Simulação do equilíbrio: o método de Monte Carlo

We make several simulations using the Monte Carlo method in order to obtain the chemical equilibrium for several first-order reactions and one second-order reaction. We study several direct, reverse and consecutive reactions. These simulations show the fluctuations and relaxation time and help to understand the solution of the corresponding differential equations of chemical kinetics. This work was done in an undergraduate physical chemistry course at UNIFIEO.

Co-eletrodeposição oscilatória de cobre e estanho

It is investigated in the present contribution the oscillatory co-electrodeposition of CuSn on a polycrystalline gold surface in the presence of Triton X-100 surfactant and citric acid as additive, in acidic media. The experiments were conducted under potentiostatic control and the system dynamics characterized in terms of the morphology and stability of the current oscillations. Besides modulations in the frequency and amplitude of the current oscillations, several patterned states were observed, including relaxation-like and mixed mode oscillations. The oscillations were found to be very robust and some time series presented regular motions up to about two hours.

Espectroscopia Mössbauer na caracterização de compostos ferrosos em solos e sua relação com retenção de fósforo

The chemical role of iron-bearing compounds on the dynamics of phosphorus in selected Brazilian latosols was investigated. The iron oxides were characterized in an attempt to assess their main chemical-mineralogical properties influencing the ion sorption mechanisms in those pedosystems. It was found that increasing total iron contents tend to increase the phosphorus adsorption capacity in the selected soils. 110 K-Mössbauer data reveal that the dominant iron oxides are hematite and goethite. Particularly for the yellower soil samples some prominent doublets, more certainly due to superparamagnetic relaxation, may be assigned to corresponding fractions of relatively small-sized particles.

Obtenção de filmes finos de TiO2 nanoestruturado pelo método dos precursores poliméricos

This work focuses in optimizing setup for obtaining TiO2 thin films by polymeric precursor route due to its advantages on stoichiometric and morphological control. Precursor stoichiometry, synthesis pH, solids concentration and rotation speed at deposition were optimized evaluating thin films morphology and thickness. Thermogravimetry and RMN were applied for precursor's characterization and AFM, XRD and ellipsometry for thin films evaluation. Results showed successful attainment of homogeneous nanocrystalline anatase TiO2 thin films with outstanding control over morphological characteristics, mean grain size of 17 nm, packing densities between 57 and 75%, estimated surface areas of 90 m²/g and monolayers thickness within 20 and 128 nm.

Esteroides produzidos por Penicillium herquei, um fungo endofítico isolado dos frutos de Melia azedarach (Meliaceae)

Six compounds comprising the groups of steroids, the ergosterol, the ergosterol peroxide, the cerevisterol, the neociclocitrinols, the ergosta-4,6,8(14),22-tetraen-3-one, the 25-hydroxy-ergosta-4,6,8(14),22-tetraen-3-one, were isolated from Penicillium herquei fungus obtained from Melia azedarach. The structures were identified by spectral methods of RMN 1D and 2D and MS.

Argilas como catalisadores verdes na esterificação do colesterol: caracterização espectroscópica e identificação de polimorfos por métodos de análise térmica. Uma proposta laboratorial interdisciplinar para o 1º ciclo universitário

A laboratory experiment that enables the professor to introduce the problematic of sustainable development in pharmaceutical chemistry to undergraduate students is proposed, using a simple synthetic procedure. Cholesteryl acetate is prepared by the esterification of cholesterol using Montmorillonite K10 as heterogeneous catalyst. Cholesterol and cholesteryl acetate are characterized by spectroscopic (¹H RMN, 13C RMN, FTIR) and thermal analysis techniques. The thermal methods are used to introduce the concepts of polymorphism and the nature of mesophases.

Viscoelásticos oftálmicos: comparação entre os comerciais e formulações de galactomanana de Dimorphandra gardneriana

Ophthalmic viscosurgical devices (OVD) are materials injected in intraocular space during cataract removal to reduce trauma in the patient's eye. Three Brazilian commercially available OVDs (Medilon®, Metilcelulose® and Ofthyal®) were evaluated as well as formulations based on Dimorphandra gardneriana galactomannan. Viscosity and viscoelastic parameters, such as viscosity at zero shear, pseudoplasticity index, elastic and viscous moduli, relaxation time, were determined and compared. Characteristics of an effective OVD were proposed. None of the Brazilian devices studied fulfill the rheological requirements. Only the galactomannan at 3% concentration showed potential to be used as effective OVD.

Preparation of association compound between rhodium(II) citrate and β-cyclodextrin

Inclusion compound of rhodium(II) citrate with β-cyclodextrin in a 1:1 molar ratio was prepared using freeze-drying method. X-ray diffactometry, thermal analysis (TG/DTG/DSC), infrared and ¹H-NMR with ¹H spin lattice relaxation (¹H T1) measurements and 13C techniques were used to characterize the system prepared. The results indicated the formation of inclusion or association compounds between rhodium(II) citrate and β-cyclodextrin.

Aplysfistularine: a novel dibromotyrosine derivative isolated from Aplysina fistularis

The new dibromotyrosine derivative 3,5-dibromo-4-[3'dimethylamonium]propoxyphenyl]-N,N,N-trimethylethanamonium, here referred to as aplysfistularine (1), was isolated from the marine sponge Aplysina fistularis along with 2-(3,5-dibromo-4methoxyphenyl)-N,N,N-trimethylethanamonium (2), aplysterol (3) and 24,28-didehydroaplysterol (4). Their identification was performed by mass spectrometry, infrared, ¹H and 13C NMR, and by comparison with literature data. Compound 2 and the mixture of 3 and 4 were tested in vitro (inhibitory activity) with supercoiled DNA relaxation techniques, and showed inhibitory activity on human DNA topoisomerase II-α. Compound 1 was not tested due to paucity of the material.

Phaeophytins from Thyrsacanthus ramosissimus Moric. with inhibitory activity on human dna topoisomerase II-α

Our study reports the extraction and isolation of a new phaeophytin derivative 15¹-hydroxy-(15¹-S)-porphyrinolactone, designated anamariaine (1) herein, isolated from the chloroform fraction of aerial parts of Thyrsacanthus ramosissimus Moric. along with the known 15¹-ethoxy-(15¹-S)-porphyrinolactone (2). These compounds were identified by usual spectroscopic methods. Both compounds were subjected to in vitro (inhibitory activity) tests by means of supercoiled DNA relaxation techniques and were shown to display inhibitory activity against human DNA topoisomerase II-α at 50 µM. Interconversion of these two pigments under the mild conditions of the isolation techniques should be highly unlikely but cannot be entirely ruled out.

Neolignans from Licaria chrysophylla and Licaria aurea with DNA topoisomerase II-α inhibitory activity

Seven natural neolignans isolated from Licaria chrysophylla and Licaria aurea along with five semisynthetic derivatives were tested for their inhibitory action on DNA-topoisomerase by relaxation assays on pBR322 plasmid DNA. All compounds tested showed strong inhibition at a concentration of 100 µM, while none showed activity between 5 and 70 µM. These results indicate that no obvious correlation can be derived between the structure of these compounds and their inhibitory effect on the DNA relaxation activity of topoisomerase II. This is the first report on DNA topoisomerase II inhibitors from Licaria chrysophylla and Licaria aurea leading to the identification of lignoids as topoisomerase II-α inhibitors.

Polymeeripinnoitteen aiheuttamat itseherätteiset värähtelyt nipillisessä telasysteemissä

Lukuisissa teollisuussovelluksissa materiaalien, kuten paperin ja teräslevyjen, muokkaamiseen käytettävät pyörivät nippitelat kärsivät aina erilaisten herätteiden synnyttämistä mekaanisista värähtelyistä, jotka voivat aiheuttaa virheitä valmistettaviin tuotteisiin. Tässä työssä tutkittiin viskoelastisia polymeerejä ja polymeeripinnoitteen nipilliseen telasysteemiin synnyttämiä haitallisia itseherätteisiä värähtelyjä. Työn polymeerejä käsittelevässä kirjallisuusosassa luotiin katsaus amorfisten polymeerien fysikaalisiin ominaisuuksiin. Kokeellisessa osuudessa tutkittiin tarkemmin kahden amorfisen telapinnoitepolymeerin termoreologisia ja mekaanisia ominaisuuksia suoritettujen DMTA-mittausten perusteella. Sovittamalla toisen polymeerin master-käyrään yleistetty lineaarisen standardiaineen malli saatiin selville polymeerin mekaaniset parametrit ja approksimaatio sen relaksaatiospektrille. Telapinnoitteen nipilliseen systeemiin synnyttämiä itseherätteisiä värähtelyjä ja niiden seurauksia tarkasteltiin kahdelle telalle ja polymeeripinnoitteelle kehitetyn analyyttisen mallin ja numeeristen laskujen avulla. Pinnoite mallinnettiin lineaarisen standardiaineen mukaisesti. Telasysteemin parametrit määritettiin DMTA-mittaustuloksista ja systeemiä vastaavasta koelaitteesta kokeellisella moodianalyysillä ja elementtimenetelmällä. Numeerisesta stabiilisuusanalyysistä ja liikeyhtälöiden integroinneista saadut tulokset kertovat telapinnoitteen aaltomaisista deformaatiomuodoista ja niiden synnyttämistä taajuusalueittain esiintyvistä epästabiileista värähtelyistä. Telasysteemi on epästabiili pinnoitedeformaatiokuvion systeemiin aiheuttaman herätevoiman taajuuden ollessa lähellä systeemin korkeampaa ominaistaajuutta. Numeerisista tuloksista voitiin ennustaa nopean ja hitaan barringin olemassaolo.

Comportamento térmico de composto ciclopaladados binucleares contendo azo-ligantes aniônicos

No presente trabalho é descrita a investigação do comportamento térmico de uma nova série de complexos ciclopaladados, obtidos a partir de reações do azido-complexo [Pd(dmba)(mi-N3)]2 (1) (dmba = N,N-dimetilbenzilamina) com os azo-ligantes aniônicos pirazolato (pz), imidazolato (imz) e 3,5-dimetil-pirazolato (3,5-dmpz). Os compostos binucleares [Pd(dmba)(mi-pz)]2 (2), [Pd(dmba)(mi-imz)]2 (3) e [Pd(dmba)(mi-3,5-dmpz)]2 (4) foram caracterizados por análise elementar, espectroscopia de absorção na região do infravermelho, espectroscopia de RMN de 13C{¹H} e ¹H e análise termogravimétrica. O produto final de decomposição térmica, paládio metálico, foi caracterizado pela difratometria de raios-X, método do pó.

Síntese, caracterização e estudos de transferencia de energia do complexo dimérico constituído por Zn e Mn porfirina

Muitos compostos modelo contendo porfirinas têm sido preparados num esforço para entender o sistema de fotossíntese e os processos de aproveitamento de energia solar. Sistemas doadores-receptores contendo porfirinas têm sido freqüentemente estudados para testar várias descrições teóricas sobre transferência de elétrons. O estudo de parâmetros fotoquímicos e fotofísicos como a distância para transferência de energia, geometria molecular e a diferença de potencial eletrônico, tem se mostrado importante para a definição da transferência eletrônica em porfirinas. Neste trabalho apresentamos a síntese, purificação e caracterização por espectroscopia UV/Vis, ¹H e 19F RMN, luminescência e tempos de vida de novos modelos moleculares de porfirinas, que permitam investigar esses parâmetros. Utilizou-se o dímero Zn,Mn(TPPF4)2pip e seus monômeros ZnTPPF4pipH e MnF5TPP. A caracterização do ZnMn(TPPF4)2pip, foi dificultada devido a presença de Mn+3, devido ao forte acoplamento dos orbitais dpi do manganês e o sistema pi da porfirina, que aumenta a interação manganês-porfirina mudando o espectro eletrônico UV/Vis e distorcendo os sinais de ¹H e 19F RMN do dímero. A presença de Mn+3 desloca E1/2 do anel porfirínico para valores mais negativos, o que resulta em reduções mais difíceis, impedindo a transferência de energia da Znporfirina para a Mnporfirina.

Dielectric spectroscopy and thermally stimulated discharge current in PEEK film

The complex permittivity of films of polyether ether ketone (PEEK) has been investigated over a wide range of frequency. There is no relaxation peak in the range of 1Hz to 10(5) Hz but in the low-frequency side (10-4 Hz) there is an evidence of a peak that also can be observed by thermally stimulated discharge current measurements. That peak is related with the glass transition temperature (Tg) of the polymer. The activation energy of the relaxation was found to be 0.44 eV, similar to that of several synthetic polymers. Space charges are important in the conduction mechanism as shown by discharging transient.