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Made available in DSpace on 2019-10-03T17:32:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-12-01 Metal-Organic Frameworks (MOFs) are, according to IUPAC, coordination polymers with an open framework containing potential voids, which can be accessible after activation processes. These materials have aroused interest in the academic environment – and more recently in industry - because their properties such as high crystallinity, permanent microporosity, high surface areas, and the possibility of functionalization. This has enabled applications in different areas, such as gas adsorption, catalysis, drug delivery, photonics and others. Depending on the judicious choice of the metals and the organic linkers, MOFs with different topologies and functions can be created. Synthetic routes for the preparation of these materials will be discussed, highlighting those in consonance with the Green Inorganic Chemistry. Strategies for controlling the size and morphology of the crystals will also be presented, as well the most recent methodologies for the large-scale production. This review will also discuss the use of MOFs in the context of energy and environment, particularly referring to the adsorption and/or transformation of CO2, storage of H2 and CH4 as well potable water capture. Universidade Estadual de São Paulo Instituto de Química Departamento de Química Geral e Inorgânica

A simple and fast method for the determination of nimesulide (NI) using flow injection analysis with multiple-pulse amperometric (FIA-MPA) detection at a boron-doped diamond (BDD) electrode was developed. The method was based mainly on the application of a four-potential waveform, E1(det) = -0.8 V / 30 ms, E2(det) = 0.6 V / 30 ms, E3(det) = -0.4 V / 30 ms and E4(cleaning) = -0.45 V / 300 ms versus Ag/AgCl (3.0 mol L-1 KCl). NI was detected at three different electrode potentials, at which the nitro group undergoes different redox reactions. The proposed method was selective and sensitive (detection limit of 81.0 nmol L-1), and successfully applied for the determination of NI in pharmaceutical formulations, yielding similar results to those obtained by the reference method.

PbO2 films were electroformed onto carbon cloth substrates (twill woven type) in acid conditions using the nitrate precursor by changing the electrodeposition current density, temperature and pH, in order to optimize the formation of the β-PbO2 phase. The crystal structure and morphology of the PbO2 films were investigated using X-ray diffraction (XRD) and scanning electronic microscopy (SEM) techniques. The optimum conditions obtained for formation of the β-PbO2 were presented and discussed.

The discoloration and degradation of the textile dye RED GRLX-220 using the electrochemically generated ozone was investigated. Total discoloration was rapidly achieved in both acid and basic conditions. A pseudo-first order kinetics was observed for discoloration, influenced by pH and ozonation time. A considerable degree of mineralization (60%) was obtained after 30 min of ozonation in alkaline medium. The feasibility of organic matter oxidation during the ozonation process increased in both acidic and alkaline media. The toxicity decreased after the ozonation process, suggesting that the byproducts are less toxic than the parental compound.

This article describes the preparation of 5-nitroisatin and of 5-chloroisatin from isonitrosoacetanilide in a single step, using readily available and inexpensive reagents. These reactions require around 90 minutes and may be carried out as an undergraduate experiment, providing an opportunity to discuss the electrophilic aromatic substitution mechanism, as well as spectroscopic techniques for product identification.

Structure and first hyperpolarizability for a series of armchair a(5,5) chemically modified carbon nanotubes (CNT) were calculated at semiempirical and density functional levels of theory. The 4,4´-substituted stilbenes were selected as chromophore with substituents at position 4´ set to X=NO2, H, Cl, OH and NH2. The calculated values for static first hyperpolarizability (β) were almost linearly dependent on the electronic effect of the group X, increasing from NO2 to NH2. At DFT level the effect of inserting the chromophore in the CNT surface was to enhance the β value up to 70% relative to the free 4,4´-substituted stilbene.

Structure and first hyperpolarizability for a series of armchair a(5,5) chemically modified carbon nanotubes (CNT) were calculated at semiempirical and density functional levels of theory. The 4,4´-substituted stilbenes were selected as chromophore with substituents at position 4´ set to X=NO2, H, Cl, OH and NH2. The calculated values for static first hyperpolarizability (β) were almost linearly dependent on the electronic effect of the group X, increasing from NO2 to NH2. At DFT level the effect of inserting the chromophore in the CNT surface was to enhance the β value up to 70% relative to the free 4,4´-substituted stilbene.

FeBr2 has reacted with an equivalent of mnt2- (mnt = cis-1,2-dicyanoethylene-1,2-dithiolate) and the α-diimine L (L = 1,10'-phenantroline, 2,2'-bipyridine) in THF solution, and followed by adding of t-butyl-isocyanide to give [Fe(mnt)(L)(t-BuNC)2] neutral compound. The products were characterized by infrared, UV-visible and Mössbauer spectroscopy, besides thermogravimetric and conductivity data. The geometry in the equilibrium was calculated by the density functional theory and the electronic spectrum by the time-dependent. The experimental and theoretical results in good agreement have defined an octahedral geometry with two isocyanide neighbours. The π→π* intraligand electronic transition was not observed for cis-isomers in the near-IR spectral region.

A new white pigment made out of nano-structured non-crystalline aluminum phosphate was recently launched as an industrial product. Pigment opacifying properties are not intrinsic to aluminum phosphate but they arise as the result of a rare hollow particle nano-structure. This is in turn derived from the core-and-shell structure of amorphous aluminum phosphate precipitated under well-defined conditions. The new pigment is a product of the often neglected chemistry of non-crystalline ionic solids that can probably be a rich source of new successful products. The text describes a short account of the R&D activities, from the initial ideas to the present.

N-halosaccharins proved to be useful and alternative reagents for diverse organic transformations, such as halogenation of aromatic compounds, benzylic and alpha-carbonylic positions, cohalogenation of alkenes, oxidation of secondary alcohols, etc. Their preparation from saccharin, a cheap and readly available starting material, is simple.

Efforts presented by the scientific community in recent years towards the development of numerous green chemical processes and wastewater treatment technologies are presented and discussed. In the light of these approaches, environmentally friendly technologies, as well as the key role played by the well-known advanced oxidation processes, are discussed, giving special attention to the ones comprising ozone applications. Fundamentals and applied aspects dealing with ozone technology and its application are also presented.

Microbial lipases have a great potential for commercial applications due to their stability, selectivity and broad substrate specificity because many non-natural acids, alcohols or amines can be used as the substrate. Three microbial lipases isolated from Brazilian soil samples (Aspergillus niger; Geotrichum candidum; Penicillium solitum) were compared in terms of their stability and as biocatalysts in the enantioselective esterification using racemic substrates in organic medium. The lipase from Aspergillus niger showed the highest activity (18.2 U/mL) and was highly thermostable, retaining 90% and 60% activity at 50 ºC and 60 ºC after 1 hour, respectively. In organic medium, this lipase provided the best results in terms of enantiomeric excess of the (S)-active acid (ee = 6.1%) and conversion value (c = 20%) in the esterification of (R,S)-ibuprofen with 1-propanol in isooctane. The esterification reaction of the racemic mixture of (R,S)-2-octanol with decanoic acid proceeded with high enantioselectivity when lipase from Aspergillus niger (E = 13.2) and commercial lipase from Candida antarctica (E = 20) were employed.

The world is in a process of awakening with respect to the environment. Our society has started to recognize that the environment is one of our largest resources and has begun legally enforce its protection. In Brazil, the environmental law is constitutionally guaranteed. International treaties have been signed, amongst them the Agenda 21 which is a commitment to sustainable development. Green Chemistry is a strategy that helps make this commitment. The literature presents many examples of studies of the application of Green Chemistry philosophy. In this paper we will present some points that we believe to be important and promising.

Several polyunsaturated fatty acids (PUFA) belonging to the omega 6 series, such as cis-6,9,12 g-linolenic acid, as well as those of the omega 3 series, such as cis-5,8,11,14,17-eicosapentaenoic acid and cis-4,7,10,13,16,19-docosahexaenoic acid are of considerable interest due to their nutritional and therapeutic properties. Methods used for the concentration of PUFA from natural sources include urea adduct formation, solvent winterization, supercritical fluid extraction and lipase-catalyzed reaction. Lipases are known to have little reactivity on PUFA and these acids can be enriched by selective hydrolysis, direct esterification of glycerol with PUFA and interesterification. Since lipase reactions are advantageous with respect to fatty acid, positional specificities and mild incubation condition, these enzymes are considered to be suitable for the production of PUFA concentrates for medical purposes.

The synthesis of gold nanoparticles (Au NPs) 15, 26, and 34 nm in diameter, followed by the investigation of their size-dependent optical and catalytic properties, is described herein as an undergraduate level experiment. The proposed experiment covers concepts on the synthesis, stabilization, and characterization of Au NPs, their size-dependent optical and catalytic properties at the nanoscale, chemical kinetics, and the role of a catalyst. The experiment should be performed by groups of two or three students in three lab sessions of 3 h each and organized as follows: i) synthesis of Au NPs of different sizes and investigation of their optical properties; ii) evaluation of their catalytic activity; and iii) data analysis and discussion. We believe that this activity enables students to integrate these multidisciplinary concepts in a single experiment as well as to become introduced/familiarized with an active research field and current literature in the areas of nanoparticle synthesis and catalysis.

The use of water as solvent in organic reactions has been uncommon for several reasons, among them the low solubility of the reactants, the incompatibility of the intermediates with water, and the competition between the desired reaction and hydrolysis. Breslow in 1980, demonstrated that the hydrophobic effect accelerates Diels-Alder reactions and gives a high endo/exo selectivity. Since then, many other reactions were studied in this medium, and below we show the principal results. Besides the academic interest, human and economic aspects are included in this study. Water as a solvent minimizes environmental impact, costs and increases operational safety.

The binuclear [Fe(CNBu t)(CO)4(HgSO4 )] adduct was obtained in the reaction of HgSO4 with [Fe(CNBu t)(CO)4] in methanol. This adduct, without a similar in the homoleptic pentacarbonyliron, was characterized by analytical and spectroscopic data. Further Mössbauer and molar conductivity studies have confirmed it's adduct nature.

Submitted by Patricia Barros (patricia.barros@ufes.br) on 2011-01-31T14:09:12Z No. of bitstreams: 2 a02v24n3.pdf: 30089 bytes, checksum: 3a1dca67b5f6aaf08fd58a87b09a5210 (MD5) license_rdf: 21504 bytes, checksum: cfe16b28a928230b24b965de15e8a5ff (MD5) Approved for entry into archive by Patricia Barros(patricia.barros@ufes.br) on 2011-02-07T19:55:41Z (GMT) No. of bitstreams: 2 a02v24n3.pdf: 30089 bytes, checksum: 3a1dca67b5f6aaf08fd58a87b09a5210 (MD5) license_rdf: 21504 bytes, checksum: cfe16b28a928230b24b965de15e8a5ff (MD5) Made available in DSpace on 2011-02-07T19:55:41Z (GMT). No. of bitstreams: 2 a02v24n3.pdf: 30089 bytes, checksum: 3a1dca67b5f6aaf08fd58a87b09a5210 (MD5) license_rdf: 21504 bytes, checksum: cfe16b28a928230b24b965de15e8a5ff (MD5) Previous issue date: 2001-05 The binuclear [Fe(CNBut)(CO)4(HgSO4 )] adduct was obtained in the reaction of HgSO4 with [Fe(CNBut)(CO)4] in methanol. This adduct, without a similar in the homoleptic pentacarbonyliron, was characterized by analytical and spectroscopic data. Further Mössbauer and molar conductivity studies have confirmed it's adduct nature.

Submitted by Patricia Barros (patricia.barros@ufes.br) on 2011-01-31T13:47:58Z No. of bitstreams: 2 18814.pdf: 179348 bytes, checksum: 051459322eeb13efb0b900bae5736755 (MD5) license_rdf: 21504 bytes, checksum: cfe16b28a928230b24b965de15e8a5ff (MD5) Approved for entry into archive by Patricia Barros(patricia.barros@ufes.br) on 2011-02-07T19:49:55Z (GMT) No. of bitstreams: 2 18814.pdf: 179348 bytes, checksum: 051459322eeb13efb0b900bae5736755 (MD5) license_rdf: 21504 bytes, checksum: cfe16b28a928230b24b965de15e8a5ff (MD5) Made available in DSpace on 2011-02-07T19:49:55Z (GMT). No. of bitstreams: 2 18814.pdf: 179348 bytes, checksum: 051459322eeb13efb0b900bae5736755 (MD5) license_rdf: 21504 bytes, checksum: cfe16b28a928230b24b965de15e8a5ff (MD5) Previous issue date: 2004-01 FeBr2 reacts with the S2C2(CN)22- ion (1:1 ratio) in the presence of an excess of t-BuNC in THF to give the mixed ligand [Fe(S2C2(CN)2)(t-BuNC) 4] compound. This neutral product with a formal oxidation state of two for the iron atom was characterized by conductivity measurements, and, i.r., Mössbauer, 13C and 1H n.m.r. spectroscopy. There is a Fe-C p back-donation strengthened towards isocyanide ligands, according to the data of 13C, 1H n.m.r. and Mössbauer spectroscopy.

A review on the electrophilic addition of iodine to alkenes in the presence of oxygen containing nucleophiles (cohalogenation reaction) is presented. The intermolecular reactions are discussed with emphasis in methods of reaction and synthetic applications of the resulting vicinal iodo-functionalized products (iodohydrins, b-iodoethers and b-iodocarboxylates).

This experimental activity proposes the use of lily (Lilium sp.), agapanthus (Agapanthus sp.) and hydrangea (Hydrangea sp.) extracts to investigate the colorimetric profile of each extract between pH 1-14. Water, ethanol and ethanol/HCl 1% (w/w) were used as extractive solvents. Among the flowers tested, the extracts of orange lily and burnt yellow lily were the ones that presented the greatest color variation with the solution pH change. In addition, the total content of anthocyanins in relation to cyanidin-3-glycosidic was determined and in ascending order we have: yellow lily (LAM: 0,07 ± 0,03) < agapanthus white (AGB: 0,21 ± 0,03) < agapanthus violet (AGV: 1,72 ± 0,13) < blue hydrangea (HAZ: 1,83 ± 0,47) < orange lily (LAL: 2,87 ± 0,52) < burnt yellow lily (LAQ: 9,55 ± 0,46). For this determination methanol/HCl 1% (w/w) was used as the solvent. Using UV-Vis spectroscopy, it is suggested that the behaviors are due to the presence of cyanidin in AGB, AGV, LAL and LAQ, delphinidin in HAZ and apigeninidine in LAM. This activity can be applied in courses that have Chemistry in their curricular matrix and in General Chemistry subjects when the acid-base theme is approached.

Relevant historical aspects concerning ideal gases were briefly reviewed to provide a condensed resource for the undergraduate student of chemistry. The importance of the barometer and the concept of atmospheric pressure were reviewed and discussed. A combination of Boyle's law with the well-known equation for determining the pressure produced by a column of stationary fluid was used to obtain a graphical method for determining atmospheric pressure under isothermal conditions in the laboratory. Important aspects related to the study of ideal gases were reviewed in light of the pressure-volume data that can be obtained by physical chemistry students using a simple apparatus composed of a commercial hypodermic syringe connected to a mercury manometer. Relevant concepts associated with the measurement of a physical quantity, the importance of linear regression, as well as the use of a graphical method to test the validity of a theory were reviewed from a pedagogical perspective through the experimental study of Boyle's law during regular experimental physical chemistry classes.