Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Studies in selectivity of lipases in preparation of cyanohydrins, sugar conjugates and secondary alcohols

Biocatalysis can be applied in organic synthetic chemistry to counter challenges posed by increased demands towards chemo-, regio- and stereoselectivity, not forgetting the need for greener chemistry. During the last 30 years, biocatalysis with the use of enzymes as chiral catalysts has become more common in chemistry laboratories and industrial processes. In this thesis, the use of lipases as versatile biocatalysts in the acylation of alcohols is examined both in the light of literature examples and four original publications. In the first part of the work presented in this thesis lipases were utilized in two examples concerning secondary alcohols. First, the kinetic resolution of heterocyclic aromatic secondary alcohols through transesterification was thoroughly examined including the studies of competing hydrolysis and esterification reactions. In another example, lipases were utilized in the formation of a dynamic systemic resolution (DSR) process which in turn was used as a developmental tool in the optimization of the dynamic kinetic resolution (DKR) of five heterocyclic aromatic cyanohydrins in one pot for the preparation of cyanohydrin esters as single enantiomers. In the second part of the work, the regio- and stereoselectivity of lipases was used to form sugar conjugates of glyceric and β-amino acids. The primary hydroxyl groups of methyl α-D-galacto-, -gluco- and -mannopyranosides were now acylated trough lipasecatalyzed transesterification and enantioselective lipase-catalyzed ring-opening of β- lactams, respectively.

Aplicação e modificação química da sílica gel obtida de areia

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Los entornos virtuales como herramienta sustituta del laboratorio "real" y como complemento de la enseñanza de Química a alumnos de Ingeniería. Virtual environments as substitute tools for the "conventional" laboratories and as a complement for Chemistry teaching to Engineering students.

El presente proyecto se plantea el siguiente problema de investigación:¿Cuál es la eficacia de los entornos virtuales de enseñanza para optimizar los aprendizajes de Química? Se sostiene la hipótesis de que los entornos virtuales de enseñanza, empleados como mediación instrumental, son eficaces para optimizar los aprendizajes de química, particularmente facilitando la vinculación y reversibilidad entre "mundo micro y macroscópico"; capacidad que usualmente sólo se atribuye al trabajo experimental de laboratorio. Los objetivos propuestos son: Determinar la eficacia de entornos virtuales de enseñanza, como mediaciones instrumentales, para optimizar los aprendizajes de química en estudiantes de ingeniería. Implementar un entrono virtual de enseñanza de química, diseñado como mediación instrumental y destinado a estudiantes de dos carreras de ingeniería del IUA. Evaluar el desarrollo y los resultados de la innovación introducida. Comparar los resultados de la innovación con los resultados de la enseñanza usual. Derivar conclusiones acerca de la eficacia de la innovación propuesta. Socializar el conocimiento producido en ámbitos científico-tecnológicos reconocidos. Se generará un aula virtual en plataforma Educativa y utilidzando el laboratorio de computación de la institución se buscará desarrollar laboratorios virtuales donde se propondrán actividades de simulación de trabajo experimental. Los resultados esperados son: - Un Aula Virtual que cumpla funciones análogas a las de un laboratorio experimental. - Información válida y confiable acerca de la eficacia de la misma como medio para optimizar los aprendizajes de química. - Publicaciones en ámbitos científico-tecnológicos reconocidos que sometan a juicio público la innovación y la investigación efectuadas. La importancia del proyecto radica principalmente en poner a prueba la eficacia de los entornos virtuales para optimizar los aprendizajes de química, analogando tareas usualmente limitadas al trabajo experimental de laboratorio. Su pertinencia apunta a un replanteo del curriculo de los cursos de Química para estudiantes de Ingeniería.

Heteroscedastic controlled calibration model applied to analytical chemistry

In chemical analyses performed by laboratories, one faces the problem of determining the concentration of a chemical element in a sample. In practice, one deals with the problem using the so-called linear calibration model, which considers that the errors associated with the independent variables are negligible compared with the former variable. In this work, a new linear calibration model is proposed assuming that the independent variables are subject to heteroscedastic measurement errors. A simulation study is carried out in order to verify some properties of the estimators derived for the new model and it is also considered the usual calibration model to compare it with the new approach. Three applications are considered to verify the performance of the new approach. Copyright (C) 2010 John Wiley & Sons, Ltd.

Recommendations for CAMAC serial highway drivers and LAM graders for the SCCL2 serial crate controller : adopted by U.S. NIM Committee (Nuclear Instrumentation Methods) and ESONE Committee of European Laboratories (European Standards on Nuclear Electronics).

Issued Jan. 1978.

Towars a chemical reagents and residues management at the teaching laboratories of the Chemistry School of the Universidad Nacional

The academic activities carried out at the School of Chemistry make indispensable to develop actions oriented toward the consolidation of a reagent and residue management system, especially in the teaching laboratories. The project “Management of reagents and residues in the teaching laboratories of the School of Chemistry” works under the Green Chemistry values which designs products and chemical processes that reduce or eliminate the use and production of dangerous substances, to benefit the environment. With a preventive vision, a change from the  laboratory practices is looked to select those with less environmental impact. Additionally, residue quantification is made and its management protocols are developed for each practice. The project has several stages: diagnose, action implementation, student, teacher and administration personnel training and evaluation during the process and at the end of it. The article describes methodological aspects of the project operation emphasizing on reagent and residue quantification through flow diagrams.

Ar-40/-Ar-39 geochronology at the Instituto de Geociencias, USP: instrumentation, analytical procedures, and calibration

Laser heating Ar-40/Ar-39 geochronology provides high analytical precision and accuracy, mum-scale spatial resolution. and statistically significant data sets for the study of geological and planetary processes, A newly commissioned Ar-40/Ar-39 laboratory at CPGeo/USP, Sao Paulo, Brazil, equips the Brazilian scientific community with a new powerful tool applicable to the study of geological and cosmochemical processes. Detailed information about laboratory layout, environmental conditions, and instrumentation provides the necessary parameters for the evaluation of the CPGeo/USp Ar-40/Ar-39 suitability to a diverse range of applications. Details about analytical procedures, including mineral separation, irradiation at the IPEN/CNEN reactor at USP, and mass spectrometric analysis enable potential researchers to design the necessary sampling and sample preparation program suitable to the objectives of their study. Finally, the results of calibration tests using Ca and K salts and glasses, international mineral standards, and in-house mineral standards show that the accuracy and precision obtained at the Ar-40/Ar-39 laboratory at CPGeo/USP are comparable to results obtained in the most respected laboratories internationally. The extensive calibration and standardization procedures under-taken ensure that the results of analytical studies carried out in our laboratories will gain immediate international credibility, enabling Brazilian students and scientists to conduct forefront research in earth and planetary sciences.

IX International conference on Remote Engineering and Virtual instrumentation REV 2012

THE ninth edition of the International Conference on Remote Engineering and Virtual Instrumentation (REV) [1] was held at the Faculty of Engineering of the University of Deusto, Bilbao (Spain), from the 4th to the 6th of July, 2012. A world-class research community in the subject of remote and virtual laboratories joined the event.

Determination of 13C/12C ratios of endogenous urinary 5-amino-imidazole-4-carboxamide 1-D-ribofuranoside (AICAR)

RATIONALE: AICAR (5-aminoimidazole-4-carboxamide 1β-D-ribofuranoside) is prohibited in sport according to rules established by the World Anti-Doping Agency. Doping control laboratories identify samples where AICAR abuse is suspected by measuring its urinary concentration and comparing the observed level with naturally occurring concentrations. As the inter-individual variance of urinary AICAR concentrations is large, this approach requires a complementary method to unambiguously prove the exogenous origin of AICAR. Therefore, a method for the determination of carbon isotope ratios (CIRs) of urinary AICAR has been developed and validated. METHODS: Concentrated urine samples were fractionated by means of liquid chromatography for analyte cleanup. Derivatization of AICAR yielding the trimethylsilylated analog was necessary to enable CIR determinations by gas chromatography/combustion/isotope ratio mass spectrometry. The method was tested for its repeatability and stability over time and a linear mixing model was applied to test for possible isotopic discrimination. A reference population of n = 63 males and females was investigated to calculate appropriate reference limits to differentiate endogenous from exogenous urinary AICAR. These limits were tested by an AICAR elimination study. RESULTS: The developed method fulfills all the requirements for adequate sports drug testing and was found to be fit for purpose. The investigated reference population showed a larger variability in the CIR of AICAR than of the endogenous steroids. Nevertheless, the calculated thresholds for differences between AICAR and endogenous steroids can be applied straightforwardly to evaluate suspicious doping control samples with the same statistical confidence as established e.g. for testosterone misuse. These thresholds enabled the detection of a single oral AICAR administration for more than 40 h. CONCLUSIONS: Determination of thee CIRs is the method of choice to distinguish between an endogenous and an exogenous source of urinary AICAR. The developed method will enable investigations into doping control samples with elevated urinary concentrations of AICAR and clearly differentiate between naturally produced/elevated and illicitly administered AICAR.

2011 lAAF World Championships in Daegu: blood tests for all athletes in the framework of the Athlete Biological Passport.

The 2011 International Association of Athletics Federation (IAAF) World Championships took place in Daegu, Korea. For the first time, all athletes were blood tested prior to the competition in order to give a clear signal to the world athletic community of the wish to enter into the era of the Athlete Biological Passport and fight against doping in their sport. The hematological parameters were measured on site. Thus, a mobile-accredited laboratory for blood testing was created in Daegu. Two serum tubes were collected for clinical chemistry and hormonal analyses in order to build the bases of the endocrine and the androgen (steroid) modules of the Athlete Biological Passport in blood. This paper describes some of the main challenges the project faced with regard to the large number of athletes, competing in different disciplines, and the logistic problems that had to be solved for smart implementation of one of the most complex operations organized in the last decade in the fight against doping.

Medicinal application of long synthetic peptide technology.

This review covers the latest developments of long synthetic peptide technology for the rapid identification and development of malaria vaccine candidates and immunological modulators. A brief description of the two most common solid-phase synthetic procedures, together with the latest advances in optimisation of peptide chain assembly and analytical instrumentation, is given, with special attention to non-specialists. Several examples of vaccine candidates developed in the authors' or their collaborators' laboratories are also provided.

Reliable and fast sensor for in vitro evaluation of solar protection factor based on the photobleaching kinetics of a nanocrystalline TiO(2)/dye UV-dosimeter

A reliable and fast sensor for in vitro evaluation of solar protection factors (SPFs) of cosmetic products, based on the photobleaching kinetics of a nanocrystalline TiO(2)/dye UV-dosimeter, has been devised. The accuracy, robustness and suitability of the new device was demonstrated by the excellent matching of the predicted and the in vivo results up to SPF 70, for four standard samples analyzed in blind. These results strongly suggest that our device can be useful for routine SPF evaluation in laboratories devoted to the development or production of cosmetic formulations, since the conventional in vitro methods tend to exhibit unacceptably high errors above SPF similar to 30 and the conventional in vivo methods tend to be expensive and exceedingly time consuming. (C) 2011 Elsevier B.V. All rights reserved.

Weight loss and surface roughness of hard chairside reline resins after toothbrushing: Influence of postpolymerization treatments

Purpose: To evaluate the effect of 2 postpolymerization treatments on toothbrushing wear (weight loss) and surface roughness of 3 autopolymerized reline resins-Duraliner II (D) (Reliance Dental), Kooliner (K) (Coe Laboratories), and Tokuso Rebase Fast (T) (Tokuyama Dental)-and 1 heat-polymerized resin, Lucitone 550 (L) (Dentsply International). Materials and Methods: Specimens (40 x 10 x 2mm) of each material (n = 24) were prepared and divided into 3 groups: control (no postpolymerization treatment); water bath (immersion in water at 55°C); and microwave (microwave irradiation). Specimens were dried until constant weight was achieved and the surface roughness (Ra) was measured. Tests were performed in a toothbrush machine using 20,000 strokes of brushing at a weight of 200 g, with the specimens immersed in 1:1 dentifrice/water slurry. Specimens were reconditioned to constant weight and the weight loss (mg) and surface roughness were evaluated. Data were analyzed by 2-way analysis of variance and followed by Tukey test (α = .05). Results: In the control group, the weight loss of materials D and T was lower (P < .05) than that of L. No differences among materials were found after postpolymerization treatments (P > .05). The weight loss of material T (control = 0.5 mg) was significantly increased (P < .05) after postpolymerization treatments (water bath = 1.9 mg; microwave = 1.8 mg). For materials K and T, the toothbrushed surface roughness was higher (P < .05) after microwave and waterbath postpolymerization treatments. Material L showed increased surface roughness after microwave postpolymerization treatment. Conclusion: The toothbrushing wear resistance of L was not superior to the reline resins. The postpolymerization treatments did not improve the toothbrushing wear resistance of the materials and produced an increased surface roughness for materials L, K, and T.