Helical Twisting of Electrospun Liquid Crystalline Cellulose Micro- and Nanofibers

Helically twisted fibers can be produced by electrospinning liquid-crystalline cellulose solutions. Fiber topographies are studied by atomic force microscopy, scanning electron microscopy (see figure) and polarized optical microscopy. The fibers have a nearly universal pitch-to-diameter ratio and comprise both right- and left-handed helices.

Simulation and theory of hybrid aligned liquid crystal films

We present a study of the effects of nanoconfinement on a system of hard Gaussian overlap particles interacting with planar substrates through the hard-needle-wall potential, extending earlier work by two of us [D. J. Cleaver and P. I. C. Teixeira, Chem. Phys. Lett. 338, 1 (2001)]. Here, we consider the case of hybrid films, where one of the substrates induces strongly homeotropic anchoring, while the other favors either weakly homeotropic or planar anchoring. These systems are investigated using both Monte Carlo simulation and density-functional theory, the latter implemented at the level of Onsager's second-virial approximation with Parsons-Lee rescaling. The orientational structure is found to change either continuously or discontinuously depending on substrate separation, in agreement with earlier predictions by others. The theory is seen to perform well in spite of its simplicity, predicting the positional and orientational structure seen in simulations even for small particle elongations.

Shear-induced lamellar phase of an ionic liquid crystal at room temperature

The phase behaviour of a number of N-alkylimidazolium salts was studied using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. Two of these compounds exhibit lamellar mesophases at temperatures above 50 degrees C. In these systems, the liquid crystalline behaviour may be induced at room temperature by shear. Sheared films of these materials, observed between crossed polarisers, have a morphology that is typical of (wet) liquid foams: they partition into dark domains separated by brighter (birefringent) walls, which are approximately arcs of circle and meet at "Plateau borders" with three or more sides. Where walls meet three at a time, they do so at approximately 120 degrees angles. These patterns coarsen with time and both T1 and T2 processes have been observed, as in foams. The time evolution of domains is also consistent with von Neumann's law. We conjecture that the bright walls are regions of high concentration of defects produced by shear, and that the system is dominated by the interfacial tension between these walls and the uniform domains. The control of self-organised monodomains, as observed in these systems, is expected to play an important role in potential applications.

How foam-like is the shear-induced lamellar phase of an ionic liquid crystal?

Philosophical Magazine Letters Volume 88, Issue 9-10, 2008 Special Issue: Solid and Liquid Foams. In commemoration of Manuel Amaral Fortes

The 27th British liquid crystal society annual meeting 2013, Cambridge

Attending the British Liquid Crystal Society’s (BLCS) Annual Meeting was a formative experience in my days as a PhD student, starting way back in the 1990s. At that time, this involved travelling to (to me) exotic parts of the United Kingdom, such as Reading, Oxford or Manchester, away from Southampton where I was based. Some postdoctoral years in a different country followed, and three BLCS Meetings were missed, until in 1997 and 1998, I was able to attend again, in Southampton and Leeds, respectively. Not much had changed from my student days, the size and the format were still about the same, many of the leading characters were still around, and the closing talk would still be given by John Lydon. Well, at some point, I got myself a proper academic job on the Continent and stopped attending BLCS Annual Meetings altogether. The fond memories of my youth started to fade. Were the Meetings still on? It seemed so, as old friends and acquaintances would occasionally recount attending them, and even winning prizes at them. But, it all seemed rather remote now. Until, that is, it came to pass that the 27th BLCS Meeting would be held in Selwyn College, Cambridge, just down (or up, depending on how you look at it) the road from the Isaac Newton Institute, where I was spending part of my sabbatical leave. The opportunity to resume attendance could not be missed. A brief e-mail exchange with the organisers, and a cheque to cover the fee, duly secured this. And thus, it was with trepidation that I approached my first BLCS Annual Meeting in more than a decade.

Hélices e Espirais em Micro e Nanofibras Celulósicas

A celulose é o polímero renovável mais abundante do mundo. É conhecido pela sua excelente biocompatibilidade, propriedades térmicas e mecânicas. A celulose assim como os polipéptideos e o ADN, pertence a uma família de moléculas orgânicas que dão origem à formação de fases líquidas cristalinas (LCs) colestéricas. A Passiflora Edulis, tal como outras plantas trepadeiras, possui longas e flexíveis gavinhas que permitem à planta encontrar um suporte para se fixar. As gavinhas podem assumir a forma de espirais ou de hélices consoante sejam sustentadas por apenas uma ou por ambas as extremidades. As hélices apresentam muitas vezes duas porções helicoidais, uma esquerda e outra direita, separadas por um segmento recto denominado perversão. Este comportamento é consequência da curvatura intrínseca das gavinhas produzidas pela planta trepadeira. O mesmo comportamento pode ser observado em micro e nanofibras celulósicas fabricadas a partir de soluções líquido-cristalinas, numa escala três a quatro ordens de grandeza inferior à das gavinhas. Este facto sugere que o modelo físico utilizado tenha invariância de escala. Neste trabalho é feito o estudo de fibras e jactos que imitam as estruturas helicoidais apresentadas pelas gavinhas das plantas trepadeiras. As fibras e jactos são produzidos a partir de soluções líquidas cristalinas celulósicas. De modo a determinar as características morfológicas e estruturais, que contribuem para a curvatura das fibras, foram utilizadas técnicas de imagem por ressonância magnética (MRI), microscopia óptica com luz polarisada (MOP), microscopia electrónica de varrimento (SEM) e microscopia de força atómica (AFM) . A variação da forma das estruturas helicoidais com a temperatura parece ser relevante para o fabrico de membranas não tecidas para aplicação em sensores termo-mecânicos.

Síntese e caracterização de redes metalo-orgânicas de fármacos

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Equipamentos de congelação industrial de produtos alimentares perecíveis: análise comparada de apoio à decisão

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Biodiesel production over lithium modified lime catalysts: activity and deactivation

Biodiesel production by methanolysis of semi-refined rapeseed oil was studied over lime based catalysts. In order to improve the catalysts basicity a commercial CaO material was impregnated with aqueous solution of lithium nitrate (Li/Ca = 03 atomic ratio). The catalysts were calcined at 575 degrees C and 800 degrees C, for 5 h, to remove nitrate ions before reaction. The XRD patterns of the fresh catalysts, including the bare CaO, showed lines ascribable to CaO and Ca(OH)(2). The absence of XRD lines belonging to Li phases confirms the efficient dispersion of Li over CaO. In the tested condition (W-cat/W-oil = 5%; CH3OH/oil = 12 molar ratio) all the fresh catalysts provided similar biodiesel yields (FAME >93% after 4 h) but the bare CaO catalyst was more stable. The activity decay of the Li modified samples can be related to the enhanced, by the higher basicity, calcium diglyceroxide formation during methanolysis which promotes calcium leaching. The calcination temperature for Li modified catalysts plays an important role since encourages the crystals sinterization which appears to improve the catalyst stability. (C) 2013 Elsevier B.V. All rights reserved.

Catalytic behavior of alkali-treated Pt/HMOR n-hexane hydroisomerization

Bifunctional Pt-HMOR catalysts were prepared by incipient wetness impregnation of various desilicated MOR obtained by alkaline treatment using NaOH concentrations ranging from 0.1 to 0.5 M. The zeolite structural changes upon modification were investigated by several techniques including powder X-ray diffraction,Al-27 and Si-29 MAS-NMR spectroscopy, N-2 adsorption, pyridine adsorption followed by infrared spectroscopy and the catalytic model reaction of m-xylene transformation. For low alkaline concentration the zeolite acidity is preserved, along with a slight increase of the volume correspondent to the larger micropores due to the removal of extra-framework debris already existent at the parent zeolite. At higher NaOH concentrations there is a significant loss of crystalinity and acidity as well as the formation of mesoporosity. The characterization of the metal function shows similar patterns for Pt-HMOR and Pt-M/0.1 samples, with Pt particles located mainly inside the inner porosity. In contrast, large Pt particles become visible at the intercrystalline mesoporosity of MOR crystals developed during the desilication treatments at severe alkaline conditions. The catalytic results obtained for n-hexane hydroisomerization showed an improved selectivity for dibranched over monobranched isomers for Pt-M/0.1 sample, likely due to the preservation of the support acidity and the slight enlargement of the micropores. This work is a new example in which the mesoporous development does not improve the catalytic efficiency of the zeolites, whereas mild alkaline desilication might be considered as an effective solution to produce customized catalysts with enhanced performance for a given application. (C) 2014 Elsevier B.V. All rights reserved.

From cellulosic based liquid crystalline sheared solutions to 1D and 2D soft materials

Liquid crystalline cellulosic-based solutions described by distinctive properties are at the origin of different kinds of multifunctional materials with unique characteristics. These solutions can form chiral nematic phases at rest, with tuneable photonic behavior, and exhibit a complex behavior associated with the onset of a network of director field defects under shear. Techniques, such as Nuclear Magnetic Resonance (NMR), Rheology coupled with NMR (Rheo-NMR), rheology, optical methods, Magnetic Resonance Imaging (MRI), Wide Angle X-rays Scattering (WAXS), were extensively used to enlighten the liquid crystalline characteristics of these cellulosic solutions. Cellulosic films produced by shear casting and fibers by electrospinning, from these liquid crystalline solutions, have regained wider attention due to recognition of their innovative properties associated to their biocompatibility. Electrospun membranes composed by helical and spiral shape fibers allow the achievement of large surface areas, leading to the improvement of the performance of this kind of systems. The moisture response, light modulated, wettability and the capability of orienting protein and cellulose crystals, opened a wide range of new applications to the shear casted films. Characterization by NMR, X-rays, tensile tests, AFM, and optical methods allowed detailed characterization of those soft cellulosic materials. In this work, special attention will be given to recent developments, including, among others, a moisture driven cellulosic motor and electro-optical devices.

InOx thin films deposited by plasma assisted evaporation: application in light shutters

An integration of undoped InOx and commercial ITO thin films into laboratory assembled light shutter devices is made. Accordingly, undoped transparent conductive InOx thin films, about 100 nm thick, are deposited by radiofrequency plasma enhanced reactive thermal evaporation (rf-PERTE) of indium teardrops with no intentional heating of the glass substrates. The process of deposition occurs at very low deposition rates (0.1-0.3 nm/s) to establish an optimized reaction between the oxygen plasma and the metal vapor. These films show the following main characteristics: transparency of 87% (wavelength, lambda = 632.8 nm) and sheet resistance of 52 Omega/sq; while on commercial ITO films the transparency was of 92% and sheet resistance of 83 Omega/sq. The InOx thin film surface characterized by AFM shows a uniform grain texture with a root mean square surface roughness of Rq similar to 2.276 nm. In contrast, commercial ITO topography is characterized by two regions: one smoother with Rq similar to 0.973 nm and one with big grains (Rq similar to 3.617 nm). For the shutters assembled using commercial ITO, the light transmission coefficient (Tr) reaches the highest value (Tr-max) of 89% and the lowest (Tr-min) of 1.3% [13], while for the InOx shutters these values are 80.1% and 3.2%, respectively. Regarding the electric field required to achieve 90% of the maximum transmission in the ON state (E-on), the one presented by the devices assembled with commercial ITO coated glasses is 2.41 V/mu m while the one presented by the devices assembled with InOx coated glasses is smaller, 1.77 V/mu m. These results corroborate the device quality that depends on the base materials and fabrication process used. (C) 2014 Elsevier Ltd. All rights reserved.

Cobalt complexes bearing scorpionate ligands: Synthesis, characterization, cytotoxicity and DNA cleavage

A number of novel, water-stable redox-active cobalt complexes of the C-functionalized tripodal ligands tris(pyrazolyl)methane XC(pz)(3) (X = HOCH2, CH2OCH2Py or CH2OSO2Me) are reported along with their effects on DNA. The compounds were isolated as air-stable solids and fully characterized by IR and FIR spectroscopies, ESI-MS(+/-), cyclic voltammetry, controlled potential electrolysis, elemental analysis and, in a number of cases, also by single-crystal X-ray diffraction. They showed moderate cytotoxicity in vitro towards HCT116 colorectal carcinoma and HepG2 hepatocellular carcinoma human cancer cell lines. This viability loss is correlated with an increase of tumour cell lines apoptosis. Reactivity studies with biomolecules, such as reducing agents, H2O2, plasmid DNA and UV-visible titrations were also performed to provide tentative insights into the mode of action of the complexes. Incubation of Co(II) complexes with pDNA induced double strand breaks, without requiring the presence of any activator. This pDNA cleavage appears to be mediated by O-centred radical species.

Electrorheology study of a series of LC cyanobiphenyls: Experimental and theoretical treatment

In this work we study the electro-rheological behaviour of a series of four liquid crystal (LC) cyanobiphenyls with a number of carbon atoms in the alkyl group, ranging from five to eight (5CB–8CB). We present the flow curves for different temperatures and under the influence of an external electric field, ranging from 0 to 3 kV/mm, and the viscosity as a function of the temperature, for the same values of electric field, obtained for different shear rates. Theoretical interpretation of the observed behaviours is proposed in the framework of the continuum theory of Leslie–Ericksen for low molecular weight nematic LCs. In our analysis, the director alignment angle is only a function of the ratio between the shear rate and the square of the electric field – boundary conditions are neglected. By fitting the theoretical model to the experimental data, we are able to determine some viscosity coefficients and the dielectric anisotropy as a function of temperature. To interpret the behaviour of the flow curves near the nematic–isotropic transitions, we apply the continuum theory of Olmsted–Goldbart, which extends the theory of Leslie–Ericksen to the case where the degree of alignment of the LC molecules can also vary.

Properties of patchy colloidal particles close to a surface: a Monte Carlo and density functional study

We investigate the behavior of a patchy particle model close to a hard-wall via Monte Carlo simulation and density functional theory (DFT). Two DFT approaches, based on the homogeneous and inhomogeneous versions of Wertheim's first order perturbation theory for the association free energy are used. We evaluate, by simulation and theory, the equilibrium bulk phase diagram of the fluid and analyze the surface properties for two isochores, one of which is close to the liquid side of the gas-liquid coexistence curve. We find that the density profile near the wall crosses over from a typical high-temperature adsorption profile to a low-temperature desorption one, for the isochore close to coexistence. We relate this behavior to the properties of the bulk network liquid and find that the theoretical descriptions are reasonably accurate in this regime. At very low temperatures, however, an almost fully bonded network is formed, and the simulations reveal a second adsorption regime which is not captured by DFT. We trace this failure to the neglect of orientational correlations of the particles, which are found to exhibit surface induced orientational order in this regime.