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In this experimental study, we investigate the nonlinear dynamic response of nanocomposite beams composed of polybutylene terephthalate (PBT) and branched carbon nanotubes (bCNTs). By varying the weight fraction of bCNTs, we obtain frequency response curves for cantilever specimens under harmonic base excitations, measuring the tip displacement via 3D scanning laser vibrometry. Our findings reveal a surprising nonlinear softening trend in the steady-state response of the cantilevers, which gets switched into hardening for higher bCNT weight fractions and increasing oscillation amplitudes. The interaction of bCNTs with the thermoplastic hosting matrix results in stick-slip hysteresis, causing a softening nonlinearity that counteracts the geometric hardening associated with the nonlinear curvature of the first mode of the cantilever. However, when the weight fraction of bCNTs is greater than 1%, the bridging of the branched CNTs leads to the formation of a strong network that contributes to the hardening response at higher oscillation amplitudes. This mechanical behavior is detected by the trend of the nonlinear harmonic spectra and the equivalent damping ratio estimated using the half-power bandwidth method. To predict the observed unusual experimental behavior, we use a nonlinear mathematical model of the nanocomposite cantilever samples derived from a 3D mesoscale hysteretic model of the PBT/bCNT material. Our results suggest that the presence of bCNTs in a thermoplastic matrix is the main driver of the highly tunable nonlinear stiffness and damping capacity of the material. The reported experimental and modeling results provide valuable insights into the nonlinear dynamic behavior of PBT/bCNT nanocomposites and have potential applications in the design of advanced materials with tailored mechanical properties.

Despite significant advances in cancer treatment, several challenges persist in optimizing effective cargo delivery, including enhancing bioavailability, improving targeted delivery, and overcoming biological barriers for improved tumor tissue penetration. There is an urgent need for versatile carriers capable of multi‐functional targeting without compromising functionality. Here, we report a dual surface modification strategy to enhance the therapeutic efficacy of microrobotic platforms, through controlled, site‐specific drug release. This dual functionalization integrates two distinct pH‐sensitive polymeric nanoreservoirs with different membrane permeability. One nanoreservoir is engineered to release an antitumor agent ‐curcumin‐ in response to the acidic tumor microenvironment, while the second is designed to degrade the tumor extracellular matrix via enzymatic activity, facilitating enhanced diffussion of the therapeutic agent. This dual surface modification approach represents a significant advancement in the customizable integration of multifunctional nanoreservoirs. By leveraging dual compartmentalization, it prevents deactivation and cross‐process interference, enabling precise nanoscale combination therapies for microrobotic cancer treatment. These surface‐engineered microrobots hold promise for overcoming physiological barriers, ensuring stable cargo transport, and broadening the applicability of microrobotic platforms across diverse cancer types. A microcarrier with dual surface modification integrates two distinct pH‐sensitive nanoreservoirs, enabling precise, site‐specific drug delivery and potential extracellular matrix degradation. This dual functionalization strategy ensures the separation of therapeutic functions, effectively preventing cross‐process interference and aiming synergistic nanoscale combination therapies. This multifunctional system demonstrates strong potential for microrobotic applications in targeted cancer therapy, offering a robust and adaptable approach to enhance therapeutic efficacy.

Single-walled carbon nanotubes (SWCNTs) have unique thermal and electrical properties. Coating them with a thin metal layer can provide promising materials for many applications. This study presents a bio-inspired, environmentally friendly technique for CNT metallization using polydopamine (PDA) as an adhesion promoter, followed by electroless plating with nickel. To improve the dispersion in the aqueous reaction baths, part of the SWCNTs was oxidized prior to PDA coating. The SWCNTs were studied before and after PDA deposition and metallization by scanning and transmission electron microscopy, scanning force microscopy, and X-ray photoelectron spectroscopy. These methods verified the successful coating and revealed that the distribution of PDA and nickel was significantly improved by the prior oxidation step. Thermoelectric characterization showed that the PDA layer acted as a p-dopant, increasing the Seebeck coefficient S of the SWCNTs. The subsequent metallization decreased S, but no negative S-values were reached. Both coatings affected the volume conductivity and the power factor, too. Thus, electroless metallization of oxidized and PDA-coated SWCNTs is a suitable method to create a homogeneous metal layer and to adjust their conduction type, but more work is necessary to optimize the thermoelectric properties.

This work reports on an environmentally friendly method to produce encapsulated phase change material with a thin nickel coating, applicable for heat conversion, storage and thermal management of heat-sensitive components and suitable for active heating by electromagnetic radiation. A critical issue for the metallization is the adhesion between the polymer capsule shell and the metal layer. Based on previous studies using the bio-molecule dopamine as adhesion promoter in composites and for plastics metallization, commercial paraffin microcapsules were coated with an ultrathin polydopamine film via a simple wet chemical process. Subsequently, a thin, uniform and compact nickel layer was produced by electroless metallization. The successful deposition of both layers was verified with a broad range of imaging and spectroscopic techniques. For the first time, surface-enhanced IR spectroscopy was used to study the deposition of ultrathin PDA films. The combination of SEM and energy-dispersive X-ray spectroscopy allowed resolving the spatial distribution of the elements Ni, N, and O in the MC shell. Electrically conducting paths in the Ni shell were verified by conductive AFM. Thermal analysis revealed that the coated microcapsules show a phase change enthalpy of approx. 170 J/g, suitable for thermal storage and management. Additionally, the nickel layer enhanced the thermal diffusivity of the microcapsule powders and enables a fast heating of the PCM microcapsules by microwave radiation, demonstrating the applicability of the metallized MCs for controlled heating applications.

The crystallization behavior of fully biobased poly(butylene isophthalate) (PBI) has been investigated using calorimetric and microscopic techniques. PBI is an extremely slow crystallizing polymer that leads, after melt-crystallization, to the formation of lamellar crystals and rather large spherulites, due to the low nuclei density. Based upon quantitative analysis of the crystal-nucleation behavior at low temperatures near the glass transition, using Tammann’s two-stage nuclei development method, a nucleation pathway for an acceleration of the crystallization process and for tailoring the semicrystalline morphology is provided. Low-temperature annealing close to the glass transition temperature (Tg) leads to the formation of crystal nuclei, which grow to crystals at higher temperatures, and yield a much finer spherulitic superstructure, as obtained after direct melt-crystallization. Similarly to other slowly crystallizing polymers like poly(ethylene terephthalate) or poly(l-lactic acid), low-temperature crystal-nuclei formation at a timescale of hours/days is still too slow to allow non-spherulitic crystallization. The interplay between glass relaxation and crystal nucleation at temperatures slightly below Tg is discussed.

This study followed the approach of dispersing and localizing carbon nanotubes (CNTs) in nanostructured domains of block copolymers (BCPs) by shortening the CNTs via ball milling. The aim was to selectively tune the electrical and mechanical properties of the resulting nanocomposites, e.g., for use as sensor materials. Multiwalled carbon nanotubes (MWCNTs) were ground into different size fractions. The MWCNT length distribution was evaluated via transmission electron microscopy and dynamic light scattering. The nanostructure of the BCPs and the glass transition temperatures of the PB-rich and PS phases were not strongly affected by the addition of CNTs up to 2 wt%. However, AFM and TEM investigations indicated a partial localization of the shortened CNTs in the soft PB-rich phase or at the interface of the PB-rich and PS phase, respectively. The stress-strain behavior of the solution-mixed composites differed little from the mechanical property profile of the neat BCP and was largely independent of CNT amount and CNT size fraction. Significant changes could only be observed for Young’s modulus and strain at break and may be attributed to CNT localization and small changes in morphology. For nanocomposites with unmilled CNTs, the electrical percolation threshold was less than 0.1 wt%. As the CNTs were shortened, the resistivity increased and the percolation threshold shifted to higher CNT contents. Composites with CNTs ground for 7.5 h and 13.5 h showed no bulk conductivity but significantly decreased surface resistivity on the bottom side of the films, which could be attributed to a sedimentation process of the grind and thereby highly compressed CNT agglomerates during evaporation.

State-of-the-art Li batteries suffer from serious safety hazards caused by the reactivity of lithium and the flammable nature of liquid electrolytes. This work develops highly efficient solid-state electrolytes consisting of imidazolium-containing polyionic liquids (PILs) and lithium bis(trifluoromethane sulfonyl)imide (LiTFSI). By employing PIL/LiTFSI electrolyte membranes blended with poly(propylene carbonate) (PPC), we addressed the problem of combining ionic conductivity and mechanical properties in one material. It was found that PPC acts as a mechanically reinforcing component that does not reduce but even enhances the ionic conductivity. While pure PILs are liquids, the tricomponent PPC/PIL/LiTFSI blends are rubber-like materials with a Young’s modulus in the range of 100 MPa. The high mechanical strength of the material enables fabrication of mechanically robust free-standing membranes. The tricomponent PPC/PIL/LiTFSI membranes have an ionic conductivity of 10−6 S·cm−1 at room temperature, exhibiting conductivity that is two orders of magnitude greater than bicomponent PPC/LiTFSI membranes. At 60 °C, the conductivity of PPC/PIL/LiTFSI membranes increases to 10−5 S·cm−1 and further increases to 10−3 S·cm−1 in the presence of plasticizers. Cyclic voltammetry measurements reveal good electrochemical stability of the tricomponent PIL/PPC/LiTFSI membrane that potentially ranges from 0 to 4.5 V vs. Li/Li+. The mechanically reinforced membranes developed in this work are promising electrolytes for potential applications in solid-state batteries.

Application of Toll-like receptor (TLR) agonists is a promising approach to treat cancer. In particular, nucleic acid-based TLR agonists such as short ssRNA and dsRNA molecules, which activate endosomal TLRs, can be delivered to tumors by use of nanoparticle delivery systems. However, such delivery systems bear unspecific side effects and poor pharmacokinetics. To overcome these limitations we developed a system for targeted delivery of a 50 bp dsRNA TLR3 agonist (Riboxxol) to treat PSCA-positive tumor cells, which consists of neutravidin conjugated to mono-biotinylated dsRNA and to humanized mono-biotinylated anti-PSCA single chain antibody derivative scFv(h-AM1)-BAP. The assembly of the components resulted in the formation of nanoparticle-like immunoconjugates designated Rapid Inducer of Cellular Inflammation and Apoptosis (RICIA). Anti-PSCA-RICIA exclusively delivered Riboxxol to PSCA-positive tumor cells as well as subcutaneous tumors. Uptake of anti-PSCA-RICIA induced a type I-interferon response and apoptosis in HEK-Blue hTLR3/PSCA reporter cells and PSCA-positive HT1376 bladder cancer cells in vitro . No such effects were observed when using RICIA coupled to an unspecific control antibody or when using Riboxxol alone. Treatment of HT1376 xenografts in immune-deficient hosts with targeted delivery of TLR3 agonist did not induce adverse effects and only modestly inhibited tumor growth when compared to controls. These results suggest promising activation of innate immune response and apoptosis upon selective delivery of TLR3 agonists in tumor cells. Yet, further studies using syngeneic and orthotopic tumor models are needed to fully exploit the potential of RICIA immunoconjugates.