Morphology- and ion size-induced actuation of carbon nanotube architectures

ABSTRACT

Future adaptive applications require lightweight and stiff materials with high active strain but low energy consumption. A suitable combination of these properties is offered by carbon nanotube-based actuators. Papers made of carbon nanotubes (CNTs) are charged within an electrolyte, which results in an electrical field forming a double-layer of ions at their surfaces and a deflection of the papers can be detected. Until now, there is no generally accepted theory for the actuation mechanism. This study focuses on the actuation mechanism of CNT papers, which represent architectures of randomly oriented CNTs. The samples are tested electrochemically in an in-plane set-up to detect the free strain. The elastic modulus of the CNT papers is analyzed in a tensile test facility. The influence of various ion sizes of water-based electrolytes is investigated.

During the tests, four parameters that have a significant influence on the mechanical performance of CNT papers were identified: the test conditions, the electrical charging, the microstructure and the ion size. All of these influencing factors point to the mechanically weak inter-tube linking at which the actuation seems to take place. Quadratic voltage-strain correlation suggests a combination of electrostatic and volumetric effects as the possible reason for CNT paper actuation.

Abbreviations: CNT: carbon nanotubes; CV: cyclic voltammetry; CVD: chemical vapor deposition; HiPCO: high pressure carbon monoxide; IL: ionic liquid; MWCNT: multi-walled carbon nanotube; MW: multi-walled; NHE: normal hydrogen electrode; PDMS: polydimethylsiloxane; PMMA: polymethylmethacrylate; PPy: polypyrrole; PVDF: polyvinylidenefluoride; SCE: saturated calomel electrode; SWCNT: single-walled carbon nanotube; SW: single-walled; 1M: one molar concentration     

Long term stability of electrocaloric response in barium zirconate titanate

The stability of the electrocaloric effect under electric field cycling is an important consideration in the development of solid-state cooling devices. Here we report measurements carried out on Ba(Zr_0.2Ti_0.8)O₃ ceramics which reveal that the adiabatic temperature change, polarization-electric field hysteresis loops and dielectric permittivity/loss show stable behavior up to 10⁵ cycles. We further demonstrate that the loss in electrocaloric response observed after 10⁵ cycles is associated with the migration of oxygen vacancies. As a result, the electrical properties of the material are changed leading to an increase in leakage current and Joule heating. Reversing the polarity of the electric field after every 10⁵ cycles changes the migration direction of oxygen vacancies, thereby preventing charge accumulation at grain boundaries and electrodes. By doing so, the electrocaloric stability is improved and the adiabatic temperature remains constant even after 10⁶ cycles, much higher than achieved in commercially available barium titanate ceramics.     

Evaluation of polycaprolactone − poly‐D,L‐lactide copolymer as biomaterial for breast tissue engineering

The potential of the copolymer polycaprolactone‐co‐ poly‐d ,l ‐lactic acid (PCLLA ) as a biomaterial for scaffold‐based therapy for breast tissue engineering applications was assessed. First, the synthesized PCLLA was evaluated for its processability by means of additive manufacturing (AM ). We found that the synthesized PCLLA could be fabricated into scaffolds with an overall gross morphology and porosity similar to that of polycaprolactone. The PCLLA scaffolds possessed a compressive Young's modulus (ca 46 kPa ) similar to that of native breast (0.5 ? 25 kPa ), but lacked thermal stability and underwent thermal degradation during the fabrication process. The PCLLA scaffolds underwent rapid degradation in vitro which was characterized by loss of the scaffolds' mechanical integrity and a drastic decrease in mass‐average molar mass (M _w) and number‐average molar mass (M _n) after 4 weeks of immersion in phosphate buffer solution maintained at 37 °C. The tin‐catalysed PCLLA scaffold was also found to have cytotoxic effects on cells. Although the initial mechanical properties of the PCLLA scaffolds generally showed potential for applications in breast tissue regeneration, the thermal stability of the copolymer for AM processes, biocompatibility towards cells and degradation rate is not satisfactory at this stage. Therefore, we conclude that research efforts should be geared towards fine‐tuning the copolymer synthesizing methods. © 2016 Society of Chemical Industry     

Reactor Concept for Contactless Kinetic Measurement in Oscillating Droplets via Raman Spectroscopy

A millistructured reactor and spectroscopic setup for contactless kinetic measurements in oscillating droplets is presented in this work. The polymerization of acrylic acid serves as a model reaction. Design and construction of the reactor focus on the optical access for Raman measurement, the nearly isothermal behavior, and the preservation of droplets during long‐term reactions with a high increase of viscosity. Another key aspect is the possibility of full automation at a later stage.     

Evaluation of dynamic modulus measurement for C/C-SiC composites at different temperatures

The determination of elastic properties at application temperature is fundamental for the design of fibre reinforced ceramic composite components. An attractive method to characterize the flexural modulus at room and high temperature under specific atmosphere is the nondestructive Resonant Frequency Damping Analysis (RFDA). The objective of this paper was to evaluate and validate the modulus measurement via RFDA for orthotropic C/C-SiC composites at the application temperature. At room temperature flexural moduli of C/C-SiC with 0/90° reinforcement were measured under quasi-static 4-point bending loads and compared with dynamic moduli measured via RFDA longitudinally to fibre direction. The dynamic modulus of C/C-SiC was then measured via RFDA up to 1250°C under flowing inert gas and showed an increase with temperature which fitted with literature values. The measured fundamental frequencies were finally compared to those resulting from numerical modal analyses. Dynamic and quasi-static flexural moduli are comparable and the numerical analyses proved that bending modes are correctly modeled by means of dynamic modulus measured via RFDA. The nondestructive RFDA as well as the numerical modeling approach are suitable for evaluation of C/C-SiC and may be transferred to other fibre reinforced ceramic composite materials.     

A Highly Potent and Cellularly Active β‐Peptidic Inhibitor of the p53/hDM2 Interaction

New and improved : The incorporation of a 6‐chlorotryptophan (6‐Cl‐Trp) into a β‐peptide (M)‐3₁₄ helix leads to a high‐affinity hDM2 inhibitor, as demonstrated by fluorescence fluctuation analysis at single molecule resolution. When conjugated to penetratin, the newly derived hDM2 binder specifically inhibits tumour cell growth in vitro.

     

Stray current-induced corrosion in cathodic protection installations of steel-reinforced concrete structures: FEM study of the critical parameters

A wide range of parameters was investigated by numerical calculations concerning their impact on DC stray current corrosion of reinforced concrete (RC) structures. A simplified model geometry was used to extract the relevant parameters and their interaction in terms of stray current-affected structures. This study mainly focuses on RC structures that are fitted with cathodic protection installations. The findings reveal a complex interaction between the investigated parameters. The possible relevance of further parameters, which is not the subject of this study, was emphasised.     

De Novo Missense Mutations in TNNC1 and TNNI3 Causing Severe Infantile Cardiomyopathy Affect Myofilament Structure and Function and Are Modulated by Troponin Targeting Agents

Rare pediatric non-compaction and restrictive cardiomyopathy are usually associated with a rapid and severe disease progression. While the non-compaction phenotype is characterized by structural defects and is correlated with systolic dysfunction, the restrictive phenotype exhibits diastolic dysfunction. The molecular mechanisms are poorly understood. Target genes encode among others, the cardiac troponin subunits forming the main regulatory protein complex of the thin filament for muscle contraction. Here, we compare the molecular effects of two infantile de novo point mutations in TNNC1 (p.cTnC-G34S) and TNNI3 (p.cTnI-D127Y) leading to severe non-compaction and restrictive phenotypes, respectively. We used skinned cardiomyocytes, skinned fibers, and reconstituted thin filaments to measure the impact of the mutations on contractile function. We investigated the interaction of these troponin variants with actin and their inter-subunit interactions, as well as the structural integrity of reconstituted thin filaments. Both mutations exhibited similar functional and structural impairments, though the patients developed different phenotypes. Furthermore, the protein quality control system was affected, as shown for TnC-G34S using patient’s myocardial tissue samples. The two troponin targeting agents levosimendan and green tea extract (-)-epigallocatechin-3-gallate (EGCg) stabilized the structural integrity of reconstituted thin filaments and ameliorated contractile function in vitro in some, but not all, aspects to a similar degree for both mutations.     

Hemi- and Homozygous Loss-of-Function Mutations in DSG2 (Desmoglein-2) Cause Recessive Arrhythmogenic Cardiomyopathy with an Early Onset

About 50% of patients with arrhythmogenic cardiomyopathy (ACM) carry a pathogenic or likely pathogenic mutation in the desmosomal genes. However, there is a significant number of patients without positive familial anamnesis. Therefore, the molecular reasons for ACM in these patients are frequently unknown and a genetic contribution might be underestimated. Here, we used a next-generation sequencing (NGS) approach and in addition single nucleotide polymor-phism (SNP) arrays for the genetic analysis of two independent index patients without familial medical history. Of note, this genetic strategy revealed a homozygous splice site mutation (DSG2–c.378+1G>T) in the first patient and a nonsense mutation (DSG2–p.L772X) in combination with a large deletion in DSG2 in the second one. In conclusion, a recessive inheritance pattern is likely for both cases, which might contribute to the hidden medical history in both families. This is the first report about these novel loss-of-function mutations in DSG2 that have not been previously identi-fied. Therefore, we suggest performing deep genetic analyses using NGS in combination with SNP arrays also for ACM index patients without obvious familial medical history. In the future, this finding might has relevance for the genetic counseling of similar cases.