Estudo das interações entre o complexo polieletrolítico trimetilquitosana/carboximetilcelulose e Cu+2, ácido húmico e atrazina em solução aquosa

The polyelectrolyte complex (PEC) resulting from the reaction of sodium carboxymethylcellulose (CMC) and N,N,N-trimethylchitosan hydrochloride (TMQ) was prepared and then characterized by infrared spectroscopy and energy dispersive X rays analysis. The interactions involving the PEC and Cu2+ ions, humic acid and atrazine in aqueous medium were studied. From the adsorption isotherms the maximum amount adsorbed (Xmax) was determined as 61 mg Cu2+/g PEC, 171 mg humic acid/g PEC and 5 mg atrazine/g PEC. The results show that the CMC/TMQ complex has a high affinity for the studied species, indicating its potential application to remove them from aqueous media.

Sensores ópticos com detecção no infravermelho próximo e médio

Optical chemical sensors with detection in the near and mid infrared region are reviewed. Fundamental concepts of infrared spectroscopy and optical chemical sensors are briefly described, before presenting some aspects on optical chemical sensors, such as synthesis of NIR and IR reagents, preparation of new materials as well as application in determinations of species of biological, industrial and environmental importance.

Caracterização de argilas bentonitas e diatomitas e sua aplicação como adsorventes

Five samples of natural clays denominated: diatomite, CN-20, CN-29, CN-40 and CN-45 from Aliança Latina LTDA were characterized by differents supplementary techniques such as: XRD, chemical analysis, adsorption N2 measurements, infrared spectroscopy analysis, thermogravimetric analysis. Clays were tested in adsorption of blue methylene. All of isotherms adjust in a model of physics adsorption with formation of multilayers, however in the case of diatomite was a favorable adsorption (type II) and the CNs were a not favorable adsorption (type III). In the case of CNs had flocculation of clay in high concentration of coloring.

Biomassa residual para remoção de íons uranilo

Activities related to nuclear industry, production of phosphoric acid and hospitals have generated considerable volumes of radioactive waste containing uranyl ions. Banana pith was characterized by Scanning Electron Microscopy and Fourier Transform Infrared Spectroscopy and was investigated as a biosorbent for uranyl ions from nitric solutions by batch experiments. Influences of adsorbent size, kinetics and equilibrium adsorption were studied. The biosorption of the uranyl ions followed pseudo-second-order kinetics. The adsorption isotherm data were closely fitted to the Freundlich equation.

Uso de amêndoas de baru (Dypterix alata) para remoção de Ni(ii) em etanol combustível

The present work describes the sorption potential of Dypterix alata (baru) for removal of Ni(II) in hydrous ethanol. Infrared spectroscopy was used for elucidating possible functional groups responsible for uptaking Ni(II). Sorption studies using Ni(II) standard solutions were carried out in batch experiments as functions of extraction time and pH solution. The Ni(II) was quantified before and after the removal experiments using Flame Atomic Absorption Spectrometry. Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmuir and Freundlich models, it was possible to verify that D. alata presents a high adsorption capacity. The results show that D. alata can be used for removing Ni(II) in ethanol solutions.

Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments

The present paper focuses on improving chromium (III) uptake capacity of sugarcane bagasse through its chemical modification with citric acid and/or sodium hydroxide. The chemical modifications were confirmed by infrared spectroscopy, with an evident peak observed at 1730 cm-1, attributed to carbonyl groups. Equilibrium was reached after 24 h, and the kinetics followed the pseudo-second-order model. The highest chromium (III) maximum adsorption capacity (MAC) value was found when using sugarcane bagasse modified with sodium hydroxide and citric acid (58.00 mg g-1) giving a MAC value about three times greater (20.34 mg g-1) than for raw sugarcane bagasse.

Experimento didático de quimiometria para calibração multivariada na determinação de paracetamol em comprimidos comerciais utilizando espectroscopia no infravermelho próximo: um tutorial, parte II

The aim of this manuscript was to show the basic concepts and practical application of Partial Least Squares (PLS) as a tutorial, using the Matlab computing environment for beginners, undergraduate and graduate students. As a practical example, the determination of the drug paracetamol in commercial tablets using Near-Infrared (NIR) spectroscopy and Partial Least Squares (PLS) regression was shown, an experiment that has been successfully carried out at the Chemical Institute of Campinas State University for chemistry undergraduate course students to introduce the basic concepts of multivariate calibration in a practical way.

Preparation and immobilization of diNOsarcobalt(III) complex in zeolite y for the catalyzed production of hydrogen peroxide

A complex cation, diNOsarcobalt(III), [Co(diNOsar)]3+, (diNOsar = 1,8-dinitro-3,6,10,13,16,19-hexaazabicyclo-[6.6.6]eicosane), was synthesized and immobilized in the cavities of a Y zeolite by the reaction of precursor species in the pores of the zeolite. The encapsulated material was compared to the compound diNOsarcobalt(III) chloride, [Co(diNOsar)]Cl3. Both diNOsarcobalt(III) chloride and the zeolite-encapsulated complex, [Co(diNOsar)]3+/zeolite, were obtained in high yield and characterized by ultraviolet-visible and infrared spectroscopy. X-ray diffraction demonstrated the incorporation of the complex cation into the pores of the zeolite. The catalytic production of hydrogen peroxide from oxygenated water confirmed the successful synthesis of the complex diNOsarcobalt(III) immobilized in the zeolite.

Poliuretanos obtenidos a partir de aceite de higuerilla modificado y poli-isocianatos de lisina: síntesis, propiedades mecánicas y térmicas y degradación in vitro

Biodegradable polyurethanes (PUR) were prepared from polyols derived from castor oil by transesterification of pentaerythritol-modified castor oil and lysine polyisocyanates (LDI and LTI). The polyurethanes obtained were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). The mechanical behavior of the polyurethanes was measured by Shore A hardness and tensile testing (stress-strain curves). The biodegradable nature of the material was determined by contact angle, water absorption tests, and in vitro degradation in PBS solution. This study aims to examine the effect of the structure and functionality of diisocyanate on the mechanical properties and in vitro degradation of the material. The results were compared with homologous materials obtained from isophorone diisocyanate (IPDI) used in previous works. The objective was to evaluate candidate materials that can be potentially used in tissue engineering.

Resolução multivariada de curvas com mínimos quadrados alternantes: descrição, funcionamento e aplicações

Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) is a resolution method that has been efficiently applied in many different fields, such as process analysis, environmental data and, more recently, hyperspectral image analysis. When applied to second order data (or to three-way data) arrays, recovery of the underlying basis vectors in both measurement orders (i.e. signal and concentration orders) from the data matrix can be achieved without ambiguities if the trilinear model constraint is considered during the ALS optimization. This work summarizes different protocols of MCR-ALS application, presenting a case study: near-infrared image spectroscopy.

Upconverting Phosphor Technology: Exceptional Photoluminescent Properties Light Up Homogeneous Bioanalytical Assays

The aim of the present study was to demonstrate the wide applicability of the novel photoluminescent labels called upconverting phosphors (UCPs) in proximity-based bioanalytical assays. The exceptional features of the lanthanide-doped inorganic UCP compounds stem from their capability for photon upconversion resulting in anti-Stokes photoluminescence at visible wavelengths under near-infrared (NIR) excitation. Major limitations related to conventional photoluminescent labels are avoided, rendering the UCPs a competitive next-generation label technology. First, the background luminescence is minimized due to total elimination of autofluorescence. Consequently, improvements in detectability are expected. Second, at the long wavelengths (>600 nm) used for exciting and detecting the UCPs, the transmittance of sample matrixes is significantly greater in comparison with shorter wavelengths. Colored samples are no longer an obstacle to the luminescence measurement, and more flexibility is allowed even in homogeneous assay concepts, where the sample matrix remains present during the entire analysis procedure, including label detection. To transform a UCP particle into a biocompatible label suitable for bioanalytical assays, it must be colloidal in an aqueous environment and covered with biomolecules capable of recognizing the analyte molecule. At the beginning of this study, only UCP bulk material was available, and it was necessary to process the material to submicrometer-sized particles prior to use. Later, the ground UCPs, with irregular shape, wide size-distribution and heterogeneous luminescence properties, were substituted by a smaller-sized spherical UCP material. The surface functionalization of the UCPs was realized by producing a thin hydrophilic coating. Polymer adsorption on the UCP surface is a simple way to introduce functional groups for bioconjugation purposes, but possible stability issues encouraged us to optimize an optional silica-encapsulation method which produces a coating that is not detached in storage or assay conditions. An extremely thin monolayer around the UCPs was pursued due to their intended use as short-distance energy donors, and much attention was paid to controlling the thickness of the coating. The performance of the UCP technology was evaluated in three different homogeneous resonance energy transfer-based bioanalytical assays: a competitive ligand binding assay, a hybridization assay for nucleic acid detection and an enzyme activity assay. To complete the list, a competitive immunoassay has been published previously. Our systematic investigation showed that a nonradiative energy transfer mechanism is indeed involved, when a UCP and an acceptor fluorophore are brought into close proximity in aqueous suspension. This process is the basis for the above-mentioned homogeneous assays, in which the distance between the fluorescent species depends on a specific biomolecular binding event. According to the studies, the submicrometer-sized UCP labels allow versatile proximity-based bioanalysis with low detection limits (a low-nanomolar concentration for biotin, 0.01 U for benzonase enzyme, 0.35 nM for target DNA sequence).

Using aster multispectral imagery for mapping woody invasive species in pico da vara natural reserve (Azores Islands, Portugal)

This paper aims to assess the effectiveness of ASTER imagery to support the mapping of Pittosporum undulatum, an invasive woody species, in Pico da Vara Natural Reserve (S. Miguel Island, Archipelago of the Azores, Portugal). This assessment was done by applying K-Nearest Neighbor (KNN), Support Vector Machine (SVM) and Maximum Likelihood (MLC) pixel-based supervised classifications to 4 different geographic and remote sensing datasets constituted by the Visible, Near-Infrared (VNIR) and Short Wave Infrared (SWIR) of the ASTER sensor and by digital cartography associated to orography (altitude and "distance to water streams") of which the spatial distribution of Pittosporum undulatum directly depends. Overall, most performed classifications showed a strong agreement and high accuracy. At targeted species level, the two higher classification accuracies were obtained when applying MLC and KNN to the VNIR bands coupled with auxiliary geographic information use. Results improved significantly by including ecology and occurrence information of species (altitude and distance to water streams) in the classification scheme. These results show that the use of ASTER sensor VNIR spectral bands, when coupled to relevant ancillary GIS data, can constitute an effective and low cost approach for the evaluation and continuous assessment of Pittosporum undulatum woodland propagation and distribution within Protected Areas of the Azores Islands.

Comparison between hydrographically conditioned digital elevation models in the morphometric charaterization of watersheds

The aim of this study was to compare the hydrographically conditioned digital elevation models (HCDEMs) generated from data of VNIR (Visible Near Infrared) sensor of ASTER (Advanced Spaceborne Thermal Emission and Reflection Radiometer), of SRTM (Shuttle Radar Topography Mission) and topographical maps from IBGE in a scale of 1:50,000, processed in the Geographical Information System (GIS), aiming the morphometric characterization of watersheds. It was taken as basis the Sub-basin of São Bartolomeu River, obtaining morphometric characteristics from HCDEMs. Root Mean Square Error (RMSE) and cross validation were the statistics indexes used to evaluate the quality of HCDEMs. The percentage differences in the morphometric parameters obtained from these three different data sets were less than 10%, except for the mean slope (21%). In general, it was observed a good agreement between HCDEMs generated from remote sensing data and IBGE maps. The result of HCDEM ASTER was slightly higher than that from HCDEM SRTM. The HCDEM ASTER was more accurate than the HCDEM SRTM in basins with high altitudes and rugged terrain, by presenting frequency altimetry nearest to HCDEM IBGE, considered standard in this study.

Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

Graphene from Graphite by Chemical and Physical Techniques.

Graphene is a material with extraordinary properties. Its mechanical and electrical properties are unparalleled but the difficulties in its production are hindering its breakthrough in on applications. Graphene is a two-dimensional material made entirely of carbon atoms and it is only a single atom thick. In this work, properties of graphene and graphene based materials are described, together with their common preparation techniques and related challenges. This Thesis concentrates on the topdown techniques, in which natural graphite is used as a precursor for the graphene production. Graphite consists of graphene sheets, which are stacked together tightly. In the top-down techniques various physical or chemical routes are used to overcome the forces keeping the graphene sheets together, and many of them are described in the Thesis. The most common chemical method is the oxidisation of graphite with strong oxidants, which creates a water-soluble graphene oxide. The properties of graphene oxide differ significantly from pristine graphene and, therefore, graphene oxide is often reduced to form materials collectively known as reduced graphene oxide. In the experimental part, the main focus is on the chemical and electrochemical reduction of graphene oxide. A novel chemical route using vanadium is introduced and compared to other common chemical graphene oxide reduction methods. A strong emphasis is placed on electrochemical reduction of graphene oxide in various solvents. Raman and infrared spectroscopy are both used in in situ spectroelectrochemistry to closely monitor the spectral changes during the reduction process. These in situ techniques allow the precise control over the reduction process and even small changes in the material can be detected. Graphene and few layer graphene were also prepared using a physical force to separate these materials from graphite. Special adsorbate molecules in aqueous solutions, together with sonic treatment, produce stable dispersions of graphene and few layer graphene sheets in water. This mechanical exfoliation method damages the graphene sheets considerable less than the chemical methods, although it suffers from a lower yield.