Solid phase extraction of iron and lead in environmental matrices on amberlite xad-1180/pv

A solid phase extraction procedure using Amberlite XAD-1180/Pyrocatechol violet (PV) chelating resin for the determination of iron and lead ions in various environmental samples was established. The procedure is based on the sorption of lead(II) and iron(III) ions onto the resin at pH 9, followed by elution with 1 mol/L HNO3 and determination by flame atomic absorption spectrometry. The influence of alkaline, earth alkaline and some transition metals, as interferents, are discussed. The recoveries for the spiked analytes were greater than 95%. The detection limits for lead and iron by FAAS were 0.37 µg/L and 0.20 µg/L, respectively. Validation of the method described here was performed by using three certified reference materials (SRM 1515 Apple Leaves, SRM 2711 Montana Soil and NRCC-SLRS-4 Riverine Water). The procedure was successfully applied to natural waters and human hair.

Bowing the violin : a case study for auditory-motor pattern modelling in the context of music performance

This project addresses methodological and technological challenges in the development of multi-modal data acquisition and analysis methods for the representation of instrumental playing technique in music performance through auditory-motor patterning models. The case study is violin playing: a multi-modal database of violin performances has been constructed by recording different musicians while playing short exercises on different violins. The exercise set and recording protocol have been designed to sample the space defined by dynamics (from piano to forte) and tone (from sul tasto to sul ponticello), for each bow stroke type being played on each of the four strings (three different pitches per string) at two different tempi. The data, containing audio, video, and motion capture streams, has been processed and segmented to facilitate upcoming analyses. From the acquired motion data, the positions of the instrument string ends and the bow hair ribbon ends are tracked and processed to obtain a number of bowing descriptors suited for a detailed description and analysis of the bow motion patterns taking place during performance. Likewise, a number of sound perceptual attributes are computed from the audio streams. Besides the methodology and the implementation of a number of data acquisition tools, this project introduces preliminary results from analyzing bowing technique on a multi-modal violin performance database that is unique in its class. A further contribution of this project is the data itself, which will be made available to the scientific community through the repovizz platform.

Separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography

An effective method for the rapid separation and purification of three stilbenes from the radix of Polygonum cillinerve (Nakai) Ohwl by macroporous resin column chromatography combined with high-speed counter-current chromatography (HSCCC) was successfully established. In the present study, a two-phase solvent system composed of chloroform-n-butanol-methanol-water (4:1:4:2, v/v/v/v) was used for HSCCC separation. A one-step separation in 4 h from 150 mg of crude extract produced 26.3 mg of trans-resveratrol-3-O-glucoside, 42.0 mg of pieceid-2"-O-gallate, and 17.9 mg of trans-resveratrol with purities of 99.1%, 97.8%, and 99.4%, respectively, as determined by high-performance liquid chromatography (HPLC). The chemical structures of these compounds were identified by nuclear magnetic resonance (NMR) spectroscopy.

Pumppukäyttöjen energiankulutuksen määrittäminen prosessimittauksia käyttäen

Pumppukäytöt vastaavat noin neljännestä Euroopan alueen sähkömoottoreissa kuluvasta energiasta. Energian hinnan nousun vuoksi energian säästäminen ja energiatehokkuus ovat nousseet tärkeään asemaan paljon energiaa kuluttavassa teollisuudessa. Pumppukäyttöjen hyötysuhteen parantaminen on noussut olennaiseen osaan paperi- ja kartonkiteollisuuden energiatehokkuustarkasteluissa. Tässä työssä tarkastellaan kartonkikoneen pumppukäyttöjen toiminnan energiatehokkuutta moottorin virtamittausten perusteella. Analyysi perustuu moottorin akselitehon määrittämiseen ja sen perusteella tehtävään pumpun toimintapisteen laskentaan. Työssä esitellään käytetyt estimointimenetelmät ja niillä saadut tulokset kartonkikoneen pumppukäytöille. Lisäksi työssä arvioidaan kolmen yksittäisen pumppukäytön energiankulutuksen säästöpotentiaalia. Työssä käytettyä menetelmää voidaan käyttää sekä vakio- että vaihtonopeuspumppukäyttöjen toiminnan ja hyötysuhteen analysointiin.

Flow injection spectrophotometric determination of adrenaline using a solid-phase reactor containing triiodide ions immobilized in an anion-exchange resin

A flow injection spectrophotometric procedure with on-line solid-phase reactor containing ion triiodide immobilized in an anion-exchange resin is proposed for the determination of adrenaline (epinephrine) in pharmaceutical products. Adrenaline is oxidized by triiodide ion immobilized in an anionic-exchange resin yielding adrenochrome which is transported by the carrier solution and detected at a wavelength of 488 nm. Adrenaline was determined in three pharmaceutical products in the 6.4 x 10-6 to 3.0 x 10-4 mol L-1 concentration range with a detection limit of 4.8 x 10-7 mol L-1. The recovery of this analyte in three samples ranged from 96.0 to 105 %. The analytical frequency was 80 determinations per hour and the RSDs were less than 1 % for adrenaline concentrations of 6.4 x 10-5 and 2.0 x 10-4 mol L-1 (n=10). A paired t-test showed that all results obtained for adrenaline in commercial formulations using the proposed flow injection procedure and a spectrophotometric batch procedure agree at the 95% confidence level.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

The Shadow Moiré method using the phase shifting technique and digital image processing: computational implementation and application to the 3D-reconstruction of a buckled plate

The Shadow Moiré fringe patterns are level lines of equal depth generated by interference between a master grid and its shadow projected on the surface. In simplistic approach, the minimum error is about the order of the master grid pitch, that is, always larger than 0,1 mm, resulting in an experimental technique of low precision. The use of a phase shift increases the accuracy of the Shadow Moiré technique. The current work uses the phase shifting method to determine the surfaces three-dimensional shape using isothamic fringe patterns and digital image processing. The current study presents the method and applies it to images obtained by simulation for error evaluation, as well as to a buckled plate, obtaining excellent results. The method hands itself particularly useful to decrease the errors in the interpretation of the Moiré fringes that can adversely affect the calculations of displacements in pieces containing many concave and convex regions in relatively small areas.

Maintaining supply performance during an ERP system implementation phase : case Cloetta Suomi Oy

Implementing an enterprise resource planning (ERP) system often means a major change to an organization and involves significant risks. It is typical that many of the ERP system implementations fail resulting in tremendous damage to the business. Moreover, running normal business operations during an ERP system implementation is far more complicated than normally. This thesis focuses on how an organization should manage the ERP system implementation process in order to maintain supply performance during the implementation phase. The theoretical framework in this thesis focuses on ERP system implementations with a critical success factor approach. Critical success factors can be divided into strategic and tactical level success factors. By considering these critical success factors, ERP system implementation project’s timeline and best practices of an ERP implementation, a critical success factor based ERP system implementation management framework is presented. The framework can be used as a theoretical framework when the goal is to avoid ERP system implementation phase issues that are driven by the ERP system implementation project and that may decrease organization’s supply performance. This thesis is a case study that was written on an assignment to a confectionary company Cloetta Suomi Oy. In order to collect data, interviews of the case company personnel were conducted. In addition, several other data collection methods were used throughout the research process. These data collection methods include examination of presentations and archival records as well as direct observations in case company meetings and in various work duties. The results of this thesis indicate that there are several factors that may decrease organization’s supply performance during the ERP system implementation. These issues are categorized under external and internal issues and further into six risk drivers that are suppliers, customers, products, staff, information systems and other projects. After the description and categorization of each issue, the thesis focuses on finding solutions on how to avoid or mitigate the impact of these issues on the organization’s supply performance. This examination leads to several operational activities that are also practical to business practitioners. It is also stated that a successful ERP system implementation that also causes minimal disturbance to organization’s supply performance during the ERP system implementation, is achieved by considering three levels of actions.

Aqueous-phase reforming of renewables for selective hydrogen production in the presence of supported platinum catalysts

The evolution of our society is impossible without a constant progress in life-important areas such as chemical engineering and technology. Innovation, creativity and technology are three main components driving the progress of chemistry further towards a sustainable society. Biomass, being an attractive renewable feedstock for production of fine chemicals, energy-rich materials and even transportation fuels, captures progressively new positions in the area of chemical technology. Knowledge of heterogeneous catalysis and chemical technology applied to transformation of biomass-derived substances will open doors for a sustainable economy and facilitates the discovery of novel environmentally-benign processes which probably will replace existing technologies in the era of biorefinary. Aqueous-phase reforming (APR) is regarded as a promising technology for production of hydrogen and liquids fuels from biomass-derived substances such as C3-C6 polyols. In the present work, aqueous-phase reforming of glycerol, xylitol and sorbitol was investigated in the presence of supported Pt catalysts. The catalysts were deposited on different support materials, including Al2O3, TiO2 and carbons. Catalytic measurements were performed in a laboratory-scale continuous fixedbed reactor. An advanced analytical approach was developed in order to identify reaction products and reaction intermediates in the APR of polyols. The influence of the substrate structure on the product formation and selectivity in the APR reaction was also investigated, showing that the yields of the desired products varied depending on the substrate chain length. Additionally, the influence of bioethanol additive in the APR of glycerol and sorbitol was studied. A reaction network was advanced explaining the formation of products and key intermediates. The structure sensitivity in the aqueous-phase reforming reaction was demonstrated using a series of platinum catalysts supported on carbon with different Pt cluster sizes in the continuous fixed-bed reactor. Furthermore, a correlation between texture physico-chemical properties of the catalysts and catalytic data was established. The effect of the second metal (Re, Cu) addition to Pt catalysts was investigated in the APR of xylitol showing a superior hydrocarbon formation on PtRe bimetallic catalysts compared to monometallic Pt. On the basis of the experimental data obtained, mathematical modeling of the reaction kinetics was performed. The developed model was proven to successfully describe experimental data on APR of sorbitol with good accuracy.

A Phase Model for Building a Customer Value Based Sales Tool – Case Mining and Metals Industry

The objective of this research is to observe the state of customer value management in Outotec Oyj, determine the key development areas and develop a phase model with which to guide the development of a customer value based sales tool. The study was conducted with a constructive research approach with the focus of identifying a problem and developing a solution for the problem. As a basis for the study, the current literature involving customer value assessment and solution and customer value selling was studied. The data was collected by conducting 16 interviews in two rounds within the company and it was analyzed by coding openly. First, seven important development areas were identified, out of which the most critical were “Customer value mindset inside the company” and “Coordination of customer value management activities”. Utilizing these seven areas three functionality requirements, “Preparation”, “Outotec’s value creation and communication” and “Documentation” and three development requirements for a customer value sales tool were identified. The study concluded with the formulation of a phase model for building a customer value based sales tool. The model included five steps that were defined as 1) Enable customer value utilization, 2) Connect with the customer, 3) Create customer value, 4) Define tool to facilitate value selling and 5) Develop sales tool. Further practical activities were also recommended as a guide for executing the phase model.

High doses of riboflavin and the elimination of dietary red meat promote the recovery of some motor functions in Parkinson's disease patients

Abnormal riboflavin status in the absence of a dietary deficiency was detected in 31 consecutive outpatients with Parkinson's disease (PD), while the classical determinants of homocysteine levels (B6, folic acid, and B12) were usually within normal limits. In contrast, only 3 of 10 consecutive outpatients with dementia without previous stroke had abnormal riboflavin status. The data for 12 patients who did not complete 6 months of therapy or did not comply with the proposed treatment paradigm were excluded from analysis. Nineteen PD patients (8 males and 11 females, mean age ± SD = 66.2 ± 8.6 years; 3, 3, 2, 5, and 6 patients in Hoehn and Yahr stages I to V) received riboflavin orally (30 mg every 8 h) plus their usual symptomatic medications and all red meat was eliminated from their diet. After 1 month the riboflavin status of the patients was normalized from 106.4 ± 34.9 to 179.2 ± 23 ng/ml (N = 9). Motor capacity was measured by a modification of the scoring system of Hoehn and Yahr, which reports motor capacity as percent. All 19 patients who completed 6 months of treatment showed improved motor capacity during the first three months and most reached a plateau while 5/19 continued to improve in the 3- to 6-month interval. Their average motor capacity increased from 44 to 71% after 6 months, increasing significantly every month compared with their own pretreatment status (P < 0.001, Wilcoxon signed rank test). Discontinuation of riboflavin for several days did not impair motor capacity and yellowish urine was the only side effect observed. The data show that the proposed treatment improves the clinical condition of PD patients. Riboflavin-sensitive mechanisms involved in PD may include glutathione depletion, cumulative mitochondrial DNA mutations, disturbed mitochondrial protein complexes, and abnormal iron metabolism. More studies are required to identify the mechanisms involved.

Effects of metformin treatment on luteal phase progesterone concentration in polycystic ovary syndrome

The causes of luteal phase progesterone deficiency in polycystic ovary syndrome (PCOS) are not known. To determine the possible involvement of hyperinsulinemia in luteal phase progesterone deficiency in women with PCOS, we examined the relationship between progesterone, luteinizing hormone (LH) and insulin during the luteal phase and studied the effect of metformin on luteal progesterone levels in PCOS. Patients with PCOS (19 women aged 18-35 years) were treated with metformin (500 mg three times daily) for 4 weeks prior to the test cycle and throughout the study period, and submitted to ovulation induction with clomiphene citrate. Blood samples were collected from control (N = 5, same age range as PCOS women) and PCOS women during the late follicular (one sample) and luteal (3 samples) phases and LH, insulin and progesterone concentrations were determined. Results were analyzed by one-way analysis of variance (ANOVA), Duncan's test and Karl Pearson's coefficient of correlation (r). The endocrine study showed low progesterone level (4.9 ng/ml) during luteal phase in the PCOS women as compared with control (21.6 ng/ml). A significant negative correlation was observed between insulin and progesterone (r = -0.60; P < 0.01) and between progesterone and LH (r = -0.56; P < 0.05) concentrations, and a positive correlation (r = 0.83; P < 0.001) was observed between LH and insulin. The study further demonstrated a significant enhancement in luteal progesterone concentration (16.97 ng/ml) in PCOS women treated with metformin. The results suggest that hyperinsulinemia/insulin resistance may be responsible for low progesterone levels during the luteal phase in PCOS. The luteal progesterone level may be enhanced in PCOS by decreasing insulin secretion with metformin.

Quantitative evidence for neurofilament heavy subunit aggregation in motor neurons of spinal cords of patients with amyotrophic lateral sclerosis

Amyotrophic lateral sclerosis (ALS), a neurodegenerative disease of unknown etiology, affects motor neurons leading to atrophy of skeletal muscles, paralysis and death. There is evidence for the accumulation of neurofilaments (NF) in motor neurons of the spinal cord in ALS cases. NF are major structural elements of the neuronal cytoskeleton. They play an important role in cell architecture and differentiation and in the determination and maintenance of fiber caliber. They are composed of three different polypeptides: light (NF-L), medium (NF-M) and heavy (NF-H) subunits. In the present study, we performed a morphological and quantitative immunohistochemical analysis to evaluate the accumulation of NF and the presence of each subunit in control and ALS cases. Spinal cords from patients without neurological disease and from ALS patients were obtained at autopsy. In all ALS cases there was a marked loss of motor neurons, besides atrophic neurons and preserved neurons with cytoplasmic inclusions, and extensive gliosis. In control cases, the immunoreaction in the cytoplasm of neurons was weak for phosphorylated NF-H, strong for NF-M and weak for NF-L. In ALS cases, anterior horn neurons showed intense immunoreactivity in focal regions of neuronal perikarya for all subunits, although the difference in the integrated optical density was statistically significant only for NF-H. Furthermore, we also observed dilated axons (spheroids), which were immunopositive for NF-H but negative for NF-M and NF-L. In conclusion, we present qualitative and quantitative evidence of NF-H subunit accumulation in neuronal perikarya and spheroids, which suggests a possible role of this subunit in the pathogenesis of ALS.

Sähkökoneessa esiintyvien voimien yksityiskohtainen mittausjärjestelmä

Hissiteollisuudessa nostokoneistoina käytettyjen sähkömoottoreiden laatuvaatimukset ovat tiuken-tuneet viime vuosina. Erityisesti koneistojen tuottama ääni ja mekaaninen värähtely ovat olleet jat-kuvasti tiukentuneen tarkastelun alaisena. Hissikoriin ja hissiä ympäröiviin rakenteisiin välittyvästä värähtelystä johtuva ääni on yksi hissin laatuvaikutelmaan merkittävimmin vaikuttavia tekijöitä. Nostokoneisto on yksi tärkeimmistä äänen ja värähtelyn lähteistä hissijärjestelmässä. Koneiston suunnittelulla edellä mainittuja tekijöitä voidaan minimoida. Sähkökoneiden suunnittelussa finiit-tielementtimenetelmien (FEM) käyttö on vakiintunut haastavimmissa sovelluksissa. Kone Oyj:llä nostokoneistoina käytetään aksiaalivuokestomagneettitahtikoneita (AFPMSM), joiden FEM simu-lointiin käytetään yleisesti kolmea eri tapaa. Kukin näistä vaihtoehdoista pitää sisällään omat hyö-tynsä, että haittansa. Suunnittelun kannalta tärkeää on oikean menetelmän valinta ai-ka/informatiivisuus suhteen maksimoimiseksi. Erittäin tärkeää on myös saatujen tulosten oikeelli-suus. Tämän diplomityön tavoite on kehittää järjestelmä, jonka avulla AFPMS-koneen voimia voidaan mitata yksityiskohtaisella tasolla. Järjestelmän avulla voidaan tarkastella käytössä olevien FE-menetelmien tulosten oikeellisuutta sekä äänen että värähtelyn syntymekanismeja. Järjestelmän tarkoitus on myös syventää Kone Oyj tietotaitoa AFPMS-koneiden toiminnasta. Tässä työssä esitellään AFPMS-koneen epäideaalisuuksia, jotka voivat vaikuttaa mittajärjestelmän suunnitteluun. Myös koneen epäideaalisuuksiin lukeutuvaa ääntä on tarkasteltu tässä työssä. Jotta työn tavoitteiden mukaista FE-menetelmien vertailua ja tulosten oikeellisuuden tarkastelua voitai-siin tehdä, myös yleisimpiä AFPMS-koneen FE-menetelmiä tarkastellaan. Työn tuloksena on mittajärjestelmän suunnitelma, jonka avulla voidaan toteuttaa kuuden vapausas-teen voimamittaus jokaiselle koneistomagneetille alle 1N resoluutiolla. Suunnitellun järjestelmän toimivuutta on tarkasteltu FE-menetelmiä käyttäen ja järjestelmässä käytettävän voima-anturin ky-vykkyyttä on todennettu referenssimittauksin. Suunniteltu mittajärjestelmä mahdollistaa sähkömoottorin useiden eri epäideaalisuuksien tarkaste-lun yksityiskohtaisella tasolla. Mittausajatuksen soveltaminen myös muiden koneiden tutkimiseen tarjoaa mahdollisuuksia jatkotutkimuksille.

Profile of three Brazilian birth cohort studies in Ribeirão Preto, SP and São Luís, MA

We describe three birth cohort studies, respectively carried out in 1978/79 and 1994 in Ribeirão Preto, a city located in the most developed region of Brazil, and in 1997/98 in São Luís, a city located in a less developed region. The objective of the present report was to describe the methods used in these three studies, presenting their history, methodological design, objectives, developments, and difficulties faced along 28 years of research. The first Ribeirão Preto study, initially perinatal, later encompassed questions regarding the repercussions of intrauterine development on future growth and chronic adult diseases. The subjects were evaluated at birth (N = 6827), at school age (N = 2861), at the time of recruitment for military service (N = 2048), and at 23/25 years of age (N = 2063). The study of the second cohort, which started in 1994 (N = 2846), permitted comparison of aspects of perinatal health between the two groups in the same region, such as birth weight, mortality and health care use. In 1997/98, a new birth cohort study was started in São Luís (N = 2443), capital of the State of Maranhão. The 1994 Ribeirão Preto cohort and the São Luís cohort are in the second phase of joint follow-up. These studies permit comparative temporal analyses in the same place (Ribeirão Preto 1978/79 and 1994) and comparisons of two contrasting populations regarding cultural, economic and sociodemographic conditions (Ribeirão Preto and São Luís).