No / This paper reports on the growth of benzamide crystals in the presence of 2'-aminoacetophenone. The resulting self-replicating intergrowth of benzamide crystals gives rise to ordered crystal aggregates in which individuals share a common c*. This behavior is interpreted using the concept of a motif capper additive which is able to halt the extension of structural motifs at the surface of a growing crystal. In this case the additive was selected to terminate the hydrogen-bonding ribbons, which extend along the b axis of the benzamide structure.

Recently, the fundamental and nanoscale understanding of complex phenomena in materials research and the life sciences, witnessed considerable progress. However, elucidating the underlying mechanisms, governed by entangled degrees of freedom such as lattice, spin, orbit, and charge for solids or conformation, electric potentials, and ligands for proteins, has remained challenging. Techniques that allow for distinguishing between different contributions to these processes are hence urgently required. In this paper we demonstrate the application of scattering-type scanning near-field optical microscopy (s-SNOM) as a novel type of nano-probe for tracking transient states of matter. We introduce a sideband-demodulation technique that allows for probing exclusively the stimuli-induced change of near-field optical properties. We exemplify this development by inspecting the decay of an electron-hole plasma generated in SiGe thin films through near-infrared laser pulses. Our approach can universally be applied to optically track ultrafast/-slow processes over the whole spectral range from UV to THz frequencies.

Approved for public release, distribution is unlimited / The effect of friction-stir processing (FSP) on the microstructure of a cast nickel-aluminum bronze (NAB) material has been characterized by various micro-analytical methods including orientation imaging microscopy (OIM). Cast NAB is widely utilized in the production of propellers for the surface ships and submarines of the U.S. Navy due to excellent corrosion-resistance. New applications require improved mechanical properties that may be attainable using FSP to achieve localized microstructure modification. Friction between a rotating tool and the surface of the material results in a *stirring* action that, in turn, produces adiabatic heating and local softening of the material. The tool rotation results in very large shear deformations in the softened regions and thus microstructure refinement and homogenization; in effect FSP may convert an as-cast microstructure to a wrought condition in the absence of macroscopic shape change. In as-cast material, results of optical and scanning electron microscopy (using energy dispersive analysis) show an ` (FCC) matrix containing globular and particulate dispersions that correspond to the *I, *II and *IV second phases; these represent various morphologies of the Fe3Al intermetallic compound, which has a D03 structure. Also present are lamellar particles of *III, which is NiAl and has a B2 structure. The grain size in the ` matrix is ~ 1 mm. In OIM, the microtexture and microstructure in the ` (FCC) matrix may be readily obtained and analyzed. However, interatom distances in the Fe3Al and NiAl phases differ by only about one percent and so these phases are not distinguishable from one another during OIM. Altogether, microstructure and microtexture analysis showed that there are several regions in the thermomechanically affected zone (TMAZ) of a material subjected to FSP. From base material inward toward the TMAZ, these include: annealing effects in undeformed base material; a region just inside the TMAZ in which grain deformation and C-type shear deformation textures are observed; regions of highly refined and recrystallized grains further inside the TMAZ, wherein the grain size is < 5æm; and, finally, regions of elongated, banded and twinned grain structures that suggest grain growth following recrystalliztion. / Lieutenant, United States Navy

This paper presents a homogeneous system of magnetic colloidal particles that self-assembles via two structural patterns of different symmetry. Based on a qualitative comparison between a real magnetic particles system, analytical calculations and molecular dynamics simulations, it is shown that bistability can be achieved by a proper tailoring of an anisotropic magnetization distribution inside the particles. The presented bistability opens new possibilities to form two-dimensionally extended and flexible structures where the connectivity between the particles can be changed in vivo. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Approved for public release, distribution is unlimited / The extreme strain, strain rate and temperature gradients during Friction Stir Processing (FSP) render measurement of key parameters in the stir zone infeasible with common methods. The objective of this research was to separate the effects that temperature and deformation in an experimental study of the microstructure and mechanical properties of Ni-AL bronze (NAB). This was accomplished by subjecting as-cast NAB material to several isothermal annealing and quenching treatments as well as isothermal hot rolling processes. Sufficient material was generated to provide results and data for subsequent optical microscopy, tensile, & hardness tests. All results were then compared to similar data collected from previous works completed here at Naval Postgraduate School and with other DARPA FSP program participants. During the course of this work correlations were drawn between FSP material and the material subjected to isothermal hotworking, which may enhance our understanding of the roles that various FSP process parameters have on the microstructural transformation sequence within this material. The hot-rolling study conducted here suggests that FSP process parameters leading to severe deformation at temperatures between 950-1000 C in the NAB material provides high ductility (elongation approximately 28%) with moderate strengths. / Lieutenant, United States Coast Guard

A Terapia Fotodinâmica é um tratamento promissor no cura de várias doenças oftalmológicas e dermatológicas, assim como tumores. Este tratamento utiliza a combinação de luz e um composto fotossensível na presença de oxigênio. Neste trabalho objetivamos entender mecanismos de fotossensibilização em membranas. Para isso, estudamos os efeitos de irradiação em Vesículas Unilamelares Gigantes (GUVs) compostas de POPC e Cardiolipina (CL) e POPC e Colesterol (Col), contendo uma molécula fotoativa (diC12-porf) ancorada à superfície dessas membranas. GUVs compostas por POPC e POPC:Col na presença da molécula fotoativa reagem ao estímulo da luz exibindo um aumento de área seguido de flutuações. O mesmo foi observado para membranas de POPC contendo menos que 50mol% de CL. Já para composições contendo 50mol% de CL, a membrana passa a formar domínios lipídicos podendo ou não ser destruída durante a irradiação. Estes domínios podem ser suprimidos com a adição de EDTA (agente quelante de íons divalentes) na solução. Ao adicionarmos CaCl2 ao meio externo das GUVs contendo EDTA, percebemos que o efeito dos domínios e destruição da membrana reaparece. Tal fato evidencia que íons Ca++ presentes em solução devem complexar com as cargas da CL, levando à formação de domínios lipídicos. Ao quantificar o aumento de área sofrido pelas membranas percebemos que a presença de CL na membrana de POPC inibe o aumento de área para concentrações acima de 40mol% de CL. Já a presença de Col na membrana parece não contribuir significativamente para o aumento de área, embora o mesmo sofra oxidação. Além disso, evidenciou-se que na presença de CL/Col o tempo de fotoclareamento de diC12-porf é muito maior do que na ausência destes. Estes resultados evidenciam que a inclusão de CL na membrana oferece um número maior de sítios de reação para o oxigênio singlete reduzindo a foto-degradação da molécula fotoativa. Já a inclusão de Col aumenta o tempo de vida da molécula fotoativa provavelmente devido ao fato da dupla ligação do Col estar mais próxima ao centro produtor de oxigênio singlete do que a dupla ligação do POPC. / Photodynamic Therapy is a promising treatment for the cure of many diseases, like tumors. This treatment uses a combination of light and a photosensitive molecule in the presence of oxygen. In this way, our objective is to understand photosensibilization mechanisms on membranes. For this purpose, we studied the effects of irradiation in Giant Unilamelar Vesicles (GUVs) composed of POPC and Cardiolipin (CL) and POPC and Cholesterol (Chol) in the presence of a photosensitive molecule (diC12-porf). When the GUVs composed of POPC or POPC and Cholesterol (Chol) in the presence of the photosensitive molecule were irradiated, increase in surface area followed by fluctuations was observed. For GUVs composed of low concentrations of CL, the membrane photo-response was similar to that observed for pure POPC. For GUVs composed of 50 mol% CL different responses to light irradiation were observed. Some lipid domains appear for GUVs in water under irradiation and the GUV might be destroyed. When the irradiation was done in the presence of EDTA (chelant agent), the formation of the domains was prevented. Further addition of CaCl2 to this solution induced the formation of domains again leading eventually to membrane disruption. These results suggest that divalent cations have effect on the binding to CL negative polar heads, favoring lipid domain formation. We quantified the area increase obtained for the GUVs. For GUVs composed of CL we observed that until 40mol% of CL, the maximum expansion reached by the membrane area was similar to that obtained for pure POPC. For 50mol% of CL the increase of area is smaller than that found for GUVs composed only by POPC. For GUVs composed of Chol the behavior of the area is similar to that found for POPC. This means that the increase of area is mainly related to POPC peroxidation, although Chol hydroperoxide must be concomitantly formed too. Further, we observed that the diC12-porf photobleaching characteristic time for GUVs composed of CL/Chol is greater than that noted for GUVs composed of POPC. This means that when we introduce CL we are increasing the possibilities of reaction of the singlet oxygen and the photosensitive molecule is protected. The insertion of Chol in the membrane also protects the photosensitive molecule.

Objective: The primary objective of this study was to evaluate the roughness of CAD/CAM blocks of lithium disilicate glass-ceramic (IPS e.max CAD, Ivoclar Vivadent®, Schaan, Liechtenstein), before and after surface treatment with hydrofluoridric acid 10% and after silane coating by Atomic Force Microscopy and Optical Microscopy. The average size of silane as well as its fit to the valleys after acid etching was also studied. Methods: Ten specimens of CAD/CAM blocks of lithium disilicate glass-ceramic were analyzed by Atomic Force Microscopy. Before surface treatment with hydrofluoridric acid 10%, the specimens were also analyzed by Atomic Force Microscopy. All specimens were also analyzed by Optical Microscopy after the application of a layer of silane. Free software Gwyddion version 2.51 was used on data processing. The 3D surface measurements were: root mean square roughness, average roughness, maximum peak height, maximum pit depth, maximum height, Skewness and Kurtosis of surface and profile roughnesses. Images provided by Optical Microscopy were used to calculate the size of the silane particle, also using the free software Gwyddion version 2.5.1. Non-parametric tests were done by the free software R version 3.5.1. Results: Surface roughness and profile roughness were numerically different, but both increased after acid etching. All the skewness measurements concentrated around zero, indicating a more symmetrical behavior after acid conditioning. Silane cross-sectional area measured from 0,0374m² to 0,424351m² and its radius ranged from 0,115m to 0,3675m and could fit in on about 77,5% of the conditioned surface valleys. Significance: Roughness surface and silane layer are important factors to the bond strength between ceramic and resin cements, ensuring the success of restorative treatment. / Objetivo: O principal objetivo deste estudo in vitro foi analisar a rugosidade de superfície de blocos de CAD/CAM de cerâmica de dissilicato de lítio, antes e depois do condicionamento com ácido fluorídrico a 10% durante 20 segundos e após a aplicação de uma camada de silano, usando a Microscopia de Força Atômica e Microscopia Óptica. A média do tamanho do silano e como eles se ajustam nos vales da superfície condicionada também foram estudados. Metodologia: 10 amostras confeccionadas por blocos para CAD/CAM de cerâmica de dissilicato de lítio foram analisadas por um microscópio de força atômica. Depois do tratamento de superfície com ácido fluorídrico a 10% durante 20 segundos, os espécimes foram novamente analisados por Microscopia de Força Atômica. Todas as amostras foram analisadas em microscópio óptico depois da aplicação de uma camada de silano. O software Gwyddion (versão 2.5.1) foi usado para o processamento de dados. As medidas obtidas para as imagens 3D das superfícies foram: raiz quadrada média da rugosidade, rugosidade média, altura do pico mais alto, profundidade do vale mais baixo, máxima altura, assimetria e curtose, tanto para a análise de superfície quanto para a análise do perfil. As imagens obtidas pela Microscopia Óptica foram usadas para calcular o tamanho da partícula de silano, também usando o software Gwyddion (versão 2.5.1.). Testes não-paramétricos foram calculados pelo software R (versão 3.5.1). Resultados: As rugosidades da superfície e do perfil foram numericamente diferentes, mas ambas aumentaram após o condicionamento ácido. A assimetria concentrou-se próxima a zero, indicando um comportamento mais simétrico após o condicionamento. A área da secção transversal do silano mede entre 0,0374m² a 0,424351m² e o seu raio mediu entre 0,115m a 0,3675m. Esse tamanho de partícula pode ser acomodado em 77,5% dos vales presentes nas superfícies condicionadas. Significância: A rugosidade e a camada de silano são fatores importantes para o aumento da união entre a cerâmica e o cimento resinoso, assegurando o sucesso do tratamento restaurador.

As ligas à base de níquel de alta resistência são utilizadas em uma infinidade de sistemas avançados, onde baixo peso e sistemas de transmissão mecânica de alta densidade de energia são necessários. Componentes, tais como, engrenagens, rolamentos e eixos poderiam ser consideravelmente menor e mais durável se uma grande melhoria em propriedades mecânicas de ligas à base de níquel for alcançada. Um refinamento significativo no tamanho de grão (incluindo nível nano) é um método promissor para a obtenção de melhorias fundamentais nas propriedades mecânicas. O tamanho de grão é conhecido por ter um efeito significativo sobre o comportamento mecânico dos materiais. Um dos métodos mais favoráveis de alcançar refinamento de grão extremo é submetendo os materiais à deformação plástica intensa. As principais variáveis microestruturais nas superligas são a quantidade de precipitados e sua morfologia, o tamanho e a forma do grão e a distribuição de carbonetos (Cr7C3 e Cr23C6) que poderão reduzir propriedades mecânicas da liga. Neste trabalho é apresentada análise por microscopia óptica e eletrônica de transmissão e também os dados de dureza após deformação plástica intensa (tensão de cisalhamento puro) e alguns tratamentos térmicos. / High strength nickel based alloys are used in a multitude of advanced systems where lightweight, high power density mechanical power transmission systems are required. Components such as gears, bearings and shafts could be made significantly smaller and more durable if a major improvement in nickel based alloy mechanical properties could be achieved. A significant refinement in grain size (includes nano level) is thought to be a promising method for achieving fundamental improvements in mechanical properties. Grain size is known to have a significant effect on the mechanical behavior of materials. One of the most favorable methods of achieving extreme grain refinement is by subjecting the materials to severe plastic deformation. The principal microstructural variations in superalloys are the precipitation amount and morphology, grain size and the distribution of carbide precipitation (Cr7C3 and Cr23C6) that could reduce the mechanical properties of the alloys. This work shows optical and transmission electron microscopy analysis and also hardness data after severe plastic deformation (pure shear stress) and some thermal treatments.

As ligas à base de níquel de alta resistência são utilizadas em uma infinidade de sistemas avançados, onde baixo peso e sistemas de transmissão mecânica de alta densidade de energia são necessários. Componentes, tais como, engrenagens, rolamentos e eixos poderiam ser consideravelmente menor e mais durável se uma grande melhoria em propriedades mecânicas de ligas à base de níquel for alcançada. Um refinamento significativo no tamanho de grão (incluindo nível nano) é um método promissor para a obtenção de melhorias fundamentais nas propriedades mecânicas. O tamanho de grão é conhecido por ter um efeito significativo sobre o comportamento mecânico dos materiais. Um dos métodos mais favoráveis de alcançar refinamento de grão extremo é submetendo os materiais à deformação plástica intensa. As principais variáveis microestruturais nas superligas são a quantidade de precipitados e sua morfologia, o tamanho e a forma do grão e a distribuição de carbonetos (Cr7C3 e Cr23C6) que poderão reduzir propriedades mecânicas da liga. Neste trabalho é apresentada análise por microscopia óptica e eletrônica de transmissão e também os dados de dureza após deformação plástica intensa (tensão de cisalhamento puro) e alguns tratamentos térmicos. / High strength nickel based alloys are used in a multitude of advanced systems where lightweight, high power density mechanical power transmission systems are required. Components such as gears, bearings and shafts could be made significantly smaller and more durable if a major improvement in nickel based alloy mechanical properties could be achieved. A significant refinement in grain size (includes nano level) is thought to be a promising method for achieving fundamental improvements in mechanical properties. Grain size is known to have a significant effect on the mechanical behavior of materials. One of the most favorable methods of achieving extreme grain refinement is by subjecting the materials to severe plastic deformation. The principal microstructural variations in superalloys are the precipitation amount and morphology, grain size and the distribution of carbide precipitation (Cr7C3 and Cr23C6) that could reduce the mechanical properties of the alloys. This work shows optical and transmission electron microscopy analysis and also hardness data after severe plastic deformation (pure shear stress) and some thermal treatments.

Neste trabalho, estudamos a interação de um peptídeo antimicrobiano com membranas modelo, por meio de dicroísmo circular (CD), fluorescência e microscopia óptica. Tal peptídeo, chamado de híbrido, foi sintetizado como uma mistura das regiões mais ativas de dois outros peptídeos antimicrobianos, chamados de pediocina A e plantaricina 149. Esse peptídeo híbrido possui carga de +8, em pH fisiológico, e as membranas estudadas foram compostas por uma mistura de fosfolipídeos zwiteriônicos (cabeça polar de fosfatidilcolina, PC) e aniônicos (cabeça polar de fosfatidilglicerol, PG), em diferentes razões molares. Os resultados de CD evidenciaram que este peptídeo se apresenta de forma desordenada em solução aquosa, porém adota uma conformação helicoidal na presença de grandes vesículas unilamelares carregadas negativamente (LUVs). A quantidade de componente helicoidal é dependente da quantidade de lipídeo negativo presente na bicamada lipídica. A fluorescência do triptofano revelou um deslocamento para o azul muito significativo, chegando a 20 nm para membranas compostas por 100 mol% de PG. Os dois resultados (CD e fluorescência) indicam que a região dos aminoácidos que contém o triptofano deve estar interagindo muito fortemente com a região hidrofóbica da membrana, numa conformação tipo-helicoidal. Experimentos de vazamento de carboxifluoresceína encapsulada em LUVs, por espectroscopia de fluorescência, demonstraram a ação lítica do peptídeo induzindo a formação de poros nas membranas, independentemente da composição das LUVs. Entretanto, a razão molar peptídeo:lipídeo necessária para induzir vazamento da sonda foi menor para membranas lipídicas compostas por bicamadas contendo altas quantidades de PG. Tal fato coloca em evidência o papel fundamental da interação eletrostática entre os peptídeos carregados positivamente com as membranas carregadas negativamente para o processo de ligação e mecanismo de ação deste peptídeo. Para estudar mais detalhadamente o mecanismo de ação, realizamos experimentos de microscopia óptica em vesículas unilamelares gigantes. Concluímos que o peptídeo provoca total desestabilização das vesículas unilamelares gigantes, com formação de poros, seguidos de ruptura da bicamada lipídica e sua transformação em pequenos e mal definidos complexos de peptídeos e fosfolipídeos. / In this work, we investigated the interaction between an antibacterial peptide with model membranes, by means of circular dichroism (CD), fluorescence and optical microscopy. Such a peptide was synthesized from the most active regions of two others antimicrobial peptides, namely pediocin A and plantaricin 149. The hybrid peptide has a net charge of ~ +8, at physiological pH, and the studied model membranes were composed of a mixture of zwitterionic phospholipids (phosphatidylcholine polar head) and anionic phospholipids (phosphatidylglycerol polar head), at differente molar ratio. The CD results evidenced that the peptide was essentially structureless in aqueous solution, but acquired an helical conformation in the presence of charged large unillamellar vesicles LUVs. The helical content is dependent on the negative charge amount on membrane surface. The tryptophan fluorescence revealed a significant blue shift of the maximium emission wavelength, up to 20 nm for the membranes composed of 100 mol% of PG in respect to the peptide fluorescence in the aqueous solution. This indicates that part of the aminoacid residues, that contains the tryptophan, must be buried into the hydrophobic medium of the lipid membrane. Leakage experiments using fluorescence spectroscopy of carboxyfluorescein encapsulated in LUVs demonstrated the lytic action of the peptide, inducing the pore formation in the membrane, regardless of lipid membrane composition. However, it should be stressed that the peptide:lipid molar ratio necessary to induce probe leakage was smaller for lipid membranes made up of large PG amounts. Such evidence points out the key role of the electrostatic interaction between a positively charged peptide and the negatively charged membrane, mediated by hydrophobic contribution. To gain further insight into the lytic mechanism of the peptide, we performed single vesicle experiments using giant unilamellar vesicles under optical microscopy observations. We conclude that the peptide provokes a total membrane desestabilization, with pore formation, followed by a membrane disruption and its transformation into smaller and not well defined complexes of phospholipids and peptides.