Helical polyamines.

Polymer microstructures rely on tacticity, yet exploration in polyamines has focused predominantly on atactic polymers. We introduce a method to synthesize a diverse library of ortho and para-cyanobenzenesulfonyl-activated-methyl aziridines using R, S, and racemic alaninol. Living anionic ring-opening polymerization of racemic sulfonyl aziridines yields soluble polymers, while enantiomerically-pure sulfonyl aziridines follow a dispersion polymerization with complete monomer conversion giving access to stereoblock copolymers. Removal of activation groups is achieved using dodecanethiol and tert-butylimino-tri(pyrrolidino)phosphorane to obtain isotactic or atactic linear polypropylene imines (LPPIs). High-purity L-PPIs are obtained in salt and neutral forms with high yields. Stereoblock copolymers of poly-R-block-S-polysulfonamides and respective polypropylene imine stereoblocks are synthesized, revealing helical structures in water influenced by the monomer type and sequence in CD spectroscopy. Molecular dynamics simulations confirm the helical nature of isotactic LPPIs in water. Bulk characterization demonstrates the first crystalline isotactic polyamines via spherulite growth in polarized light, atomic force microscopy and XRD analyses. In cell-transfection studies, the synthesized isotactic LPPIs exhibit lower toxicity and transfection efficiency than commercial hyperbranched polyethylene imine, with longer chains showing increased transfection efficiency. These isotactic polymers open avenues for complex macromolecular architectures with optically active polyamines akin to poly(amino acid)s but lacking hydrolytically cleavable amide links.

Fully Degradable Polyphosphoester Cubosomes for Sustainable Agrochemical Delivery.

Microplastic pollution and the urgent need for sustainable agriculture have raised interest in developing degradable carriers for controlled agrochemical release. Porous polymeric particles are particularly promising due to their unique release profiles compared to solid or core-shell carriers. However, creating degradable, mesoporous (2-50 nm) microparticles is challenging, and their potential for agrochemical delivery is largely unexplored. A straightforward self-assembly method is demonstrated for fully degradable porous polymer cubosomes (PCs), showcasing their ability to load and release agrochemicals. Using fully degradable block copolymers (BCPs), poly(ethyl ethylene phosphate)-b-polylactide (PEEP-b-PLA), PCs are synthesized in water with high inner order and open pores averaging 19 ± 3 nm in diameter. During the self-assembly process in the presence of the hydrophobic fungicide tebuconazole, polymersomes transform into PCs by enriching the hydrophobic polymer domain and altering the BCP packing parameter. After self-assemby, highly porous and fungicide-loaded PCs are obtained. Fungicide-loaded PCs show high antimycotic activity against Botrytis cinerea (grey mold), adhere to Vitis vinifera Riesling leaves even after simulated rain, and release the fungicide continuously over several days with different release-kinetics compared to solid particles. PCs hydrolyze completely into lactic acid and phosphate derivatives, highlighting their potential as microplastic-free agrochemical delivery systems for sustainable agriculture.

Water-soluble polyphosphonate-based bottlebrush copolymers via aqueous ring-opening metathesis polymerization.

Ring-opening metathesis polymerization (ROMP) is a versatile method for synthesizing complex macromolecules from various functional monomers. In this work, we report the synthesis of water-soluble and degradable bottlebrush polymers, based on polyphosphoesters (PPEs) via ROMP. First, PPE-macromonomers were synthesized via organocatalytic anionic ring-opening polymerization of 2-ethyl-2-oxo-1,3,2-dioxaphospholane using N-(hydroxyethyl)-cis-5-norbornene-exo-2,3-dicarboximide as the initiator and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the catalyst. The resulting norbornene-based macromonomers had degrees of polymerization (DPn) ranging from 25 to 243 and narrow molar mass dispersity (D ≤ 1.10). Subsequently, these macromonomers were used in ROMP with the Grubbs 3rd-generation bispyridyl complex (Ru-G3) to produce a library of well-defined bottlebrush polymers. The ROMP was carried out either in dioxane or in aqueous conditions, resulting in well-defined and water-soluble bottlebrush PPEs. Furthermore, a two-step protocol was employed to synthesize double hydrophilic diblock bottlebrush copolymers via ROMP in water at neutral pH-values. This general protocol enabled the direct combination of PPEs with ROMP to synthesize well-defined bottlebrush polymers and block copolymers in water. Degradation of the PPE side chains was proven resulting in low molar mass degradation products only. The biocompatible and biodegradable nature of PPEs makes this pathway promising for designing novel biomedical drug carriers or viscosity modifiers, as well as many other potential applications.

Biodegradable polyphosphoester micelles act as both background-free 31P magnetic resonance imaging agents and drug nanocarriers.

In vivo monitoring of polymers is crucial for drug delivery and tissue regeneration. Magnetic resonance imaging (MRI) is a whole-body imaging technique, and heteronuclear MRI allows quantitative imaging. However, MRI agents can result in environmental pollution and organ accumulation. To address this, we introduce biocompatible and biodegradable polyphosphoesters, as MRI-traceable polymers using the 31P centers in the polymer backbone. We overcome challenges in 31P MRI, including background interference and low sensitivity, by modifying the molecular environment of 31P, assembling polymers into colloids, and tailoring the polymers' microstructure to adjust MRI-relaxation times. Specifically, gradient-type polyphosphonate-copolymers demonstrate improved MRI-relaxation times compared to homo- and block copolymers, making them suitable for imaging. We validate background-free imaging and biodegradation in vivo using Manduca sexta. Furthermore, encapsulating the potent drug PROTAC allows using these amphiphilic copolymers to simultaneously deliver drugs, enabling theranostics. This first report paves the way for polyphosphoesters as background-free MRI-traceable polymers for theranostic applications.

End-of-life biodegradation? how to assess the composting of polyesters in the lab and the field.

The aerobic composting of biodegradable plastics can be a promising solution to the growing issue of waste accumulation. Therefore, this article offers a review of papers investigating the biodegradability of polyesters (PLA, PHB, PBS and PCL) in home- and industrial composting. Not only the thermal and biodegradation properties are discussed, but also a comparison is made between the different polyesters under the same composting conditions. From this review, it becomes clear that composting shows promise for polyester waste management. However, although several methods for assessing the composting properties of polyester have been developed, the fact that they rarely follow the same standards does not allow for a comparative analysis that would clearly define composting as the most viable solution.

RNA-Inspired and Accelerated Degradation of Polylactide in Seawater.

Marine plastic pollution is a worldwide challenge making advances in the field of biodegradable polymer materials necessary. Polylactide (PLA) is a promising biodegradable polymer used in various applications; however, it has a very slow seawater degradability. Herein, we present the first library of PLA derivatives with incorporated "breaking points" to vary the speed of degradation in artificial seawater from years to weeks. Inspired by the fast hydrolysis of ribonucleic acid (RNA) by intramolecular transesterification, we installed phosphoester breaking points with similar hydroxyethoxy side groups into the PLA backbone to accelerate chain scission. Sequence-controlled anionic ring-opening copolymerization of lactide and a cyclic phosphate allowed PLA to be prepared with controlled distances of the breaking points along the backbone. This general concept could be translated to other slowly degrading polymers and thereby be able to prevent additional marine pollution in the future.

Designer Core-Shell Nanoparticles as Polymer Foam Cell Nucleating Agents: The Impact of Molecularly Engineered Interfaces.

The interface between nucleating agents and polymers plays a pivotal role in heterogeneous cell nucleation in polymer foaming. We describe how interfacial engineering of nucleating particles by polymer shells impacts cell nucleation efficiency in CO2 blown polymer foams. Core-shell nanoparticles (NPs) with a 80 nm silica core and various polymer shells including polystyrene (PS), poly(dimethylsiloxane) (PDMS), poly(methyl methacrylate) (PMMA), and poly(acrylonitrile) (PAN) are prepared and used as heterogeneous nucleation agents to obtain CO2 blown PMMA and PS micro- and nanocellular foams. Fourier transform infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy are employed to confirm the successful synthesis of core-shell NPs. The cell size and cell density are determined by scanning electron microscopy. Silica NPs grafted with a thin PDMS shell layer exhibit the highest nucleation efficiency values, followed by PAN. The nucleation efficiency of PS- and PMMA-grafted NPs are comparable with the untreated particles and are significantly lower when compared to PDMS and PAN shells. Molecular dynamics simulations (MDS) are employed to better understand CO2 absorption and nucleation, in particular to study the impact of interfacial properties and CO2-philicity. The MDS results show that the incompatibility between particle shell layers and the polymer matrix results in immiscibility at the interface area, which leads to a local accumulation of CO2 at the interfaces. Elevated CO2 concentrations at the interfaces combined with the high interfacial tension (caused by the immiscibility) induce an energetically favorable cell nucleation process. These findings emphasize the importance of interfacial effects on cell nucleation and provide guidance for designing new, highly efficient nucleation agents in nanocellular polymer foaming.

Effect of the Chain Length and Temperature on the Adhesive Properties of Alkanethiol Self-Assembled Monolayers.

Stable and hydrophobic self-assembled monolayers of alkanethiols are promising materials for use as lubricants in microdevices and nanodevices. We applied high-rate dynamic force spectroscopy measurements to study in detail the influence of the chain length and temperature on the adhesion between methyl-terminated thiol monolayers and a silicon nitride tip. We used the Johnson-Kendall-Roberts model to calculate the number of molecules in adhesive contact and then the Dudko-Hummer-Szabo model to extract the information about the position and the height of the activation barrier per single molecule. Both parameters were determined and analyzed in the temperature range from 25 to 65 °C for three thiols: 1-decanethiol (measured previously), 1-tetradecanethiol, and 1-hexadecanethiol. We associate the increase of the activation barrier parameters versus the chain length with lower stiffness of longer molecules and higher effectiveness of adhesive bond formation. However, we relate the thermal changes of the parameters rather to rearrangements of molecules than to the direct influence of temperature on the adhesive bonds.

Dataset for acrylate/silica nanoparticles formulations and photocured composites: Viscosity, filler dispersion and bulk Poisson׳s ratio.

UV-curable polymer composites are of importance in industry, biomedical applications, scientific fields, and daily life. Outstanding physical properties of polymer composites were achieved with nanoparticles as filler, primarily in enhancing mechanical strength or barrier properties. Structure-property relationships of the resulting nanocomposites are dictated by the polymer-filler molecular architecture, i.e. interactions between polymer matrix and filler, and high surface area to volume ratio of the filler particles. Among monomers, acrylates and methacrylates attracted wide attention due to their ease of polymerization and excellent physicochemical and mechanical properties of the derived polymers. We prepared and photopolymerized two series of formulations containing hydrophobized silica nanofiller (Aerosil R7200) dispersed in 2-hydroxyethyl acrylate (HEA) or polyethylene glycol diacrylate (PEGDA) monomers. We compared selected physical properties of the formulations, both before and after photocuring; specifically the viscosity of formulations and dispersion of the filler in the polymer matrices. Additionally, we estimated the bulk Poisson׳s ratio of the investigated nanocomposites. This article contains data related to the research article entitled "Nanoscale Young׳s modulus and surface morphology in photocurable polyacrylate/nanosilica composites" (Gojzewski et al., 2017) [1].

Pick up, move and release of nanoparticles utilizing co-non-solvency of PNIPAM brushes.

A critical complication in handling nanoparticles is the formation of large aggregates when particles are dried e.g. when they need to be transferred from one liquid to another. The particles in these aggregates need to disperse into the destined liquid medium, which has been proven difficult due to the relatively large interfacial interaction forces between nanoparticles. We present a simple method to capture, move and release nanoparticles without the formation of large aggregates. To do so, we employ the co-non-solvency effect of poly(N-isopropylacrylamide) (PNIPAM) brushes in water-ethanol mixtures. In pure water or ethanol, the densely end-anchored macromolecules in the PNIPAM brush stretch and absorb the solvent. We show that under these conditions, the adherence between the PNIPAM brush and a silicon oxide, gold, polystyrene or poly(methyl methacrylate) colloid attached to an atomic force microscopy cantilever is low. In contrast, when the PNIPAM brushes are in a collapsed state in a 30-70 vol% ethanol-water mixture, the adhesion between the brush and the different counter surfaces is high. For potential application, we demonstrate that this difference in adhesion can be utilized to pick up, move and release 900 silicon oxide nanoparticles of diameter 80 nm using only 10 × 10 µm2 PNIPAM brush.

Influence of Temperature on the Nanoadhesion of a Methyl-Terminated Thiol Monolayer: A New Insight with High-Rate Dynamic Force Spectroscopy.

Alkanethiols form stable, homogeneous, and well-organized self-assembled monolayers and can be used as lubricants in micro- and nanodevices when sufficiently hydrophobic and resistant to sudden temperature changes. In this paper, we demonstrate a new analysis method which provides a deep physical insight into adhesive interactions and their temperature dependencies at the single molecule level. We have focused on the adhesion between a silicon nitride tip and a 1-decanethiol self-assembled monolayer in the temperature range from 25 to 85 °C. We performed dynamic force spectroscopy measurements and applied theoretical models of adhesive-mechanical interactions and thermally activated unbinding to obtain detailed information on the adhesive interactions. The parameters of the interaction potential describing a single adhesive bond were calculated, and their temperature dependence was discussed. Although the changes of the adhesion force versus temperature are significant and nonmonotonic, the energy of the activation barrier of a single adhesive bond appears temperature independent. We attribute observed changes in the position of the activation barrier to the interplay between the rupture and rebinding of adhesive bonds, as well as to thermal reorganization, in particular the change of the tilt angle of thiol molecules in the self-assembled monolayer.

Nanoadhesion on rigid methyl-terminated biphenyl thiol monolayers: a high-rate dynamic force spectroscopy study.

Nanoadhesion on a self-assembled monolayer of 4-methyl-4'-mercaptobiphenyl is measured using a modified atomic force microscope. The dependence of the adhesion force on the loading rate is analyzed with the Dudko-Hummer-Szabo model, and the kinetic and interaction potential parameters for a single terminal group are extracted. The energy and location of the activation barrier suggest that the adhesion is dominated by van der Waals dispersion forces. The humidity effect on the nanoadhesion is also studied. The results are compared with previously measured values for methyl-terminated alkane thiols and the influence of the thiol rigidity on the adhesion force is discussed.

Magnetosomes on surface: an imaging study approach.

In this study, we deposited isolated magnetosomes from magnetotactic bacteria Magnetospirillum strain AMB-1 onto solid surfaces using spin coating (SC) and drop coating (DC) techniques. Four imaging techniques have been used to visualize the sample structure: scanning and transmission electron microscopy (SEM, TEM), atomic and magnetic force microscopy (AFM, MFM). Additionally, dynamic light scattering was applied to measure the hydrodynamic radius of agglomerated/aggregated magnetosomes in a liquid environment. This manuscript discusses observed differences between structures obtained by two deposition techniques, i.e. possible interactions and factors responsible for magnetosomes' formation, their morphology on surfaces as a result of agglomeration and aggregation phenomena. Moreover, topography and homogeneity of obtained structures as well as thickness of protein-based membrane were also examined and described. Using high-resolution TEM, we analyzed the size of magnetic cores, their crystal structure and quality. We found that the SC technique provides a homogenous layer of magnetosomes and hydrophilization of silicon surfaces improves the deposition of magnetosomes. However, due to strong hydrogen interaction to the hydrophilic silicone surface, the organic membrane of magnetosomes is mostly flattened. As a matter of fact, the size distributions of magnetosomes deposited by SC and DC techniques (logarithmic-normal tendency) differ from the Feret diameter distribution (normal). Furthermore, our study confirms the good crystalline quality of magnetosomes' cores. It also shows that they are magnetic in the all their volume.

Effect of humidity on nanoscale adhesion on self-assembled thiol monolayers studied by dynamic force spectroscopy.

The adhesion force between silicon nitride tips of an atomic force microscope and different self-assembled thiol monolayers (SAMs) was measured at different loading rates and humidity. SAMs were formed from HS(CH(2))(n)CH(3) with n = 6, 8, 9, 10, 15 and HS(CH(2))(n)OH with n = 6, 9, 11, 16. With a special setup, the loading rate could be increased to 10(7) nN s(-1). For the interaction with two-dimensional crystalline CH(3)-terminated SAMs (n > or = 8), two regimes can be distinguished. At loading rates below 10(4)-10(5) nN s(-1), the adhesion force increased proportional to the logarithm of the loading rate. Adhesion is most likely dominated by van der Waals attraction. At higher loading rates, the adhesion forces increased steeper with the logarithm of the loading rate. The specific process limiting separation is not yet identified. On OH-terminated SAMs, the adhesion force was approximately 6 times higher than on the CH(3)-terminated SAMs, even at low humidity. This can partially, but not fully, be explained by hydrogen bridges forming between the hydroxyl groups of the monolayer and silanol groups of the tip. For relative humidity above 10%, the capillary force further increased the adhesion force, which reached a maximum at values of relative humidity between 40% and 80%. Adhesion force versus loading rate (F(ad) versus r(F)) curves increased roughly linearly over the whole range of loading rates. The slope depended on the humidity, and it is correlated with the absolute strength of the capillary force.

Quantitative characterization of nanoadhesion by dynamic force spectroscopy.

We present a method for the characterization of adhesive bonds formed in nanocontacts. Using a modified atomic force microscope, the nanoadhesion between a silicon nitride tip and a self-assembled monolayer of 1-nonanethiol on gold(111) was measured at different loading rates. Adhesion force-versus-loading rate curves could be fitted with two logarithmic terms, indicating a two step (two energy barrier) process. The application of the Bell-Evans model and classical contact mechanics allows the extraction of quantitative information about the effective adhesion potential and characterization of the different components contributing to nanoadhesion.