Uso de modelagem molecular no estudo dos conceitos de nucleofilicidade e basicidade

Molecular modeling enables the students to visualize the abstract relationships underlying theoretical concepts that explain experimental data on the molecular and atomic levels. With this aim we used the free software "Arguslab 4.0.1" (semi-empirical method) to study the reaction of 1-chloropropane with ethoxide in solution, known to lead to methyl propyl ether, through the S N2 mechanism, and propene, through the E2 mechanism. This tool allows users to calculate some properties (i. e. heat formation or electric charges) and to produce 3D images (molecular geometry, electrostatic potential surface, etc.) that render the comprehension of the factors underlying the reaction's progress, which are related to the structure of the reagents, and the process kinetic clearer and easier to understand by the students

SAPT: ligação de hidrogênio ou interação de van der Waals?

It is through the application of an electronic partition approach called Symmetry-Adapted Perturbation Theory (SAPT) that the nature of hydrogen bonds and van der Waals interactions can be unveiled according to the contribution of electrostatic, charge transfer, exchange repulsion, polarization, and dispersion terms. Among these, electrostatic partition governs the formation of the hydrogen bonds, whose energies are arguably high. However, the weakness of the interaction strength is caused by dispersion forces, whose contribution decisively lead to the stabilization of complexes formed via van der Waals interactions.

Inovação para a sustentabilidade

The transition to sustainable standards of production and consumption within a scenario of decreased availability of natural resources, growing population and climate change is essential to meet current challenges facing mankind. A strategy to meet these challenges should contain elements different from current approaches for industrial production. This work concentrates on the possibilities for the intensive use of sustainable biomass, abundant minerals and every type of residue, a task that can largely benefit from the application of nanotechnology and biotechnology platforms for material design and transformation. This strategy cannot be solely based on existing knowledge and requires new science, new knowledge including supposedly well-known themes, like the tribochemistry of electrostatic charging and friction. It is especially relevant within the Brazilian context, where many recent successful innovations are related to biomass production and transformation. Implementation of this strategy requires converging efforts by personnel from many different organizations and professions, while making sound risk assessment to produce significant innovation leading to sustainable development.

Acúmulo de cargas elétricas em propelente sólido compósito com matriz de polibutadieno líquido hidroxilado

Composite solid propellants prepared with HTPB prepolymer - Hydroxyl Terminated Polybutadiene, AP - Ammonium Perchlorate as oxidizer and aluminum particles as an additive metal, have characteristics of high electrical resistivity. The loading process of the polymer matrix did not obtain homogeneity, resulting in clusters, mainly of metal particles. The effect of clustering in the composite was studied and observed experimentally, and this effect was one of the factors explaining the phenomenon of electrical charging of the composite. This electrical potential, when discharged abruptly, can generate an electric spark with sufficient energy for sustained ignition of a solid rocket motor.

Carcinogenicidade do carbendazim e seus metabólitos

The carcinogenic potential of carbendazim and its metabolites was analyzed using statistical treatment of electronic parameters obtained from DFT/ 6-311++G(d,p) and AM1 calculations. The carcinogen-DNA interaction is described in the framework of the theory of unsynchronized resonance of covalent bond as a process of electron transfer involving the HOMO and LUMO frontier orbitals. Through a Principal Component Analysis (PCA) of the electron affinity, carcinogen-DNA interaction energy, electrostatic attraction and cell membrane permeability (dipole moment m and partition coefficient LogP) evidence was obtained showing carbendazim displays carcinogenic activity. For the metabolites of carbendazim, no evidence was found in the literature of their carcinogenic activities. However, the electronic parameters for these metabolites exhibited similarity to known carcinogens, thereby showing the importance of the results obtained in this study for a policy based on the precautionary principle.

Interactions of chitosan/genipin hydrogels during drug delivery: a QSPR approach

A hydrogel comprised of chitosan crosslinked using the low-toxicity crosslinker genipin was prepared, and the absorption of glibenclamide by the hydrogel was investigated. Optimized structures and their molecular electrostatic potentials were calculated using the AM1 method, and the results were used to evaluate the molecular interactions between the three compounds. The quantitative structure-property relationship model was also used to estimate the activity of the chemicals on the basis their molecular structures. In addition, theoretical Fourier transform infrared spectra were calculated to analyze the intermolecular interactions in the proposed system. Finally, the hydrophilicity of the hydrogel and its influence on the absorption process were also estimated.

O ESTADO DA ARTE DA LIGAÇÃO DE HIDROGÊNIO

Along the historical background of science, the hydrogen bond became widely known as the universal interaction, thus playing a key role in many molecular processes. Through the available theoretical approaches, many of these processes can be unveiled on the basis of the molecular parameters of the subject intermolecular system, such as the variation of bond length and mainly the frequency shift observed in the proton donor. Supported by the natural bond analysis (NBO) with the quantification of the hybridization contributions, the structural deformations and vibrational effects cited above are also attributed to the outcome of the intermolecular interaction strength, which consequently can be estimated by means of the quantum theory of atoms in molecules (QTAIM) as well as evaluated by the symmetry-adapted perturbation theory (SAPT). Moreover, to identify the preferential interaction sites for proton donors and acceptors, the molecular electrostatic potential (MEP) is useful in this regard.

Magnesiumhydroksidialkalin käytön vaikutukset päällystämättömän aikakauslehtipaperin valmistukseen

Magnesiumhydroksidin on havaittu soveltuvan natriumhydroksidin korvaajaksi mekaanisen massan peroksidivalkaisun alkalina. Työssä selvitettiin, miten magnesiumhydroksidi vaikuttaa paperin valmistukseen ja valmiin paperin ominaisuuksiin. Laboratoriokokeet osoittivat magnesiumhydroksidin soveltuvan mekaanisen massan peroksidivalkaisun alkaliksi, sillä vaaleustavoite saavutettiin sen avulla. Valkaistun massan varaustila, johtokyky sekä ζ -potentiaali laskivat magnesiumhydroksidin vaikutuksesta. Nämä johtivat huomattavasti korkeampaan paperin täyteaineretentioon. Massan vedenpidätyskyky kasvoi korvattaessa natriumhydroksidi magnesiumhydroksidilla. Arkkien ominaisuuksista vetoindeksi, valonsirontakerroin ja taivutusjäykkyys kasvoivat. Kaikki edellä mainitut ominaisuudet viittaavat siihen, että magnesiumhydroksidin käyttö parantaa hienoaineen sitoutumista paperiin.

Puupohjaisten kuitukomposiittien materiaalitekniset mahdollisuudet veneteollisuudessa

Tämän diplomityön tavoitteena oli selvittää puupohjaisten kuitukomposiittimateriaalien soveltuvuutta veneteollisuuden valmistusmateriaaliksi. Huviveneiden rakennusta säätelee huvivenedirektiivi ja lukuisat standardit. Standardien mukaan uusien materiaalien käyttö veneenrakennuksessa on mahdollista, mikäli materiaalin ominaisuudet todetaan muun muassa laboratoriotesteissä soveltuviksi kyseiseen käyttötarkoitukseen. Tutkimusta varten valmistettiin kuusi erilaista kuitukomposiittimateriaalia. Tutkimuksessa käytettiin myös neljän kaupallisen puumuovikomposiittivalmistajan materiaalia. Vertailumateriaaleiksi valittiin puuraaka-aineista mänty, saarni ja mahonki sekä muoviraakaaineista ABS – muovi. Tarkisteltaville materiaaleille määriteltiin standardien mukaisin testein taivutuslujuus, vetolujuus, Charpy – iskulujuus, Brinell – kovuus, veden absorptio sekä paksuusturpoama. Saatuja arvoja vertailtiin vertailumateriaalien kirjallisuudessa mainittuihin arvoihin. Puupohjaisten kuitukomposiittien ominaisuudet jäivät vertailumateriaalien vastaavista lukuun ottamatta Brinell – kovuutta. Taivutus- ja vetolujuuden osalta eräiden kaupallisten puumuovikomposiittivalmistajien ilmoittamat lujuusarvot olivat lähellä veneenrakennuksessa käytettyjen materiaalien vastaavia. Suurimpana yksittäisenä haasteena puukuitupohjaisilla kuitukomposiiteilla havaittiin Charpy – iskulujuus. Myös veden absorption saattaminen alhaiseksi havaittiin tärkeäksi veneilysovelluksissa. Ominaisuuksien kehittäminen on kuitenkin käytettävissä olevan tutkimustiedon perusteella mahdollista. Diplomityössä saatujen tulosten perusteella on puupohjaisilla kuitukomposiiteilla potentiaalia veneteollisuudessa. Jatkotutkimusta tulisikin kohdistaa materiaalin ominaisuuksien kehittämiseen.

Särmäyksen kustannusperusteinen hinnoittelu

Tässä diplomityössä on tutkittu särmäyksen eri muuttujien vaikutusta kustannusrakenteeseen. Tutkimusmenetelminä on käytetty kirjallisuusselvitystä sekä särmäysaikojen mittausta tuotannossa. Diplomityön tavoitteena oli saada aikaan kustannusperusteinen hinnoittelumalli, jonka avulla särmäyksen hinnoittelu on yksinkertaista ja nopeaa. Särmäysaikoja mitattiin erikokoisille ja -muotoisille kappaleille. Levyn paksuus mitattavilla kappaleilla oli alle 1mm. Muut mitat vaihtelivat alle 200 mm:stä yli 2000 mm:iin. Käytetyt materiaalit olivat sähkö- ja kuumasinkitty teräs. Mitattavia aikoja olivat aika, joka kuluu yhden särmän taivutukseen, aika, joka kuluu yhden kappaleen valmistamiseen sekä ohjelmointiin ja asetuksiin kuluva aika. Särmäysaikoihin vaikuttavat kymmenet eri muuttujat liittyen särmäyspuristimiin, särmättäviin kappaleisiin ja työkaluihin, jne. Osa muuttujista vaikuttaa hyvin vähän kokonaisaikaan, joten kaikkia muuttujia ei lähdetty mittaamaan erikseen. Lisäksi käytössä ollut mittausvälineistö ei ollut riittävän tarkka kaikkien muuttujien mittaamiseen. Aikaansaatu hinnoittelumalli huomioi eri muuttujat ajassa, joka kuluu kappaleiden valmistamiseen, jolloin kaikki muuttujat tulee huomioitua lopullisessa hinnassa.

Joustavan särmäyssolun kehittäminen

Tässä diplomityössä esitellään robotisoinnin teoria ja robottisolun oheislaitteet, vaihtoehdot, toiminta ja turvallisuus. Joustavalla tuotantosolulla tarkoitetaan automaattista valmistusjärjestelmää, jossa on useita toisiinsa liitettyjä koneita yhteisellä ohjausjärjestelmällä. Solun komponentteja ovat tuotantolaitteet ja -koneet, ohjausjärjestelmät, valvontalaitteet ja anturit, toimi- ja säätölaitteet sekä ohjelmointijärjestelmä. Joustavaa tuotantosolua voidaan kehittää tehostamalla työntekijöiden koulutusta, ohjelmointia, asetusten tekemistä ja layouttia. Diplomityöhön liittyvä kehitystehtävä koskee heinäveteläisen alihankintakonepajan, Metalliset Oy:n, tuotannon tehostamista robotisoinnin avulla. Metalliset Oy:n joustavan särmäyssolun kehittämiskeinoiksi valittiin nykyisen järjestelmän tehostaminen, uuden tuotantosolun luominen olemassa olevia laitteita hyödyntäen ja tulevaisuuden tuotantosolun kehittäminen. Vertailussa parhaimmaksi osoittautui uuden tuotantosolun luominen olemassa olevia laitteita hyödyntäen.

Magnetic, thermal and spectral properties of Ni(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

Complexes of Ni(II) 2,3-, 3,5- and 2,6-dimethoxybenzoates have been synthesized, their physico-chemical properties have been compared and the influence of the position of -OCH3 substituent on their properties investigated. The analysed compounds are crystalline, hydrated salts with green colour. The carboxylate ions show a bidentate chelating or bridging coordination modes. The thermal stabilities of Ni(II) dimethoxybenzoates were investigated in air in the range of 293-1173 K. The complexes decompose in three steps, yelding the NiO as the final product of decomposition. Their solubilities in water at 293 K are in the order of 10-2-10-4 mol×dm-3. The magnetic susceptibilities for the analysed dimethoxybenzoates of Ni(II) were measured over the range of 76-303 K and the magnetic moments were calculated. The results reveal that the complexes are the high-spin ones and the ligands form the weak electrostatic field in the octahedral coordination sphere of the central Ni(II) ion. The various position -OCH3 groups in benzene ring cause the different steric, mesomeric and inductive effects on the electron density in benzene ring.

Rigid Rod Polymer Fillers in Acrylic Denture and Dental Adhesive Resin Systems

Polymeric materials have been used in dental applications for decades. Adhesion of polymeric materials to each other and to the tooth substrate is essential to their successful use. The aim of this series of studies was two-folded. First, to improve adhesion of poly(paraphenylene) based rigid rod polymer (RRP) to other dental polymers, and secondly, to evaluate the usability of a new dentin primer system based on RRP fillers. Poly(paraphenylene) based RRP would be a tempting material for dental applications because of its good mechanical properties. To be used in dental applications, reliable adhesion between RRP and other dental polymers is required. In this series of studies, the adhesion of RRP to denture base polymer and the mechanical properties of RRP-denture base polymer-material combination were evaluated. Also adhesion of BisGMA-TEGDMA-resin to RRP was determined. Different surface treatments were tested to improve the adhesion of BisGMA-TEGDMA-resin to RRP. Results were based on three-point bending testing, Vickers surface hardness test and scanning electron microscope analysis (SEM), which showed that no reliable adhesion between RRP and denture base polymer was formed. Addition of RRP filler to denture base polymer increased surface hardness and flexural modulus but flexural strength decreased. Results from the shear bond strength test and SEM revealed that adhesion between resin and RRP was possible to improve by surface treatment with dichloromethane (DCM) based primer and a new kind of adhesive surface can be designed. The current dentin bonding agents have good immediate bond strength, but in long term the bond strength may decrease due to the detrimental effect of water and perhaps by matrix metalloproteinases. This leads to problems in longevity of restorations. Current bonding agents use organic monomers. In this series of studies, RRP filled dentin primer was tested in order to decrease the water sorption of the monomer system of the primers. The properties of new dentin primer system were evaluated in vitro by comparing it to commercial etch and rinse adhesive system. The results from the contact angle measurements and SEM showed that experimental primer with RRP reinforcement provided similar resin infiltration to dentin collagen and formed the resin-dentin interface as the control primer. Microtensile bond strength test and SEM revealed that in short term water storing, RRP increased bond strength and primer with BMEP-monomer (bis[2-(methacryloyloxy)-ethyl]phosphate) and high solvent concentration provided comparable bonding properties to the commercial control primers. In long term water storing, the high solvent-monomer concentration of the experimental primers decreased bond strength. However, in low solvent-monomer concentration groups, the long-term water storing did not decrease the bond strength despite the existence of hydrophilic monomers which were used in the system. These studies demonstrated that new dentin primer system reached the mechanical properties of current traditional etch and rinse adhesive system in short time water storing. Improved properties can be achieved by further modifications of the monomer system. Studies of the adhesion of RRP to other polymers suggest that adhesion between RRP and other dental polymers is possible to obtain by certain surface treatments.

Product costing model for laser welded hollow core steel panels

The aim of the study was to create an easily upgradable product costing model for laser welded hollow core steel panels to help in pricing decisions. The theory section includes a literature review to identify traditional and modern cost accounting methodologies, which are used by manufacturing companies. The theory section also presents the basics of steel panel structures and their manufacturing methods and manufacturing costs based on previous research. Activity-Based costing turned out to be the most appropriate methodology for the costing model because of wide product variations. Activity analysis and the determination of cost drivers based on observations and interviews were the key steps in the creation of the model. The created model was used to test how panel parameters affect the costs caused by the main manufacturing stages and materials. By comparing cost structures, it was possible to find the panel types that are the most economic and uneconomic to manufacture. A sensitivity analysis proved that the model gives sufficiently reliable cost information to support pricing decisions. More reliable cost information could be achieved by determining the cost drivers more accurately. Alternative methods for manufacturing the cores were compared with the model. The comparison proved that roll forming can be more advantageous and flexible than press brake bending. However, more extensive research showed that roll forming is possible only when the cores are designed to be manufactured by roll forming. Due to that fact, when new panels are designed consideration should be given to the possibility of using roll forming.

Structural studies on enzymes of biotechnological and biomedical interest

Structural studies of proteins aim at elucidating the atomic details of molecular interactions in biological processes of living organisms. These studies are particularly important in understanding structure, function and evolution of proteins and in defining their roles in complex biological settings. Furthermore, structural studies can be used for the development of novel properties in biomolecules of environmental, industrial and medical importance. X-ray crystallography is an invaluable tool to obtain accurate and precise information about the structure of proteins at the atomic level. Glutathione transferases (GSTs) are amongst the most versatile enzymes in nature. They are able to catalyze a wide variety of conjugation reactions between glutathione (GSH) and non-polar components containing an electrophilic carbon, nitrogen or sulphur atom. Plant GSTs from the Tau class (a poorly characterized class) play an important role in the detoxification of xenobiotics and stress tolerance. Structural studies were performed on a Tau class fluorodifen-inducible glutathione transferase from Glycine max (GmGSTU4-4) complexed with GSH (2.7 Å) and a product analogue Nb-GSH (1.7 Å). The three-dimensional structure of the GmGSTU4-4-GSH complex revealed that GSH binds in different conformations in the two subunits of the dimer: in an ionized form in one subunit and a non-ionized form in the second subunit. Only the ionized form of the substrate may lead to the formation of a catalytically competent complex. Structural comparison between the GSH and Nb-GSH bound complexes revealed significant differences with respect to the hydrogen-bonding, electrostatic interaction pattern, the upper part of -helix H4 and the C-terminus of the enzyme. These differences indicate an intrasubunit modulation between the G-and Hsites suggesting an induced-fit mechanism of xenobiotic substrate binding. A novel binding site on the surface of the enzyme was also revealed. Bacterial type-II L-asparaginases are used in the treatment of haematopoietic diseases such as acute lymphoblastic leukaemia (ALL) and lymphomas due to their ability to catalyze the conversion of L-asparagine to L-aspartate and ammonia. Escherichia coli and Erwinia chrysanthemi asparaginases are employed for the treatment of ALL for over 30 years. However, serious side-effects affecting the liver and pancreas have been observed due to the intrinsic glutaminase activity of the administered enzymes. Structural studies on Helicobacter pylori L-asparaginase (HpA) were carried out in an effort to discover novel L-asparaginases with potential chemotherapeutic utility in ALL treatment. Detailed analysis of the active site geometry revealed structurally significant differences between HpA and other Lasparaginases that may be important for the biological activities of the enzyme and could be further exploited in protein engineering efforts.