Characterization of Unye bentonite after treatment with sulfuric acid

Unye bentonite was found to consist predominantly of a dioctahedral smectite along with quartz, tridymite, cristobalite, and minor fractions of feldspar and anatase. A considerable amount of Al was retained as a constituent in acid-resistant impurities following the decomposition of the montmorillonite via acid treatment at an acid/clay ratio of 0.4. These impurities were mesoporous with a maximum surface area of 303.9±0.4 m² g-1. A sharp decrease in the d001 lattice spacing of the montmorillonite to 15.33 Å reflected the reduction of the crystallinity in the activated products. In addition, the increase in the ease with which newly formed hydroxyl groups were lost paralleled the severity of the acid treatment.

Cinética e caracterização de ramnolipídeos produzidos por Pseudomonas aeruginosa MSIC02 utilizando glicerol como fonte de carbono

Glycerol, a co-product of biodiesel production, was used as a carbon source for the kinetics studies and production of biosurfactants by P. aeruginosa MSIC02. The highest fermentative parameters (Y PX = 3.04 g g-1; Y PS = 0.189 g g-1, P B = 31.94 mg L-1 h-1 and P X = 10.5 mg L-1 h-1) were obtained at concentrations of 0.4% (w/v) NaNO3 and 2% (w/v) glycerol. The rhamnolipid exhibited 80% of emulsification on kerosene, surface tension of 32.5 mN m-1, CMC = 28.2 mg L-1, C20 (concentration of surfactant in the bulk phase that produces a reduction of 20 dyn/cm in the surface tension of the solvent) = 0.99 mg L-1, Γm (surface concentration excess) = 2.4 x 10-26 mol Å-2 and S (surface area) = 70.4 Ų molecule-1 with solutions containing 10% NaCl. A mathematical model based on logistic equation was considered to representing the process. Model parameters were estimated by non-linear regression method. This approach was able to give a good description of the process.

SÍNTESE E CARACTERIZAÇÃO DE COMPÓSITOS ORGÂNICO-INORGÂNICOS MACROPOROSOS PARA O SENSORIAMENTO DE H2O2

Electrodes modified with poly(5-amino-1-naphthol)/Prussian blue (poly(5-NH2-1-NAP)/PB) hybrid films are able to electrochemically reduce H2O2 in medium containing an excess of Na+ cations. This is an important advantage for biosensing applications over electrodes in which only conventionally (electro) deposited Prussian blue is present. Consequently, the aim of this work was to examine the application of templates of ordered arrays of colloidal poly(styrene) spheres (800, 450 and 100 nm in diameter) to produce inverse opal structures of poly(5-NH2-1-NAP)/PB hybrid platforms, in an effort to study the influence of the increase in surface area/volume ratio and higher exposition of the mediator active sites on material performance during H2O2 determination employing the different sized porous structures. Moreover, since the accentuated hydrophilic character of poly(5-NH2-1-NAP)/PB also allows H2O2 electrochemical reduction in inner active sites, issues concerning the amount of mediator electrodeposited on the electrode were also reflected in the observed results.

METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Immersion enthalpy variation of surface-modified mineral activated carbon in lead (II) aqueous solution adsorption: the relation between immersion enthalpy and adsorption capacity

An activated carbon was obtained by chemical activation with phosphoric acid, CM, from a mineral carbon. Afterwards, the carbon was modified with 2 and 5 molL-1, CMox2 and CMox5 nitric acid solutions to increase the surface acid group contents. Immersion enthalpy at pH 4 values and Pb2+ adsorption isotherms were determined by immersing activated carbons in aqueous solution. The surface area values of the adsorbents and total pore volume were approximately 560 m².g-1 and 0.36 cm³g-1, respectively. As regards chemical characteristics, activated carbons had higher acid sites content, 0.92-2.42 meq g-1, than basic sites, 0.63-0.12 meq g-1. pH values were between 7.4 and 4.5 at the point of zero charge, pH PZC. The adsorbed quantity of Pb2+ and the immersion enthalpy in solution of different pH values for CM activated carbon showed that the values are the highest for pH 4, 15.7 mgg-1 and 27.6 Jg-1 respectively. Pb2+ adsorption isotherms and immersion enthalpy were determined for modified activated carbons and the highest values were obtained for the activated carbon that showed the highest content of total acid sites on the surface.

Biochemical Modification of Thermomechanical Pulp Fibers

The first objective of this study was to find out reliable laboratory methods to predict the effect of enzymes on specific energy consumption and fiber properties of TMP pulp. The second one was to find with interactive software called “Knowledge discovery in databases” enzymes or other additives that can be used in finding a solution to reduce energy consumption of TMP pulp. The chemical composition of wood and enzymes, which have activity on main wood components were presented in the literature part of the work. The results of previous research in energy reduction of TMP process with enzymes were also highlighted. The main principles of knowledge discovery have been included in literature part too. The experimental part of the work contains the methods description in which the standard size chip, crushed chip and fiberized spruce chip (fiberized pulp) were used. Different types of enzymatic treatment with different dosages and time were tested during the experiments and showed. Pectinase, endoglucanase and mixture of enzymes were used for evaluation of method reliability. The fines content and fiber length of pulp was measured and used as evidence of enzymes' effect. The refining method with “Bauer” laboratory disc refiner was evaluated as not highly reliable. It was not able to provide high repeatability of results, because of uncontrolled feeding capacity and refining consistency. The refining method with Valley refiner did not have a lot of variables and showed stable and repeatable results in energy saving. The results of experiments showed that efficient enzymes impregnation is probably the main target with enzymes application for energy saving. During the work the fiberized pulp showed high accessibility to enzymatic treatment and liquid penetration without special impregnating equipment. The reason was that fiberized pulp has larger wood surface area and thereby the contact area between the enzymatic solution and wood is also larger. Standard size chip and crushed chip treatment without special impregnator of enzymatic solution was evaluated as not efficient and did not show visible, repeatable results in energy consumption decrease. Thereby it was concluded that using of fiberized pulp and Valley refiner for measurements of enzymes' effectiveness in SEC decrease is more suitable than normal size chip and crushed chip with “Bauer” refiner. Endoglucanase with 5 kg/t dosage showed about 20% energy consumption decrease. Mixture of enzymes with 1.5 kg/t dosage showed about 15% decrease of energy consumption during the refining. Pectinase at different dosages and treatment times did not show significant effect on energy consumption. Results of knowledge discovery in databases showed the xylanase, cellulase and pectinase blend as most promising for energy reduction in TMP process. Surfactants were determined as effective additives for energy saving with enzymes.

Ligniinin hienojauhatus planeettamyllyllä

Kirjallisuusosassa tarkastellaan ligniiniä luonnon polymeerinä sekä sen kemiallisia perustietoja. Aiheena on myös sen tuotanto ja käyttö uusiutuvana raaka-ainelähteenä energian-, materiaali- ja kemikaalituotantoon sekä niiden mahdolliset tulevaisuudennäkymät. Mekaanisten prosessien osalta keskitytään kiintoaineen hienontamiseen. Lisäksi perehdytään planeettamyllyn toiminnan teoriaan sekä tuoreimpiin tutkimuksiin planeettamyllyjauhatukseen liittyen. Työn kokeellisen osan tarkoituksena oli tutkia ligniinin jauhautuvuutta, sillä partikkelien pienentämisellä voidaan kasvattaa ligniininijauheen ominaisalaa ja tasoittaa sen kokojakaumaa. Jauhautuvuuden avulla voidaan esimerkiksi arvioida ligniinille tehtävän hienojauhatuksen kannattavuutta jatkoprosesseja varten. Tutkimuskysymyksinä oli ”kuinka hyvin ligniini jauhautuu planeettamyllyllä?”, ”onko kylmäkäsittelyllä vaikutusta jauhatustulokseen?”, ”miten eri parametrit (jauhatusaika, kuulakoko ja kierrosnopeus) vaikuttavat jauhatustulokseen?” sekä ”muuttaako hienojauhatus ligniinin kemiallista koostumusta?”. Tutkittavana materiaalina oli kaupallinen kraft-ligniini ja koelaitteena käytettiin planeettamyllyä. Syötölle ja kaikille jauhatustuotteille suoritettiin partikkelikokoanalyysi, ja lisäksi syötölle ja erittäin hienoksi jauhetulle tuotteelle suoritettiin FTIR-analyysi. Kokeiden mukaan ligniini oli hyvin jauhautuvaa, eikä kylmäkäsittelyllä ollut merkittävää vaikutusta jauhatukseen. Kuulakoon pienentäminen sekä jauhatusajan ja kierrosnopeuden kasvattaminen alensivat ligniininjauheen partikkelikokoa. Lisäksi hienojauhatuksen ei todettu muuttaneen ligniinin kemiallista koostumusta.

Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

Influence of surface functionalization on the behavior of silica nanoparticles in biological systems

Personalized nanomedicine has been shown to provide advantages over traditional clinical imaging, diagnosis, and conventional medical treatment. Using nanoparticles can enhance and clarify the clinical targeting and imaging, and lead them exactly to the place in the body that is the goal of treatment. At the same time, one can reduce the side effects that usually occur in the parts of the body that are not targets for treatment. Nanoparticles are of a size that can penetrate into cells. Their surface functionalization offers a way to increase their sensitivity when detecting target molecules. In addition, it increases the potential for flexibility in particle design, their therapeutic function, and variation possibilities in diagnostics. Mesoporous nanoparticles of amorphous silica have attractive physical and chemical characteristics such as particle morphology, controllable pore size, and high surface area and pore volume. Additionally, the surface functionalization of silica nanoparticles is relatively straightforward, which enables optimization of the interaction between the particles and the biological system. The main goal of this study was to prepare traceable and targetable silica nanoparticles for medical applications with a special focus on particle dispersion stability, biocompatibility, and targeting capabilities. Nanoparticle properties are highly particle-size dependent and a good dispersion stability is a prerequisite for active therapeutic and diagnostic agents. In the study it was shown that traceable streptavidin-conjugated silica nanoparticles which exhibit a good dispersibility could be obtained by the suitable choice of a proper surface functionalization route. Theranostic nanoparticles should exhibit sufficient hydrolytic stability to effectively carry the medicine to the target cells after which they should disintegrate and dissolve. Furthermore, the surface groups should stay at the particle surface until the particle has been internalized by the cell in order to optimize cell specificity. Model particles with fluorescently-labeled regions were tested in vitro using light microscopy and image processing technology, which allowed a detailed study of the disintegration and dissolution process. The study showed that nanoparticles degrade more slowly outside, as compared to inside the cell. The main advantage of theranostic agents is their successful targeting in vitro and in vivo. Non-porous nanoparticles using monoclonal antibodies as guiding ligands were tested in vitro in order to follow their targeting ability and internalization. In addition to the targeting that was found successful, a specific internalization route for the particles could be detected. In the last part of the study, the objective was to clarify the feasibility of traceable mesoporous silica nanoparticles, loaded with a hydrophobic cancer drug, being applied for targeted drug delivery in vitro and in vivo. Particles were provided with a small molecular targeting ligand. In the study a significantly higher therapeutic effect could be achieved with nanoparticles compared to free drug. The nanoparticles were biocompatible and stayed in the tumor for a longer time than a free medicine did, before being eliminated by renal excretion. Overall, the results showed that mesoporous silica nanoparticles are biocompatible, biodegradable drug carriers and that cell specificity can be achieved both in vitro and in vivo.

Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Metal oxides prepared through the nanocasting approach-mechanistic study, surface interactions and applications in separation

Mesoporous metal oxides are nowadays widely used in various technological applications, for instance in catalysis, biomolecular separations and drug delivery. A popular technique used to synthesize mesoporous metal oxides is the nanocasting process. Mesoporous metal oxide replicas are obtained from the impregnation of a porous template with a metal oxide precursor followed by thermal treatment and removal of the template by etching in NaOH or HF solutions. In a similar manner to the traditional casting wherein the product inherits the features of the mold, the metal oxide replicas are supposed to have an inverse structure of the starting porous template. This is however not the case, as broken or deformed particles and other structural defects have all been experienced during nanocasting experiments. Although the nanocasting technique is widely used, not all the processing steps are well understood. Questions over the fidelity of replication and morphology control are yet to be adequately answered. This work therefore attempts to answer some of these questions by elucidating the nanocasting process, pin pointing the crucial steps involved and how to harness this knowledge in making wholesome replicas which are a true replication of the starting templates. The rich surface chemistry of mesoporous metal oxides is an important reason why they are widely used in applications such as catalysis, biomolecular separation, etc. At times the surface is modified or functionalized with organic species for stability or for a particular application. In this work, nanocast metal oxides (TiO2, ZrO2 and SnO2) and SiO2 were modified with amino-containing molecules using four different approaches, namely (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine and (d) adsorption of poly(ethylenimine) (PEI) through electrostatic interactions. Afterwards, the hydrolytic stability of each functionalization was investigated at pH 2 and 10 by zeta potential measurements. The modifications were successful except for the AEDP approach which was unable to produce efficient amino-modification on any of the metal oxides used. The APTES, aziridine and PEI amino-modifications were fairly stable at pH 10 for all the metal oxides tested while only AZ and PEI modified-SnO2 were stable at pH 2 after 40 h. Furthermore, the functionalized metal oxides (SiO2, Mn2O3, ZrO2 and SnO2) were packed into columns for capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Among the functionalized metal oxides, aziridinefunctionalized SiO2, (SiO2-AZ) showed good chemical stability, and was the most useful packing material in both CLC and CEC. Lastly, nanocast metal oxides were synthesized for phosphopeptide enrichment which is a technique used to enrich phosphorylated proteins in biological samples prior to mass spectrometry analysis. By using the nanocasting technique to prepare the metal oxides, the surface area was controlled within a range of 42-75 m2/g thereby enabling an objective comparison of the metal oxides. The binding characteristics of these metal oxides were compared by using samples with different levels of complexity such as synthetic peptides and cell lysates. The results show that nanocast TiO2, ZrO2, Fe2O3 and In2O3 have comparable binding characteristics. Furthermore, In2O3 which is a novel material in phosphopeptide enrichment applications performed comparably with standard TiO2 which is the benchmark for such phosphopeptide enrichment procedures. The performance of the metal oxides was explained by ranking the metal oxides according to their isoelectric points and acidity. Overall, the clarification of the nanocasting process provided in this work will aid the synthesis of metal oxides with true fidelity of replication. Also, the different applications of the metal oxides based on their surface interactions and binding characteristics show the versatility of metal oxide materials. Some of these results can form the basis from which further applications and protocols can be developed.

Les effets de la stimulation électrique transcrânienne à courant direct appliquée au cortex somatosensoriel primaire sur la perception vibrotactile

La stimulation électrique transcrânienne à courant direct (tDCS) est une technique non invasive de neuromodulation qui modifie l’excitabilité corticale via deux grosses électrodes de surface. Les effets dépendent de la polarité du courant, anodique = augmentation de l’excitabilité corticale et cathodique = diminution. Chez l’humain, il n’existe pas de consensus sur des effets de la tDCS appliquée au cortex somatosensoriel primaire (S1) sur la perception somesthésique. Nous avons étudié la perception vibrotactile (20 Hz, amplitudes variées) sur le majeur avant, pendant et après la tDCS appliquée au S1 controlatéral (anodale, a; cathodale, c; sham, s). Notre hypothèse « shift-gain » a prédit une diminution des seuils de détection et de discrimination pour la tDCS-a (déplacement vers la gauche de la courbe stimulus-réponse et une augmentation de sa pente). On attendait les effets opposés avec la tDCS-c, soit une augmentation des seuils (déplacement à droite et diminution de la pente). Chez la majorité des participants, des diminutions des seuils ont été observées pendant et immédiatement suivant la tDCS-a (1 mA, 20 min) en comparaison à la stimulation sham. Les effets n’étaient plus présents 30 min plus tard. Une diminution du seuil de discrimination a également été observée pendant, mais non après la tDCS-c (aucun effet pour détection). Nos résultats supportent notre hypothèse, uniquement pour la tDCS-a. Une suite logique serait d’étudier si des séances répétées de tDCS-a mènent à des améliorations durables sur la perception tactile. Ceci serait bénéfique pour la réadaptation sensorielle (ex. suite à un accident vasculaire cérébral).

Copper(II) complexes of embelin and 2-aminobenzimidazole encapsulated in zeolite Y-potential as catalysts

Copper(II) complexes of two biologically important ligands, viz., embelin (2,5-dihydroxy-3-undecyl-2,5-cyclohexadien 1,4-dione) and 2-aminobenzimidazole were entrapped in the cages of zeolite Y by the flexible ligand method. The capability of these compounds in catalyzing the reduction of oxygen (industrially known as deoxo reaction) was explored and the results indicate an enhancement of the catalytic properties from that of the simple copper ion exchanged zeolite. These point to the ability of the ligands in enhancing the oxygen binding capability of the metal ion. Elemental analyses, Fourier transform infrared (FTIR), diffuse reflectance and EPR spectral studies, magnetic susceptibility measurements, TG, surface area analyses and powder X-ray diffraction studies were used in understanding the presence, composition and structure of the complexes inside the cages. The study also reveals the increased thermal and mechanical stability of the complexes as a result of encapsulation.

Surface properties and catalytic activity of vanadia supported on samaria

Sm2O3 - vanadia catalysts have been prepared by wet impregnation method using NH4VO3 solution. The surface properties of the prepared catalysts have been studied using FTIR. XRD. surface area and pore volume data. The acid-base properties of the system have been investigated by titrimetric method using Hammett indicators. adsorption of electron acceptors as well as decomposition of cyclohexanol. Phenol alkylation reaction by methanol has been carried out to investigate the catalytic activity. It has been observed that the selectivity of the products depends upon the composition of the supported system

Glucoamylase immobilized on montmorillonite: influence of nature of binding on surface properties of clay-support and activity of enzyme

Glucoamylase was immobilized on acid activated montmorillonite clay via two different procedures namely adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and the activity of immobilized glucoamylase for starch hydrolysis was determined in a batch reactor. XRD shows intercalation of enzyme into the clay matrix during both immobilization procedures. Intercalation occurs via the side chains of the amino acid residues, the entire polypeptide backbone being situated at the periphery of the clay matrix. 27Al NMR studies revealed the different nature of interaction of enzyme with the support for both immobilization techniques. N2 adsorption measurements indicated a sharp drop in surface area and pore volume for the covalently bound glucoamylase that suggested severe pore blockage. Activity studies were performed in a batch reactor. The adsorbed and covalently bound glucoamylase retained 49% and 66% activity of the free enzyme respectively. They showed enhanced pH and thermal stabilities. The immobilized enzymes also followed Michaelis–Menten kinetics. Km was greater than the free enzyme that was attributed to an effect of immobilization. The immobilized preparations demonstrated increased reusability as well as storage stability.