Fuel-Driven Enzymatic Reaction Networks to Program Autonomous Thiol/Disulfide Redox Systems

Fuel-driven dissipative formation of disulfide bonds using competing oxidative activation and reductive deactivation presents a possibly very versatile avenue for autonomous materials design. However, this is challenging to realize because of the direct annihilation of oxidizing fuel and a deactivating reducing agent. We overcome this challenge by introducing a redox-based enzymatic reaction network (ERN), enabling the dissipative disulfide formation for molecularly dissolved thiols in a fully autonomous manner. Moreover, the ERN allows for programming hydrogel lifetimes by utilizing thiol-terminated star polymers (sPEG-SH). The ERN can be customized to operate with aliphatic and aromatic thiols and should thus be broadly applicable to functional thiols

Janus Triad: Three Types of Nonspherical, Nanoscale Janus Particles from One Single Triblock Terpolymer

We report the synthesis of three different Janus topologies from one single specific triblock terpolymer, poly(tert-butoxystyrene)-block-polybutadiene-block-poly(tert-butyl methacrylate) (tSBT). By controlling the phase transitions via pretreatment and cross-linking conditions of the lamella–cylinder equilibrium bulk morphology of the polymer, we were able to obtain Janus cylinders, sheets, and previously unknown Janus ribbons. Here, a delicate balance of experimental parameters allows to manipulate the microphase morphologies as needed. The attained control even realizes the trapping of a complex intermediate phase, where every second intercylinder distance in the lamella–cylinder morphology is connected by a thin lamella. Furthermore, we also show that casting from a selective solvent can be used to access the lamella–sphere morphology and fabricate spherical Janus particles. What is more, poly(tert-butoxystyrene) can be hydrolyzed to polyhydroxystyrene, which is water-soluble at high pH and thus pH-responsive. It also represents a reaction site for further functionalizations and is thus an attractive alternative to the commonly used polystyrene. We furthermore present cryo-TEM images of water-soluble Janus cylinders that include one of the best quasi in-situ real-space proofs for the Janus character of nanosized, anisometric polymer-based particles

Fuel-Driven Enzymatic Reaction Networks to Program Autonomous Thiol/Disulfide Redox Systems

Fuel-driven dissipative formation of disulfide bonds using competing oxidative activation and reductive deactivation presents a possibly very versatile avenue for autonomous materials design. However, this is challenging to realize because of the direct annihilation of oxidizing fuel and a deactivating reducing agent. We overcome this challenge by introducing a redox-based enzymatic reaction network (ERN), enabling the dissipative disulfide formation for molecularly dissolved thiols in a fully autonomous manner. Moreover, the ERN allows for programming hydrogel lifetimes by utilizing thiol-terminated star polymers (sPEG-SH). The ERN can be customized to operate with aliphatic and aromatic thiols and should thus be broadly applicable to functional thiols

Waterborne Methacrylate-Based Vitrimers

We demonstrate waterborne, unimolecularly dissolved vitrimer prepolymer systems that can be transferred into a vitrimer material using catalytic transesterification. The one-component prepolymer system can be processed via film casting and subsequent heat-induced cross-linking. A variation of the density of side chain hydroxy groups over ester and amide groups in the methacrylate/methacrylamide backbone, as well as of the Lewis acid catalyst loading, allow control of the extent of cross-linking and exchange rates. The increase of the amount of both catalyst and hydroxy groups leads to an acceleration of the relaxation times and a decrease of the activation energy of the transesterification reactions. The system features elastomeric properties, and the tensile properties are maintained after two recycling steps. Thus far, vitrimers have been limited largely to hydrophobic polymers; this system is a step forward toward waterborne, one-component materials, and we demonstrate its use in waterborne bioinspired nanocomposites

Dynamic Multicompartment-Core Micelles in Aqueous Media

We investigate micellar aggregates of amphiphilic block terpolymers, polybutadiene-block-poly(2-vinyl pyridine)-block-poly(methacrylic acid) (PB800P2VP190PMAA550) and their quaternized analogues polybutadiene-block-poly(N-methyl-2-vinylpyridinium)-block-poly(methacrylic acid) (PB800P2VPq190PMAA550) in aqueous solution using light scattering (DLS, SLS) and cryogenic transmission electron microscopy (cryo-TEM). At high pH, PB800P2VP190PMAA550 forms core−shell−corona micelles with a hydrodynamic radius Rh ∼ 100 nm and a continuous shell of P2VP. However, at pH 4 partial intramicellar interpolyelectrolyte complex (im-IPEC) formation between P2VP and PMAA results in a patchy, collapsed shell. This is far more pronounced for the quaternized analogue, PB800P2VPq190PMAA550, which forms aggregates of similar size, also exhibiting a noncontinuous, patchy shell. Here, these im-IPECs of the positively charged P2VPq and the partially negatively charged PMAA are present over the whole investigated pH range (4−10). We further demonstrate that size and charge of the corona can be tuned through the block terpolymer composition, in particular, the ratio between P2VPq and PMAA. These micelles are dynamic and able to react to changes in pH or salinity in terms of corona diameter and aggregation number

Polyglycidol-Based Prepolymers to Tune the Nanostructure of Microgels

The use of prepolymers for microgel synthesis via miniemulsification allows predefining the chemical functionality and the nanostructure of microgels. We report on tailor-made polyglycidol-based prepolymers using three protected glycidol monomers (allyl glycidyl ether, AGE; ethoxy ethyl glycidyl ether, EEGE; and <i>tert</i>-butyl glycidyl ether, tBGE). AGE with its pendant double bonds serves as site for cross-linking or functionalization, whereas the EEGE and tBGE building blocks represent precursors for hydroxyl functionalities. Following the prepolymer approach, we design statistical and block copolymers to control the nanostructure of the microgel. Cross-linking of the prepolymers is achieved in miniemulsions under UV irradiation in a thiol–ene click type reaction addressing the allyl groups with 2,2′-(ethylenedioxy)­diethanethiol. Analysis with cryo-TEM reveals that microgels derived from poly­(glycidol)-<i>block</i>-poly­(AGE) show larger hydrophobic domains than microgels derived from statistical copolymers. Additionally, the cross-linking of pH responsive tBGE/AGE prepolymers with different microstructures leads to microgels with nanostructures differing in local charge distributions

Switchable Hydrophobic Pockets in DNA Protocells Enhance Chemical Conversion

Synthetic cell models help us understand living cells and the origin of life. Key aspects of living cells are crowded interiors where secondary structures, such as the cytoskeleton and membraneless organelles/condensates, can form. These can form dynamically and serve structural or functional purposes, such as protection from heat shock or as crucibles for various biochemical reactions. Inspired by these phenomena, we introduce a crowded all-DNA protocell and encapsulate a temperature-switchable DNA-b-polymer block copolymer, in which the synthetic polymer phase-segregates at elevated temperatures. We find that thermoreversible phase segregation of the synthetic polymer occurs via bicontinuous phase separation, resulting in artificial organelle structures that can reorient into larger domains depending on the viscoelastic properties of the protocell interior. Fluorescent sensors confirm the formation of hydrophobic compartments, which enhance the reactivity of bimolecular reactions. This study leverages the strengths of biological and synthetic polymers to construct advanced biohybrid artificial cells that provide insights into phase segregation under crowded conditions and the formation of organelles and microreactors in response to environmental stress

Table_1_The Relation Between Steroid Secretion Patterns and the Androgen Receptor Gene Polymorphism on Physical Health and Psychological Well-Being—Longitudinal Findings From the Men’s Health 40+ Study.docx

Research is increasingly focusing on promoting healthy aging and the related extension of the health span by targeting crucial biological processes responsible for age-related conditions. While age-related gradual changes in steroid hormones such as testosterone, estradiol, or cortisol are well described in men, their interactions among each other or with genetic markers have not been sufficiently investigated with regard to physical health or psychological well-being. More specifically, the examination of age-related alterations in hormone interactions and the androgen receptor polymorphism, which modulates androgen action on target cells, in relation to physical health and psychological well-being represents a promising avenue for research on healthy aging in men. A total of 97 healthy aging men provided complete data on psychometric health measures as well as hormonal and genetic parameters at baseline and a 4-year follow-up assessment. Fasting saliva samples were taken at 8:00 am under standardized laboratory conditions, while the androgen receptor gene polymorphism was analyzed from dried blood spots. Longitudinal analyses revealed that psychological well-being and physical health remained stable over time. Analyses indicated that E2 moderated the course of psychological well-being, while the androgen receptor gene polymorphism moderated the course of physical health. Further, T was a strong predictor of physical health. These results suggest that the hypothalamic-pituitary-gonadal (HPG) axis might be important for the maintenance of psychological well-being in men, while physical health depends more on interindividual differences in the androgen receptor gene and T.</p

sj-docx-1-jiv10.1177_08862605231169766 – Supplemental material for Not Always a “Buffer”: Self-Compassion as Moderator of the Link Between Masculinity Ideologies and Help-Seeking Intentions After Experiences of Intimate Partner Violence

Supplemental material, sj-docx-1-jiv10.1177_08862605231169766 for Not Always a “Buffer”: Self-Compassion as Moderator of the Link Between Masculinity Ideologies and Help-Seeking Intentions After Experiences of Intimate Partner Violence by Nikola Komlenac, Elisa Lamp, Franziska Maresch, Andreas Walther and Margarethe Hochleitner in Journal of Interpersonal Violence</p