Moderating effect of ammonia on particle growth and stability of quasi-monodisperse silver nanoparticles synthesized by the Turkevich method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Orange pectin mediated growth and stability of aqueous gold and silver nanocolloids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Complex materials via colloidal crystallization

The work presented in this thesis deals with complex materials, which were obtained by self-assembly of monodisperse colloidal particles, also called colloidal crystallization. Two main fields of interest were investigated, the first dealing with the fabrication of colloidal monolayers and nanostructures, which derive there from. The second turned the focus on the phononic properties of colloidal particles, crystals, and glasses. For the fabrication of colloidal monolayers a method is introduced, which is based on the sparse distribution of dry colloidal particles on a parent substrate. In the ensuing floating step the colloidal monolayer assembles readily at the three-phase-contact line, giving a 2D hexagonally ordered film under the right conditions. The unique feature of this fabrication process is an anisotropic shrinkage, which occurs alongside with the floating step. This phenomenon is exploited for the tailored structuring of colloidal monolayers, leading to designed hetero-monolayers by inkjet printing. Furthermore, the mechanical stability of the floating monolayers allows the deposition on hydrophobic substrates, which enables the fabrication of ultraflat nanostructured surfaces. Densely packed arrays of crescent shaped nanoparticles have also been synthesized. It is possible to stack those arrays in a 3D manner allowing to mutually orientate the individual layers. In a step towards 3D mesoporous materials a methodology to synthesize hierarchically structured inverse opals is introduced. The deposition of colloidal particles in the free voids of a host inverse opal allows for the fabrication of composite inverse opals on two length scales. The phononic properties of colloidal crystals and films are characterized by Brillouin light scattering (BLS). At first the resonant modes of colloidal particles consisting of polystyrene, a copolymer of methylmethacrylate and butylacrylate, or of a silica core-PMMA shell topography are investigated, giving insight into their individual mechanical properties. The infiltration of colloidal films with an index matching liquid allows measuring the phonon dispersion relation. This leads to the assignment of band gaps to the material under investigation. Here, two band gaps could be found, one originating from the fcc order in the colloidal crystal (Bragg gap), the other stemming from the vibrational eigenmodes of the colloidal particles (hybridization gap).

Electrophoretic Deposition of Transparent ZnO Thin Films from Highly Stabilized Colloidal Suspensions

The parameters that control the stability of ZnO-nanoparticles suspensions and their deposition by electrophoretic deposition were studied, so as to organize the assembly and compaction of nanoparticles. The addition of cationic polyelectrolyte - Polyethylenimine (PEI) - with different molecular weights was investigated, in order to study their effectiveness and the influence of the molecular weight of the organic chain on suspensions dispersion. It was found that PEI with the highest molecular weight provided better dispersion conditions. Cathodic EPD was performed under previously optimized suspensions conditions and over electropolished stainless steel substrates. Experimental results showed that the EPD process in these conditions allows obtaining dense transparent ZnO thin films. Deposition times and intensities were optimized by analyzing the resulting thin films characteristics. Finally, the deposits were characterized by FE-SEM, AFM, and different spectroscopic techniques.

Investigation of the Nucleation and Growth of Colloidal Indium Phosphide: from Molecular Precursors to Semiconductor Nanocrystals through In37P20(O2CR)51 as a Magic-Size Intermediate

Thesis (Ph.D.)--University of Washington, 2016-06

DIFFUSE-INTERFACE FIELD APPROACH TO MODELING SELF-ASSEMBLY OF HETEROGENEOUS COLLOIDAL SYSTEMS AND RELATED DIPOLE-DIPOLE INTERACTION PHENOMENA

Colloid self-assembly under external control is a new route to fabrication of advanced materials with novel microstructures and appealing functionalities. The kinetic processes of colloidal self-assembly have attracted great interests also because they are similar to many atomic level kinetic processes of materials. In the past decades, rapid technological progresses have been achieved on producing shape-anisotropic, patchy, core-shell structured particles and particles with electric/magnetic charges/dipoles, which greatly enriched the self-assembled structures. Multi-phase carrier liquids offer new route to controlling colloidal self-assembly. Therefore, heterogeneity is the essential characteristics of colloid system, while so far there still lacks a model that is able to efficiently incorporate these possible heterogeneities. This thesis is mainly devoted to development of a model and computational study on the complex colloid system through a diffuse-interface field approach (DIFA), recently developed by Wang et al. This meso-scale model is able to describe arbitrary particle shape and arbitrary charge/dipole distribution on the surface or body of particles. Within the framework of DIFA, a Gibbs-Duhem-type formula is introduced to treat Laplace pressure in multi-liquid-phase colloidal system and it obeys Young-Laplace equation. The model is thus capable to quantitatively study important capillarity related phenomena. Extensive computer simulations are performed to study the fundamental behavior of heterogeneous colloidal system. The role of Laplace pressure is revealed in determining the mechanical equilibrium of shape-anisotropic particles at fluid interfaces. In particular, it is found that the Laplace pressure plays a critical role in maintaining the stability of capillary bridges between close particles, which sheds light on a novel route to in situ firming compact but fragile colloidal microstructures via capillary bridges. Simulation results also show that competition between like-charge repulsion, dipole-dipole interaction and Brownian motion dictates the degree of aggregation of heterogeneously charged particles. Assembly and alignment of particles with magnetic dipoles under external field is studied. Finally, extended studies on the role of dipole-dipole interaction are performed for ferromagnetic and ferroelectric domain phenomena. The results reveal that the internal field generated by dipoles competes with external field to determine the dipole-domain evolution in ferroic materials.

Comparison Of Postoperative Stability Of Three Rigid Internal Fixation Techniques After Sagittal Split Ramus Osteotomy For Mandibular Advancement.

The aim of this investigation was to compare the skeletal stability of three different rigid fixation methods after mandibular advancement. Fifty-five class II malocclusion patients treated with the use of bilateral sagittal split ramus osteotomy and mandibular advancement were selected for this retrospective study. Group 1 (n = 17) had miniplates with monocortical screws, Group 2 (n = 16) had bicortical screws and Group 3 (n = 22) had the osteotomy fixed by means of the hybrid technique. Cephalograms were taken preoperatively, 1 week within the postoperative care period, and 6 months after the orthognathic surgery. Linear and angular changes of the cephalometric landmarks of the chin region were measured at each period, and the changes at each cephalometric landmark were determined for the time gaps. Postoperative changes in the mandibular shape were analyzed to determine the stability of fixation methods. There was minimum difference in the relapse of the mandibular advancement among the three groups. Statistical analysis showed no significant difference in postoperative stability. However, a positive correlation between the amount of advancement and the amount of postoperative relapse was demonstrated by the linear multiple regression test (p < 0.05). It can be concluded that all techniques can be used to obtain stable postoperative results in mandibular advancement after 6 months.

Effects Of High Pressure Homogenization On The Activity, Stability, Kinetics And Three-dimensional Conformation Of A Glucose Oxidase Produced By Aspergillus Niger.

High pressure homogenization (HPH) is a non-thermal method, which has been employed to change the activity and stability of biotechnologically relevant enzymes. This work investigated how HPH affects the structural and functional characteristics of a glucose oxidase (GO) from Aspergillus niger. The enzyme was homogenized at 75 and 150 MPa and the effects were evaluated with respect to the enzyme activity, stability, kinetic parameters and molecular structure. The enzyme showed a pH-dependent response to the HPH treatment, with reduction or maintenance of activity at pH 4.5-6.0 and a remarkable activity increase (30-300%) at pH 6.5 in all tested temperatures (15, 50 and 75°C). The enzyme thermal tolerance was reduced due to HPH treatment and the storage for 24 h at high temperatures (50 and 75°C) also caused a reduction of activity. Interestingly, at lower temperatures (15°C) the activity levels were slightly higher than that observed for native enzyme or at least maintained. These effects of HPH treatment on function and stability of GO were further investigated by spectroscopic methods. Both fluorescence and circular dichroism revealed conformational changes in the molecular structure of the enzyme that might be associated with the distinct functional and stability behavior of GO.

In Vitro Evaluation Of Sun Protection Factor And Stability Of Commercial Sunscreens Using Mass Spectrometry.

Sunlight exposure causes several types of injury to humans, especially on the skin; among the most common harmful effects due to ultraviolet (UV) exposure are erythema, pigmentation and lesions in DNA, which may lead to cancer. These long-term effects are minimized with the use of sunscreens, a class of cosmetic products that contains UV filters as the main component in the formulation; such molecules can absorb, reflect or diffuse UV rays, and can be used alone or as a combination to broaden the protection on different wavelengths. Currently, worldwide regulatory agencies define which ingredients and what quantities must be used in each country, and enforce companies to conduct tests that confirm the Sun Protection Factor (SPF) and the UVA (Ultraviolet A) factor. Standard SPF determination tests are currently conducted in vivo, using human subjects. In an industrial mindset, apart from economic and ethical reasons, the introduction of an in vitro method emerges as an interesting alternative by reducing risks associated to UV exposure on tests, as well as providing assertive analytical results. The present work aims to describe a novel methodology for SPF determination directly from sunscreen formulations using the previously described cosmetomics platform and mass spectrometry as the analytical methods of choice.

Effect of staining solutions and repolishing on color stability of direct composites

OBJECTIVES: The purpose of this study was to assess the color change of three types of composite resins exposed to coffee and cola drink, and the effect of repolishing on the color stability of these composites after staining. MATERIALS AND METHODS: Fifteen specimens (15 mm diameter and 2 mm thick) were fabricated from microhybrid (Esthet-X; Dentsply and Filtek Z-250; 3M ESPE) and high-density hybrid (Surefil; Dentsply) composites, and were finished and polished with aluminum oxide discs (Sof-Lex; 3M ESPE). Color of the specimens was measured according to the CIE L*a*b* system in a refection spectrophotometer (PCB 6807; BYK Gardner). After baseline color measurements, 5 specimens of each resin were immersed in different staining solutions for 15 days: G1 - distilled water (control), G2 - coffee, G3 - cola soft drink. Afterwards, new color measurement was performed and the specimens were repolished and submitted to new color reading. Color stability was determined by the difference (ΔE) between the coordinates L*, a*, and b* obtained from the specimens before and after immersion into the solutions and after repolishing. RESULTS: There was no statistically signifcant difference (ANOVA, Tukey's test; p>0.05) among the ΔE values for the different types of composites after staining or repolishing. For all composite resins, coffee promoted more color change (ΔE>3.3) than distilled water and the cola soft drink. After repolishing, the ΔE values of the specimens immersed in coffee decreased to clinically acceptable values (ΔE<3.3), but remained signifcantly higher than those of the other groups. CONCLUSIONS: No signifcant difference was found among composite resins or between color values before and after repolishing of specimens immersed in distilled water and cola. Immersing specimens in coffee caused greater color change in all types of composite resins tested in this study and repolishing contributed to decrease staining to clinically acceptable ΔE values.

Composite resin color stability: influence of light sources and immersion media

OBJECTIVE: This study evaluated the influence of light sources and immersion media on the color stability of a nanofilled composite resin. MATERIAL AND METHODS: Conventional halogen, high-power-density halogen and high-power-density light-emitting diode (LED) units were used. There were 4 immersion media: coffee, tea, Coke® and artificial saliva. A total of 180 specimens (10 mm x 2 mm) were prepared, immersed in artificial saliva for 24 h at 37±1ºC, and had their initial color measured with a spectrophotometer according to the CIELab system. Then, the specimens were immersed in the 4 media during 60 days. Data from the color change and luminosity were collected and subjected to statistical analysis by the Kruskall-Wallis test (p<0.05). For immersion time, the data were subjected to two-way ANOVA test and Fisher's test (p<0.05). RESULTS: High-power-density LED (ΔE=1.91) promoted similar color stability of the composite resin to that of the tested halogen curing units (Jet Lite 4000 plus - ΔE=2.05; XL 3000 - ΔE=2.28). Coffee (ΔE=8.40; ΔL=-5.21) showed the highest influence on color stability of the studied composite resin. CONCLUSION: There was no significant difference in color stability regardless of the light sources, and coffee was the immersion medium that promoted the highest color changes on the tested composite resin.

Evaluation of iris color stability in ocular prosthesis

Accurate iris reproduction in the fabrication of ocular prosthesis in order to match the remaining eye is a key factor to mask the loss and achieve an esthetic outcome for anophthalmic patients. This study evaluated the stability of acrylic paints used for replicating iris color in ocular prostheses by the analysis of two factors: the temperature of the acrylic resin polymerization cycle during prosthesis fabrication and the incidence of sun light, which is the main photodegrading agent undermining the longevity of ocular prostheses. An accelerated aging assay was used for both analyses. Specimens simulating the prosthetic iris in the colors blue, yellow, black, brown and green were fabricated, and were submitted to a colorimetric reading before and after undergoing the thermal conditions of acrylic resin polymerization. Next, the specimens were submitted to an artificial accelerated aging assay with ultraviolet radiation A and weekly colorimetric readings during a 3-week period. The color change (??*) values for the four specimens painted with the same color paint were averaged and the resulting values were considered for statistical analysis. Levine's test and Student's t-test were used to analyze the influence of the temperature of the polymerization cycle during prosthesis fabrication on the color stability of each acrylic resin paint. Friedman's test for three dependent samples was used for analysis of color photodegradation as function of time. Significance level was set at 0.05 for all analyses. It was observed that, after the action of the temperature of the polymerization cycle, alteration above clinically acceptable level of ??*> 3.3 was observed only for the yellow color. After the accelerated aging assay, there were statistically significant differences (p<0.05) as a function of time in the green, brown, black and blue colors. Changes were clinically acceptable for the brown and black colors; slightly above the clinically acceptable limit for the green color; and significantly high and impracticable from a clinical standpoint for the blue color. There was no statistically significant differences (p>0.05) for the yellow color, which presented color change only a little above the clinically acceptable limit. In conclusion: 1. Only the yellow color presented alterations above the clinically acceptable levels after the polymerization cycle; 2. After accelerated aging, there was no changes in the yellow color above the clinically acceptable levels; 3. For the green color, degradation was significant and slightly above the clinically acceptable levels; 4. The black, brown and blue colors presented significant alterations as function of time; the alterations of the brown and black colors were within acceptable clinical levels, while the blue color presented a more accentuated degradation over time.

Nanostructured thin films obtained by electrodeposition over a colloidal crystal template: applications in electrochemical devices

Colloidal particles have been used to template the electrosynthesis of several materials, such as semiconductors, metals and alloys. The method allows good control over the thickness of the resulting material by choosing the appropriate charge applied to the system, and it is able to produce high density deposited materials without shrinkage. These materials are a true model of the template structure and, due to the high surface areas obtained, are very promising for use in electrochemical applications. In the present work, the assembly of monodisperse polystyrene templates was conduced over gold, platinum and glassy carbon substrates in order to show the electrodeposition of an oxide, a conducting polymer and a hybrid inorganic-organic material with applications in the supercapacitor and sensor fields. The performances of the resulting nanostructured films have been compared with the analogue bulk material and the results achieved are depicted in this paper.

Stability of fruit bases and chocolate fillings

Syrups with high sugar content and dehydrated fruits in its composition can be added to chocolate fillings to reduce the need of artificial flavor and dyes attributing a natural appeal to the product. Fruit bases were produced with lyophilized strawberry, passion fruit, and sliced orange peel. Rheological dynamic oscillatory tests were applied to determine the products stability and tendency of shelf life. Values of G´< G´´ were observed for strawberry and passion fruit flavor, whereas values of G´ > G´´ were found for orange flavor during the 90 days of storage. It was observed that shear stress values did not vary significantly suggesting product stability during the studied period. For all fillings, it was found a behavior similar to the fruit base indicating that it has great influence on the filling behavior and its stability. The use of a sugar matrix in fillings provided good shelf life for the fruit base, which could be kept under room temperature conditions for a period as long as one year. The good stability and storage conditions allow the use of fruit base for handmade products as well as for industrialized products.

Headland-bay beach planform stability of Santa Catarina State and of the Northern Coast of São Paulo State

This paper presents the results of the planform stability classification for the headland-bay beaches of the State of Santa Catarina and of the Northern Coast of São Paulo, based on the application of the Parabolic Bay-Shape Equation (PBSE) to aerial images of the beaches, using the software MEPBAY®. For this purpose, georeferenced mosaics of the QuickBird2® satellite imagery (for the State of Santa Catarina) and vertical aerial photographs (for the northern coast of São Paulo State) were used. Headland-bay beach planform stability can be classified as: (1) in static equilibrium, (2) in dynamic equilibrium, (3) unstable or (4) in a state of natural beach reshaping. Static equilibrium beaches are the most frequent along the coast of the State of Santa Catarina and the Northern Shore of São Paulo, notably along the most rugged sectors of the coast and those with experiencing lower fluvial discharge. By comparison, dynamic equilibrium beaches occur primarily on the less rugged sectors of the coast and along regions with higher fluvial discharge. Beaches in a state of natural beach reshaping have only been found in SC, associated with stabilized estuarine inlets or port breakwaters. However, it is not possible to classify any of these beaches as unstable because only one set of images was used. No clear relation was observed between a beach's planform stability and other classification factors, such as morphodynamics or orientation.