Glass in Cultural Heritage – An Introduction

Proceedings of the Chemistry and Conservation Science

Serum Trace Elements in Dysphagic Gastrostomy Candidates Before Endoscopic Gastrostomy for Long Term Enteral Feeding

BACKGROUND & AIMS: Patients who underwent endoscopic gastrostomy (PEG) present protein-energy malnutrition, but little is known about Trace Elements (TE), Zinc (Zn), Copper (Cu), Selenium (Se), Iron (Fe), Chromium (Cr). Our aim was the evaluation of serum TE in patients who underwent PEG and its relationship with serum proteins, BMI and nature of underlying disorder. METHODS: A prospective observational study was performed collecting: patient's age, gender, underlying disorder, NRS-2002, BMI, serum albumin, transferrin and TE concentration. We used ferrozine colorimetric method for Fe; Inductively Coupled Plasma-Atomic Emission Spectroscopy for Zn/Cu; Furnace Atomic Absorption Spectroscopy for Se/Cr. The patients were divided into head and neck cancer (HNC) and neurological dysphagia (ND). RESULTS: 146 patients (89 males), 21-95 years: HNC-56; ND-90. Low BMI in 78. Low values mostly for Zn (n = 122) and Fe (n = 69), but less for Se (n = 31), Cu (n = 16), Cr (n = 7); low albumin in 77, low transferrin in 94 and 66 with both proteins low. Significant differences between the groups of underlying disease only for Zn (t140.326 = -2,642, p < 0.01) and a correlation between proteins and TE respectively albumin and Zn (r = 0.197, p = 0.025), and albumin and Fe (r = 0.415, p = 0.000). CONCLUSIONS: When gastrostomy was performed, patients display low serum TE namely Zn, but also Fe, less striking regarding others TE. It was related with prolonged fasting, whatever the underlying disease. Low proteins were associated with low TE. Teams taking care of PEG-patients should use Zn supplementation and include other TE evaluation as part of the nutritional assessment of PEG candidates.

Efficient energy transfer from Si clusters to Er3+ in complex silicate glasses

We present an extensive study of the structural and optical emission properties in aluminum silicates and soda-lime silicates codoped with Si nanoclusters (Si-nc) and Er. Si excess of 5 and 15¿at.¿% and Er concentrations ranging from 2×1019 up to 6×1020¿cm¿3 were introduced by ion implantation. Thermal treatments at different temperatures were carried out before and after Er implantation. Structural characterization of the resulting structures was performed to obtain the layer composition and the size distribution of Si clusters. A comprehensive study has been carried out of the light emission as a function of the matrix characteristics, Si and Er contents, excitation wavelength, and power. Er emission at 1540¿nm has been detected in all coimplanted glasses, with similar intensities. We estimated lifetimes ranging from 2.5¿to¿12¿ms (depending on the Er dose and Si excess) and an effective excitation cross section of about 1×10¿17¿cm2 at low fluxes that decreases at high pump power. By quantifying the amount of Er ions excited through Si-nc we find a fraction of 10% of the total Er concentration. Upconversion coefficients of about 3×10¿18¿cm¿3¿s¿1 have been found for soda-lime glasses and one order of magnitude lower in aluminum silicates.

Measurement Problems and Problem-Solving in Kraft Pulping

Tämän työn tarkoituksena on koota yhteen selluprosessin mittausongelmat ja mahdolliset mittaustekniikat ongelmien ratkaisemiseksi. Pääpaino on online-mittaustekniikoissa. Työ koostuu kolmesta osasta. Ensimmäinen osa on kirjallisuustyö, jossa esitellään nykyaikaisen selluprosessin perusmittaukset ja säätötarpeet. Mukana on koko kuitulinja puunkäsittelystä valkaisuun ja kemikaalikierto: haihduttamo, soodakattila, kaustistamo ja meesauuni. Toisessa osassa mittausongelmat ja mahdolliset mittaustekniikat on koottu yhteen ”tiekartaksi”. Tiedot on koottu vierailemalla kolmella suomalaisella sellutehtaalla ja haastattelemalla laitetekniikka- ja mittaustekniikka-asiantuntijoita. Prosessikemian paremmalle ymmärtämiselle näyttää haastattelun perusteella olevan tarvetta, minkä vuoksi konsentraatiomittaukset on valittu jatkotutkimuskohteeksi. Viimeisessä osassa esitellään mahdollisia mittaustekniikoita konsentraatiomittausten ratkaisemiseksi. Valitut tekniikat ovat lähi-infrapunatekniikka (NIR), fourier-muunnosinfrapunatekniikka (FTIR), online-kapillaarielektroforeesi (CE) ja laserindusoitu plasmaemissiospektroskopia (LIPS). Kaikkia tekniikoita voi käyttää online-kytkettyinä prosessikehitystyökaluina. Kehityskustannukset on arvioitu säätöön kytketylle online-laitteelle. Kehityskustannukset vaihtelevat nollasta miestyövuodesta FTIR-tekniikalle viiteen miestyövuoteen CE-laitteelle; kehityskustannukset riippuvat tekniikan kehitysasteesta ja valmiusasteesta tietyn ongelman ratkaisuun. Työn viimeisessä osassa arvioidaan myös yhden mittausongelman – pesuhäviömittauksen – ratkaisemisen teknis-taloudellista kannattavuutta. Ligniinipitoisuus kuvaisi nykyisiä mittauksia paremmin todellista pesuhäviötä. Nykyään mitataan joko natrium- tai COD-pesuhäviötä. Ligniinipitoisuutta voidaan mitata UV-absorptiotekniikalla. Myös CE-laitetta voitaisiin käyttää pesuhäviön mittauksessa ainakin prosessikehitysvaiheessa. Taloudellinen tarkastelu pohjautuu moniin yksinkertaistuksiin ja se ei sovellu suoraan investointipäätösten tueksi. Parempi mittaus- ja säätöjärjestelmä voisi vakauttaa pesemön ajoa. Investointi ajoa vakauttavaan järjestelmään on kannattavaa, jos todellinen ajotilanne on tarpeeksi kaukana kustannusminimistä tai jos pesurin ajo heilahtelee eli pesuhäviön keskihajonta on suuri. 50 000 € maksavalle mittaus- ja säätöjärjestelmälle saadaan alle 0,5 vuoden takaisinmaksuaika epävakaassa ajossa, jos COD-pesuhäviön vaihteluväli on 5,2 – 11,6 kg/odt asetusarvon ollessa 8,4 kg/odt. Laimennuskerroin vaihtelee tällöin välillä 1,7 – 3,6 m3/odt asetusarvon ollessa 2,5 m3/odt.

Turvallisuusanalyysi korkeajännitesähkönpurkauslaitteistolle

Työssä tehtiin turvallisuusanalyysi Lappeenrannan teknillisen yliopiston tutkimuskäyttöön tarkoitetulle korkeajännitesähkönpurkauslaitteistolle. Sähkönpurkauslaite on uutta teknologiaa jätevedenkäsittelyyn. Työssä tutkittiin useita eri analyysimenetelmiä turvallisuusanalyysin tekemiseen, jotta löydettäisiin sopiva menetelmä korkeajännitesähkönpurkauslaitteistolle. Tutustuttiin lähemmin kolmeen analyysimenetelmään, jotka olivat Dow’s Fire And Explosion Index, HAZOP-poikkeamatarkastelu ja vaarallisten skenaarioiden analyysi HAZSCAN. Lopullinen turvallisuusanalyysi tehtiin HAZSCAN-turvallisuusanalyysimenetelmän avulla. HAZSCAN valittiin koska se oli vaihtoehdoista joustavin ja sen avulla oli mahdollista tutkia kaikkia turvallisuuden osa-alueita. Suurimmaksi turvallisuusriskiksi havaittiin korkeajännitesähkönpurkauslaitteiston kennoston kuumeneminen. Riskien vähyys johtuu lähinnä siitä, että tutkimuskäytössä oleva laite on pienessä mittakaavassa. Tehty turvallisuusanalyysi ei itsessään parantanut laboratoriomittakaavassa olevan laitteen turvallisuutta, sillä toistaiseksi muutosten täytäntöönpanosta ei ole tehty päätöstä. Turvallisuusanalyysi ei sovellu suoraan käytettäväksi teollisuudessa, sillä se on tehty tutkimuskäytössä olevalle korkeajännitesähkönpurkauslaitteistolle. Se toimii kuitenkin hyvänä pohjana jatkossa tehtäville turvallisuusanalyyseille.

Construção de um espectrógrafo de projeção e sua utilização em demonstrações de espectroscopia óptica

This article describes a projection spectrograph for use in optical spectroscopy classrooms demonstrations. The apparatus is based on an overhead projector and permits the visualization of several phenomena such as, light dispersion by diffraction gratings, diffraction order, optical fluorescence, continuous and discrete optical emission spectra, and light absorption by liquids and solids. A historical survey about the optical spectroscopy development is also presented.

Flow injection analysis (FIA) determination of lead by hydride generation in banded coral skeletons /

A flow injection hydride generation direct current plasma atomic emission spectrometric (FI-HG-DCP-AES) method was developed for the determination of lead at ng.ml-l level. Potassium ferricyanide (K3Fe(CN)6) was used along with sodium tetrahydroborate(III) (NaBH4) to produce plumbane (PbH4) in an acid medium. The design of a gas-liquid separator (hydride generator) was tested and the parameters of the flow injection system were optimized to achieve a good detection limit and sample throughput. The technique developed gave a detection limit of 0.7 ng.ml-l(3ob). The precision at 20 ng.ml"* level was 1.6 % RSD with 1 1 measurements (n=l 1). Volume of sample loop was 500 |J.l. A sample throughput of 120 h"^ was achieved. The transition elements, Fe(II), FeOH), Cd(n), Co(II), Mn(n), Ni(II) and Zn(n) do not interfere in this method but 1 mg,l'l Cu(II) will suppress 50 % of the signal from a sample containing 20 ng.ml'l Pb. This method was successfully applied to determine lead in a calcium carbonate (CaC03) matrix of banded coral skeletons from Si-Chang Island in Thailand.

Synthesis of ZnO nanoparticles by hydrothermal method

Stable, OH free zinc oxide (ZnO) nanoparticles were synthesized by hydrothermal method by varying the growth temperature and concentration of the precursors. The formation of ZnO nanoparticles were confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies. The average particle size have been found to be about 7-24 nm and the compositional analysis is done with inductively coupled plasma atomic emission spectroscopy (ICP-AES). Diffuse reflectance spectroscopy (DRS) results shows that the band gap of ZnO nanoparticles is blue shifted with decrease in particle size. Photoluminescence properties of ZnO nanoparticles at room temperature were studied and the green photoluminescent emission from ZnO nanoparticles can originate from the oxygen vacancy or ZnO interstitial related defects.

Rice husk ash – A valuable reinforcement for high density polyethylene

This paper presents the results of a study on the use of rice husk ash (RHA) for property modification of high density polyethylene (HDPE). Rice husk is a waste product of the rice processing industry. It is used widely as a fuel which results in large quantities of RHA. Here, the characterization of RHA has been done with the help of X-ray diffraction (XRD), Inductively Coupled Plasma Atomic Emission Spectroscopy (ICPAES), light scattering based particle size analysis, Fourier transform infrared spectroscopy (FTIR) and Scanning Electron Microscope (SEM). Most reports suggest that RHA when blended directly with polymers without polar groups does not improve the properties of the polymer substantially. In this study RHA is blended with HDPE in the presence of a compatibilizer. The compatibilized HDPE-RHA blend has a tensile strength about 18% higher than that of virgin HDPE. The elongation-at-break is also higher for the compatibilized blend. TGA studies reveal that uncompatibilized as well as compatibilized HDPERHA composites have excellent thermal stability. The results prove that RHA is a valuable reinforcing material for HDPE and the environmental pollution arising from RHA can be eliminated in a profitable way by this technique.

The Surface Plasmon Resonance of Supported Noble Metal Nanoparticles: Characterization, Laser Tailoring, and SERS Application

This work deals with the optical properties of supported noble metal nanoparticles, which are dominated by the so-called Mie resonance and are strongly dependent on the particles’ morphology. For this reason, characterization and control of the dimension of these systems are desired in order to optimize their applications. Gold and silver nanoparticles have been produced on dielectric supports like quartz glass, sapphire and rutile, by the technique of vapor deposition under ultra-high vacuum conditions. During the preparation, coalescence is observed as an important mechanism of cluster growth. The particles have been studied in situ by optical transmission spectroscopy and ex situ by atomic force microscopy. It is shown that the morphology of the aggregates can be regarded as oblate spheroids. A theoretical treatment of their optical properties, based on the quasistatic approximation, and its combination with results obtained by atomic force microscopy give a detailed characterization of the nanoparticles. This method has been compared with transmission electron microscopy and the results are in excellent agreement. Tailoring of the clusters’ dimensions by irradiation with nanosecond-pulsed laser light has been investigated. Selected particles are heated within the ensemble by excitation of the Mie resonance under irradiation with a tunable laser source. Laser-induced coalescence prevents strongly tailoring of the particle size. Nevertheless, control of the particle shape is possible. Laser-tailored ensembles have been tested as substrates for surface-enhanced Raman spectroscopy (SERS), leading to an improvement of the results. Moreover, they constitute reproducible, robust and tunable SERS-substrates with a high potential for specific applications, in the present case focused on environmental protection. Thereby, these SERS-substrates are ideally suited for routine measurements.

Goldnanoteilchen auf Titandioxid

In dieser Arbeit wurde das Wachstum sowie die ultraschnelle Elektronendynamik des Oberflächenplasmon Polaritons von Goldnanoteilchen auf Titandioxid untersucht. Die Messung der Dephasierungszeit des Oberflächenplasmons von Nanoteilchen mit definierter Form und Größe erfolgte dabei mit der Methode des spektralen Lochbrennens. Die Nanoteilchen wurden durch Deposition von Goldatomen aus einem thermischen Atomstrahl mit anschließender Diffussion und Nukleation, d.h. Volmer-Weber-Wachstum, auf Titandioxidsubstraten hergestellt und mittels einer Kombination aus optischer Spektroskopie und Rasterkraftmikroskopie systematisch untersucht. Dabei lässt sich das Nanoteilchenensemble durch das mittlere Achsverhältnis und den mittleren Äquivalentradius charakterisieren. Die Messungen zeigen, dass die Proben große Größen- und Formverteilungen aufweisen und ein definierter Zusammenhang zwischen Größe und Form der Teilchen existiert. Während kleine Goldnanoteilchen nahezu kugelförmig sind, flachen die Teilchen mit zunehmender Größe immer mehr ab. Des Weiteren wurde in dieser Arbeit die Methode des lasergestützten Wachstums auf das System Gold auf Titandioxid angewendet. Systematische Untersuchungen zeigten, dass sich das Achsverhältnis der Teilchen durch geeignete Wahl von Photonenenergie und Fluenz des eingestrahlten Laserlichts definiert und gezielt vorgeben lässt. Die Methode des lasergestützten Wachstums erschließt damit den Bereich außerhalb der Zugänglichkeit des natürlichen Wachstums. Aufgrund der Formabhängigkeit der spektrale Lage der Plasmonresonanz ist man somit in der Lage, die optischen Eigenschaften der Nanoteilchen gezielt einzustellen und z.B. für technische Anwendungen zu optimieren. Die Untersuchung der ultraschnellen Elektronendynamik von Goldnanoteilchen auf Titandioxid mit äquivalenten Radien zwischen 8 bis 15 nm erfolgte in dieser Arbeit mit der Methode des spektralen Lochbrennes. Hierzu wurde die Dephasierungszeit des Oberflächenplasmons systematisch als Funktion der Photonenenergie in einem Bereich von 1,45 bis 1,85 eV gemessen. Es zeigte sich, dass die gemessenen Dephasierungszeiten von 8,5 bis 16,2 fs deutlich unter den in der dielektrischen Funktion von Gold enthaltenen Werten lagen, was den erwarteten Einfluss der reduzierten Dimension der Teilchen demonstriert. Um die Messwerte trotz verschiedener Teilchengrößen untereinander vergleichen und den Einfluss der intrinsischen Dämpfung quantifizieren zu können, wurde zusätzlich der Dämpfungsparameter A bestimmt. Die ermittelten A-Faktoren zeigten dabei eine starke Abhängigkeit von der Plasmonenergie. Für Teilchen mit Plasmonenergien von 1,45 bis 1,55 eV wurde ein Dämpfungsfaktor von A ~ 0,2 nm/fs ermittelt, der lediglich Oberflächenstreuung als dominierenden Dämpfungsmechanismus widerspiegelt. Hingegen wurde für Teilchen mit Plasmonenergien oberhalb von 1,55 eV ein drastischer Anstieg der Dämpfung auf A ~ 0,4 nm/fs beobachtet. Die erhöhte Dämpfung wurde dabei dem zusätzlichen Vorliegen einer chemischen Dämpfung durch das Titandioxidsubstrat zugeschrieben. Zusammenfassend zeigen die Ergebnisse somit, dass eine starke Abhängigkeit der chemischen Dämpfung von der Photonenenergie vorliegt. Es konnte erstmals nachgewiesen werden, dass die chemische Dämpfung erst ab einer bestimmten unteren Schwelle der Photonenenergie einsetzt, die für Goldnanoteilchen auf Titandioxid bei etwa 1,6 eV liegt.

Molecular Beam Epitaxial Growth of III-V Semiconductor Nanostructures on Silicon Substrates

The main focus and concerns of this PhD thesis is the growth of III-V semiconductor nanostructures (Quantum dots (QDs) and quantum dashes) on silicon substrates using molecular beam epitaxy (MBE) technique. The investigation of influence of the major growth parameters on their basic properties (density, geometry, composition, size etc.) and the systematic characterization of their structural and optical properties are the core of the research work. The monolithic integration of III-V optoelectronic devices with silicon electronic circuits could bring enormous prospect for the existing semiconductor technology. Our challenging approach is to combine the superior passive optical properties of silicon with the superior optical emission properties of III-V material by reducing the amount of III-V materials to the very limit of the active region. Different heteroepitaxial integration approaches have been investigated to overcome the materials issues between III-V and Si. However, this include the self-assembled growth of InAs and InGaAs QDs in silicon and GaAx matrices directly on flat silicon substrate, sitecontrolled growth of (GaAs/In0,15Ga0,85As/GaAs) QDs on pre-patterned Si substrate and the direct growth of GaP on Si using migration enhanced epitaxy (MEE) and MBE growth modes. An efficient ex-situ-buffered HF (BHF) and in-situ surface cleaning sequence based on atomic hydrogen (AH) cleaning at 500 °C combined with thermal oxide desorption within a temperature range of 700-900 °C has been established. The removal of oxide desorption was confirmed by semicircular streaky reflection high energy electron diffraction (RHEED) patterns indicating a 2D smooth surface construction prior to the MBE growth. The evolution of size, density and shape of the QDs are ex-situ characterized by atomic-force microscopy (AFM) and transmission electron microscopy (TEM). The InAs QDs density is strongly increased from 108 to 1011 cm-2 at V/III ratios in the range of 15-35 (beam equivalent pressure values). InAs QD formations are not observed at temperatures of 500 °C and above. Growth experiments on (111) substrates show orientation dependent QD formation behaviour. A significant shape and size transition with elongated InAs quantum dots and dashes has been observed on (111) orientation and at higher Indium-growth rate of 0.3 ML/s. The 2D strain mapping derived from high-resolution TEM of InAs QDs embedded in silicon matrix confirmed semi-coherent and fully relaxed QDs embedded in defectfree silicon matrix. The strain relaxation is released by dislocation loops exclusively localized along the InAs/Si interfaces and partial dislocations with stacking faults inside the InAs clusters. The site controlled growth of GaAs/In0,15Ga0,85As/GaAs nanostructures has been demonstrated for the first time with 1 μm spacing and very low nominal deposition thicknesses, directly on pre-patterned Si without the use of SiO2 mask. Thin planar GaP layer was successfully grown through migration enhanced epitaxy (MEE) to initiate a planar GaP wetting layer at the polar/non-polar interface, which work as a virtual GaP substrate, for the GaP-MBE subsequently growth on the GaP-MEE layer with total thickness of 50 nm. The best root mean square (RMS) roughness value was as good as 1.3 nm. However, these results are highly encouraging for the realization of III-V optical devices on silicon for potential applications.

Cloning, expression, and characterization of human cytosolic aminopeptidase P: a single manganese(II)-dependent enzyme

The mammalian bradykinin-degrading enzyme aminopeptidase P (AP-P; E. C. 3.4.11.9) is a metal-dependent enzyme and is a member of the peptidase clan MG. AP-P exists as membrane-bound and cytosolic forms, which represent distinct gene products. A partially truncated clone encoding the cytosolic form was obtained from a human pancreatic cDNA library and the 5' region containing the initiating Met was obtained by 5' rapid accumulation of cDNA ends (RACE). The open reading frame encodes a protein of 623 amino acids with a calculated molecular mass of 69,886 Da. The full-length cDNA with a C-terminal hexahistidine tag was expressed in Escherichia coli and COS-1 cells and migrated on SDS-PAGE with a molecular mass of 71 kDa. The expressed cytosolic AP-P hydrolyzed the X-Pro bond of bradykinin and substance P but did not hydrolyze Gly-Pro-hydroxyPro. Hydrolysis of bradykinin was inhibited by 1,10-phenanthroline and by the specific inhibitor of the membrane-bound form of mammalian AP-P, apstatin. Inductively coupled plasma atomic emission spectroscopy of AP-P expressed in E. coli revealed the presence of 1 mol of manganese/mol of protein and insignificant amounts of cobalt, iron, and zinc. The enzymatic activity of AP-P was promoted in the presence of Mn(II), and this activation was increased further by the addition of glutathione. The only other metal ion to cause slight activation of the enzyme was Co(II), with Ca(II), Cu(II), Mg(II), Ni(II), and Zn(II) all being inhibitory. Removal of the metal ion from the protein was achieved by treatment with 1,10-phenanthroline. The metal-free enzyme was reactivated by the addition of Mn(II) and, partially, by Fe(II). Neither Co(II) nor Zn(II) reactivated the metal-free enzyme. On the basis of these data we propose that human cytosolic AP-P is a single metal ion-dependent enzyme and that manganese is most likely the metal ion used in vivo.

How grain boundaries modify the high-temperature dielectric response of ferroelectric electroceramics like BaTiO(3)?

Dielectric properties of BaTiO(3) ferroelectric ceramics were studied over wide frequency and temperature ranges. The materials showed complex dielectric behaviors, which included an anomalous increase of permittivity towards higher temperatures. Important, this property tended however to saturate to values that varied with grain-boundary density. Application of impedance spectroscopy and consideration of the series-layer model allowed a coherent discussion of these and other interesting observations from this work. In particular, analysis of the relationship existing in this model between macroscopic and microscopic dielectric properties rendered possible to account for grain vs. grain-boundary dielectric behaviors, in harmony with microstructure features, and to know the dielectric anomaly strength to be in fact expected from grain boundaries in such polycrystalline materials. (C) 2010 Elsevier Ltd. All rights reserved.