Fabrication of sub-10 nm lamellar structures by solvent vapour annealing of block copolymers

Fabrication of nanoscale patterns through the bottom-up approach of self-assembly of phase-separated block copolymers (BCP) holds promise for nanoelectronics applications. For lithographic applications, it is useful to vary the morphology of BCPs by monitoring various parameters to make “from lab to fab” a reality. Here I report on the solvent annealing studies of lamellae forming polystyrene-blockpoly( 4-vinylpyridine) (PS-b-P4VP). The high Flory-Huggins parameter (χ = 0.34) of PS-b-P4VP makes it an ideal BCP system for self-assembly and template fabrication in comparison to other BCPs. Different molecular weights of symmetric PS-b-P4VP BCPs forming lamellae patterns were used to produce nanostructured thin films by spin-coating from mixture of toluene and tetrahydrofuran(THF). In particular, the morphology change from micellar structures to well-defined microphase separated arrangements is observed. Solvent annealing provides a better alternative to thermal treatment which often requires long annealing periods. The choice of solvent (single and dual solvent exposure) and the solvent annealing conditions have significant effects on the morphology of films and it was found that a block neutral solvent was required to realize vertically aligned PS and P4VP lamellae. Here, we have followed the formation of microdomain structures with time development at different temperatures by atomic force microscopy (AFM). The highly mobilized chains phase separate quickly due to high Flory-Huggins (χ) parameter. Ultra-small feature size (~10 nm pitch size) nanopatterns were fabricated by using low molecular weight PSb- P4VP (PS and P4VP blocks of 3.3 and 3.1 kg mol-1 respectively). However, due to the low etch contrast between the blocks, pattern transfer of the BCP mask is very challenging. To overcome the etch contrast problem, a novel and simple in-situ hard mask technology is used to fabricate the high aspect ratio silicon nanowires. The lamellar structures formed after self-assembly of phase separated PS-b-P4VP BCPs were used to fabricate iron oxide nanowires which acted as hard mask material to facilitate the pattern transfer into silicon and forming silicon nanostructures. The semiconductor and optical industries have shown significant interest in two dimensional (2D) molybdenum disulphide (MoS2) as a potential device material due to its low band gap and high mobility. However, current methods for its synthesis are not ‘fab’ friendly and require harsh environments and processes. Here, I also report a novel method to prepare MoS2 layered structures via self-assembly of a PS-b-P4VP block copolymer system. The formation of the layered MoS2 was confirmed by XPS, Raman spectroscopy and high resolution transmission electron microscopy.

Diversity in a simple co-crystal: racemic and kryptoracemic behaviour.

The crystal structure containing (+/-)-3-methyl-2-phenylbutyramide with salicylic acid is the first example of a kryptoracemate co-crystal. It exhibits the first temperature mediated reversible single-crystal to single-crystal transition between two kryptoracemate forms, in addition to crystallising in another, racemic, form. Theoretical calculations and structural analysis reveal that there are only small differences in both energy and packing arrangements between the three forms. These results suggest that co-crystals can be an opportunity to investigate kryptoracemate behaviour.

A Micro-Opto-Electro-Mechanical System (MOEMS) for Microstructure Manipulation

Microstructure manipulation is a fundamental process to the study of biology and medicine, as well as to advance micro- and nano-system applications. Manipulation of microstructures has been achieved through various microgripper devices developed recently, which lead to advances in micromachine assembly, and single cell manipulation, among others. Only two kinds of integrated feedback have been demonstrated so far, force sensing and optical binary feedback. As a result, the physical, mechanical, optical, and chemical information about the microstructure under study must be extracted from macroscopic instrumentation, such as confocal fluorescence microscopy and Raman spectroscopy. In this research work, novel Micro-Opto-Electro-Mechanical-System (MOEMS) microgrippers are presented. These devices utilize flexible optical waveguides as gripping arms, which provide the physical means for grasping a microobject, while simultaneously enabling light to be delivered and collected. This unique capability allows extensive optical characterization of the structure being held such as transmission, reflection, or fluorescence. The microgrippers require external actuation which was accomplished by two methods: initially with a micrometer screw, and later with a piezoelectric actuator. Thanks to a novel actuation mechanism, the “fishbone”, the gripping facets remain parallel within 1 degree. The design, simulation, fabrication, and characterization are systematically presented. The devices mechanical operation was verified by means of 3D finite element analysis simulations. Also, the optical performance and losses were simulated by the 3D-to-2D effective index (finite difference time domain FDTD) method as well as 3D Beam Propagation Method (3D-BPM). The microgrippers were designed to manipulate structures from submicron dimensions up to approximately 100 µm. The devices were implemented in SU-8 due to its suitable optical and mechanical properties. This work demonstrates two practical applications: the manipulation of single SKOV-3 human ovarian carcinoma cells, and the detection and identification of microparts tagged with a fluorescent “barcode” implemented with quantum dots. The novel devices presented open up new possibilities in the field of micromanipulation at the microscale, scalable to the nano-domain.

Raman Analysis of Dilute Aqueous Samples by Localized Evaporation of Submicroliter Droplets on the Tips of Superhydrophobic Copper Wires

Raman analysis of dilute aqueous solutions is normally prevented by their low signal levels. A very general method to increase the concentration to detectable levels is to evaporate droplets of the sample to dryness, creating solid deposits which are then Raman probed. Here, superhydrophobic (SHP) wires with hydrophilic tips have been used as supports for drying droplets, which have the advantage that the residue is automatically deposited at the tip. The SHP wires were readily prepared in minutes using electroless galvanic deposition of Ag onto copper wires followed by modification with a polyfluorothiol (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanethiol, HDFT). Cutting the coated wires with a scalpel revealed hydrophilic tips which could support droplets whose maximum size was determined by the wire diameter. Typically, 230 μm wires were used to support 0.6 μL droplets. Evaporation of dilute melamine droplets gave solid deposits which could be observed by scanning electron microscopy (SEM) and Raman spectroscopy. The limit of detection for melamine using a two stage evaporation procedure was 1 × 10^-6 mol dm^-3. The physical appearance of dried droplets of sucrose and glucose showed that the samples retained significant amounts of water, even under high vacuum. Nonetheless, the Raman detection limits of sucrose and glucose were 5 × 10^-4 and 2.5 × 10^-3 mol dm^-3, respectively, which is similar to the sensitivity reported for surface-enhanced Raman spectroscopy (SERS) detection of glucose. It was also possible to quantify the two sugars in mixtures at concentrations which were similar to those found in human blood through multivariate analysis.

Nucleophilic addition of Nitrones to Electron deficient acetylenes and related studies

Nitrones or azomethine-N-oxides are important precursors for the synthesis of several heterocyclic systems. They belong to the allyl anion type 1,3-dipoles and possess unique structural features which make them extraordinarily useful synthons. They behave as 1,3-dipoles in 1,3-dipolar cycloaddition reactions and as electrophiles in reactions with organometallic reagents. These are the two basic reactions given by nitrones. Nitrones also act as ‘spin traps’ in which they react with short-lived radicals to furnish stable nitroxide radicals which can be detected and identified by electron paramagnetic resonance (EPR) spectroscopy. Recently SmI2 catalysed reductive cross-coupling reactions of nitrones have gained significant interest in which the reactions are initiated by single electron transfer (SET) to nitrones. Apart from these reactions, nitrones are also known to participate in reactions which are initiated by the nucleophilic attack of nitrone-oxygen. In our group, we have also explored the nucleophilic character of nitrones through various reactions. The results obtained enabled us to develop a novel two-step one-pot strategy for quinolines and indoles - the heterocycles renowned for their pharmacological applications, from nitrones and electron deficient acetylenes. Using dibenzoylacetylene and phenylbenzoylacetylene as dipolarophiles, we could introduce a desired functional group at a predetermined position of the quinolines or indoles to be synthesised. In this context, the thesis entitled “NUCLEOPHILIC ADDITION OF NITRONES TO ELECTRON DEFICIENT ACETYLENES AND RELATED STUDIES” portrays our attempt to expand the scope of our x novel synthetic protocol using ester functionalised acetylenes: dimethyl acetylenedicarboxylate (DMAD) and methyl propiolate. The thesis is organised in to five chapters. The first chapter briefly describes the different classes of reactions that nitrone functionality can tolerate. The research problem is defined at the end of this chapter. The second chapter describes the synthesis of different nitrones used for the present study. The optimisation and expansion of scope of the novel strategy towards quinoline synthesis is discussed in the third chapter. The fourth chapter portrays the synthesis of indole-3-carboxylates using the novel strategy. In the fifth chapter, the reaction of N-(2,6-dimethylphenyl) and N-(2,4,6-trimethylphenyl)nitrones are discussed. Here we also discuss the mechanistic reinvestigation of Baldwin’s proposal in the isoxazoline-oxazoline rearrangement. The major outcome of the work is given at the end of the thesis. The structural formulae, schemes, tables and figures are numbered chapter-wise since each chapter of the thesis is organized as an independent unit. All new compounds (except two compounds reported in fourth chapter) are fully characterised on the basis of spectral and analytical data and single crystal X-ray analysis on representative examples. Relevant references are included at the end of individual chapters.

Transition metal complexes of some N4-phenylsemicarbazones: crystal structures and spectral studies

The work embodied in this thesis was carried out by the author in the Department of Applied Chemistry, CUSAT, Kochi, during the period 2009-2012. The thesis is an introduction to our attempts to evaluate the coordination behavior of some compounds of our interest. The biological activities of semicarbazones and their metal complexes have been an active area of research during the past years because of their significant role in naturally occurring biological systems. Tridentate NNO and ONO semicarbazone systems formed from heterocyclic and aromatic carbonyl compounds and their transition metal complexes are wellauthenticated compounds in this field and their synthesis, crystal structures and spectral studies are well desirable. Hence, we decided to develop a research program aimed at the syntheses, crystal structures and spectral studies of new N4- phenylsemicarbazones derived from 2-formylpyridine and 3-ethoxysalicylaldehyde and their transition metal complexes and new transition metal complexes of 2- benzoylpyridine-N4-phenylsemicarbazone. In addition to various physicochemical methods of analysis, single crystal X-ray diffraction studies were also used for the characterization of the complexes.

BETA-GA2O3: A TRANSPARENT CONDUCTIVE OXIDE FOR POTENTIAL RESISTIVE SWITCHING APPLICATIONS

Thesis (Ph.D.)--University of Washington, 2016-08

Aroylhydrazone Cu(II) complexes in keto form: structural characterization and catalytic cctivity towards cyclohexane oxidation

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with a copper(II) salt of a base of a strong acid, i.e., nitrate, chloride or sulphate, yielded the mononuclear complexes [Cu(H2L)(NO3)(H2O)] (1), [Cu(H2L)Cl]center dot 2MeOH (2) and the binuclear complex [{Cu(H2L)}(2)(mu-SO4)]center dot 2MeOH (3), respectively, with H2L- in the keto form. Compounds 1-3 were characterized by elemental analysis, Infrared (IR) spectroscopy, Electrospray Ionisation-Mass Spectrometry (ESI-MS) and single crystal X-ray crystallography. All compounds act as efficient catalysts towards the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, under mild conditions. In the presence of an acid promoter, overall yields (based on the alkane) up to 25% and a turnover number (TON) of 250 (TOF of 42 h(-1)) after 6 h, were achieved.

Atomic resolution studies of oxide superlattices and ultrathin films

The ability to grow ultrathin films layer-by-layer with well-defined epitaxial relationships has allowed research groups worldwide to grow a range of artificial films and superlattices, first for semiconductors, and now with oxides. In the oxides thin film research community, there have been concerted efforts recently to develop a number of epitaxial oxide systems grown on single crystal oxide substrates that display a wide variety of novel interfacial functionality, such as enhanced ferromagnetic ordering, increased charge carrier density, increased optical absorption, etc, at interfaces. The magnitude of these novel properties is dependent upon the structure of thin films, especially interface sharpness, intermixing, defects, and strain, layering sequence in the case of superlattices and the density of interfaces relative to the film thicknesses. To understand the relationship between the interfacial thin film oxide atomic structure and its properties, atomic scale characterization is required. Transmission electron microscopy (TEM) offers the ability to study interfaces of films at high resolution. Scanning transmission electron microscopy (STEM) allows for real space imaging of materials with directly interpretable atomic number contrast. Electron energy loss spectroscopy (EELS), together with STEM, can probe the local chemical composition as well as local electronic states of transition metals and oxygen. Both techniques have been significantly improved by aberration correctors, which reduce the probe size to 1 Å, or less. Aberration correctors have thus made it possible to resolve individual atomic columns, and possibly probe the electronic structure at atomic scales. Separately, using electron probe forming lenses, structural information such as the crystal structure, strain, lattice mismatches, and superlattice ordering can be measured by nanoarea electron diffraction (NED). The combination of STEM, EELS, and NED techniques allows us to gain a fundamental understanding of the properties of oxide superlattices and ultrathin films and their relationship with the corresponding atomic and electronic structure. In this dissertation, I use the aforementioned electron microscopy techniques to investigate several oxide superlattice and ultrathin film systems. The major findings are summarized below. These results were obtained with stringent specimen preparation methods that I developed for high resolution studies, which are described in Chapter 2. The essential materials background and description of electron microscopy techniques are given in Chapter 1 and 2. In a LaMnO3-SrMnO3 superlattice, we demonstrate the interface of LaMnO3-SrMnO3 is sharper than the SrMnO3-LaMnO3 interface. Extra spectral weights in EELS are confined to the sharp interface, whereas at the rougher interface, the extra states are either not present or are not confined to the interface. Both the structural and electronic asymmetries correspond to asymmetric magnetic ordering at low temperature. In a short period LaMnO3-SrTiO3 superlattice for optical applications, we discovered a modified band structure in SrTiO3 ultrathin films relative to thick films and a SrTiO3 substrate, due to charge leakage from LaMnO3 in SrTiO3. This was measured by chemical shifts of the Ti L and O K edges using atomic scale EELS. The interfacial sharpness of LaAlO3 films grown on SrTiO3 was investigated by the STEM/EELS technique together with electron diffraction. This interface, when prepared under specific conditions, is conductive with high carrier mobility. Several suggestions for the conductive interface have been proposed, including a polar catastrophe model, where a large built-in electric field in LaAlO3 films results in electron charge transfer into the SrTiO3 substrate. Other suggested possibilities include oxygen vacancies at the interface and/or oxygen vacancies in the substrate. The abruptness of the interface as well as extent of intermixing has not been thoroughly investigated at high resolution, even though this can strongly influence the electrical transport properties. We found clear evidence for cation intermixing through the LaAlO3-SrTiO3 interface with high spatial resolution EELS and STEM, which contributes to the conduction at the interface. We also found structural defects, such as misfit dislocations, which leads to increased intermixing over coherent interfaces.

Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work.

A contribution towards the performance and structural understanding of copper and nickel salts as ammonia stores

The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

Síntese de ligantes Bis-amida e aplicação em reações de acoplamento Suzuki

As amidas constituem uma classe de moléculas com amplo perfil farmacológico e que despertam atenção também pela capacidade de coordenar metais de transição. Esta proposta de trabalho compreende, inicialmente, a síntese de 3 ligantes bis-amidas simétricas tendo como reagentes de partida etilenodiamina, orto-fenilenodiamina, salicilato de metila e cloreto de benzoíla. Esses compostos foram caracterizados por espectroscopia no infravermelho (IV), ressonância magnética nuclear de hidrogênio (RMN 1H) e difração de raios X em monocristal (DRX). Após sintetizar e caracterizar esses compostos, a outra etapa do trabalho foi a utilização dessas bis-amidas como ligante na reação catalítica de acoplamento Suzuki. O sistema catalítico otimizado à base destes ligantes na presença de paládio, foi capaz de promover a formação de bifenilas com rendimentos superiores a 90% à temperatura de 50 °C e tempo reacional de 1 h. Este sistema se mostrou eficiente para reagentes com diversos grupos substituintes (eletroretiradores e eletrodoadores) nos anéis aromáticos dos haletos de arila e ácidos arilborônicos.

Exploring redox-driven self-assembly of mixed metal polyoxometalates

How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.

Nanotubos de carbono de parede simples funcionalizados com polietilenoglicol: avaliação de parâmetros in vivo e in vitro

Os nanomateriais apresentam uma escala na qual ao menos uma das dimensões varia entre 1 e 100 nm e possuem propriedades químicas, físicas ou biológicas dependentes da nanoestrutura e que lhes confere características funcionais de interesse para fins comerciais ou aplicações na área médica. Dentre os nanomateriais mais estudados e utilizados, destacam-se os de carbono, que incluem os fulerenos e os nanotubos de carbono (NT). Uma potencial utilização dos nanomateriais de carbono é na área biomédica, já que estes podem interagir com os sistemas biológicos em nível molecular e supramolecular com alto grau de especificidade. Em contrapartida, é importante considerar que os nanotubos de carbono podem exercer efeitos tóxicos, tendo como possível mecanismo o estresse oxidativo. Sendo assim, o objetivo desse trabalho foi investigar a ação dos nanotubos de carbono de parede única funcionalizados com polietilenoglicol (SWNT-PEG) em Danio rerio “zebrafish” (Teleostei, Cyprinidae). Avaliaram-se parâmetros bioquímicos, histológicos, comportamentais e de biodistribuição para entender como esse material se comporta in vitro e in vivo. Foi observado que o tipo de funcionalização é determinante para a ação desse material em meio biológico. No experimento in vitro o SWNT-PEG não mostrou efeito pró-oxidante nas avaliações de peroxidação lipídica, capacidade antioxidante total, conteúdo de GSH e atividade de GCL. Na exposição intraperitoneal em zebrafish constatou-se a agregação e geração de processo inflamatório, o que sugere que a cadeia de PEG utilizada para a funcionalização dos NT possui um tamanho inadequado e/ou uma funcionalização ineficiente para manter a estabilidade do material em meio biológico e evitar uma resposta inflamatória por parte do organismo exposto. Possivelmente devido a esta característica do nanomaterial, nas análises de biodistribuição, através de espectroscopia Raman, não se observou distribuição de SWNT-PEG no sistema nervoso central de zebrafish. No entanto, através da análise histológica foi observado processo inflamatório no tecido nervoso central, bem como alterações comportamentais avaliadas na tarefa de campo aberto.

MEMS SENSOR PLATFORMS FOR IN SITU CHARACTERIZATION OF LI-ION BATTERY ELECTRODES

Lithium-ion batteries provide high energy density while being compact and light-weight and are the most pervasive energy storage technology powering portable electronic devices such as smartphones, laptops, and tablet PCs. Considerable efforts have been made to develop new electrode materials with ever higher capacity, while being able to maintain long cycle life. A key challenge in those efforts has been characterizing and understanding these materials during battery operation. While it is generally accepted that the repeated strain/stress cycles play a role in long-term battery degradation, the detailed mechanisms creating these mechanical effects and the damage they create still remain unclear. Therefore, development of techniques which are capable of capturing in real time the microstructural changes and the associated stress during operation are crucial for unravelling lithium-ion battery degradation mechanisms and further improving lithium-ion battery performance. This dissertation presents the development of two microelectromechanical systems sensor platforms for in situ characterization of stress and microstructural changes in thin film lithium-ion battery electrodes, which can be leveraged as a characterization platform for advancing battery performance. First, a Fabry-Perot microelectromechanical systems sensor based in situ characterization platform is developed which allows simultaneous measurement of microstructural changes using Raman spectroscopy in parallel with qualitative stress changes via optical interferometry. Evolutions in the microstructure creating a Raman shift from 145 cm−1 to 154 cm−1 and stress in the various crystal phases in the LixV2O5 system are observed, including both reversible and irreversible phase transitions. Also, a unique way of controlling electrochemically-driven stress and stress gradient in lithium-ion battery electrodes is demonstrated using the Fabry-Perot microelectromechanical systems sensor integrated with an optical measurement setup. By stacking alternately stressed layers, the average stress in the stacked electrode is greatly reduced by 75% compared to an unmodified electrode. After 2,000 discharge-charge cycles, the stacked electrodes retain only 83% of their maximum capacity while unmodified electrodes retain 91%, illuminating the importance of the stress gradient within the electrode. Second, a buckled membrane microelectromechanical systems sensor is developed to enable in situ characterization of quantitative stress and microstructure evolutions in a V2O5 lithium-ion battery cathode by integrating atomic force microscopy and Raman spectroscopy. Using dual-mode measurements in the voltage range of the voltage range of 2.8V – 3.5V, both the induced stress (~ 40 MPa) and Raman intensity changes due to lithium cycling are observed. Upon lithium insertion, tensile stress in the V2O5 increases gradually until the α- to ε-phase and ε- to δ-phase transitions occur. The Raman intensity change at 148 cm−1 shows that the level of disorder increases during lithium insertion and progressively recovers the V2O5 lattice during lithium extraction. Results are in good agreement with the expected mechanical behavior and disorder change in V2O5, highlighting the potential of microelectromechanical systems as enabling tools for advanced scientific investigations. The work presented here will be eventually utilized for optimization of thin film battery electrode performance by achieving fundamental understanding of how stress and microstructural changes are correlated, which will also provide valuable insight into a battery performance degradation mechanism.