NMR imaging of water sorption into poly(hydroxyethyl methacrylate-co-tetrahydrofurfuryl methacrylate)

The diffusion of water into a series of hydroxyethyl methacrylate, HEMA, copolymers with tetrahydrofurfuryl methacrylate, THFMA, has been studied over a range of copolymer compositions using NMR imaging analyses. For polyHEMA the diffusion was found to be consistent with a Fickian model. The mass diffusion coefficient of water in polyHEMA at 37 degreesC was determined from the profiles of the diffusion front to be 1.5 x 10(-11) m(2) s(-1), which is less than the value based upon mass uptake, 2.0 x 10(-11) m(2) s(-1). The profiles of the water diffusion front obtained from the NMR images showed that stress was induced at the interface between the rubbery and glassy regions which led to formation of small cracks in this region of the glassy matrix of polyHEMA and its copolymers with mole fractions of HEMA greater than 0.6. Water was shown to be able to enter these cracks forming water pools. For copolymers of HEMA and THFMA with mole fractions of HEMA less than 0.6 the absence of cracks was attributed to the ability of the THFMA sequences to undergo stress relaxation by creep.

Free radical copolymerization of methyl methacrylate and allyl acetate Part 2 structure and properties

The structure of the product from the free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) was investigated. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. Molecular weight (MW) and molecular weight distribution (MWD) are completely altered when the feed composition is dominantly AAc. NMR spectroscopy confirmed the incorporation of AAc into the polymer. However, no allyl-allyl linkages were observed at low conversions. T-g was found to be affected by the incorporation of AAc into the polymer. (C) 2001 Society of Chemical Industry.

Copolymerization of methyl methacrylate and allyl acetate Part I. Rate of reaction

Free radical bulk copolymerization of methyl methacrylate (MMA) and allyl acetate (AAc) has been investigated using electron spin resonance (ESR) and FT-near infrared (FTNIR) spectroscopy. Data are used to evaluate the rate constants. The mole fraction of AAc plays an important role in the copolymerization of these two monomers. AAc not only delays the Trommsdorff effect but also increases the onset of percentage total conversion at which the Trommsdorff region begins. With AAc fraction 0.5 and higher, no Trommsdorff effect was observed. Inclusion of AAc into copolymer structure mainly occurs in the Trommsdorf region or when the AAc fraction in the comonomer feed is dominant. This is associated with a drop in the concentration of propagating radicals. However, ESR spectra indicate that the MMA propagating radical is predominant during the reaction. In the comonomer mixtures where a Trommsdorff region can be observed, the addition of AAc does not produce any significant change in k(p) and k(t) in the steady state region. Major changes in k(p) and k(t) are observed after the gel point and glassy state, respectively. (C) 2001 Society of Chemical Industry.

The use of F-19 NMR for new structure determination in the radiolysis of FEP

The radiation chemistry of poly(tetrafluoroethylene-co-perfluoropropylene), FEP, with a mole fraction of tetrafluoroethylene, TFE, of 0.90 has been studied under vacuum using Co-60 gamma -radiation over absorbed dose ranges up to 3.0 MGy. The radiolysis temperatures were 300, 363, 423 and 523 K. New structure formation in the copolymers was analyzed by solid-state F-19 NMR. The new structures formed in the copolymers have been identified and the G-values for the formation of new -CF3 groups was 2.2 at the lower temperatures and increased to 2.9 at 523 K. The G-value for the loss of original -CF3 groups was approximate to1.0 at all temperatures. At the lower temperatures there was a net loss of -CF-groups on irradiation, G(CF) of -1.3, -0.9 and -0.5 at 300, 363 and 423 K, respectively, but at 523 K there was a net gain with G(CF) equal to 0.8. (C) 2001 Elsevier Science B.V. All rights reserved.

Solid state F-19 NMR determination of new structure formation in FEP following radiolysis at 300 and 363 K

The radiation chemistry of FEP copolymer with a mole fraction TFE of 0.90 has been studied using Co-60 gamma -radiation at temperatures of 300 and 363 K. New structure formation in the copolymers was analysed by solid state F-19 NMR. New chain scission products were the principal new structures found. The G-value for the formation of new -CF3 groups was 2.2 and 2.1 for the radiolysis of FEP at 300 and 363 K, respectively, and the G-value for the loss of original -CF3 groups was G(-CF3) = 1.0 and 0.9 at these two temperatures, respectively. There was a nett loss of -CF- groups on irradiation, with G(-CF) of 1.3 and 0.9 at 300 and 363 K, respectively. (C) 2001 Elsevier Science Ltd. All rights reserved.

The use of NMR for determination of new structures in irradiated TFE/PMVE fluoropolymers

The radiation chemistry of two TFE/PMVE copolymers with TFE mole fractions of 0.66 and 0.81 has been studied under vacuum using Co-60 gamma -radiation over absorbed dose ranges up to 4.2 MGy. The radiolysis temperature was 313 K for both TFE/PMVE copolymers. New structure formation in the copolymers was identified by solid-state F-19 NMR and the G-values for new chain ends of 2.1 and 0.5 and for branching sites of 0.9 and 0.2 have been obtained for the TFE/PMVE with TFE mole fractions of 0.66 and 0.81, respectively. The relative yields of-O-CF3 and -CF2-CF3 chain ends were found to be proportional to the copolymer composition, but the yields of the -CF2-CF3 chain ends and -CF- branch points mere not linearly related ia the composition. rather they wets correlated with the radical yields measured at 77 K. (C) 2001 Elsevier Science Ltd. All rights reserved.

Structural effects of lipophilic methotrexate conjugates on model phospholipid biomembranes

Lipophilic conjugates of the antitumor drug methotrexate (MTX) with lipoamino acids (LAAs) have been previously described as a tool to enhance MTX passive entrance into cells, overcoming a form of transport resistance which makes tumour cells insensitive to the antimetabolite. A knowledge of the mechanisms of interaction of such lipophilic derivatives with cell membranes could be useful for planning further lipophilic MTX derivatives with an optimal antitumour activity. To this aim, a calorimetric study was undertaken using a biomembrane model made from synthetic 1,2-dipalmitoyl-glycero-3-phosphocholine (DPPC) multilamellar liposomes. The effects of MTX and conjugates on the phase transition of liposomes were investigated using differential scanning calorimetry. The interaction of pure MTX with the liposomes was limited to the outer part of the phospholipid bilayers, due to the polar nature of the drug. Conversely, its lipophilic conjugates showed a hydrophobic kind of interaction, perturbing the packing order of DPPC bilayers. In particular, a reduction of the enthalpy of transition from the gel to the liquid crystal phase of DPPC membranes was observed. Such an effect was related to the structure and mole fraction of the conjugates in the liposomes. The antitumour activity of MTX conjugates was evaluated against cultures of a CCRF-CEM human leukemic T-cell line and a related MTX resistant sub-line. The in vitro cell growth inhibitory activity was higher for bis(tetradecyl) conjugates than for both the other shorter- and longer-chain derivatives. The biological effectiveness of the various MTX derivatives correlated very well with the thermotropic effects observed on the phase transition of DPPC biomembranes. (C), 2001 Elsevier Science B.V All rights reserved.

The role of melanocortin-1 receptor polymorphism in skin cancer risk phenotypes

We have examined melanocortin-1 receptor (MC1R) variant allele frequencies in the general population and in a collection of adolescent dizygotic and monozygotic twins to determine statistical associations of pigmentation phenotypes with increased skin cancer risk. This included hair and skin color, freckling, mole count and sun exposed skin reflectance. Nine variants were studied and designated as either strong R (OR = 63; 95% CI 32-140) or weak r (OR = 5; 95% CI 3-11) red hair alleles. Penetrance of each MC1R variant allele was consistent with an allelic model where effects were multiplicative for red hair but additive for skin reflectance. To assess the interaction of the brown eye color gene BEY2/OCA2 on the phenotypic effects of variant MC1R alleles we imputed OCA2 genotype in the twin collection. A modifying effect of OCA2 on MC1R variant alleles was seen on constitutive skin color, freckling and mole count. In order to study the individual effects of these variants on pigmentation phenotype we have established a series of human primary melanocyte strains genotyped for the MC1R receptor. These include strains which are MC1R wild-type consensus, variant heterozygotes, and homozygotes for strong R alleles Arg151Cys and Arg160Trp. Ultrastructural analysis demonstrated that only consensus strains contained stage III and IV melanosomes in their terminal dendrites whereas Arg151Cys and Arg160Trp homozygous strains contained only immature stage I and II melanosomes. Such genetic association studies combined with the functional analysis of MC1R variant alleles in melanocytic cells should provide a link in understanding the association between pigmentary phototypes and skin cancer risk.

Linkage and Association Analysis of Radiation Damage Repair Genes XRCC3 and XRCC5 with Nevus Density in Adolescent Twins

Previous studies have shown that a deficiency in DNA damage repair is associated with increased cancer risk, and exposure to UV radiation is a major risk factor for the development of malignant melanoma. High density of common nevi (moles) is a major risk factor for cutaneous melanoma. A nevus may result from a mutation in a single UV-exposed melanocyte which failed to repair DNA damage in one or more critical genes. XRCC3 and XRCC5 may have an effect on nevus count through their function as components of DNA repair processes that may be involved directly or indirectly in the repair of DNA damage due to UV radiation. This study aims to test the hypothesis that the frequency of flat or raised moles is associated with polymorphism at or near these DNA repair genes, and that certain alleles are associated with less efficient DNA repair, and greater nevus density. Twins were recruited from schools in south eastern Queensland and were examined close to their 12th birthday. Nurses examined each individual and counted all moles on the entire body surface. A 10cM genome scan of 274 families (642 individuals) was performed and microsatellite polymorphisms in XRCC3 and adjacent to XRCC5 were also typed. Linkage and association of nevus count to these loci were tested simultaneously using a structural-equation modeling approach implemented in MX. There is weak evidence for linkage of XRCC5 to a QTL influencing raised mole count, and also weak association. There is also weak evidence for association between flat mole count and XRCC3. No tests were significant after correction for testing multiple alleles, nor were any of the tests for total association significant. If variation in XRCC3 or XRCC5 influences UV sensitivity, and indirectly affects nevus density, then the effects are small.

Analysis of multicomponent adsorption kinetics on activated carbon

An integrated mathematical model for the kinetics of multicomponent adsorption on microporous carbon was developed. Transport in this bidisperse solid is represented by balance equations in the macropore and micropore phases, in which gas-phase diffusion dominates the mass transfer in the macropores, with the phenomenological diffusivities represented by the generalized Maxwell-Stefan (GMS) formulation. Viscous flow also contributes to the macropore fluxes and is included in the MS expressions. Diffusion of the adsorbed phase controls the mass transfer in the micro ore phase, p which is also described in a similar way by the MS method. The adsorption isotherms are represented by a new heterogeneous modified vacancy solution theory formulation of adsorption, which has proved to be a robust method for adsorption on activated carbons. The model is applied to the coadsorption and codesorption of C2H6 and C3H8 on Ajax and Norit carbon, as well as the displacement on Ajax carbon. The effect of the viscous flow in the macropore phase is not significant for the cases studied. The model accurately predicts the overshoot behavior and rollup of C2H6 during coadsorption. The prediction for the heavier compound C3H8 is always satisfactory, though at higher C3H8 mole fraction, the overshoot extent of C2H6 is overpredicted, possibly due to neglect of heat effects.

Estudo da resistência não drenada de solo de baixa consistência por meio de ensaios de campo e laboratório

A variabilidade natural dos solos torna complexo o conhecimento de suas propriedades na elaboração de projetos geotécnicos, sendo a determinação da resistência ao cisalhamento não drenada um parâmetro importante nas análises de estabilidade de solos moles. Os ensaios de laboratório de cone e palheta, não convencionais, os ensaios de campo de palheta e piezocone e os ensaios de compressão simples e triaxial não adensado e não drenado foram utilizados para mensurar a resistência não drenada de uma camada de argila marinha mole localizada na planície costeira central brasileira. Os ensaios de laboratório foram realizados em amostras indeformadas coletadas com amostradores de pistão estacionário em vertical próxima à realização dos ensaios de campo. O sítio foi investigado preliminarmente por sondagens de simples reconhecimento, sendo apresentado o perfil estratigráfico por meio de modelagem computacional. Foram também realizados ensaios para caracterização física (análise granulométrica, teor de umidade, limites de liquidez e plasticidade, densidade real dos grãos) e mineralógica (difração de raios X), e ensaios de adensamento para obtenção do histórico de tensões e classificação de qualidade das amostras indeformadas. Os valores de resistência não drenada obtidos pelos ensaios de laboratório foram comparados ao perfil contínuo de resistência determinado empiricamente pelo ensaio de piezocone, com fator de cone Nkt calibrado pelo ensaio de palheta de campo, apresentando boa concordância, com a variabilidade natural do solo influenciando de forma preponderante a qualidade das amostras na variação entre os resultados. Os valores de resistência obtidos pelos ensaios de laboratório de cone e palheta foram comparados entre si, apresentando boa compatibilidade. Ambos, quando comparados ao ensaio de palheta de campo, não apresentaram boa concordância. Os resultados de resistência obtidos pelos ensaios de compressão simples e triaxial apresentaram boa compatibilidade com os resultados do ensaio de laboratório de cone, o que não ocorreu com os resultados do ensaio de laboratório de palheta. Na comparação entre a resistência normalizada pela tensão de sobreadensamento obtida pelos diversos métodos e algumas correlações empíricas da literatura internacional, foi observado para as amostras de solo com índice de plasticidade superior a 60% boa concordância com as correlações de Mesri (1975) e Jamiolkowski et al (1985). Os ensaios não convencionais apresentaram boa confiabilidade, que aliado a simplicidade e agilidade de execução, justificam a difusão destes na prática da investigação geotécnica brasileira como método alternativo para complementar e dar suporte às estimativas de resistência não drenada de solos moles.

A mucosa oral na hanseníase: um estudo clínico e histopatológico

INTRODUÇÃO: a anseníase multibacilar pode causar comprometimento da mucosa oral, com ou sem lesões aparentes. Há poucos estudos que tratam deste assunto na era da multidrogaterapia. OBJETIVO: Verificar a freqüência do comprometimento da mucosa oral em pacientes de hanseníase multibacilar. CASUÍSTICA E MÉTODOS: Foi realizado um estudo transversal em vinte pacientes de hanseníase multibacilar, não-tratados, atendidos consecutivamente em Dracena, São Paulo, entre o período de 2000 e 2002. Foi realizado exame clínico completo da mucosa oral. Os pacientes foram submetidos a biópsias na mucosa jugal, na língua e no palato mole, em alteração ou em pontos pré-estabelecidos. Os cortes foram corados pelas técnicas da hematoxilina-eosina e Ziehl-Neelsen. O encontro de granuloma e bacilos álcool-ácido-resistentes ao exame histopatológico determinou o comprometimento específico. RESULTADOS: O estudo envolveu 19 pacientes multibacilares com tempo médio de evolução de 2,5 anos. Ocorreu comprometimento histopatológico específico em apenas um paciente virchowiano, com mucosa oral clinicamente normal, na língua e no palato mole. CONCLUSÕES: 1. Alteração clínica na mucosa oral não implica em comprometimento pela doença, é necessário confirmação histopatológica. 2. Alterações clínicas específicas aparentes são raras. 3. A mucosa oral clinicamente normal pode exibir comprometimento histopatológico específico.

Complicações bucais da radioterapia em cabeça e pescoço

A radioterapia é uma forma terapêutica amplamente utilizada para o tratamento das neoplasias malignas da cabeça e pescoço. Porém, altas doses de radiação em extensos campos que irão incluir a cavidade bucal, maxila, mandíbula e glândulas salivares freqüentemente resultam em diversas reações indesejadas. Dentre as complicações da radioterapia estão a mucosite, candidose, disgeusia, cárie por radiação, osteorradionecrose, necrose do tecido mole e xerostomia. OBJETIVO: O objetivo deste artigo é fazer uma breve revisão das reações adversas que podem ser detectadas durante o tratamento radioterápico em região de cabeça e pescoço. MÉTODO: A literatura pertinente que trata do assunto foi revisada. FORMA DE ESTUDO: Revisão de literatura. RESULTADOS: A radioterapia ainda está associada a diversas reações adversas, que afetam de forma significativa a qualidade de vida dos pacientes. CONCLUSÕES: O tratamento multidisciplinar, incluindo a equipe médica, o cirurgião-dentista, o fonoaudiólogo, o nutricionista e o psicólogo é a melhor alternativa para minimizar ou mesmo prevenir tais complicações.

Cisto nasolabial: apresentação de um caso e descrição em imagens por TC e RM

O cisto nasolabial é um cisto não odontogênico raro que se desenvolve na região inferior da asa nasal, com patogênese ainda incerta. Esta lesão, que possui crescimento lento e dimensões variáveis (1,5-3cm), caracteriza-se clinicamente por uma tumefação flutuante na região do sulco nasolabial ao redor da asa do nariz, causando uma elevação do lábio superior. Seu diagnóstico pode ser feito basicamente pelo quadro clínico e, se necessário, complementando-se com exames auxiliares por imagens. O presente trabalho relata o caso de uma paciente do sexo feminino de 48 anos, que se queixava da presença de uma massa consistente na região da asa esquerda do nariz e cujas características clínicas eram compatíveis com cisto nasolabial. As imagens de TC demonstraram uma formação expansiva com densidade de tecido mole, localizadas na região nasal esquerda medindo cerca de 1,2cm de diâmetro e apresentando contornos nítidos e bem definidos e densidade homogenia ao redor de 50 UH. Já as imagens de RM mostraram uma lesão de aspecto circular localizada em tecido mole, apresentando hiperintensidade nas imagens ponderadas em T1, T2 e no recurso de supressão da gordura, sendo a hipótese diagnóstico de cisto nasolabial, confirmado pelo exame histopatológico depois da cirurgia.

Acesso transmaxilar à base do crânio: avaliação de 11 casos

O acesso cirúrgico à região de base do crânio é sempre difícil principalmente pelas estruturas anatômicas nobres associadas. A osteotomia maxilar proporciona visão direta à região de clivus e coluna cervical, além de apresentar uma menor morbidade em relação aos diversos acessos descritos na literatura. OBJETIVO: Avaliar 11 casos submetidos à osteotomia transmaxilar, descrevendo técnica cirúrgica, resultados e complicações pós-operatórias. PACIENTES E MÉTODOS: O estudo retrospectivo de onze pacientes foi submetido à cirurgia transmaxilar para acesso à região do tronco encefálico. Registros quanto à oclusão dentária, hemorragia trans e pós-operatória, necrose óssea e alterações de tecido mole foram estudados. Todos seguiram o mesmo protocolo cirúrgico e acompanhamento médio de dois anos. RESULTADOS: Após o tratamento todos os pacientes apresentaram melhora do quadro clínico e nenhum dano neurológico, hemorragia trans e pós-operatória ou intercorrências maiores foram identificadas. Dentre as complicações, em dois pacientes ocorreu fratura incompleta da maxila, dois apresentaram laceração da mucosa nasal e um apresentou como complicação tardia uma fístula bucossinusal. CONCLUSÃO: A osteotomia transmaxilar possibilitou adequado acesso a região de clivus para descompressão do tronco encefálico com baixo índice de complicações nesta série de casos.