Diblock copolymers (BCP) consisting of poly(methyl methacrylate) (PMMA) and poly(1H,1H,2H,2H-perfluorodecyl methacrylate) (PsfMA) blocks are employed as templates for controlled dispersion and localization of multi-walled carbon nanotubes (MWCNT). Short MWCNT are modified with perfluoroalkyl groups to increase the compatibility between MWCNT and the semifluorinated (PsfMA) phase and to promote a defined arrangement of MWCNT in the BCP morphology. Thin BCP and BCP/MWCNT composite films are prepared by dip-coating using tetrahydrofuran as solvent with dispersed MWCNT. Atomic force microscopy, scanning and transmission electron microscopy reveal a strong tendency of the BCP to form micelle-like domains consisting of a PMMA shell and a semifluorinated PsfMA core, embedded in a soft phase, containing also semifluorinated blocks. MWCNT preferentially localized in the embedding phase outside the micelles. Perfluoroalkyl-modification leads to significant improvement in the dispersion of MWCNT, both in the polymer solution and the resulting nanocomposite film due to increased interaction of MWCNT with the semifluorinated side chains in the soft phase outside the micelle domains. As a result, reliable electrical conductivity is observed in contrast to films with non-modified MWCNT. Thus, well-dispersed, modified MWCNT provide a defined electrical conduction path at the micrometer level, which is interesting for applications in electronics and vapor sensing.

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.

The kinetics of homogeneous crystal nucleation and the stability of nuclei were analyzed for a random butylene succinate/butylene adipate copolymer (PBSA), employing Tammann's two-stage crystal nuclei development method, with a systematic variation of the condition of nuclei transfer from the nucleation to the growth stage. Nuclei formation is fastest at around 0 degrees C, which is about 50 K higher than the glass transition temperature and begins after only a few seconds. Due to the high nuclei number, spherulitic growth of lamellae is suppressed. In contrast, numerous mu m-sized birefringent objects are detected after melt-crystallization at high supercooling, which, at the nanometer-scale, appear composed of short lamellae with a thickness of a few nanometers only. Regarding the stability of nuclei generated at -30 degrees C for 100 s, it was found that the largest nuclei of the size-distribution survive temperature jumps of close to 80 K above their formation temperature. The critical transfer-heating rate to suppress the reorganization of isothermally formed nuclei as well as the formation of additional nuclei during heating increases with the growth temperature at temperatures lower than the maximum of the crystallization rate. This observation highlights the importance of careful selection of the transfer-heating rate and nuclei development temperature in Tammann's experiment for evaluation of the nucleation kinetics.

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.

Crystallization of poly(l-lactic acid) (PLLA) at temperatures lower and higher than about 100-120 degrees C leads to the formation of alpha '- and alpha-crystals, respectively. Related to the formation of different crystal polymorphs after crystallization at different temperatures, the small-angle X-ray scattering (SAXS) patterns only show a long-period maximum after crystallization at high temperatures, when alpha-crystals are present. Reason for the absence of a long-period peak after low-temperature crystallization is insufficient density contrast between the formed alpha '-crystals and the amorphous phase but not the absence of lamellar stacks and long-range periodicity. This conclusion is based on the observation of a long period after the transformation of alpha '-crystals of rather low density into alpha-crystals of higher density, by thermal treatment, while keeping the semicrystalline morphology quasi-unchanged. Long-range periodicity and formation of lamellae in PLLA containing alpha '-crystals are ultimately proven by atomic force microscopy, despite a long period is not detected by SAXS.

Melt-crystallization of poly (butylene succinate) (PBS) at largely different melt-supercooling was analyzed by Xray scattering techniques, direct imaging using microscopy, and by fast scanning chip calorimetry, with the latter employed to achieve high melt-supercooling. Crystallization at 100 and 20 degrees C, representing structure formation at low and high melt-supercooling, respectively, yields lamellae with thicknesses of around 8 and 4 nm. In both cases, lamellar thickening is excluded as main mechanism of isothermal secondary crystallization, suggesting that absence of intracrystalline chain-sliding diffusion is not dependent on the absolute value of the thickness of lamellae. The wide-angle X-ray pattern of PBS crystallized at low temperature shows less and broader peaks than in case of PBS crystallized at high temperature, pointing to presence of crystal defects, and causing an enlargement of the unit cell. Secondary crystallization leads to an increase of the melting temperature, being distinctly larger (per unit annealing time) for low-temperature crystallized PBS. Since lamellar thickening is absent, and imperfection of the bulk crystal structure persists even on long-term annealing, merging of crystalline blocks and lateral crystal growth at the crystallization temperature, for explaining the observed increases of the crystallinity and melting temperature, are suggested. Though there is detected a large rigid amorphous fraction in PBS crystallized at high supercooling, vitrification only occurs continuously on cooling, after the isothermal crystallization process.

Abstract The unusual features of the nonlinear dynamic response of nanocomposite beams made of polybutylene terephthalate (PBT) and branched carbon nanotubes (bCNTs) are documented experimentally. The frequency response curves for cantilever specimens with different bCNTs weight fractions (wt%) are obtained under harmonic base excitations by measuring the free tip displacement via 3D scanning laser vibrometry. The steady-state response acquired for different excitation levels exhibits a surprising nonlinear softening trend which is switched into hardening for higher bCNTs wt% and increasing oscillation amplitudes. The stick-slip hysteresis, caused by the interaction of the bCNTs with the thermoplastic hosting matrix, determines a softening nonlinearity of the material that counteracts the well-known geometric hardening associated with the nonlinear curvature of the first mode of the cantilever. However, for bCNTs weight fractions greater than 1%, the bridging of the branched CNTs gives rise to the formation of a strong network which contributes to the hardening response at higher oscillation amplitudes. This mechanical behavior is detected by the trend of the nonlinear harmonic spectra and by the estimation of the equivalent damping ratio using the half power bandwidth method. A nonlinear mathematical model of the nanocomposite cantilever samples derived from a 3D mesoscale hysteretic model of the PBT/bCNT material is shown to predict the observed unusual experimental behavior. The presence of bCNTs in a thermoplastic matrix seems to be the main driver of the highly tunable nonlinear stiffness and damping capacity.

Crystallization of PBN at high temperature leads to growth of highly non-isometric beta'-crystals, with their long and short dimensions being several mu m and 10-20 nm, respectively. In the needle-like or lamellar crystals, molecular segments/stems are oriented parallel to their short dimension, as concluded from polarized-light optical microscopy (POM). In the early stage, the growth of beta'-crystals is straight while in the later stages, when exceeding a critical length, distinct bending and circular growth occurs. These features cause an unusual appearance of the semicrystalline structure when viewed by POM. The spherulitic growth is uneven in the various directions of space, the spherulite surface appears frayed due to missing space-filling and reduced branching, and the finally curly crystal morphology yields a spotty decoration. The analysis of the morphology of beta'-crystals of PBN is expected yielding an improved understanding of structure-property-relations, as these crystals may form at specific melt-processing conditions.

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.

Amyloid β peptide can aggregate into thin β-sheet fibrils or plaques deposited on the extracellular matrix, which is the hallmark of Alzheimer's disease. Multifunctional macromolecular structures play an important role in inhibiting the aggregate formation of amyloidogenic materials and thus are promising candidates with antiamyloidogenic characteristics for the development of next-generation therapeutics. In this study, we evaluate how small differences in the dendritic topology of these structures influence their antiamyloidogenic activity by the comparison of "perfectly dendritic" and "pseudodendritic" macromolecules, both decorated with mannose units. Their compactness, the position of surface units, and the size of glyco-architectures influence their antiamyloidogenic activity against Aβ 40, a major component of amyloid plaques. For the advanced analysis of the aggregation of the Aβ peptide, we introduce asymmetric flow field flow fractionation as a suitable method for the quantification of large and delicate structures. This alternative method focuses on the quantification of complex aggregates of Aβ 40 and glycodendrimer/glyco-pseudodendrimer over different time intervals of incubation, showing a good correlation to ThT assay and CD spectroscopy results. Kinetic studies of the second-generation glyco-pseudodendrimer revealed maximum inhibition of Aβ 40 aggregates, verified with atomic force microscopy. The second-generation glyco-pseudodendrimer shows the best antiamyloidogenic properties confirming that macromolecular conformation in combination with optimal functional group distribution is the key to its performance. These molecular properties were validated and confirmed by molecular dynamics simulation.

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.

Poly(epsilon-caprolactone) (PCL) was crystallized at high melt-supercooling in a fast scanning chip calorimeter, with this instrumentation needed to reach the temperature range of homogenous crystal nucleation by fast cooling the melt. Subsequently, after slow heating the polymer to ambient temperature, the semicrystalline morphology and X-ray structure were evaluated. Nucleation and crystallization at low temperature yields a featureless structure at the micrometer-length scale, indicating non-spherulitic crystal growth. Images of the nanometer-scale structure suggest presence of irregular grown short lamellae or particle-like domains, and the absence of sharp peaks in the X-ray scattering pattern indicates formation of small or defective crystals. In conclusion, due to the high nuclei density, crystallization of PCL near the glass transition leads to formation of imperfect crystals, and slow heating to ambient temperature does not allow their reorganization to yield long-range orthorhombic order, typically observed on crystallization at low melt-supercooling.

Self-powered tactile module-based electronic skins incorporating triboelectric nanogenerator (TENG) appears to be a worthwhile alternative for smart monitoring devices in terms of sustainable energy harvesting. On top of it, ultra-stretchability and detection sensitivity are imperative to mimic human skin. We report, for the first time, a metal-free single electrode TENG-based self-powered tactile module comprising of microwells (diameters 2 μm and 200 nm, respectively) on fluoroelastomer (FKM) and laser induced graphene (LIG) electrodes by in situ simultaneous transfer printing method. Direct imprinting of both the active surface and LIG electrode on a tribonegative FKM has not been attempted before. The resulting triboelectric module exhibits impressive maximum power density of 715 mW m-2, open circuit voltage and maximum output current of 148 V and 9.6 μA respectively for a matching load of 10 MΩ. Moreover, the TENG unit is very robust and sustained high electrical output even at 200% elongation. A dielectric-to-dielectric TENG-based tactile sensor is also constructed using FKM (negative tribolayer) and TiO2 deposited micropatterned PDMS. Resulting tribo-sensor demonstrates remarkable motion and force sensitivity. It can also distinguish subtle human contact force that can simulate skin with high sensitivity and therefore, can be utilized for potential e-skin/bionic skin applications in health and human-machine interfaces.

This work discusses the mechanical and dissipative properties of nanocomposite materials made of a high-performance thermoplastic polymer (polybutylene terephthalate, PBT) integrated with branched carbon nanotubes (bCNTs) as nanofiller. The storage and loss moduli as well as the loss factor/damping ratio of the nanocomposites are experimentally characterized for increasing bCNT weight fractions (wt% bCNT) upon variations of the input cyclic strain amplitude and of the input frequency, respectively. The trends obtained for the nanocomposites mechanical properties indicate improvements both in storage and loss modulus by increasing the bCNT weight fraction from 0.5% to 2%. The striking differences between the damping capacities exhibited by CNT/polymer and bCNT/polymer nanocomposites are discussed to shed light onto the different underlined mechanics of the nanocomposites. Due to the stick–slip relative sliding motion of the polymer chains with respect to the straight CNTs, CNT/PBT nanocomposites are known to exhibit a peak in the damping vs. strain amplitude curves, past which, the damping capacity shows a monotonically increasing trend due to the conjectured sliding of the polymer crystals. On the other hand, we show for the first time that bCNT/PBT nanocomposites do not exhibit a peak in the damping capacity but rather a plateau after an initial drop at low strains. This behavior is attributed to the much reduced mobility of the branched CNTs and the lack of formation of crystalline structures around the bCNTs.

Most sophisticated biological functions and features of cells are based on self-organization, and the coordination and connection between their cell organelles determines their key functions. Therefore, spatially ordered and controllable self-assembly of polymersomes to construct clusters to simulate complex intracellular biological functions has attracted widespread attention. Here, we present a simple one-step copper-free click strategy to cross-link nanoscale pH-responsive and photo-cross-linked polymersomes (less than 100 nm) to micron-level clusters (more than 90% in 0.5-2 μm range). Various influencing factors in the clustering process and subsequent purification methods were studied to obtain optimal clustered polymeric vesicles. Even when polymeric vesicles separately loaded with different enzymes (glucose oxidase and myoglobin) are coclustered, the overall permeability of the clusters can still be regulated through tuning the pH values on demand. Compared with simple blending of those enzyme-loaded polymersomes, the rate of enzymatic cascade reaction increased significantly due to the interconnected complex microstructure established. The connection of catalytic nanocompartments into clusters confining different enzymes of a cascade reaction provides an excellent platform for the development of artificial systems mimicking natural organelles or cells.

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.

The polymer/solvent system poly (L-lactic acid)/ethyl butylacetylaminopropionate (PLLA/IR3535) is regarded as an insect-repellent-delivery system, serving, e.g., for fighting mosquito-borne tropical diseases. In such systems the solid polymer hosts the liquid repellent, with the latter slowly released to the environment, expelling mosquitoes. As a new approach, exceeding prior work about application of different technologies to obtain such devices, in this work, samples of the polymer/repellent system PLLA/IR3535 were prepared by 3D-printing. The experiments showed that it is possible to print 3D-parts containing up to 25 m% repellent, with an only minor loss of repellent during the printing process. For samples containing low amount of repellent, crystallization of PLLA was suppressed due to the rather fast cooling step and the low bed temperature of around 25.C, being lower than the glass transition temperature of the homogeneous polymer/repellent strands. At higher repellent concentration, due to the lowering of the glass transition temperature to near or even below ambient temperature, the crystallinity slowly increased during storage after printing. For all samples, regardless of the initial repellent concentration, the repellent-release rate increases with temperature, and at ambient temperature the release-time constant is in the order of 10 days. The study successfully proved the applicability of the technology of extrusion-based 3D-printing for the preparation of polymer parts with a specific shape/design containing mosquito-repellent at a concentration which raises the expectation to be used as a repellent delivery-device.

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. Graphical abstract

Demand for direct chemical modification of functional material on a surface is increasing in various fields. A new approach for a functionalized surface is investigated by applying a conventional laser in order to generate chemical activation by photothermal energy. Poly(ethyleneimine) (PEI), with a high density of amino groups, is chemically grafted on poly(methyl methacrylate) (PMMA) by irradiation of a CO2 laser (10.6 μm). Laser parameters such as power, scan rate, and focal length are observed to play an important role in order to introduce effective photothermal energy for the chemical reaction between PEI and PMMA. By optimization of laser parameters, the amide compound is produced as a result of the reaction of amine from PEI and the ester of PMMA successfully. The PMMA surface modified with PEI is analyzed by XPS and TOF-SIMS to identify the functional groups. Furthermore, the surface is characterized in terms of wettability, adhesion force, and surface charge for various applications. Finally, reaction with dye and metal on the amine-terminated PMMA shows promising results in supplying a selective and reliable functional substrate.

The different thermal stabilities of shear-induced pointlike and shishlike crystallization precursors of polyamide 11, generated in a parallel-plate rheometer and coexisting in the same sample, were quantified by hot-stage microscopy, by performing self-seed crystallization experiments. Crystals formed at low supercooling of the melt from these different types of precursors melt at about the same temperature. Annealing of the melt at different temperatures for a predefined time revealed dissolution/disordering of these precursors at 10-15 K higher temperature, near the equilibrium melting point. Despite their similar thermal stabilities, pointlike and shishlike crystallization precursors exhibit distinctly different nucleation efficacies. Under identical crystallization conditions, shishlike precursors cause faster crystallization than pointlike crystal nuclei. The faster crystallization of the shishlike nuclei can be explained, for example, by (a) the larger size of the shishlike precursors, providing numerous nucleation sites; (b) the more perfect chain conformation at the shish surface, which serves as a substrate for crystallization; or perhaps (c) the higher local orientation of the surrounding melt compared with molecular segments near pointlike nuclei, reducing the activation energy for crystallization.