fabrication-carbon-based-ionic-electromechanically-active-soft

Fabrication of Carbon-Based Ionic Electromechanically Active Soft Actuators

Ionic electromechanically active capacitive laminates are a type of smart material that move in response to electrical stimulation. Due to the soft, ...

University of Tartu

An artificial muscle composite material consisting of carbide derived carbon (CDC) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF(4)) ionic liquid was modeled using molecular dynamics (MD) simulations, in order to determine the molecular structural rearrangements causing actuation. CDC was represented as separate curved graphene-like flakes with charges of +2, 0 or -2 on each flake, with 24-27 aromatic rings each. The charge distribution in the flakes was determined by PM6 semi-empirical optimization. The pore size distribution of CDC and the density of the material were comparable to experimental data. Molecular structure analysis revealed a preferential parallel orientation for the cations over the negatively charged CDC surfaces, while cationic rotations and reorientations could be observed for positively charged CDC. Changes in the pore occupancy for each ionic type were observed for pore sizes between 4 and 7 Å, which, together with the replacement of large cations with smaller anions, could explain the volume decrease in the anodes (and, vice versa, the volume increase in the cathodes) in this type of actuator.

Molecular dynamics simulations of EMI-BF₄ in nanoporous carbon actuators.

A large-scale effort was carried out to test the performance of seven types of ionic electroactive polymer (IEAP) actuators in space-hazardous environmental factors in laboratory conditions. The results substantiate that the IEAP materials are tolerant to long-term freezing and vacuum environments as well as ionizing Gamma-, X-ray, and UV radiation at the levels corresponding to low Earth orbit (LEO) conditions. The main aim of this material behaviour investigation is to understand and predict device service time for prolonged exposure to space environment. 

Ionic electroactive polymer artificial muscles in space applications.

Structure-activity relationships in a data set of HPV6-E1 helicase ATPase inhibitors were investigated based on two different sets of descriptors. Statistically significant four parameter Quantitative Structure-Activity Relationships (QSAR) models were constructed and validated in both cases (R(2)=0.849; R(2) cv=0.811; F=52.20; s(2)=0.25; N=42). A Fragment based QSAR (FQSAR) approach was applied for developing a fragment-QSAR equation, which enabled the construction of virtual structures for novel ATPase inhibitors with desired or pre-defined activity.

Theoretical modeling of HPV: QSAR and novodesign with fragment approach.

The article deals with a challenging attempt to model and predict "difficult" properties as long-term subchronic oral and inhalation toxicities (90 days) using nonlinear QSAR approach. This investigation is one of the first to tackle such multicomplex properties where we have employed nonlinear models based on artificial neural network for the prediction of NOAEL (no observable adverse effect level). Despite the complex nature of the NOAEL property based on in vivo rat experiments, the successful models can be used as alternative tools to non-animal tests for the initial assessment of these chronic toxicities. The model for oral subchronic toxicity is able to describe 88 %, and the inhalation model 87 % of the statistical variance. For the sake of future predictions, we have also defined in a quantitative way the applicability domain of all neural network models. 

Subchronic Oral and Inhalation Toxicities: a Challenging Attempt for Modeling and Prediction.

The development and implementation of safe-by-design strategies is key for the safe development of future generations of nanotechnology enabled products. The safety testing of the huge variety of nanomaterials that can be synthetized is unfeasible due to time and cost constraints. Computational modeling facilitates the implementation of alternative testing strategies in a time and cost effective way. The development of predictive nanotoxicology models requires the use of high quality experimental data on the structure, physicochemical properties and bioactivity of nanomaterials. The FP7 Project MODERN has developed and evaluated the main components of a computational framework for the evaluation of the environmental and health impacts of nanoparticles. This chapter describes each of the elements of the framework including aspects related to data generation, management and integration; development of nanodescriptors; establishment of nanostructure-activity relationships; identification of nanoparticle categories; hazard ranking and risk assessment.

An Integrated Data-Driven Strategy for Safe-by-Design Nanoparticles: The FP7 MODERN Project.

Human papillomaviruses (HPVs) are oncogenic viruses that cause numerous different cancers as well as benign lesions in the epithelia. To date, there is no effective cure for an ongoing HPV infection. Here, we describe the generation process of a platform for the development of anti-HPV drugs. This system consists of engineered full-length HPV genomes that express reporter genes for evaluation of the viral copy number in all three HPV replication stages. We demonstrate the usefulness of this system by conducting high-throughput screens to identify novel high-risk HPV-specific inhibitors. At least five of the inhibitors block the function of Tdp1 and PARP1, which have been identified as essential cellular proteins for HPV replication and promising candidates for the development of antivirals against HPV and possibly against HPV-related cancers.

Identification of several high-risk HPV inhibitors and drug targets with a novel high-throughput screening assay.

Cancer cells have unique but widely varying characteristics that have proven them difficult to be treated by classical therapeutics and calls for novel and selective treatment options. Nanomaterials (NMs) have been shown to display biological effects as a function of their chemical composition, and the extent and exact nature of these effects can vary between different biological environments. Here, ZnO NMs are doped with increasing levels of Fe, which allows to finely tune their dissolution rate resulting in significant differences in their biological behavior on cancer or normal cells. Based on in silico analysis, 2% Fe-doped ZnO NMs are found to be optimal to cause selective cancer cell death, which is confirmed in both cultured cells and syngeneic tumor models, where they also reduce metastasis formation. These results show that upon tuning NM chemical composition, NMs can be designed as a targeted selective anticancer therapy.

In Silico Design of Optimal Dissolution Kinetics of Fe-Doped ZnO Nanoparticles Results in Cancer-Specific Toxicity in a Preclinical Rodent Model.

In the search for novel tools to combat cancer, nanoparticles (NPs) have attracted a lot of attention. Recently, the controlled release of cancer-cell-killing metal ions from doped NPs has shown promise, but fine tuning of dissolution kinetics is required to ensure specificity and minimize undesirable toxic side-effects. Theoretical tools to help in reaching a proper understanding and finally be able to control the dissolution kinetics by NP design have not been available until now. Here, we present a novel set of true nanodescriptors to analyze the charge distribution, the effect of doping and surface coating of whole metal oxide NP structures. The polarizable model of oxygen atoms enables light to be shed on the charge distribution on the NP surface, allowing the in detail study of the factors influencing the release of metal ions from NPs. The descriptors and their capabilities are demonstrated on a Fe-doped ZnO nanoparticle system, a system with practical outlook and available experimental data.

Fe-Doped ZnO nanoparticle toxicity: assessment by a new generation of nanodescriptors.

Either as salts or room temperature ionic liquids, fluorinated anion-based electrolytes have been a common choice for ionic electroactive polymer actuators, both linear and bending. In the present work, propylene carbonate solutions of four electrolytes of the three hugely popular anions-triflouromethanesulfonate, bis(trifluoromethane)sulfonimide, and hexafluorophosphate were compared and evaluated in polypyrrole linear actuators. The actuation direction, the characteristics-performance relations influence the behavior of the actuators. Isotonic Electro-chemo-mechanical deformation (ECMD) measurements were performed to study the response of the PPy/DBS samples. The highest strain for pristine PPy/DBS linear actuators was found in range of 21% for LiTFSI, while TBAPF had the least cation involvement, suggesting the potential for application in durable and controllable actuators. Interesting cation effects on the actuation of the same anions (CFSO) were also observed.

Comparative Analysis of Fluorinated Anions for Polypyrrole Linear Actuator Electrolytes.

Glucose-gelatin nanofiber scaffolds were made conductive and electroactive by chemical (conductive fiber scaffolds, CFS) and additionally electrochemical polypyrrole deposition (doped with triflouromethanesulfonate CFSO, CFS-PPyTF). Both materials were investigated in their linear actuation properties in cell culture medium (CCM), as they could be potential electro-mechanically activated cell growth substrates. Independent of the deposition conditions, both materials showed relatively stable cation-driven actuation in CCM, based on the flux of mainly Na ions from CCM. The surprising result was attributed to re-doping by sulfate anions in CCM, as also indicated by energy-dispersive X-ray (EDX) spectroscopy results. Overall, the electrochemically coated material outperformed the one with just chemical coating in conductivity, charge density and actuation response.

Electrochemomechanical Behavior of Polypyrrole-Coated Nanofiber Scaffolds in Cell Culture Medium.

An inseparable part of ionic actuator characterization is a set of adequate measurement devices. Due to significant limitations of available commercial systems, in-house setups are often employed. The main objective of this work was to develop a software solution for running isotonic and isometric experiments on a hardware setup consisting of a potentiostat, a linear displacement actuator, a force sensor, and a voltmeter for measuring the force signal. A set of functions, hardware drivers, and measurement automation algorithms were developed in the National Instruments LabVIEW 2015 system. The result is a software called isotonic (displacement) and isometric (force) electro-chemo-measurement software (IIECMS), that enables the user to control isotonic and isometric experiments over a single compact graphical user interface. The linear ionic actuators chosen as sample systems included different materials with different force and displacement characteristics, namely free-standing polypyrrole films doped with dodecylbenzene sulfonate (PPy/DBS) and multiwall carbon nanotube/carbide-derived carbon (MWCNT-CDC) fibers. The developed software was thoroughly tested with numerous test samples of linear ionic actuators, meaning over 200 h of experimenting time where over 90% of the time the software handled the experiment process autonomously. The uncertainty of isotonic measurements was estimated to be 0.6 µm (0.06%). With the integrated correction algorithms, samples with as low as 0 dB signal-to-noise ratio (SNR) can be adequately described.

Hardware and Software Development for Isotonic Strain and Isometric Stress Measurements of Linear Ionic Actuators.

Polypyrrole (PPy) based electroactive materials are important building blocks for the development of flexible electronics, bio-sensors and actuator devices. As the properties and behavior of PPy depends strongly on the operating environment-electrolyte, solvent, etc., it is desirable to plant immobile ionic species into PPy films to ensure stable response. A premade ionic polymer is not optimal in many cases, as it enforces its own structure on the conducting polymer, therefore, polymerization during fabrication is preferred. Pyrrole (Py) was electropolymerized at low temperature together with a polymerizable ionic liquid (PIL) monomer in a one-step polymerization, to form a stable film on the working electrode. The structure and morphology of the PPyPIL films were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), Fourier-transform infrared (FTIR) spectroscopy and solid-state NMR (ssNMR) spectroscopy. The spectroscopy results confirmed the successful polymerization of Py to PPy and PIL monomer to PIL. The presence of (TFSI) anions that balance the charge in PPyPIL was confirmed by EDX analysis. The electrical properties of PPyPIL in lithium bis(trifluoromethanesulfonyl)-imide (LiTFSI) aqueous and propylene carbonate solutions were examined with cyclic voltammetry (CV), chronoamperometry, and chronopotentiometry. The blend of PPyPIL had mixed electronic/ionic conductive properties that were strongly influenced by the solvent. In aqueous electrolyte, the electrical conductivity was 30 times lower and the diffusion coefficient 1.5 times higher than in the organic electrolyte. Importantly, the capacity, current density, and charge density were found to stay consistent, independent of the choice of solvent.

Improving the Electrochemical Performance and Stability of Polypyrrole by Polymerizing Ionic Liquids.

Combining ink-jet printing and one of the most stable electroactive materials, PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)), is envisaged to pave the way for the mass production of soft electroactive materials. Despite its being a well-known electroactive material, widespread application of PEDOT:PSS also requires good understanding of its response. However, agreement on the interpretation of the material's activities, notably regarding actuation, is not unanimous. Our goal in this work is to study the behavior of trilayers with PEDOT:PSS electrodes printed on either side of a semi-interpenetrated polymer network membrane in propylene carbonate solutions of three different electrolytes, and to compare their electroactive, actuation, and energy storage behavior. The balance of apparent faradaic and non-faradaic processes in each case is discussed. The results show that the primarily cation-dominated response of the trilayers in the three electrolytes is actually remarkably different, with some rather uncommon outcomes. The different balance of the apparent charging mechanisms makes it possible to clearly select one electrolyte for potential actuation and another for energy storage application scenarios.

Article	Year
Molecular dynamics simulations of EMI-BF₄ in nanoporous carbon actuators. Journal of molecular modeling\| PubMed ID: 21805129	2012
Ionic electroactive polymer artificial muscles in space applications. Scientific reports\| PubMed ID: 25372857	2014
Theoretical modeling of HPV: QSAR and novodesign with fragment approach. Current computer-aided drug design\| PubMed ID: 25479379	2014
Subchronic Oral and Inhalation Toxicities: a Challenging Attempt for Modeling and Prediction. Molecular informatics\| PubMed ID: 27480232	2013
An Integrated Data-Driven Strategy for Safe-by-Design Nanoparticles: The FP7 MODERN Project. Advances in experimental medicine and biology\| PubMed ID: 28168671	2017
Identification of several high-risk HPV inhibitors and drug targets with a novel high-throughput screening assay. PLoS pathogens\| PubMed ID: 28182794	2017
In Silico Design of Optimal Dissolution Kinetics of Fe-Doped ZnO Nanoparticles Results in Cancer-Specific Toxicity in a Preclinical Rodent Model. Advanced healthcare materials\| PubMed ID: 28230930	2017
Fe-Doped ZnO nanoparticle toxicity: assessment by a new generation of nanodescriptors. Nanoscale\| PubMed ID: 30452031	2018
Comparative Analysis of Fluorinated Anions for Polypyrrole Linear Actuator Electrolytes. Polymers\| PubMed ID: 31083347	2019
Electrochemomechanical Behavior of Polypyrrole-Coated Nanofiber Scaffolds in Cell Culture Medium. Polymers\| PubMed ID: 31200448	2019
Hardware and Software Development for Isotonic Strain and Isometric Stress Measurements of Linear Ionic Actuators. Polymers\| PubMed ID: 31212942	2019
Improving the Electrochemical Performance and Stability of Polypyrrole by Polymerizing Ionic Liquids. Polymers\| PubMed ID: 31935858	2020
Printed PEDOT:PSS Trilayer: Mechanism Evaluation and Application in Energy Storage. Materials (Basel, Switzerland)\| PubMed ID: 31968612	2020

Tarmo Tamm

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