Grapefruit-Inspired Polymeric Capsule with Hierarchical Microstructure: Advanced Nanomaterial Carrier Platform for Energy Storage, Drug Delivery, Catalysis, and Environmental Applications.

Efficient support materials are crucial for maximizing the efficacy of nanomaterials in various applications such as energy storage, drug delivery, catalysis, and environmental remediation. However, traditional supports often hinder nanomaterial performance due to their high weight ratio and limited manageability, leading to issues like tube blocking and secondary pollution. To address this, a novel grapefruit-inspired polymeric capsule (GPC) as a promising carrier platform is introduced. The millimeter-scale GPC features a hydrophilic shell and an internal hierarchical microstructure with 80% void volume, providing ample space for encapsulating diverse nanomaterials including metals, polymers, metal-organic frameworks, and silica. Through liquid-phase bottom-up methods, it is successfully loaded Fe2O3, SiO2, polyacrylic acid, and Prussian blue nanomaterials onto the GPC, achieving high mass ratio (1776, 488, 898, and 634 wt.%, respectively). The GPC shell prevents nanomaterial leakage and the influx of suspended solids, while its internal framework enhances structural stability and mass transfer rates. With long-term storage stability, high carrying capacity, and versatile applicability, the GPC significantly enhances the field applicability of nanomaterials.

Efficient recovery and recycling/upcycling of precious metals using hydrazide-functionalized star-shaped polymers.

There is a growing demand for adsorption technologies for recovering and recycling precious metals (PMs) in various industries. Unfortunately, amine-functionalized polymers widely used as metal adsorbents are ineffective at recovering PMs owing to their unsatisfactory PM adsorption performance. Herein, a star-shaped, hydrazide-functionalized polymer (S-PAcH) is proposed as a readily recoverable standalone adsorbent with high PM adsorption performance. The compact chain structure of S-PAcH containing numerous hydrazide groups with strong reducibility promotes PM adsorption by enhancing PM reduction while forming large, collectable precipitates. Compared with previously reported PM adsorbents, commercial amine polymers, and reducing agents, S-PAcH exhibited significantly higher adsorption capacity, selectivity, and kinetics toward three PMs (gold, palladium, and platinum) with model, simulated, and real-world feed solutions. The superior PM recovery performance of S-PAcH was attributed to its strong reduction capability combined with its chemisorption mechanism. Moreover, PM-adsorbed S-PAcH could be refined into high-purity PMs via calcination, directly utilized (upcycled) as catalysts for dye reduction, or regenerated for reuse, demonstrating its high practical feasibility. Our proposed PM adsorbents would have a tremendous impact on various industrial sectors from the perspectives of environmental protection and sustainable development.

Modeling the compaction of bacterial chromosomes by biomolecular crowding and the cross-linking protein H-NS.

Cells orchestrate the action of various molecules toward organizing their chromosomes. Using a coarse-grained computational model, we study the compaction of bacterial chromosomes by the cross-linking protein H-NS and cellular crowders. In this work, H-NS, modeled as a mobile "binder," can bind to a chromosome-like polymer with a characteristic binding energy. The simulation results reported here clarify the relative role of biomolecular crowding and H-NS in condensing a bacterial chromosome in a quantitative manner. In particular, they shed light on the nature and degree of crowder and H-NS synergetics: while the presence of crowders enhances H-NS binding to a chromosome-like polymer, the presence of H-NS makes crowding effects more efficient, suggesting two-way synergetics in chain compaction. Also, the results show how crowding effects promote clustering of bound H-NS. For a sufficiently large concentration of H-NS, the cluster size increases with the volume fraction of crowders.

Visible-light-induced self-propelled nanobots against nanoplastics.

The accumulation of plastic debris in aquatic organisms has raised serious concerns about the potential health implications of their incorporation into the food chain. However, conventional water remediation techniques are incapable of effectively removing nanoplastics (NPs) smaller than 200 nm, which can have harmful effect on animal and human health. Herein, we demonstrate the "on-the-fly" capture of NPs through their enlargement (approximately 4,100 times) using self-propelled nanobots composed of a metal-organic framework. Under visible-light irradiation, the iron hexacyanoferrate (FeHCF) nanobot exhibits fuel-free motion by electrostatically adsorbing NPs. This strategy can contribute to reducing plastic pollution in the environment, which is a significant environmental challenge. Light-induced intervalence charge transfer in the FeHCF nanobot lattice induces bipolarity on the nanobot surface, leading to the binding of negatively charged NPs. The local electron density in the lattice then triggers self-propulsion, thereby inducing agglomeration of FeHCF@NP complexes to stabilize their metastable state. The FeHCF nanobot exhibits a maximum removal capacity of 3,060 mg∙g-1 and rate constant of 0.69 min-1, which are higher than those recorded for materials reported in the literature.

Nitrogen-Doped Titanium Carbide (Ti3 C2 Tx ) MXene Nanosheet Stack For Long-Term Stability and Efficacy in Au and Ag Recovery.

The development of efficient adsorbents for the practical recovery of precious metals from electronic waste is vital to advanced energy/environment industries. Ti3 C2 Tx MXene-based materials are promising adsorbents for aqueous environments; however, the highly defective and super hydrophilic nature of the MXene surface hinders its practical applications. Here, we report that nitrogen-doped MXene (N-MXene) nanosheet stacks, prepared via high-energy planetary ball milling under N2 purging, exhibited a long-term stable and excellent recovery capability for Au and Ag ions via the nitrogenation of defective vacancies. Notably, these microscale nanosheets could facilitate the sustainable production of Au and Ag from secondary sources, exhibiting a high recovery rate and capability (1198 mg g-1 for Au and 1528 mg g-1 for Ag), long-term stable storability (21 d), and high selectivity (Kd of 1.67 × 106 for Au and 2.07 × 107 for Ag). Furthermore, the reversible redox chemistry of N-MXene facilitated its repeated use in adsorption/desorption cycles.

Polyelectrolytes: From Seminal Works to the Influence of the Charge Sequence.

We propose a selected tour of the physics of polyelectrolytes (PE) following the line initiated by de Gennes and coworkers in their seminal 1976 paper. The early works which used uniform charge distributions along the PE backbone achieved tremendous progress and set most milestones in the field. Recently, the focus has shifted to the role of the charge sequence. Revisited topics include PE complexation and polyampholytes (PA). We develop the example of a random PE in poor solvent forming pearl-necklace structures. It is shown that the pearls typically adopt very asymmetric mass and charge distributions. Individual sequences do not necessarily reflect the ensemble statistics and a rich variety of behaviors emerges (specially for PA). Pearl necklaces are dynamic structures and switch between various types of pearl-necklace structures, as described for both PE and PA.

Partially Globular Conformations from Random Charge Sequences.

Overall charged polymers with quenched charge sequences often adopt partially globular structures which result from the interplay between the disorder in charge sequences and thermal fluctuations. Simple energetic considerations show that structures consisting of alike (equal-size-equal-charge) globules are not favorable: the structures are intrinsically heterogeneous. We predict the globule distributions with the lowest energies in the size-charge space. The favorable structures comprise large (undercharged) and a majority of small (overcharged) globules. These distributions build a well characterized compact subset, which suggests some order. We also perform large scale molecular dynamics simulations on random quenched +/- sequences. Simulation results show that, despite disorder, the random charge sequences preferentially visit the predicted low energy structures and the predicted order emerges in the pearl-size distribution. This good agreement validates a posteriori the simple expression used for the energy. Implications for polyampholytes, polyelectrolytes, and intrinsically disordered proteins are discussed.

Collapse transition of a heterogeneous polymer in a crowded medium.

Long chain molecules can be entropically compacted in a crowded medium. We study the compaction transition of a heterogeneous polymer with ring topology by crowding effects in a free or confined space. For this, we use molecular dynamics simulations in which the effects of crowders are taken into account through effective interactions between chain segments. Our parameter choices are inspired by the Escherichia coli chromosome. The polymer consists of small and big monomers; the big monomers dispersed along the backbone are to mimic the binding of RNA polymerases. Our results show that the compaction transition is a two-step process: initial compaction induced by the association (clustering) of big monomers followed by a gradual overall compaction. They also indicate that cylindrical confinement makes the initial transition more effective; for representative parameter choices, the initial compaction accounts for about 60% reduction in the chain size. Our simulation results support the view that crowding promotes clustering of active transcription units into transcription factories.

Securely anchored Prussian blue nanocrystals on the surface of porous PAAm sphere for high and selective cesium removal.

Prussian blue (PB) has been well known as a pigment crystal to selectively sequestrate the radioactive cesium ion released from aqueous solutions owing to PB cage size similar to the cesium ion. Because the small size of PB is hard to deal with, the adsorbents containing PB have been prepared in the form of composites causing low sequestration efficiency of cesium. In this study, securely anchored PB nanocrystals on the surface of millimeter-sized porous polyacrylamide (PAAm) spheres (PB@PAAm) have been prepared by the crystallization of PB on the Fe3+ adsorbed PAAm. The securely anchored PB nanocrystals have been demonstrated to be selective and efficient adsorbents for sequestration of the radioactive cesium. The well-interconnected-spherical pores and millimeter-sized diameter of the PB@PAAm adsorbents facilitated permeation of Cs+ into the adsorbent and ease of handling respectively. Especially the well-interconnected-spherical pores allowed that PB@PAAm showed 90% of its maximum Cs+ adsorption capacity within 30 min. The PB@PAAm showed an outstanding Cs+ capture ability of 374 mg/g, high removal efficiency of 85% even at low concentration of Cs+ (10 ng/L), and superior selectivity of Cs+ against interference ions of Na+, K+, Mg2+, and Ca2+.

Highly Durable and Thermally Conductive Shell-Coated Phase-Change Capsule as a Thermal Energy Battery.

Robust and thermally conductive phase-change capsules (PCCs) can be effectively used as dispersoids for heat transfer fluids (HTFs) to utilize waste heat. Here, we demonstrate PCCs encapsulated with a cross-linked poly(2-hydroxyethyl methacrylate) shell that showed high durability and low thermal hysteresis for effective heat uptake and release. The circulation system was manufactured by mimicking the 4th Generation District Heating (4GDH) system to confirm the heat delivery efficiencies of PCC-dispersed slurries (PCSs) as the HTFs. The enthalpy change of water after it received heat from the PCS improved by up to 41.1% on increasing the amount of PCCs in the PCS. Furthermore, a high PCC recovery of 92 wt % was achieved after 1500 cycles, which accompanied a phase transition. The PCC developed by us can thus enable effective storage/delivery of waste heat-driven energy for zero-energy buildings and a 4GDH system, as well as thermal management of electronics.

Core/shell hybrid fiber with aminated PAN and Fe2O3 as a high-capacity adsorbent for phosphate ions.

APANF@Fe2O3, a phosphate adsorbent, was synthesized in two steps: the immobilization of an amine group onto polyacrylonitrile fiber (PANF) and the adsorption of an iron ion on aminated PANF (APANF). The amination degree of the PANF was adjusted considering its mechanical properties. The Fe2O3 on the surface of the APANF played a role as a phosphate-grasping layer via a ligand-exchange reaction. The APANF@Fe2O3 showed a considerable PO43- adsorption amount of ca. 6 mmol/g at a low pH region (ca. 2-7) and 3 mmol/g at a high pH region (ca. 8-12). The adsorption data were interpreted with various kinetic and isotherm models. The Langmuir model was more suitable than the Freundlich and Redlich-Peterson models to fit the experimental data of the phosphate adsorption on the APANF@Fe2O3 and the pseudo-second-order model was better matched than the pseudo-first-order and Elovich's models. The results of this study demonstrate that the surface of the fibrous adsorbent was homogenous and the phosphate adsorption behavior of the APANF@Fe2O3 followed a simultaneous chemisorption process into the Fe2O3 layer.

Confinement induces helical organization of chromosome-like polymers.

Helical organization is commonly observed for a variety of biopolymers. Here we study the helical organization of two types of biopolymers, i.e., DNA-like semiflexible and bottle-brush polymers, in a cell-like confined space. A bottle-brush polymer consists of a backbone and side chains emanating from the backbone, resembling a supercoiled bacterial chromosome. Using computer simulations, we calculate 'writhe' distributions of confined biopolymers for a wide range of parameters. Our effort clarifies the conditions under which biopolymers are helically organized. While helical organization is not easily realized for DNA-like biomolecules, cylindrical confinement can induce spiral patterns in a bottle brush, similarly to what was observed with bacterial chromosomes. They also suggest that ring-shape bottle brushes have a stronger tendency for helical organization. We discuss how our results can be used to interpret chromosome experiments. For instance, they suggest that experimental resolution has unexpected consequences on writhe measurements (e.g., narrowing of the writhe distribution and kinetic separation of opposite helical states).

Understanding Uniform, Fast, and Scalable Buoyancy-Driven Macro-Sized Drop Generations.

Generating uniform drops with fast production rate and tunable volume in a high-throughput way is important in various academic and industrial disciplines. In this study, we propose a strategy to produce milliscale drop in a size-tunable way and model its formation processes. The size of generated drops is uniform (<1% of the standard deviation) and tunable by controlling the flow rate, the pore diameter in membrane, and the surface hydrophobicity of membranes in the dripping regime. Also, their production rates range from ca. 0.1-2.1 Hz. The drop formation is successfully investigated by our five-force balance model. On hydrophobic membranes, the range of the dripping regime for uniform drops is wider (from ca. 5.7 to 10.4 mm) than that on hydrophilic membranes (from ca. 3.8 to 7.0 mm). Also, in the dripping regime in hydrophilic membranes, the production rates of the drop are faster than those of the hydrophobic membrane.

Switchable electrorheological activity of polyacrylonitrile microspheres by thermal treatment: from negative to positive.

The study focuses on the effect of thermal deformation degree of polyacrylonitrile (PAN) particles on the electrorheological (ER) properties of their suspensions. The heat-treated PAN particles are manufactured as ER materials using a thermocatalytic processes. The molecular structures of ER materials are analyzed to confirm a stabilization or a carbonization degree. We categorized the prepared ER particles into three basic types according to their deformation degree: Thermal dried PAN, stabilized PAN, and pre-carbonized PAN. The raw, stabilized, and pre-carbonized PAN particle-dispersed suspensions showed positive ER properties. The ER properties are enhanced as the heat-treatment temperature increases due to improved dielectric property. However, the thermal dried PAN particle ER suspensions showed negative ER behavior though the particles have higher conductivity and dielectric constants than those of the host fluid, which is contrary to the conduction model. XRD results indicate that the ER materials could show contradictory ER behavior even if they have the same molecular structures due to their crystallinity. This discovery is expected to boost the development of both positive ER and negative ER suspensions based on carbonaceous ER materials.

A ring-polymer model shows how macromolecular crowding controls chromosome-arm organization in Escherichia coli.

Macromolecular crowding influences various cellular processes such as macromolecular association and transcription, and is a key determinant of chromosome organization in bacteria. The entropy of crowders favors compaction of long chain molecules such as chromosomes. To what extent is the circular bacterial chromosome, often viewed as consisting of "two arms", organized entropically by crowding? Using computer simulations, we examine how a ring polymer is organized in a crowded and cylindrically-confined space, as a coarse-grained bacterial chromosome. Our results suggest that in a wide parameter range of biological relevance crowding is essential for separating the two arms in the way observed with Escherichia coli chromosomes at fast-growth rates, in addition to maintaining the chromosome in an organized collapsed state. Under different conditions, however, the ring polymer is centrally condensed or adsorbed onto the cylindrical wall with the two arms laterally collapsed onto each other. We discuss the relevance of our results to chromosome-membrane interactions.

How are molecular crowding and the spatial organization of a biopolymer interrelated.

In a crowded cellular interior, dissolved biomolecules or crowders exert excluded volume effects on other biomolecules, which in turn control various processes including protein aggregation and chromosome organization. As a result of these effects, a long chain molecule can be phase-separated into a condensed state, redistributing the surrounding crowders. Using computer simulations and a theoretical approach, we study the interrelationship between molecular crowding and chain organization. In a parameter space of biological relevance, the distributions of monomers and crowders follow a simple relationship: the sum of their volume fractions rescaled by their size remains constant. Beyond a physical picture of molecular crowding it offers, this finding explains a few key features of what has been known about chromosome organization in an E. coli cell.

Effects of molecular crowding and confinement on the spatial organization of a biopolymer.

A chain molecule can be entropically collapsed in a crowded medium in a free or confined space. Here, we present a unified view of how molecular crowding collapses a flexible polymer in three distinct spaces: free, cylindrical, and (two-dimensional) slit-like. Despite their seeming disparities, a few general features characterize all these cases, even though the ϕc-dependence of chain compaction differs between the two cases: a > ac and a < ac, where ϕc is the volume fraction of crowders, a is the monomer size, and ac is the crowder size. For a > ac (applicable to a coarse-grained model of bacterial chromosomes), chain size depends on the ratio aϕc/ac, and "full" compaction occurs universally at aϕc/ac ≈ 1; for ac > a (relevant for protein folding), it is controlled by ϕc alone and crowding has a modest effect on chain size in a cellular environment (ϕc ≈ 0.3). Also for a typical parameter range of biological relevance, molecular crowding can be viewed as effectively reducing the solvent quality, independent of confinement.

Chromosome-like organization of an asymmetrical ring polymer confined in a cylindrical space.

To what extent does a confined polymer show chromosome-like organization? Using molecular dynamics simulations, we study a model Escherichia coli (E. coli) chromosome: an asymmetrical ring polymer, formed by small monomers on one side and big monomers on the other confined in a concentric-shell or simple cylinder with closed ends. The ring polymer is organized in the way observed for the E. coli chromosome: if the big monomers are assumed to be localized in the inner cylinder, the two "subchains" forming the ring are spontaneously partitioned in a parallel orientation with the "body" (big-monomer) chain linearly organized with a desired precision and the crossing (small-monomer) chain residing preferentially in the peripheral region. Furthermore, we show that the introduction of a "fluctuating boundary" between the two subchains leads to a double-peak distribution of ter-proximate loci, as seen in experiments, which would otherwise remain single-peaked. In a simple cylinder, however, a chromosome-like organization of the ring polymer typically requires an external mechanism such as cell-wall attachment. Finally, our results clarify to what degree the spatial organization of the chromosomes can be accomplished solely by ring asymmetry and anisotropic confinement.

Polymers under confinement: single polymers, how they interact, and as model chromosomes.

How confinement or a physical constraint modifies polymer chains is not only a classical problem in polymer physics but also relevant in a variety of contexts such as single-molecule manipulations, nanofabrication in narrow pores, and modelling of chromosome organization. Here, we review recent progress in our understanding of polymers in a confined (and crowded) space. To this end, we highlight converging views of these systems from computational, experimental, and theoretical approaches, and then clarify what remains to be clarified. In particular, we focus on exploring how cylindrical confinement reshapes individual chains and induces segregation forces between them - by pointing to the relationships between intra-chain organization and chain segregation. In the presence of crowders, chain molecules can be entropically phase-separated into a condensed state. We include a kernel of discussions on the nature of chain compaction by crowders, especially in a confined space. Finally, we discuss the relevance of confined polymers for the nucleoid, an intracellular space in which the bacterial chromosome is tightly packed, in part by cytoplasmic crowders.

A polymer in a crowded and confined space: effects of crowder size and poly-dispersity.

DNA compaction in a bacterial cell is in part carried out by entropic (depletion) forces induced by "free" proteins or crowding particles in the cytoplasm. Indeed, recent in vitro experiments highlight these effects by showing that they alone can condense the E. coli chromosome to its in vivo size. Using molecular dynamics simulations and a theoretical approach, we study how a flexible chain molecule can be compacted by crowding particles with variable sizes in a (cell-like) cylindrical space. Our results show that with smaller crowding agents the compaction occurs at a lower volume fraction but at a larger concentration such that doubling their size is equivalent to increasing their concentration fourfold. Similarly, the effect of polydispersity can be correctly mimicked by adjusting the size of crowders in a homogeneous system. Under different conditions, however, crowding particles can induce chain adsorption onto the cylinder wall, stretching the chain, which would otherwise remain condensed.