Handbook of instrumental techniques for materials, chemical and biosciences research

This Handbook contains a collection of articles describing instrumental techniques used for Materials, Chemical and Biosciences research that are available at the Scientific and Technological Centers of theUniversity of Barcelona (CCiTUB). The CCiTUB are a group of facilities of the UB that provide both the research community and industry with ready access to a wide range of major instrumentation.Together with the latest equipment and technology, the CCiTUB provide expertise in addressing the methodological research needs of the user community and they also collaborate in R+D+i Projectswith industry. CCiTUB specialists include technical and Ph.D.-level professional staff members who are actively engaged in methodological research. Detailed information on the centers’ resources andactivities can be found at the CCiTUB website www.ccit.ub.edu ...

The chemical variability at the surface of Mars: implications for exogenic processes

The chemical composition of sediments and rocks, as well as their distribution at theMartian surface, represent a long term archive of processes, which have formed theplanetary surface. A survey of chemical compositions by means of Compositional DataAnalysis represents a valuable tool to extract direct evidence for weathering processesand allows to quantify weathering and sedimentation rates. clr-biplot techniques areapplied for visualization of chemical relationships across the surface (“chemical maps”).The variability among individual suites of data is further analyzed by means of clr-PCA,in order to extract chemical alteration vectors between fresh rocks and their crusts andfor an assessment of different source reservoirs accessible to soil formation. Bothtechniques are applied to elucidate the influence of remote weathering by combinedanalysis of several soil forming branches. Vector analysis in the Simplex provides theopportunity to study atmosphere surface interactions, including the role andcomposition of volcanic gases

Study of chemical modification of alkaline lignin by the glyoxalation reaction

In this study, glyoxalated alkaline lignins with a non-volatile and non-toxic aldehyde, which can be obtained from several natural resources, namely glyoxal, were prepared and characterized for its use in wood adhesives. The preparation method consisted of the reaction of lignin with glyoxal under an alkaline medium. The influence of reaction conditions such as the molar ratio of sodium hydroxide-to-lignin and reaction time were studied relative to the properties of the prepared adducts. The analytical techniques used were FTIR and 1H-NMR spectroscopies, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Results from both the FTIR and 1H-NMR spectroscopies showed that the amount of introduced aliphatic hydroxyl groups onto the lignin molecule increased with increasing reaction time and reached a maximum value at 10 h, and after they began to decrease. The molecular weights remained unchanged until 10 h of reaction time, and then started to increase, possibly due to the repolymerization reactions. DSC analysis showed that the glass transition temperature (Tg) decreased with the introduction of glyoxal onto the lignin molecule due to the increase in free volume of the lignin molecules. TGA analysis showed that the thermal stability of glyoxalated lignin is not influenced and remained suitable for wood adhesives. Compared to the original lignin, the improved lignin is reactive and a suitable raw material for adhesive formula

Microstructure and secondary phases in coevaporated CuInS2 films: Dependence on growth temperature and chemical composition

The microstructure of CuInS2-(CIS2) polycrystalline films deposited onto Mo-coated glass has been analyzed by Raman scattering, Auger electron spectroscopy (AES), transmission electron microscopy, and x-ray diffraction techniques. Samples were obtained by a coevaporation procedure that allows different Cu-to-In composition ratios (from Cu-rich to Cu-poor films). Films were grown at different temperatures between 370 and 520-°C. The combination of micro-Raman and AES techniques onto Ar+-sputtered samples has allowed us to identify the main secondary phases from Cu-poor films such as CuIn5S8 (at the central region of the layer) and MoS2 (at the CIS2/Mo interface). For Cu-rich films, secondary phases are CuS at the surface of as-grown layers and MoS2 at the CIS2/Mo interface. The lower intensity of the MoS2 modes from the Raman spectra measured at these samples suggests excess Cu to inhibit MoS2 interface formation. Decreasing the temperature of deposition to 420-°C leads to an inhibition in observing these secondary phases. This inhibition is also accompanied by a significant broadening and blueshift of the main A1 Raman mode from CIS2, as well as by an increase in the contribution of an additional mode at about 305 cm-1. The experimental data suggest that these effects are related to a decrease in structural quality of the CIS2 films obtained under low-temperature deposition conditions, which are likely connected to the inhibition in the measured spectra of secondary-phase vibrational modes.

Nonlinear inverse dynamic models of gas sensing systems based on chemical sensor arrays for quantitative measurements

Gas sensing systems based on low-cost chemical sensor arrays are gaining interest for the analysis of multicomponent gas mixtures. These sensors show different problems, e.g., nonlinearities and slow time-response, which can be partially solved by digital signal processing. Our approach is based on building a nonlinear inverse dynamic system. Results for different identification techniques, including artificial neural networks and Wiener series, are compared in terms of measurement accuracy.

Chemical variability in clays and pottery from a traditional cooking pot production village: Testing assumptions in Pereruela

This paper explores analytically the contemporary pottery-making community of Pereruela (north-west Spain) that produces cooking pots from a mixture of red clay and kaolin. Analyses by different techniques (XRF, NAA, XRD, SEM and petrography) showed an extremely high variability for cooking ware pottery produced in a single production centre, by the same technology and using local clays. The main source of chemical variation is related to the use of different red clays and the presence of non-normally distributed inclusions of monazite. These two factors induce a high chemical variability, not only in the output of a single production centre, but even in the paste of a single pot, to an extent to which chemical compositions from one"workshop", or even one"pot", could be classified as having different provenances. The implications for the chemical characterization and for provenance studies of archaeological ceramics are addressed.

Assessment of dissolution techniques for the analysis of ceramic samples by plasma spectrometry

In this study, 13 ceramic samples were subjected to dissolution using three different procedures: (a) acid attack in open PTFE vessels with a mixture of HF-HClO4, (b) fusion of the sample with lithium metaborate and (c) microwave digestion in PTFE bombs. The samples used in the study had been previously analyzed by neutron activation analysis (NAA), X-ray fluorescence (XRF) and X-ray diffraction (XRD) and they cover a wide range of ceramics fired in different atmospheres and temperatures as well as different mineralogical and chemical compositions. The effectiveness of each procedure is evaluated in terms of its ability to dissolve the various mineralogical phases of the samples, of the number of elements that can be determined and of the time needed for the whole scheme of analysis to be completed.

Standardisation of elemental analytical techniques applied to provenance studies of archaeological ceramics: an inter laboratory calibration study

Chemical analysis is a well-established procedure for the provenancing of archaeological ceramics. Various analytical techniques are routinely used and large amounts of data have been accumulated so far in data banks. However, in order to exchange results obtained by different laboratories, the respective analytical procedures need to be tested in terms of their inter-comparability. In this study, the schemes of analysis used in four laboratories that are involved in archaeological pottery studies on a routine basis were compared. The techniques investigated were neutron activation analysis (NAA), X-ray fluorescence analysis (XRF), inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). For this comparison series of measurements on different geological standard reference materials (SRM) were carried out and the results were statistically evaluated. An attempt was also made towards the establishment of calibration factors between pairs of analytical setups in order to smooth the systematic differences among the results.

Chemical and mineralogical alteration of ceramics from a Late Bronze Age kiln at Kommos, Crete: the effect on the formation of a reference group

The formation of reference groups comprises an important procedure in chemical provenance studies of archaeological pottery. Material from ancient kilns is thought to be especially suitable for reference groups, as it comprises a definite unit of past production. Pottery from the Late Minoan IA kiln excavated at Kommos, Crete was analysed in order to produce a reference group in this important area of Minoan ceramic production. The samples were characterized by a combination of techniques providing information on the chemistry, mineralogy and microstructure of the ceramic body. Initially, the study was unable to establish, in a straightforward manner, a chemical reference group. Different ceramic pastes and a range of selective alterations and contaminations, affected by variable firing temperatures and burial environment, were shown to be responsible for the compositional variability. Procedures are described to compensate for such alterations and the perturbations in the data that they produce.

Characterization and Control Strategies of an Integrated Chemical-Biological System for the Remediation of Toxic Pollutants in Wastewater: A case of study

In a previous work, a hybrid system consisting of an advanced oxidation process (AOP) named Photo-Fenton (Ph-F) and a fixed bed biological treatment operating as a sequencing batch biofilm reactor (SBBR) was started-up and optimized to treat 200 mg·L-1 of 4-chlorophenol (4-CP) as a model compound. In this work, studies of reactor stability and control as well as microbial population determination by molecular biology techniques were carried out to further characterize and control the biological reactor. Results revealed that the integrated system was flexible and even able to overcome toxic shock loads. Oxygen uptake rate (OUR) in situ was shown to be a valid tool to control the SBBR operation, to detect toxic conditions to the biomass, and to assess the recovery of performance. A microbial characterization by 16S rDNA sequence analysis reveals that the biological population was varied, although about 30% of the bacteria belonged to the Wautersia genus.

Micro- and nanostructuring of poly(ethylene-2,6-naphthalate) surfaces, for biomedical applications, using polymer replication techniques

Here we investigate the formation of superficial micro- and nanostructures in poly(ethylene-2,6-naphthalate) (PEN), with a view to their use in biomedical device applications, and compare its performance with a polymer commonly used for the fabrication of these devices, poly(methyl methacrylate) (PMMA). The PEN is found to replicate both micro- and nanostructures in its surface, albeit requiring more forceful replication conditions than PMMA, producing a slight increase in surface hydrophilicity. This ability to form micro/nanostructures, allied to biocompatibility and good optical transparency, suggests that PEN could be a useful material for production of, or for incorporation into, transparent devices for biomedical applications. Such devices will be able to be autoclaved, due to the polymer's high temperature stability, and will be useful for applications where forceful experimental conditions are required, due to a superior chemical resistance over PMMA.

Image registration techniques with multiresolution analysis in satellite oceanography

En aquest article es fa una descripció dels procediments realitzats per enregistrar dues imatges geomètricament, de forma automàtica, si es pren la primera com a imatge de referència. Es comparen els resultats obtinguts mitjançant tres mètodes. El primer mètode és el d’enregistrament clàssic en domini espacial maximitzant la correlació creuada (MCC)[1]. El segon mètode es basa en aplicar l’enregistrament MCC conjuntament amb un anàlisi multiescala a partir de transformades wavelet [2]. El tercer mètode és una variant de l’anterior que es situa a mig camí dels dos. Per cada un dels mètodes s’obté una estimació dels coeficients de la transformació que relaciona les dues imatges. A continuació es transforma per cada cas la segona imatge i es georeferencia respecte la primera. I per acabar es proposen unes mesures quantitatives que permeten discutir i comparar els resultats obtinguts amb cada mètode.

Desenvolupament d'hidrogels superficials que contenen motius d'adhesió cel·lular

Projecte de recerca elaborat a partir d’una estada al Departament d’Enginyeria Química del Massachusetts Institute of Technology entre abril i octubre del 2006. S’ha dissenyat i sintetitzat uns nous films polimèrics, amb aplicacions en l’àmbit de l’enginyeria de teixits, utilitzant la tècnica anomenada iCVD (initiated Chemical Vapor Deposition), prèviament desenvolupada pel grup receptor. Es tracta d’uns hidrogels superficials de gruix controlable, que incorporen un monòmer fluorat, el qual s’havia estudiat extensament en el grup d’origen. Aquest monòmer es caracteritza per reaccionar molt fàcilment amb pèptids, de manera que aquests queden units covalentment a la superfície. Diferents estratègies pel desenvolupament d’aquests copolímers han estat avaluades, tant des del punt de vista purament sintètic com de la pròpia aplicació. Les condicions de polimerització han estat optimitzades i els hidrogels s’han caracteritzat químicament per tècniques espectroscòpiques (FTIR, XPS), i físicament per angle de contacte i el·lipsometria. D’aquesta manera, s’ha estudiat la capacitat dels hidrogels d’absorbir aigua i alhora augmentar el seu gruix, depenent de la quantitat d’agent reticulant introduït i de la incorporació del nou monòmer. A continuació, s’han optimitzat les condicions de reacció d’aquestes superfícies amb pèptids que incorporen una molècula fluorescent, la qual permet detectar fàcilment per microscòpia de fluorescència si la reacció ha tingut lloc. Una vegada la plataforma ha estat posada a punt, s’han iniciat assajos cel·lulars tant amb fibroblasts embriònics de ratolí com amb cèl·lules humanes umbilicals. Els resultats preliminars suggereixen una morfologia diferent de les cèl·lules segons si es cultiven sobre films modificats amb pèptids que promouen l’adhesió cel·lular o sobre les seves seqüències permutades no actives. Però, el més interessant és que també s’han observat certes diferències depenent si els films contenen el component hidrogel o no, fet que suggeriria un paper actiu d’aquests noves superfícies en el comportament cel·lular.

Combining classification techniques to define topo-climatic landscapes

Landscape classification tackles issues related to the representation and analysis of continuous and variable ecological data. In this study, a methodology is created in order to define topo-climatic landscapes (TCL) in the north-west of Catalonia (north-east of the Iberian Peninsula). TCLs relate the ecological behaviour of a landscape in terms of topography, physiognomy and climate, which compound the main drivers of an ecosystem. Selected variables are derived from different sources such as remote sensing and climatic atlas. The proposed methodology combines unsupervised interative cluster classification with a supervised fuzzy classification. As a result, 28 TCLs have been found for the study area which may be differentiated in terms of vegetation physiognomy and vegetation altitudinal range type. Furthermore a hierarchy among TCLs is set, enabling the merging of clusters and allowing for changes of scale. Through the topo-climatic landscape map, managers may identify patches with similar environmental conditions and asses at the same time the uncertainty involved.