Desenvolvimento de um material têxtil termosenssível com micro/nanocápsulas imobilizadas em fibras regeneradas

Intelligent and functional Textile Materials have been widely developed and researched with the purpose of being used in several areas of science and technology. These fibrous materials require different chemical and physical properties to obtain a multifunctional material. With the advent of nanotechnology, the techniques developed, being used as essential tools to characterize these new materials qualitatively. Lately the application of micro and nanomaterials in textile substrates has been the objective of many studies, but many of these nanomaterials have not been optimized for their application, which has resulted in increased costs and environmental pollution, because there is still no satisfactory effluent treatment available for these nanomaterials. Soybean fiber has low adsorption for thermosensitive micro and nanocapsules due to their incompatibility of their surface charges. For this reason, in this work initially chitosan was synthesized to functionalise soybean fibres. Chitosan is a natural polyelectrolyte with a high density of positive charges, these fibres have negative charges as well as the micro/nanocápsules, for this reason the chitosan acts as auxiliary agent to cationize in order to fix the thermosensitive microcapsules in the textile substrate. Polyelectrolyte was characterized using particle size analyses and the measurement of zeta potential. For the morphological analysis scanning Electron Microscopy (SEM) and x-Ray Diffraction (XRD) and to study the thermal properties, thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Near Infrared Spectroscopy analysis in the Region of the Fourier Transform Infrared (FTIR), colourimetry using UV-VIS spectrum were simultaneously performed on the substrate. From the measurement of zeta potential and in the determination of the particle size, stability of electrostatic chitosan was observed around 31.55mV and 291.0 nm respectively. The result obtained with (GD) for chitosan extracted from shrimp was 70 %, which according to the literature survey can be considered as chitosan. To optimize the dyeing process a statistical software, Design expert was used. The surface functionalisation of textile substrate with 2% chitosan showed the best result of K/S, being the parameter used for the experimental design, in which this showed the best response of dyeing absorbance in the range of 2.624. It was noted that soy knitting dyed with the thermosensitive micro andnanocapsules property showed excellent washing solidity, which was observed after 25 home washes, and significant K/S values.

Enzymatic Polymerization of High Molecular Weight DNA

The use of DNA as a polymeric building material transcends its function in biology and is exciting in bionanotechnology for applications ranging from biosensing, to diagnostics, and to targeted drug delivery. These applications are enabled by DNA’s unique structural and chemical properties, embodied as a directional polyanion that exhibits molecular recognition capabilities. Hence, the efficient and precise synthesis of high molecular weight DNA materials has become key to advance DNA bionanotechnology. Current synthesis methods largely rely on either solid phase chemical synthesis or template-dependent polymerase amplification. The inherent step-by-step fashion of solid phase synthesis limits the length of the resulting DNA to typically less than 150 nucleotides. In contrast, polymerase based enzymatic synthesis methods (e.g., polymerase chain reaction) are not limited by product length, but require a DNA template to guide the synthesis. Furthermore, advanced DNA bionanotechnology requires tailorable structural and self-assembly properties. Current synthesis methods, however, often involve multiple conjugating reactions and extensive purification steps.

The research described in this dissertation aims to develop a facile method to synthesize high molecular weight, single stranded DNA (or polynucleotide) with versatile functionalities. We exploit the ability of a template-independent DNA polymerase−terminal deoxynucleotidyl transferase (TdT) to catalyze the polymerization of 2’-deoxyribonucleoside 5’-triphosphates (dNTP, monomer) from the 3’-hydroxyl group of an oligodeoxyribonucleotide (initiator). We termed this enzymatic synthesis method: TdT catalyzed enzymatic polymerization, or TcEP.

Specifically, this dissertation is structured to address three specific research aims. With the objective to generate high molecular weight polynucleotides, Specific Aim 1 studies the reaction kinetics of TcEP by investigating the polymerization of 2’-deoxythymidine 5’-triphosphates (monomer) from the 3’-hydroxyl group of oligodeoxyribothymidine (initiator) using in situ 1H NMR and fluorescent gel electrophoresis. We found that TcEP kinetics follows the “living” chain-growth polycondensation mechanism, and like in “living” polymerizations, the molecular weight of the final product is determined by the starting molar ratio of monomer to initiator. The distribution of the molecular weight is crucially influenced by the molar ratio of initiator to TdT. We developed a reaction kinetics model that allows us to quantitatively describe the reaction and predict the molecular weight of the reaction products.

Specific Aim 2 further explores TcEP’s ability to transcend homo-polynucleotide synthesis by varying the choices of initiators and monomers. We investigated the effects of initiator length and sequence on TcEP, and found that the minimum length of an effective initiator should be 10 nucleotides and that the formation of secondary structures close to the 3’-hydroxyl group can impede the polymerization reaction. We also demonstrated TcEP’s capacity to incorporate a wide range of unnatural dNTPs into the growing chain, such as, hydrophobic fluorescent dNTP and fluoro modified dNTP. By harnessing the encoded nucleotide sequence of an initiator and the chemical diversity of monomers, TcEP enables us to introduce molecular recognition capabilities and chemical functionalities on the 5’-terminus and 3’-terminus, respectively.

Building on TcEP’s synthesis capacities, in Specific Aim 3 we invented a two-step strategy to synthesize diblock amphiphilic polynucleotides, in which the first, hydrophilic block serves as a macro-initiator for the growth of the second block, comprised of natural and/or unnatural nucleotides. By tuning the hydrophilic length, we synthesized the amphiphilic diblock polynucleotides that can self-assemble into micellar structures ranging from star-like to crew-cut morphologies. The observed self-assembly behaviors agree with predictions from dissipative particle dynamics simulations as well as scaling law for polyelectrolyte block copolymers.

In summary, we developed an enzymatic synthesis method (i.e., TcEP) that enables the facile synthesis of high molecular weight polynucleotides with low polydispersity. Although we can control the nucleotide sequence only to a limited extent, TcEP offers a method to integrate an oligodeoxyribonucleotide with specific sequence at the 5’-terminus and to incorporate functional groups along the growing chains simultaneously. Additionally, we used TcEP to synthesize amphiphilic polynucleotides that display self-assemble ability. We anticipate that our facile synthesis method will not only advance molecular biology, but also invigorate materials science and bionanotechnology.

PEDOT:PSS thin films: Applications in Bioelectronics

Owing to their capability of merging the properties of metals and conventional polymers, Conducting Polymers (CPs) are a unique class of carbon-based materials capable of conducting electrical current. A conjugated backbone is the hallmark of CPs, which can readily undergo reversible doping to different extents, thus achieving a wide range of electrical conductivities, while maintaining mechanical flexibility, transparency and high thermal stability. Thanks to these inherent versatility and attracting properties, from their discovery CPs have experienced incessant widespread in a great plethora of research fields, ranging from energy storage to healthcare, also encouraging the spring and growth of new scientific areas with highly innovative content. Nowadays, Bioelectronics stands out as one of the most promising research fields, dealing with the mutual interplay between biology and electronics. Among CPs, the polyelectrolyte complex poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), especially in the form of thin films, has been emphasized as ideal platform for bioelectronic applications. Indeed, in the last two decades PEDOT:PSS has played a key role in the sensing of bioanalytes and living cells interfacing and monitoring. In the present work, development and characterization of two kinds of PEDOT:PSS-based devices for applications in Bioelectronics are discussed in detail. In particular, a low-cost amperometric sensor for the selective detection of Dopamine in a ternary mixture was optimized, taking advantage of the electrocatalytic and antifouling properties that render PEDOT:PSS thin films appealing tools for electrochemical sensing of bioanalytes. Moreover, the potentialities of this material to interact with live cells were explored through the fabrication of a microfluidic trapping device for electrical monitoring of 3D spheroids using an impedance-based approach.

Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Enhancement of ‘dry’ proton conductivity by self-assembled nanochannels in all-solid polyelectrolytes

Proton transport has been recognized as an essential process in many biological systems, as well as electrochemical devices including fuel cells and redox flow batteries. In the present study, we address the pressing need for solvent-free proton conducting polymer electrolytes for high-temperature PEM fuel cell applications by developing a novel all-solid polyelectrolyte membrane with a self-assembled proton-channel structure. We show that this self-assembled nanostructure endows the material with exciting ‘dry’ proton conductivity at elevated temperatures, as high as 0.3 mS cm−1 at 120 °C, making it an attractive candidate for high-temperature PEM fuel cell applications. Based on the combined investigation of solid-state NMR, FTIR and conductivity measurements, we propose that both molecular design and nano-scale structures are essential for obtaining highly conductive anhydrous proton conductors.

Synthesis of Anisotropic Magnetic Nanoobjects Designed for Locomotion in External Magnetic Fields

The subject of the present work is the synthesis of novel nanoscale objects, designed for self-propulsion under external actuation. The synthesized objects present asymmetric hybrid particles, consisting of a magnetic core and polymer flagella and their hydrodynamic properties under the actuation by external magnetic fields are investigated. The single-domain ferromagnetic cobalt ferrite nanoparticles are prepared by thermal decomposition of a mixture of metalorganic complexes based on iron (III) cobalt (II) in non-polar solvents. Further modification of the particles includes the growth of the silver particle on the surface of the cobalt ferrite particle to form a dumbbell-shaped heterodimer. Different possible mechanisms of dumbbell formation are discussed. A polyelectrolyte tail with ability to adjust the persistence length of the polymer, and thus the stiffness of the tail, by variation of pH is attached to the particles. A polymer tail consisting of a polyacrylic acid chain is synthesized by hydrolysis of poly(tert-butyl acrylate) obtained by atom transfer radical polymerization (ATRP). A functional thiol end-group enables selective attachment of the tail to the silver part of the dumbbell, resulting in an asymmetric functionalization of the dumbbells. The calculations on the propulsion force and the sperm number for the resulting particles reveal a theoretical possibility for the propelled motion. Under the actuation of the particles with flagella by alternating magnetic field an increase in the diffusion coefficient compared to non-actuated or non-functionalized particles is observed. Further development of such systems for application as nanomotors or in drug delivery is promising.