Experimental and computational study on the synthesis and characterization of self-assembling meso/macroporous materials in highly concentrated emulsions

Report for the scientific sojourn carried out at Massachusetts General Hospital Cancer Center-Harvard Medical School, Estats Units, from 2010 to 2011. The project aims to study the aggregation behavior of amphiphilic molecules in the continuous phase of highly concentrated emulsions, which can be used as templates for the synthesis of meso/macroporous materials. At this stage of the project, we have investigated the self-assembly of diblock and triblock surfactants under the effect of a confined geometry being surrounded by the droplets of the dispersed phase. These droplets limit the growth of the aggregates, deeply modify their orientation and hence alter their spatial arrangement as compared to the self-assembly taking place far enough from any boundary surface, that is in the bulk. By performing Monte Carlo simulations, we have showed that the interface between the dispersed and continuous phases as well as its shape has a significant impact on the structural order of the resulting aggregates and hence on the potential applications of highly concentrated emulsions as reaction media, drug delivery systems, or templates for meso/macroporous materials. Due to the combined effect of symmetry breaking and morphological frustration, very intriguing structures, such as square columnar liquid crystals, twisted X-shaped aggregates, and helical phases of cylindrical aggregates, never observed in the bulk for the same model surfactant, have been found. The presence of other more conventional structures, such as micelles and cubic and hexagonal liquid crystals, formed at low and high amphiphilic concentrations, respectively, further enhance the interest on this already rich aggregation behavior.

Scale-up model obtained from the rheological analysis of highly concentrated emulsions prepared at three scales

We examine the scale invariants in the preparation of highly concentrated w/o emulsions at different scales and in varying conditions. The emulsions are characterized using rheological parameters, owing to their highly elastic behavior. We first construct and validate empirical models to describe the rheological properties. These models yield a reasonable prediction of experimental data. We then build an empirical scale-up model, to predict the preparation and composition conditions that have to be kept constant at each scale to prepare the same emulsion. For this purpose, three preparation scales with geometric similarity are used. The parameter N¿D^α, as a function of the stirring rate N, the scale (D, impeller diameter) and the exponent α (calculated empirically from the regression of all the experiments in the three scales), is defined as the scale invariant that needs to be optimized, once the dispersed phase of the emulsion, the surfactant concentration, and the dispersed phase addition time are set. As far as we know, no other study has obtained a scale invariant factor N¿Dα for the preparation of highly concentrated emulsions prepared at three different scales, which covers all three scales, different addition times and surfactant concentrations. The power law exponent obtained seems to indicate that the scale-up criterion for this system is the power input per unit volume (P/V).

Highly concentrated bitumen emulsions. A state of the art, review of experimental results

Les emulsions concentrades o altament concentrades de betum són un camp molt poc estudiat avui en dia. El treball és un estat de l'art de tots els papers que hi ha sobre aquest tema desde el mètode tradicional fins el HIPR (High Internal Phase Ratio).

Effect of a highly concentrated lipopeptide extract of Bacillus subtilis on fungal and bacterial cells

Lipopeptides produced by Bacillus subtilis are known for their high antifungal activity. The aim of this paper is to show that at high concentration they can damage the surface ultra-structure of bacterial cells. A lipopeptide extract containing iturin and surfactin (5 mg mL-1) was prepared after isolation from B. subtilis (strain OG) by solid phase extraction. Analysis by atomic force microscope (AFM) showed that upon evaporation, lipopeptides form large aggregates (0.1-0.2 mu m2) on the substrates silicon and mica. When the same solution is incubated with fungi and bacteria and the system is allowed to evaporate, dramatic changes are observed on the cells. AFM micrographs show disintegration of the hyphae of Phomopsis phaseoli and the cell walls of Xanthomonas campestris and X. axonopodis. Collapses to fungal and bacterial cells may be a result of formation of pores triggered by micelles and lamellar structures, which are formed above the critical micelar concentration of lipopeptides. As observed for P. phaseoli, the process involves binding, solubilization, and formation of novel structures in which cell wall components are solubilized within lipopeptide vesicles. This is the first report presenting evidences that vesicles of uncharged and negatively charged lipopeptides can alter the morphology of gram-negative bacteria.

The efficacy of a highly concentrated fluoride dentifrice on bovine enamel subjected to erosion and abrasion

Background. Researchers have proposed the use of fluoride for the prevention of enamel wear; however, only limited information is available about the impact of fluoridated dentifrices. Because tooth wear is a well-recognized dental problem, the authors conducted an in situ, ex vivo study to assess the efficacy of a highly concentrated fluoride dentifrice on bovine enamel subjected to erosion and abrasion. Methods. The authors conducted a double-blind, crossover in situ study consisting of three phases (seven days each). In each phase, the authors tested one of the dentifrices (5,000 parts per million fluoride [F]; 1,100 ppm F; no F). They performed erosive challenges with the use of cola drink (60 seconds, four times per day) and abrasive challenges via toothbrushing (30 seconds, four times per day). The authors determined the enamel loss via profilometry. Results. The authors tested the data by using two-way analysis of variance (P <.05). For the erosion-plus-abrasion condition, the study results showed that enamel wear was significantly higher than that with erosion alone. The findings showed no significant differences between the dentifrices regarding enamel wear. Conclusions. Within the in situ, ex vivo conditions of this study, the authors concluded that the highly concentrated fluoride dentifrice did not have a protective effect on enamel against erosion and erosion plus toothbrushing abrasion. Clinical Implications. Patients at risk of developing enamel erosion should benefit from preventive measures other than fluoride dentifrice, because even a highly concentrated fluoride dentifrice does not appear to prevent enamel erosion.

Phase behavior and rheological analysis of reverse liquid crystals and W/I2, W/H2 gel emulsions using an amphiphilic block copolymer.

This article reports the phase behavior determi- nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural proper- ties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. TheH2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elasticmodulus (G0) in the I2 phase was around 1 order of magnitude higher than in theH2 phase. G0 was predominantly higher than the viscousmodulus (G00). In the gel emulsions,G0 was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G0, the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the con- tinuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volumefraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

Generation and characterization of stable, highly concentrated titanium dioxide nanoparticle aerosols for rodent inhalation studies

The intensive use of nano-sized titanium dioxide (TiO2) particles in many different applications necessitates studies on their risk assessment as there are still open questions on their safe handling and utilization. For reliable risk assessment, the interaction of TiO2 nanoparticles (NP) with biological systems ideally needs to be investigated using physico-chemically uniform and well-characterized NP. In this article, we describe the reproducible production of TiO2 NP aerosols using spark ignition technology. Because currently no data are available on inhaled NP in the 10–50 nm diameter range, the emphasis was to generate NP as small as 20 nm for inhalation studies in rodents. For anticipated in vivo dosimetry analyses, TiO2 NP were radiolabeled with 48V by proton irradiation of the titanium electrodes of the spark generator. The dissolution rate of the 48V label was about 1% within the first day. The highly concentrated, polydisperse TiO2 NP aerosol (3–6 × 106 cm−3) proved to be constant over several hours in terms of its count median mobility diameter, its geometric standard deviation, and number concentration. Extensive characterization of NP chemical composition, physical structure, morphology, and specific surface area was performed. The originally generated amorphous TiO2 NP were converted into crystalline anatase TiO2 NP by thermal annealing at 950 °C. Both crystalline and amorphous 20-nm TiO2 NP were chain agglomerated/aggregated, consisting of primary particles in the range of 5 nm. Disintegration of the deposited TiO2 NP in lung tissue was not detectable within 24 h.

Preparation of particle-stabilized emulsions using membrane emulsification

There is currently significant interest in particle-stabilized emulsions for a variety of applications and as precursors to other materials such as micro-capsules or colloidosomes. A prerequisite for many applications is the ability to produce stable droplets with a well-controlled size. The preparation of oil-in-water (o/w) emulsions stabilized by silica colloids has been demonstrated here using membrane ulsification techniques. Emulsions were produced using both a cross-flow membrane device and a rotating membrane reactor. Under the correct conditions, highly stable emulsions with very narrow droplet size distributions can be produced. Investigations into the effects of changing the cross-flow shear rate at a fixed droplet production rate illustrate the fine control over mean droplet size that is possible with these emulsification techniques. Evidence for the importance of particle adsorption kinetics onto growing droplets prior to detachment from the membrane surface was obtained by varying the droplet production rate under fixed shear conditions. The presence of a critical surface coverage by the stabilizing particles to prevent droplet coalescence was clearly seen. Comparison with samples produced using conventional high-shear homogenization highlights the improved control over size distribution available from these membrane techniques.

Demonstrando os fundamentos, potencialidades e limitações da análise por injeção seqüencial

The sensitivity and accuracy of sequential injection methods are dependent on efficient overlapping of reagent and sample zones as they are propelled toward the detector cell. The formation of the reduced phosphomolybdic acid is used to demonstrate that the overlapping efficiency in a fixed reaction coil relies on a suitable choice of reagent to sample volume ratio. Additionally, under poor mixing conditions or highly concentrated samples, the reaction extension is strongly dependent on the reagent concentration. The zone-sampling concept is exploited to determine phosphate in cola-based soft drinks after in-line dilution in an auxiliary coil.

Escape patterns of chaotic magnetic field lines in a tokamak with reversed magnetic shear and an ergodic limiter

The existence of a reversed magnetic shear in tokamaks improves the plasma confinement through the formation of internal transport barriers that reduce radial particle and heat transport. However, the transport poloidal profile is much influenced by the presence of chaotic magnetic field lines at the plasma edge caused by external perturbations. Contrary to many expectations, it has been observed that such a chaotic region does not uniformize heat and particle deposition on the inner tokamak wall. The deposition is characterized instead by structured patterns called magnetic footprints, here investigated for a nonmonotonic analytical plasma equilibrium perturbed by an ergodic limiter. The magnetic footprints appear due to the underlying mathematical skeleton of chaotic magnetic field lines determined by the manifold tangles. For the investigated edge safety factor ranges, these effects on the wall are associated with the field line stickiness and escape channels due to internal island chains near the flux surfaces. Comparisons between magnetic footprints and escape basins from different equilibrium and ergodic limiter characteristic parameters show that highly concentrated magnetic footprints can be avoided by properly choosing these parameters. (c) 2008 American Institute of Physics.

Mapping the Contemporary Studies on Alliances and Strategic Networks

The competition among the companies depends on the velocity and efficience they can create and commercialize knowledge in a timely and cost-efficient manner. In this context, collaboration emerges as a reaction to the environmental changes. Although strategic alliances and networks have been exploited in the strategic literature for decades, the complexity and continuous usage of these cooperation structures, in a world of growing competition, justify the continuous interest in both themes. This article presents a scanning of the contemporary academic production in strategic alliances and networks, covering the period from January 1997 to august 2007, based on the top five journals accordingly to the journal of Citation Report 2006 in the business and management categories simultaneously. The results point to a retraction in publications about strategic alliances and a significant growth in the area of strategic. networks. The joint view of strategic alliances and networks, cited by some authors a the evolutionary path of study, still did not appear salient. The most cited topics found in the alliance literature are the governance structure, cooperation, knowledge transfer, culture, control, trust, alliance formation,,previous experience, resources, competition and partner selection. The theme network focuses mainly on structure, knowledge transfer and social network, while the joint vision is highly concentrated in: the subjects of alliance formation and the governance choice.

Bleaching Agents with Varying Concentrations of Carbamide and/or Hydrogen Peroxides: Effect on Dental Microhardness and Roughness

To evaluate the effect of low and highly concentrated bleaching agents on microhardness and surface roughness of bovine enamel and root dentin. According to a randomized complete block design, 100 specimens of each substrate were assigned into five groups to be treated with bleaching agents containing carbamide peroxide (CP) at 10% (CP10); hydrogen peroxide (HP) at 7.5% (HP7.5) or 38% (HP38), or the combination of 18% of HP and 22% of CP (HP18/CP22), for 3 weeks. The control group was left untreated. Specimens were immersed in artificial saliva between bleaching treatments. Knoop surface microhardness (SMH) and average surface roughness (Ra) were measured at baseline and post-bleaching conditions. For enamel, there were differences between bleaching treatments for both SMH and Ra measurements (p = 0.4009 and p = 0.7650, respectively). SMH significantly increased (p < 0.0001), whereas Ra decreased (p = 0.0207) from baseline to post-bleaching condition. For root dentin, the group treated with CP10 exhibited the significantly highest SMH value differing from those groups bleached with HP18/CP22, HP7.5, which did not differ from each other. Application of HP38 resulted in intermediate SMH values. No significant differences were found for Ra (p = 0.5975). Comparing the baseline and post-bleaching conditions, a decrease was observed in SMH (p < 0.0001) and an increase in Ra (p = 0.0063). Bleaching agents with varying concentrations of CP and/or HP are capable of causing mineral loss in root dentin. Enamel does not perform in such bleaching agent-dependent fashion when one considers either hardness or surface roughness evaluations. Bleaching did not alter the enamel microhardness and surface roughness, but in root dentin, microhardness seems to be dependent on the bleaching agent used.

Co-crystallization of sucrose at high concentration in the presence of glucose and fructose

Co-crystallization of sucrose from a highly concentrated sucrose syrup (less than or equal to 7% moisture, w/w) at 131 degreesC with 0, 5, 10, 15, and 20% of fructose, glucose, or a mixture of fructose and glucose was investigated. The crystallization of sucrose was delayed in presence of these lower molecular weight sugars. The DSC melting endotherm of cocrystallized samples exhibited a decrease in crystalline sucrose in the sample as a function of increased level of glucose and fructose. The mechanical strength of co-crystallized granules was found to be related to the moisture content and the amount of glucose or fructose content in the sample. The samples containing 10, 15, and 20% glucose in co-crystallized product demonstrated crystallization of glucose in its monohydrate form during 1 mo of storage.

Disseminated cutaneous sporotrichosis in a patient with AIDS: report of a case

We describe a case report of disseminated cutaneous sporotrichosis as the initial presentation of AIDS in a 24-year-old HIV-positive male patient. He presented multiple ulcerated skin lesions distributed over the face, thorax, legs and arms. Biopsy of one of the cutaneous lesions was suggestive of sporotrichosis and culture isolated Sporothrix schenckii. Itraconazole was started and the lesions progressively resolved after 15 days of medication. The patient was discharged with this medication but he did not return for follow-up. He died three months later in another hospital. Therapy of sporotrichosis in HIV-infected patients remains unclear and the response to therapy is variable. Itraconazole is highly concentrated in the skin and is one of the options for treatment of disseminated sporotrichosis.

Evaluation of uv spectrophotometry for estimation of nitrite and nitrate in nitrified urine

Water is a limited resource for which demand is growing. Contaminated water from inadequate wastewater treatment provides one of the greatest health challenges as it restricts development and increases poverty in emerging and developing countries. Therefore, the connection between wastewater and human health is linked to access to sanitation and to human waste disposal. Adequate sanitation is expected to create a barrier between disposed human excreta and sources of drinking water. Different approaches to wastewater management are required for different geographical regions and different stages of economic governance depending on the capacity to manage wastewater. Effective wastewater management can contribute to overcome the challenges of water scarcity. Separate collection of human urine at its source is one promising approach that strongly reduces the economic and load demands on wastewater treatment plants (WWTP). Treatment of source-separated urine appears as a sanitation system that is affordable, produces a valuable fertiliser, reduces pollution of water resources and promotes health. However, the technical realisation of urine separation still faces challenges. Biological hydrolysis of urea causes a strong increase of ammonia and pH. Under these conditions ammonia volatilises which can cause odour problems and significant nitrogen losses. The above problems can be avoided by urine stabilisation. Biological nitrification is a suitable process for stabilisation of urine. Urine is a highly concentrated nutrient solution which can lead to strong inhibition effects during bacterial nitrification. This can further lead to process instabilities. The major cause of instability is accumulation of the inhibitory intermediate compound nitrite, which could lead to process breakdown. Enhanced on-line nitrite monitoring can be applied in biological source-separated urine nitrification reactors as a sustainable and efficient way to improve the reactor performance, avoiding reactor failures and eventual loss of biological activity. Spectrophotometry appears as a promising candidate for the development and application of on-line nitrite monitoring. Spectroscopic methods together with chemometrics are presented in this work as a powerful tool for estimation of nitrite concentrations. Principal component regression (PCR) is applied for the estimation of nitrite concentrations using an immersible UV sensor and off-line spectra acquisition. The effect of particles and the effect of saturation, respectively, on the UV absorbance spectra are investigated. The analysis allows to conclude that (i) saturation has a substantial effect on nitrite estimation; (ii) particles appear to have less impact on nitrite estimation. In addition, improper mixing together with instabilities in the urine nitrification process appears to significantly reduce the performance of the estimation model.