Molecular dynamics simulation of polymer helix formation using rigid-link methods

Molecular dynamics simulations are used to study structure formation in simple model polymer chains that are subject to excluded volume and torsional interactions. The changing conformations exhibited by chains of different lengths under gradual cooling are followed until each reaches a state from which no further change is possible. The interactions are chosen so that the true ground state is a helix, and a high proportion of simulation runs succeed in reaching this state; the fraction that manage to form defect-free helices is a function of both chain length and cooling rate. In order to demonstrate behavior analogous to the formation of protein tertiary structure, additional attractive interactions are introduced into the model, leading to the appearance of aligned, antiparallel helix pairs. The simulations employ a computational approach that deals directly with the internal coordinates in a recursive manner; this representation is able to maintain constant bond lengths and angles without the necessity of treating them as an algebraic constraint problem supplementary to the equations of motion.Comment: 15 pages, 14 figure

Augmenting Control over Exploration Space in Molecular Dynamics Simulators to Streamline De Novo Analysis through Generative Control Policies

This study introduces the P5 model - a foundational method that utilizes reinforcement learning (RL) to augment control, effectiveness, and scalability in molecular dynamics simulations (MD). Our innovative strategy optimizes the sampling of target polymer chain conformations, marking an efficiency improvement of over 37.1%. The RL-induced control policies function as an inductive bias, modulating Brownian forces to steer the system towards the preferred state, thereby expanding the exploration of the configuration space beyond what traditional MD allows. This broadened exploration generates a more varied set of conformations and targets specific properties, a feature pivotal for progress in polymer development, drug discovery, and material design. Our technique offers significant advantages when investigating new systems with limited prior knowledge, opening up new methodologies for tackling complex simulation problems with generative techniques.Comment: ICML 2023 Workshop on Structured Probabilistic Inference (SPIGM) and Generative Modeling, of the International Conference of Machine Learning (ICML

New generation of interactive platforms based on novel printed smart materials

Programa doutoral em Engenharia Eletrónica e de Computadores (área de Instrumentação e Microssistemas Eletrónicos)The last decade was marked by the computer-paradigm changing with other digital devices suddenly becoming available to the general public, such as tablets and smartphones. A shift in perspective from computer to materials as the centerpiece of digital interaction is leading to a diversification of interaction contexts, objects and applications, recurring to intuitive commands and dynamic content that can proportionate more interesting and satisfying experiences. In parallel, polymer-based sensors and actuators, and their integration in different substrates or devices is an area of increasing scientific and technological interest, which current state of the art starts to permit the use of smart sensors and actuators embodied within the objects seamlessly. Electronics is no longer a rigid board with plenty of chips. New technological advances and perspectives now turned into printed electronics in polymers, textiles or paper. We are assisting to the actual scaling down of computational power into everyday use objects, a fusion of the computer with the material. Interactivity is being transposed to objects erstwhile inanimate. In this work, strain and deformation sensors and actuators were developed recurring to functional polymer composites with metallic and carbonaceous nanoparticles (NPs) inks, leading to capacitive, piezoresistive and piezoelectric effects, envisioning the creation of tangible user interfaces (TUIs). Based on smart polymer substrates such as polyvinylidene fluoride (PVDF) or polyethylene terephthalate (PET), among others, prototypes were prepared using piezoelectric and dielectric technologies. Piezoresistive prototypes were prepared with resistive inks and restive functional polymers. Materials were printed by screen printing, inkjet printing and doctor blade coating. Finally, a case study of the integration of the different materials and technologies developed is presented in a book-form factor.A última década foi marcada por uma alteração do paradigma de computador pelo súbito aparecimento dos tablets e smartphones para o público geral. A alteração de perspetiva do computador para os materiais como parte central de interação digital levou a uma diversificação dos contextos de interação, objetos e aplicações, recorrendo a comandos intuitivos e conteúdos dinâmicos capazes de tornarem a experiência mais interessante e satisfatória. Em simultâneo, sensores e atuadores de base polimérica, e a sua integração em diferentes substratos ou dispositivos é uma área de crescente interesse científico e tecnológico, e o atual estado da arte começa a permitir o uso de sensores e atuadores inteligentes perfeitamente integrados nos objetos. Eletrónica já não é sinónimo de placas rígidas cheias de componentes. Novas perspetivas e avanços tecnológicos transformaram-se em eletrónica impressa em polímeros, têxteis ou papel. Neste momento estamos a assistir à redução da computação a objetos do dia a dia, uma fusão do computador com a matéria. A interatividade está a ser transposta para objetos outrora inanimados. Neste trabalho foram desenvolvidos atuadores e sensores e de pressão e de deformação com recurso a compostos poliméricos funcionais com tintas com nanopartículas (NPs) metálicas ou de base carbónica, recorrendo aos efeitos capacitivo, piezoresistivo e piezoelétrico, com vista à criação de interfaces de usuário tangíveis (TUIs). Usando substratos poliméricos inteligentes tais como fluoreto de polivinilideno (PVDF) ou politereftalato de etileno (PET), entre outos, foi possível a preparação de protótipos de tecnologia piezoelétrica ou dielétrica. Os protótipos de tecnologia piezoresistiva foram feitos com tintas resistivas e polímeros funcionais resistivos. Os materiais foram impressos por serigrafia, jato de tinta, impressão por aerossol e revestimento de lâmina doctor blade. Para terminar, é apresentado um caso de estudo da integração dos diferentes materiais e tecnologias desenvolvidos sob o formato de um livro.This project was supported by FCT – Fundação para a Ciência e a Tecnologia, within the doctorate grant with reference SFRH/BD/110622/2015, by POCH – Programa Operacional Capital Humano, and by EU – European Union

Cubosomes from hierarchical self-assembly of poly(ionic liquid) block copolymers

Cubosomes are micro- and nanoparticles with a bicontinuous cubic two-phase structure, reported for the self-assembly of low molecular weight surfactants, for example, lipids, but rarely formed by polymers. These objects are characterized by a maximum continuous interface and high interface to volume ratio, which makes them promising candidates for efficient adsorbents and host-guest applications. Here we demonstrate self-assembly to nanoscale cuboidal particles with a bicontinuous cubic structure by amphiphilic poly(ionic liquid) diblock copolymers, poly(acrylic acid)-block-poly(4-vinylbenzyl)-3-butyl imidazolium bis(trifluoromethylsulfonyl)imide, in a mixture of tetrahydrofuran and water under optimized conditions. Structure determining parameters include polymer composition and concentration, temperature, and the variation of the solvent mixture. The formation of the cubosomes can be explained by the hierarchical interactions of the constituent components. The lattice structure of the block copolymers can be transferred to the shape of the particle as it is common for atomic and molecular faceted crystals

Microencapsulation of Corrosion Indicators for Smart Coatings

A multifunctional smart coating for the autonomous detection, indication, and control of corrosion is been developed based on microencapsulation technology. This paper summarizes the development, optimization, and testing of microcapsules specifically designed for early detection and indication of corrosion when incorporated into a smart coating. Results from experiments designed to test the ability of the microcapsules to detect and indicate corrosion, when blended into several paint systems, show that these experimental coatings generate a color change, indicative of spot specific corrosion events, that can be observed with the naked eye within hours rather than the hundreds of hours or months typical of the standard accelerated corrosion test protocols.. Key words: smart coating, corrosion detection, microencapsulation, microcapsule, pH-sensitive microcapsule, corrosion indicator, corrosion sensing pain

Cyclopentyl Trisilanol Silsesquioxanes – Modified Natural Rubber (CpSSQ(OH)3 – ENR-50) Nanocomposite In The Presence Of Tin (II) Chloride Dihydrate

A nanocomposite comprising cyclopentyl trisilanol silsesquioxanes (CpSSQ(OH)3) and 50% epoxidized natural rubber (ENR-50) was prepared at reflux temperature with Tin (II) chloride dihydrate (SnCl2.2H2O) as catalyst. SnCl2.2H2O was found to be an affective catalyst to promote ring opening in ENR-50 and tailored it to CpSSQ(OH)3 via chemical reaction. The generation of carbonyl functional groups arising from epoxide ring opening can be clearly seen in FTIR spectra. 1H and 29Si NMR analyses further proved that the incorporation of CpSSQ(OH)3 in ENR-50 occured. TGA studies showed a degradation temperature with 10% weight decreased and DSC thermogram indicates a single Tg. Single peak in XRD diffractogram at 2-Theta angle further confirmed the surface modification

Fully (Re)configurable Interactive Material through a Switchable Photothermal Charge Transfer Complex Gated by a Supramolecular Liquid Crystal Elastomer Actuator

Charge transfer complexes (CTCs) based on self-assembled donor and acceptor molecules allow light absorption of significantly redshifted wavelengths to either the donor or acceptor. In this work, we demonstrate a CTC embedded in a hydrogen-bonded liquid crystal elastomer (LCE), which in itself is fully reformable and reprocessable. The LCE host acts as a gate, directing the self-assembly of the CTC. When hydrogen bonding is present, the CTC behaves as a near-infrared (NIR) dye allowing photothermal actuation of the LCE. The CTC can be disassembled in specific regions of the LCE film by disrupting the hydrogen bond interactions, allowing selective NIR heating and localized actuation of the films. The metastable non-CTC state may persist for weeks or can be recovered on demand by heat treatment. Besides the CTC variability, the capability of completely reforming the shape, color, and actuation mode of the LCE provides an interactive material with unprecedented application versatility