crystal growth of CaCO3. The CDs are entrapped and distributed uniformly in the matrix of CaCO3 microparticles during crystallization. The hydrophobic fluorescent molecules coumarin and Nile red (NR) are efficiently encapsulated into these composite CD-CaCO3 porous particles through supramolecular inclusion complexation between entrapped CDs and hydrophobic molecules. Thermogravimetric (TGA) and infrared spectroscopy (IR) analysis of composite CD-CaCO3 particles reveals the presence of large CDs and their strong interaction with calcium carbonate nanoparticles. The resulting composite CD-CaCO3 microparticles are utilized as sacrificial templates for preparation of CD-modified layer-by-layer (LbL) capsules. After dissolution of the carbonate core, CDs are retained in the interior of the capsules in a network fashion and assist in the encapsulation of hydrophobic molecules. The efficient encapsulation of the hydrophobic fluorescent dye, coumarin, was successfully demonstrated using CD-modified capsules. In vitro release of the encapsulated coumarin from the CD-CaCO3 and CD-modified capsules has been demonstrated.

Síntese, caracterização e estudo da ação antituberculose e citotóxica de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III)

No presente trabalho é descrita a obtenção de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III) candidatos a protótipos de fármacos antituberculose e antitumoral. Para investigar o efeito da modificação química sobre as bioatividades do fármaco isoniazida, foram preparados cinco derivados hidrazônicos: 2-piridinocarboxaldeído isonicotinoil hidrazona (HPCIH, 1), 2-acetilpiridina isonicotinoil hidrazona (HAPIH, 2), 2-benzoilpiridina isonicotinoil hidrazona (HBPIH, 3), 2-piridinoformamida isonicotinoil hidrazona (HPAmIH, 4) e 2-pirazinoformamida isonicotinoil hidrazona (HPzAmIH, 5), sendo o composto HPAmIH (4) inédito. Análises de ponto de fusão, espectroscopia de infravermelho (IV), espectrometria de massas, ressonância magnética nuclear (RMN), análise elementar e termogravimetria confirmaram a obtenção e pureza das hidrazonas. Foi determinada ainda a estrutura de HPCIH (1) por difração de raios X de monocristal. Essas moléculas foram efetivas em inibir o crescimento de cepas de micobactérias Mycobacterium tuberculosis H37Rv (ATCC 27294) nas concentrações testadas, com exceção de HPzAmIH (5). As hidrazonas HAPIH (2) e HBPIH (3) foram os compostos orgânicos mais ativos (concentração inibitória mínima, CIM = 0,625 g/mL), apresentando atividade antimicobacteriana apenas duas vezes inferior à do fármaco isoniazida.Quanto à ação contra células tumorais, as hidrazonas HAPIH (2) e HBPIH (3) foram as mais potentes contra as linhagens OVCAR-8 (tumor de ovário - humano), HCT-116 (tumor de cólon - humano) e SF-295 (glioblastoma humano), com inibições de 34,98 a 98,63% do crescimento celular, na concentração de 5 g/mL, enquanto que a isoniazida não foi efetiva contra as linhagens estudadas. Para avaliar o efeito da coordenação a metais sobre a atividade farmacológica das hidrazonas, foram sintetizados os complexos de cobre(II) e gálio(III), sendo todos inéditos: [Cu(HPCIH)Cl2]∙H2O (6), [Cu(HAPIH)Cl2]∙H2O (7), [Cu2(HBPIH)2Cl2]Cl2∙4H2O(8), [Cu(HPAmIH)Cl2]∙H2O (9), [Cu(HPzAmIH)Cl2]∙H2O (10), [Ga(HPCIH)2](NO3)32H2O (11), [Ga(HAPIH)(APIH)](NO3)22H2O (12), [Ga(HPAmIH)(PAmIH)](NO3)22H2O(13) e [Ga(HPzAmIH)(PzAmIH)](NO3)2H2O (14). Os complexos foram caracterizados por espectroscopia de IV, análise elementar, condutivimetria, RMN e espectroscopia eletrônica. Em geral, os complexos também demonstraram ação contra M. tuberculosis, sendo que apenas para 6, 9, 10 e 14 foi verificada melhor atividade em relação às hidrazonas livres. Os complexos metálicos foram tanto quanto ou mais ativos contra as células tumorais OVCAR-8, HCT-116 e SF-295 do que as hidrazonas livres. Merecem destaque os complexos 79 e 12, que apresentaram inibição de crescimento celular de 72,2100%, na concentração de 5 g/mL. Os resultados demonstram portanto que em geral os compostos 114 são menos ativos do que a isoniazida contra M. tuberculosis, enquanto que a modificação química do fármaco, formando-se hidrazonas com posterior complexação cobre(II) e gálio(III) constituíram uma estratégia interessante na obtenção de compostos mais potentes contra células tumorais

Hydrothermal synthesis and luminescent properties of Y2O3:Tb3+ and Gd2O3:Tb3+ microrods

One-dimensional (1D) Y2O3:Tb3+ and Gd2O3:Tb3+ microrods have been successfully prepared through a large-scale and facile hydrothermal method followed by a subsequent calcination process in N-2/H-2 mixed atmosphere. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (IR), thermogravimetric analysis (TGA), energy-dispersive X-ray spectra (EDX). scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), photoluminescence (PL) and cathodoluminescence (CL) spectra as well as kinetic decays were used to characterize the samples. The as-formed products via the hydrothermal process could transform to cubic Y2O3:Tb3+ and Gd2O3:Tb3+ with the same morphology and slight shrinking in size after a postannealing process.

Preparation of KMgF3 and Eu-doped KMgF3 nanocrystals in water-in-oil microemulsions

In this study, KMgF3:Eu2+ luminescent nanocrystals (NCs) were prepared in water/cetyltrimethylammonium bromide (CTAB)/2-octanol microemulsions. The KMgF3:Eu2+ NCs were characterized by transmission electron microscopy (TEM), X-ray diffractometer (XRD), fluorescence spectrum, infrared spectroscopy (IR) and elementary analysis. The results showed that the size of the KMgF3:Eu2+ NCs was hardly affected by water content and surfactant (CTAB) concentration. The emission spectrum showed that the position of the 362 nm peak is due to the K+ sites substituted Eu2+. Two emission peaks located at 589 and 612 nm can be attributed to Eu3+, which exist at two different types of Eu3+ centers: one is Eu3+ at a K+ site, the other is clustering of Eu3+ ions in the interstices of KMgF3 host lattice.

Polylactide-based polyurethane and its shape-memory behavior

A series of polylactide polyurethanes (PLAUs) were synthesized from poly(L-lactide) diols, hexamethylene diisocyanate (HDI), and 1,4-butanediol (BDO). Their thermal and mechanical properties and shape-memory behavior were studied by infrared spectroscopy (IR), differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXID), tensile testing, and thermal mechanical analysis (TMA). The T(g)s of these polymers were in the range of 33-53 degrees C, and influenced by the Mn of the PLA diol and the ratio of the soft-segment to the hard-segment. These materials can restore their shapes almost completely after 150% elongation or twofold compression. By changing the M-n of the PLA diol and the ratio of the hard-to-soft-segment, their Ts and shape-recovery temperatures can be adjusted to the neighborhood of the body temperature. Therefore, these PLAUs are expected to find practical medical applications.