Nanoscale effects and applications of self-organized nanostructured thin films

A nanostructured thin film is a thin material layer, usually supported by a (solid) substrate, which possesses subdomains with characteristic nanoscale dimensions (10 ~ 100 nm) that are differentiated by their material properties. Such films have captured vast research interest because the dimensions and the morphology of the nanostructure introduce new possibilities to manipulating chemical and physical properties not found in bulk materials. Block copolymer (BCP) self-assembly, and anodization to form nanoporous anodic aluminium oxide (AAO), are two different methods for generating nanostructures by self-organization. Using poly(styrene-block-methyl methacrylate) (PS-b-PMMA) nanopatterned thin films, it is demonstrated that these polymer nanopatterns can be used to study the influence of nanoscale features on protein-surface interactions. Moreover, a method for the directed assembly of adsorbed protein nanoarrays, based on the nanoscale juxtaposition of the BCP surface domains, is also demonstrated. Studies on protein-nanopattern interactions may inform the design of biomaterials, biosensors, and relevant cell-surface experiments that make use of nanoscale structures. In addition, PS-b-PMMA and AAO thin films are also demonstrated for use as optical waveguides at visible wavelengths. Due to the sub-wavelength nature of the nanostructures, scattering losses are minimized, and the optical response is amenable to analysis with effective medium theory (EMT). Optical waveguide measurements and EMT analysis of the films’ optical anisotropy enabled the in situ characterization of the PS-b-PMMA nanostructure, and a variety of surface processes within the nanoporous AAO involving (bio)macromolecules at high sensitivity.

From amphiphilic block copolymers to ferrocenyl-functionalized polymers for biosensoric applications

The present thesis can be divided in three main parts. In all parts new polymer architecturesrnwere synthesized and characterized concerning their special features.rnThe first part will emphasize the advantage of a polystyrene-block-(hyperbranchedrnpolyglycerol) copolymer in comparison to an analogue polystyrene-block-(linear polyglycerol)rncopolymer. Therefore a synthethic route to prepare linear block copolymersrnhas been developed. Two strategies were examined. One strategy was based on thernclassic, sequential anionic polymerization; the second strategy was based on arn“Click-Chemistry” coupling reaction. In a following step glycidol was hypergraftedrnfrom these block copolymers by applying a hypergrafting reaction with glycidol. Thernbehavior of the amphiphilic block copolymers synthesized was studied in differentrnsolvents. Furthermore the polarity of the solvent was changed to form the correspondingrninverse micelles. DLS, SLS, SEC-MALLS-VISCO, AFM and Cyro TEMrnmeasurements were performed to obtain a visual image from the appearance of thernaggregates. It was found that a linear-hyperbranched architecture is necessary, ifrnwell defined, monodisperse aggregates are required, e.g. for the preparation of orderedrnnanoarrays. Linear-linear block copolymers formed only polydisperse aggregates.rnAdditionally it was found that size distribution could be improved dramaticallyrnby passing the aggregates through a SEC column with large pores. The SEC columnsrnacted like a template in which the aggregates adopt a more stable conformation.rnIn the second part anionic polymerization was employed to synthesize silaneendfunctionalizedrnmacromonomers with different molecular weights based on polybutadienernand polyisoprene. These were polymerized by a hydrosilylation reaction inrnbulk to obtain branched polymers, using Karstedt’s catalyst. Surprisingly the additionrnof monofunctional silanes during the polymerization had only a minimal effect concerningrnthe degree of polymerization. It was possible to introduce silanes without increasingrnthe overall number of reaction steps by a very convenient “pseudo-copolymerization”rnmethod. All branched polymers were analyzed by SEC, SEC-MALLS,rnSEC-viscometry, 1H-NMR-spectroscopy and DSC concerning their branching ratio.rnThe branching parameters for the branched polymers exhibited similar characteristicsrnas hyperbranched polymers based on AB2 monomers. Detailed kinetic study showedrnthat the polymerization occurred very rapidly in comparison to the hydrosilylation polymerizationrnof classical AB2 type carbosilanes monomers.rnThe last part will deal with ferrocenyl-functionalized polymers. On the one hand,rnferrocenyl-functionalized polyglycerols (PG) were studied. Esterification of PGs withrndifferent molecular weight using ferrocenemonocarboxylic acid gave the ferrocenylrnfuntionalized polymers in high yields. On the other hand three different block copolymersrnwere prepared with different ratios of styrene to butadiene units (10:1, 4:1, 2:1).rnThe double bonds of the 1,2-PB block were hydrosilylated using silanes bearing onern(HSiMe2Fc) or two (HSiMeFc2) ferrocene units. High degrees of functionalizationrnwere obtained (up to 83 %). In this manner, six different ferrocenyl-rich block copolymersrnwith different fractions of ferrocene were prepared and analyzed, employingrnNMR-spectroscopy, SEC, SEC/MALLS/viscometry, DLS and cyclic voltammetry. Thernredox properties of the studied polymers varied primarily with the nature of the silanernunit attached. Additionally, the redox properties in solution of the studied polymersrnwere influenced by the block length ratio of the block copolymers. Unexpectedly, withrnincreasing block length of the ferrocenyl block the fraction of active ferrocenes decreased.rnNevertheless, in case of thin monolayer films this behaviour was not observed.rnAll polymers (PG and PS-b-PB based) exhibited good electrochemical propertiesrnin a wide range of solvents, which rendered them very interesting for biosensoricrnapplications.

The performance of poly(styrene)-block-poly(2-vinyl pyridine)-block- poly(styrene) triblock copolymers as pH-driven actuators

Poly(styrene)-block-poly(2-vinyl pyridine)-block-poly(styrene) (PS-b-P2VP-b-PS) triblock copolymers were synthesised by anionic polymerisation. Thick films were cast from solution and their structure analysed by small angle X-ray scattering (SAXS). Longer annealing times led to more ordered structures whereas short evaporation times effectively "lock" the polymer chains in a disordered state by vitrification. Well-ordered structures not only provide an isotropic network, which reduces localised stress within the material, but are also essential for fundamental studies of soft matter because their activity on the molecular scale must be analysed and understood prior to their use in technological applications. Well-characterised PS-b-P2VP-b-PS materials have been coupled to a pH-oscillating reaction and their potential application as responsive actuators is discussed. This journal is © The Royal Society of Chemistry.

Nanostructured copper oxides and phosphates from a new solid-state route

Nanostructured copper containing materials of CuO, Cu3(PO4)3 and Cu2P2O7 have been prepared by solid-state pyrolysis of molecular CuCl2·NC5H4OH (I), CuCl2·CNCH2C6H4OH (II), oligomeric [Cu(PPh3)Cl]4 (III), N3P3[OC6H4CH2CN·CuCl]6[PF6] (IV), N3P3[OC6H5]5[OC5H4N·Cu][PF6] (V), polymeric chitosan·(CuCl2)n (VI) and polystyrene-co-4-vinylpyridine PS-b-4-PVP·(CuCl2) (VII) precursors. The products strongly depend on the precursor used. The pyrolytic products from phosphorus-containing precursors (III), (IV) and (V) are Cu phosphates or pyrophosphates, while non-phosphorous-containing precursors (VI) and (VII), result in mainly CuO. The use of chitosan as a solid-state template/stabilizer induces the formation of CuO and Cu2O nanoparticles. Copper pyrophosphate (Cu2P2O7) deposited on Si using (IV) as the precursor exhibits single-crystal dots of average diameter 100 nm and heights equivalent to twice the unit cell b-axis (1.5–1.7 nm) and an areal density of 5.1–7.7 Gigadots/in.2. Cu2P2O7 deposited from precursor (VI) exhibits unique labyrinthine high surface area deposits. The morphology of CuO deposited on Si from pyrolysis of (VI) depends on the polymer/Cu meta ratio. Magnetic measurements performed using SQUID on CuO nanoparticle networks suggest superparamagnetic behavior. The results give insights into compositional, shape and morphological control of the as-formed nanostructures through the structure of the precursors.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

Fabrication of sub-10 nm lamellar structures by solvent vapour annealing of block copolymers

Fabrication of nanoscale patterns through the bottom-up approach of self-assembly of phase-separated block copolymers (BCP) holds promise for nanoelectronics applications. For lithographic applications, it is useful to vary the morphology of BCPs by monitoring various parameters to make “from lab to fab” a reality. Here I report on the solvent annealing studies of lamellae forming polystyrene-blockpoly( 4-vinylpyridine) (PS-b-P4VP). The high Flory-Huggins parameter (χ = 0.34) of PS-b-P4VP makes it an ideal BCP system for self-assembly and template fabrication in comparison to other BCPs. Different molecular weights of symmetric PS-b-P4VP BCPs forming lamellae patterns were used to produce nanostructured thin films by spin-coating from mixture of toluene and tetrahydrofuran(THF). In particular, the morphology change from micellar structures to well-defined microphase separated arrangements is observed. Solvent annealing provides a better alternative to thermal treatment which often requires long annealing periods. The choice of solvent (single and dual solvent exposure) and the solvent annealing conditions have significant effects on the morphology of films and it was found that a block neutral solvent was required to realize vertically aligned PS and P4VP lamellae. Here, we have followed the formation of microdomain structures with time development at different temperatures by atomic force microscopy (AFM). The highly mobilized chains phase separate quickly due to high Flory-Huggins (χ) parameter. Ultra-small feature size (~10 nm pitch size) nanopatterns were fabricated by using low molecular weight PSb- P4VP (PS and P4VP blocks of 3.3 and 3.1 kg mol-1 respectively). However, due to the low etch contrast between the blocks, pattern transfer of the BCP mask is very challenging. To overcome the etch contrast problem, a novel and simple in-situ hard mask technology is used to fabricate the high aspect ratio silicon nanowires. The lamellar structures formed after self-assembly of phase separated PS-b-P4VP BCPs were used to fabricate iron oxide nanowires which acted as hard mask material to facilitate the pattern transfer into silicon and forming silicon nanostructures. The semiconductor and optical industries have shown significant interest in two dimensional (2D) molybdenum disulphide (MoS2) as a potential device material due to its low band gap and high mobility. However, current methods for its synthesis are not ‘fab’ friendly and require harsh environments and processes. Here, I also report a novel method to prepare MoS2 layered structures via self-assembly of a PS-b-P4VP block copolymer system. The formation of the layered MoS2 was confirmed by XPS, Raman spectroscopy and high resolution transmission electron microscopy.

Desenvolvimento e caracterização de um compósito matriz metálica (CMM): aço EUROFER97 reforçado com Carbeto de Tântalo - TaC

Steel is an alloy EUROFER promising for use in nuclear reactors, or in applications where the material is subjected to temperatures up to 550 ° C due to their lower creep resistance under. One way to increase this property, so that the steel work at higher temperatures it is necessary to prevent sliding of its grain boundaries. Factors that influence this slip contours are the morphology of the grains, the angle and speed of the grain boundaries. This speed can be decreased in the presence of a dispersed phase in the material, provided it is fine and homogeneously distributed. In this context, this paper presents the development of a new material metal matrix composite (MMC) which has as starting materials as stainless steel EUROFER 97, and two different kinds of tantalum carbide - TaC, one with average crystallite sizes 13.78 nm synthesized in UFRN and another with 40.66 nm supplied by Aldrich. In order to improve the mechanical properties of metal matrix was added by powder metallurgy, nano-sized particles of the two types of TaC. This paper discusses the effect of dispersion of carbides in the microstructure of sintered parts. Pure steel powders with the addition of 3% TaC UFRN and 3% TaC commercial respectively, were ground in grinding times following: a) 5 hours in the planetary mill for all post b) 8 hours of grinding in the mill Planetary only for steel TaC powders of commercial and c) 24 hours in the conventional ball mill mixing the pure steel milled for 5 hours in the planetary mill with 3% TaC commercial. Each of the resulting particulate samples were cold compacted under a uniaxial pressure of 600MPa, on a cylindrical matrix of 5 mm diameter. Subsequently, the compressed were sintered in a vacuum furnace at temperatures of 1150 to 1250 ° C with an increment of 20 ° C and 10 ° C per minute and maintained at these isotherms for 30, 60 and 120 minutes and cooled to room temperature. The distribution, size and dispersion of steel and composite particles were determined by x-ray diffraction, scanning electron microscopy followed by chemical analysis (EDS). The structures of the sintered bodies were observed by optical microscopy and scanning electron accompanied by EDS beyond the x-ray diffraction. Initial studies sintering the obtained steel EUROFER 97 a positive reply in relation to improvement of the mechanical properties independent of the processing, because it is obtained with sintered microhardness values close to and even greater than 100% of the value obtained for the HV 333.2 pure steel as received in the form of a bar

O peptídeo natriurético do tipo B é preditor de eventos em pós-operatório de cirurgia ortopédica

FUNDAMENTO: A avaliação clínica nem sempre é suficiente para predizer complicações cardíacas pós-operatórias (PO). O peptídeo natriurético do tipo B (BNP) tem grande valor prognóstico em pacientes (pts) com insuficiência cardíaca. Seu valor como preditor de eventos em cirurgias ortopédicas ainda não foi testado. OBJETIVO: Avaliar o valor do BNP em predizer complicações cardíacas no PO de cirurgia ortopédica. MÉTODOS: Avaliados de modo prospectivo, 208 pts submetidos à cirurgia para correção de fratura de fêmur e artroplastia de quadril ou de joelho. Foram 149 (71,6%) mulheres e a idade média foi de 72,6 ± 8,8 anos. Os pacientes foram submetidos, no pré-operatório, à avaliação clínica convencional e estimativa do risco cirúrgico pela classificação da American Society of Anesthesiologists (ASA). O BNP foi dosado no pré-operatório e avaliou-se a sua capacidade de predizer eventos cardíacos (morte, infarto agudo do miocárdio, angina instável, fibrilação atrial, taquicardia ventricular ou insuficiência cardíaca) no PO, através de análise multivariada por regressão logística. RESULTADOS: Dezessete (8,0%) pacientes apresentaram eventos cardíacos. A mediana de BNP foi significativamente maior nesses pacientes quando comparada a dos sem eventos cardíacos (93 [variação interquartil 73-424] vs 26,6 [13,2-53,1], p = 0,0001). O BNP foi o principal preditor independente de eventos (p = 0,01). A classificação da ASA não foi preditor independente. A análise de curva ROC demonstrou que para um corte de 60 pg/ml, o BNP apresentou sensibilidade de 76,0% e especificidade de 79,0% para predizer eventos, com área sob a curva de 83,0%. CONCLUSÃO: O BNP é um preditor independente de eventos cardíacos no PO de cirurgias ortopédicas.

O controle da hemorragia pós-parto com a técnica de sutura de B-Lynch: série de casos

OBJETIVO: apresentar uma técnica cirúrgica para pacientes submetidas ao parto cesáreo e que evoluem com hemorragia refratária ao uso de medicamentos. MÉTODOS: o critério de seleção das pacientes era falha do tratamento farmacológico no controle da hemorragia pós-parto e o desejo da paciente em preservar o útero. As pacientes foram submetidas ao parto cesáreo e evoluíram com hemorragia pós-parto imediata refratária ao uso de ocitocina, ergometrina e misoprostol. Aplicamos a técnica de sutura descrita por B-Lynch sem modificações. Com fio cromado catgut-2 ou poliglactina-1, transfixamos o útero em seis pontos, conforme padronização. Após compressão manual do útero realizada pelo assistente, o fio é tracionado pelas suas extremidades pelo cirurgião e é aplicado um nó duplo seguido de dois nós simples, para em seguida realizar-se a histerorrafia. RESULTADOS: utilizamos o fio cromado catgut-2 agulhado em três casos e poliglactina-1 agulhado em um. Nos quatro casos houve parada imediata do sangramento vaginal após aplicação da sutura. Não houve qualquer complicação durante a realização do procedimento e nem no puerpério imediato e tardio das quatro pacientes. CONCLUSÕES: esta técnica representa uma alternativa cirúrgica para o manejo da hemorragia pós-parto. Com sua aplicação relativamente fácil, rápida e segura, pode representar uma redução da morbimortalidade materna em nosso país.

Efeitos da intervenção nutricional pós-operatória com vitaminas do complexo B sobre os indicadores metabólicos da via sulfurada e a sobrevida de pacientes com câncer de esôfago

Pós-graduação em Bases Gerais da Cirurgia - FMB

Protein encapsulation and release from PEO-b-polyphosphoester templated calcium carbonate particles

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Avaliação física do tomate de mesa 'Romana' durante manuseio na pós-colheita

Tomato postharvest losses are very high in Brazil and the goal of this research was to evaluate the effect of handling and the transport of tomato fruits, cultivar Romana on the steps of harvesting, weight and transportation to the packinghouse, pointing some critical points. Tomatoes were harvested at plastic boxes, weighted and shipped to a packinghouse. Fruits taken directly from the plant were determined as reference. The parameters evaluated were weight loss and mechanical injury and tomato physical quality after storage during 21 days. It was observed an increasing on the weight loss, external damage, and postharvest losses, after storage. Handling and transportation were the cause of an increase in 6.6% in external damage and 1.93% of weight loss after storage, when comparing harvested fruits and fruits evaluated on the packing-house. The main reason for postharvest losses was due to mechanical injury caused during transportation mainly due to the compressure force among fruits and against the plastic boxes.

Biodegradable nanosize particles of poly(L,L-lactide)-b-poly(ethylene glycol)-b-poly(L,L-lactide)

Two series of poly(L,L-lactide-b-ethylene glycol-b-L,L-lactide) copolymers, PLA-PEO-PLA, were synthesized by polymerization Of L,L-lactide using a dihydroxy-terminated poly(ethylene glycol) (PEG) (M-n = 4000 or 600 g/mol) as coinitiator and stannous 2-ethylhexanoate, Sn(Oct)(2), as initiator. The synthesized copolymers have shown high stereoregularity as observed by C-13 NMR analyses. The nanoparticles were prepared by using a solvent diffusion method and the self-assemblage process and were characterized by NMR and SEM. It was possible to conclude that the self-assembled particles presented a core-shell structure characterized by a hydrophobic PLA core and a hydrophilic PEG shell, thus the NMR of the aqueous solutions indicated a quasi-solid behavior for the particles` interior. The diameters of the spherical particles as observed by SEM were in the 50-250 nm range, depending on the copolymer composition and the preparation procedure.

Estudo clínico e ultraestrutural pós-turbinectomia inferior parcial

O presente trabalho refere-se ao estudo dos resultados clínicos e histológicos obtidos após a turbinectomia inferior parcial (TIP), cirurgia indicada no tratamento da obstrução nasal crônica causada pela hipertrofia das conchas nasais inferiores. MATERIAL E MÉTODOS: Foram estudados vinte pacientes, divididos em dois grupos de dez cada (grupos A e B), submetidos à TIP, associada à septoplastia ou não. Os pacientes foram reavaliados clinicamente e histologicamente (com biópsia das áreas regeneradas das conchas inferiores), em dois períodos pós-operatórios diferentes: um grupo após oito a doze meses (grupo A) e outro após dois anos de TIP (grupo B). RESULTADOS: Os resultados clínicos mostraram-se satisfatórios para o alívio da obstrução nasal no grupo A, e insatisfatórios no grupo B. Entretanto, melhores resultados histológicos, com maior recuperação e diferenciação epitelial da mucosa regenerada das conchas inferiores após a TIP foram observados no grupo B, com sua ultraestrutura ciliar normal. CONCLUSÕES: A cirurgia revelou ser eficaz a curto, mas não em médio prazo, apesar da recuperação histológica ter sido importante.

Conservação pós-colheita de fisális e desempenho produtivo em condições edafoclimáticas de Minas Gerais

O Physalis sp., popularmente conhecido como fisális, é um gênero com mais de 100 espécies, pertencente à família Solanaceae, caracterizado pelo cálice concrescido, que envolve e protege o fruto contra herbívoros e intempéries. Os frutos, de sabor agridoce, são muito utilizados na culinária, podendo também ser processados em geleias, doces e licores, consumidos in natura, por seu alto teor de vitamina C e antioxidantes, além de apresentarem inúmeras propriedades medicinais. Este trabalho objetivou analisar a produtividade de fisális na região sul do Estado de Minas Gerais e observar aspectos de sua conservação pós-colheita. Os experimentos relacionados com a produtividade foram instalados na Fazenda Experimental da EPAMIG, em Maria da Fé, MG, e os demais experimentos, relacionados com a conservação pós-colheita, instalados no Laboratório de Tecnologia de Alimentos da UNIOESTE. Para avaliação da produtividade, instalou-se experimento contendo três blocos, com quatro plantas, e, para avaliação pós-colheita, foram utilizadas três repetições de cinco frutos, armazenados em câmara controlada tipo B.O.D, sem atmosfera modificada, por 28 dias, à temperatura de 5ºC, e avaliados no momento da instalação, aos 7, 14, 21 e 28 dias. Foram avaliados diâmetros longitudinal e transversal (mm), peso médio do fruto (g), com e sem cálice, peso total da colheita (g) e teor de sólidos solúveis totais. Em laboratório, avaliaram-se perda de peso, acidez (ATT), pH, sólidos solúveis totais (SST) e teor de vitamina C. Os frutos cultivados em Minas Gerais apresentaram características semelhantes às de frutos produzidos em regiões tradicionais de cultivo e podem facilmente ser armazenados por um período de 28 dias.