Cylindrical Zwitterionic Particles via Interpolyelectrolyte Complexation on Molecular Polymer Brushes

The fabrication of macromolecular architectures with high aspect ratio and well‐defined internal and external morphologies remains a challenge. The combination of template chemistry and self‐assembly concepts to construct peculiar polymer architectures via a bottom‐up approach is an emerging approach. In this study, a cylindrical template—namely a core–shell molecular polymer brush—and linear diblock copolymers (DBCP) associate to produce high aspect ratio polymer particles via interpolyelectrolyte complexation. Induced, morphological changes are studied using cryogenic transmission electron and atomic force microscopy, while the complexation is further followed by isothermal titration calorimetry and ξ‐potential measurements. Depending on the nature of the complexing DBCP, distinct morphological differences can be achieved. While polymers with a non‐ionic block lead to internal compartmentalization, polymers featuring zwitterionic domains lead to a wrapping of the brush template

The Impact of Differential Privacy on Recommendation Accuracy and Popularity Bias

Collaborative filtering-based recommender systems leverage vast amounts of behavioral user data, which poses severe privacy risks. Thus, often, random noise is added to the data to ensure Differential Privacy (DP). However, to date, it is not well understood, in which ways this impacts personalized recommendations. In this work, we study how DP impacts recommendation accuracy and popularity bias, when applied to the training data of state-of-the-art recommendation models. Our findings are three-fold: First, we find that nearly all users' recommendations change when DP is applied. Second, recommendation accuracy drops substantially while recommended item popularity experiences a sharp increase, suggesting that popularity bias worsens. Third, we find that DP exacerbates popularity bias more severely for users who prefer unpopular items than for users that prefer popular items.Comment: Accepted at the IR4Good track at ECIR'24, 17 page

Magnetic Material with Large Magnetic-Field-Induced Deformation

A magnetic materials construct and a method to produce the construct are disclosed. The construct exhibits large magnetic-field-induced deformation through the magnetic-field-induced motion of crystallographic interfaces. The construct is a porous, polycrystalline composite structure of nodes connected by struts wherein the struts may be monocrystalline or polycrystalline. If the struts are polycrystalline, they have a bamboo microstructure wherein the grain boundaries traverse the entire width of the strut. The material from which the construct is made is preferably a magnetic shape memory alloy, including polycrystalline Ni-Mn-Ga. The construct is preferably an open-pore foam. The foam is preferably produced with a space-holder technique. Space holders may be dissolvable ceramics and salts including NaAlO2

Visible Light-Driven MADIX Polymerisation via a Reusable, Low-Cost and Non-Toxic Bismuth Oxide Photocatalyst

The continuous amalgamation of photocatalysis into existing reversible deactivation radical polymerisation processes has initiated a rapidly propagating area of polymer research in recent years. We introduce bismuth oxide (Bi2O3) as a heterogeneous photocatalyst for polymerisations, operating at room temperature with visible light. We demonstrate formidable control over degenerative chain-transfer polymerisations, such as macromolecular design by interchange of xanthate (MADIX) and reversible addition-fragmentation chain transfer (RAFT) polymerisation. We achieved narrow molecular weight distributions and attribute the excellent temporal control to a photo-induced electron transfer (PET) process. This methodology was employed to synthesise diblock copolymers combining differently activated monomers. The Bi2O3 catalyst system has the additional benefits of low toxicity, reusability, low-cost, and ease of removal from the reaction mixture.Australian Research Counci

Aspect-ratio-dependent interaction of molecular polymer brushes and multicellular tumour spheroids

Polymer nanoparticles based on molecular polymer brushes allow precise and independent tailoring of nanoparticle characteristics. This enables the synthesis of soft hydrophilic polymer particles with matching composition and surface chemistry where only the aspect-ratio is varied. PEGylated brush nanoparticles revealed that brush nanorods exhibit higher association and penetration into multicellular tumour spheroids compared to their spherical or filamentous counterparts.Australian Research Counci

Self-assembly of diblock molecular polymer brushes in the spherical confinement of nanoemulsion droplets

Understanding the self-assembly behavior of polymers of various topologies is key to a reliable design of functional polymer materials. Self-assembly under confinement conditions emerges as a versatile avenue to design polymer particles with complex internal morphologies while simultaneously facilitating scale-up. However, only linear block copolymers have been studied to date, despite the increasing control over macromolecule composition and architecture available. This study extends the investigation of polymer self-assembly in confinement from regular diblock copolymers to diblock molecular polymer brushes (MPBs). Block-type MPBs with polystyrene (PS) and polylactide (PLA) compartments of different sizes are incorporated into surfactant-stabilised oil-in-water (chloroform/water) emulsions. The increasing confinement in the nanoemulsion droplets during solvent evaporation directs the MPBs to form solid nano/microparticles. Microscopy studies reveal an intricate internal particle structure, including interpenetrating networks and axially-stacked lamellae of PS and PLA, depending on the PS/PLA ratio of the brushes.Australian Research Council. Grant Number: DE180100007 endowed professorship. Grant Number: 2016‐2022 German Research Foundation (DFG). Grant Numbers: 2017‐2022, 37692067

Recent Developments in Ni-Mn-Ga Foam Research

Grain boundaries hinder twin boundary motion in magnetic shape-memory alloys and suppress magnetic-field-induced deformation in randomly textured polycrystalline material. The quest for high-quality single crystals and the associated costs are a major barrier for the commercialization of magnetic shape-memory alloys. Adding porosity to polycrystalline magnetic-shape memory alloys presents solutions for (i) the elimination of grain boundaries via the separation of neighboring grains by pores, and (ii) the reduction of production cost via replacing the directional solidification crystal growth process by conventional casting. Ni-Mn-Ga foams were produced with varying pore architecture and pore fractions. Thermo-magnetic training procedures were applied to improve magnetic-field-induced strain. The cyclic strain was measured in-situ while the sample was heated and cooled through the martensitic transformation. The magnetic field-induced strain amounts to several percent in the martensite phase, decreases continuously during the transformation upon heating, and vanishes in the austenite phase. Upon cooling, cyclic strain appears below the martensite start temperature and reaches a value larger than the initial strain in the martensite phase, thereby confirming a training effect. For Ni-Mn-Ga single crystals, external constraints imposed by gripping the crystal limit lifetime and/or magnetic-field-induced deformation. These constraints are relaxed for foams

A Regenerable Biosensing Platform for Bacterial Toxins

Waterborne diarrheal diseases such as travelers’ diarrhea and cholera remain a threat to public health in many countries. Rapid diagnosis of an infectious disease is critical in preventing the escalation of a disease outbreak into an epidemic. Many of the diagnostic tools for infectious diseases employed today are time-consuming and require specialized laboratory settings and trained personnel. There is hence a pressing need for fit-for-purpose point-of-care diagnostic tools with emphasis in sensitivity, specificity, portability, and low cost. We report work toward thermally reversible biosensors for detection of the carbohydrate-binding domain of the Escherichia coli heat-labile enterotoxin (LTB), a toxin produced by enterotoxigenic E. coli strains, which causes travelers’ diarrhea. The biosensing platform is a hybrid of two materials, combining the optical properties of porous silicon (pSi) interferometric transducers and a thermoresponsive multivalent glycopolymer, to enable recognition of LTB. Analytical performance of our biosensors allows us to detect, using a label-free format, sub-micromolar concentrations of LTB in solution as low as 0.135 μM. Furthermore, our platform shows a temperature-mediated “catch-and-release” behavior, an exciting feature with potential for selective protein capture, multiple readouts, and regeneration of the sensor over consecutive cycles of use

Confinement Assembly of ABC Triblock Terpolymers for the High-Yield Synthesis of Janus Nanorings

Block copolymers are versatile building blocks for the self-assembly of functional nanostructures in bulk and solution. While spheres, cylinders, and bilayer sheets are thermodynamically preferred shapes and frequently observed, ring-shaped nanoparticles are more challenging to realize due to energetic penalties that originate from their anisotropic curvature. Today, a handful of concepts exist that produce core-shell nanorings, while more complex (e.g. patchy) nanorings are currently out of reach and have only been predicted theoretically. Here, we demonstrate that confinement assembly of properly designed ABC triblock terpolymers is a general route to synthesize Janus nanorings in high purity. The triblock terpolymer self-assembles in the spherical confinement of nanoemulsion droplets into prolate ellipsoidal microparticles with an axially-stacked lamellar-ring (lr)-morphology. We clarified and visualized this complex, yet well-ordered, morphology with transmission electron tomography (ET). Blocks A and C formed stacks of lamellae with the B microdomain sandwiched in-between as nanorings. Cross-linking of the B-rings allows disassembly of the microparticles into Janus nanorings (JNRs) carrying two strictly separated polymer brushes of A and C on top and bottom. Decreasing the B volume leads to Janus spheres and rods, while an increase of B results in perforated and filled Janus disks. The confinement assembly of ABC triblock terpolymers is a general process that can be extended to other block chemistries and will allow to synthesize a large variety of complex micro- and nanoparticles that inspire studies in self-assembly, interfacial stabilization, colloidal packing, and nanomedicine

Heme oxygenase-1 genotype and restenosis after balloon angioplasty: a novel vascular protective factor

AbstractObjectivesWe investigated the association of the heme oxygenase-1 (HO-1) promoter genotype with the inflammatory response and restenosis after balloon angioplasty.BackgroundHeme oxygenase-1, which is induced by balloon angioplasty, can inhibit neointima formation and vascular remodeling. A dinucleotide repeat in the HO-1 gene promoter shows a length polymorphism that modulates HO-1 gene transcription. Short (<25 guanosine thymidine [GT]) repeats are associated with a 10-fold greater up-regulation of HO-1 than are longer repeats.MethodsWe studied 381 consecutive patients who underwent femoropopliteal balloon angioplasty (n = 210) and comparison groups with femoropopliteal stenting (n = 68) and lower limb angiography (n = 103). C-reactive protein (CRP) was measured at baseline, 24, and 48 h. We evaluated patency at six months by duplex sonography and assessed the association of the length of GT repeats in the HO-1 gene promoter with postintervention CRP and restenosis.ResultsRestenosis within six months was found in 74 patients (35%) after balloon angioplasty and in 21 patients (31%) after stenting. After balloon angioplasty, carriers of the short length (<25 GT) dinucleotide repeats had a lower postintervention CRP at 24 h (p = 0.009) and 48 h (p < 0.001) and a reduced risk for restenosis (adjusted relative risk 0.43, 95% confidence interval: 0.24 to 0.71, p < 0.001) compared with patients with longer alleles. After stenting or angiography, we found no association between the HO-1 genotype with CRP or restenosis.ConclusionsThe HO-1 promoter genotype that controls the degree of HO-1 up-regulation in response to stress stimuli is associated with the postintervention inflammatory response and the restenosis risk after balloon angioplasty