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This paper theoretically proposes and systematically studies a novel two-dimensional carbon material, namely, Sq-biphenylene, for the first time using first-principles calculations. The research reveals that this structure exhibits excellent mechanical, thermal, and dynamic stability, demonstrating its potential as a stable carbon-based material. Analysis of the electronic structure indicates that it is a direct band gap semiconductor featuring significant anisotropy in electronic properties. The material also exhibits high in-plane stiffness, an adjustable Poisson's ratio, and effective mass. The linear and nonlinear optical properties of the material are comprehensively studied by introducing the scissors correction based on the HSE06 band gap and the volume correction for two-dimensional systems. The calculations demonstrate that it exhibits strong in-plane and out-of-plane optical anisotropy. Notably, the material exhibits an exceptional second-order nonlinear optical response (χzyy(2) = χzxx(2)) near 2.3 eV, reaching a maximum value of 769 pm/V. This value significantly surpasses those of traditional nonlinear crystals, such as LiNbO3 (50 pm/V) and GaAs (340 pm/V), and the material exhibits distinct polarization selectivity. This work theoretically expands the family of two-dimensional carbon materials and systematically reveals the unique advantages of Sq-biphenylene in terms of structural stability, electronic and mechanical properties, and linear and nonlinear optical responses. These findings provide solid theoretical guidance for subsequent experimental synthesis and functional device development.
This paper proposes and designs a reconfigurable antenna-based multifrequency encodable RFID sensor integrated with a random forest machine learning algorithm, enabling full-spectrum, dual-parameter, high-precision synchronous wireless monitoring of O2 and CO2 in fermentation tank environments. First, a reconfigurable RFID tag antenna based on two sets of complementary split-ring resonators (CSRR) and photodiodes is designed, with each set integrating one sensing ring and four encoding rings to form 28 coding combinations. This design significantly improves the system's coding capacity and multimeasurement signal resolution, and it is the first application of reconfigurable optically controlled antenna technology to wine fermentation gas monitoring. Second, SnS2/ZnO/NiO and SnO2/CuO/TiO2 nanocomposites are employed as gas-sensitive layers. The interfacial synergistic effect enhances gas adsorption and conductivity modulation, realizing direct wireless conversion from chemical gas signals to radio-frequency (RF) signals and addressing the limitations of narrow detection range and low sensitivity in traditional materials. Finally, a multidimensional RF feature-decoding framework based on random forest regression is constructed. By extracting multidimensional features such as resonant frequency shift and amplitude variation, a nonlinear mapping model from RF responses to gas concentrations is established, breaking the accuracy bottleneck of traditional linear fitting methods in multidimensional nonlinear signal inversion. Experimental results show that the sensor can detect O2 within the range of 1000-250,000 ppm, with a response/recovery time of 29.8/39.4 s, an amplitude change of 14.79 dB, and a linear fitting R2 of 0.99523; for CO2, the detection range is 500-50,000 ppm, with a response/recovery time of 27.3/35.8 s, an amplitude change of 17.13 dB, and a linear fitting R2 of 0.99894, demonstrating excellent repeatability and long-term stability. The random forest model shows high accuracy and strong generalization ability in gas concentration inversion, and its prediction results are highly consistent with the actual values, significantly outperforming traditional fitting methods. This research facilitates the digital and refined transformation of the traditional brewing industry. It not only improves the stability of product quality and reduces energy consumption and labor costs but also provides core support for the upgradation of industrial technical standards and the collaborative innovation among industry, universities, and research institutions.
N-doped graphene (NG) is a promising electrocatalyst for the oxygen reduction reaction (ORR) at the cathodes of Polymer Electrolyte Fuel Cells (PEFCs). The NG catalyst is generally supported on an electrode substrate composed of carbon materials. However, the influence of the carbon substrate on the ORR performance of the NG catalyst has not been systematically explored. In this study, we have systematically investigated the impact of the carbon substrate on the ORR activity of the NG catalyst using first-principles calculations based on density functional theory. Specifically, we have examined the ORR activity of the NG catalyst on graphene-based substrates with a van der Waals (vdW) interface. It has been revealed that the difference in work function between the substrate and the NG catalyst dominates the ORR activity; the maximum electrode potential (UMax) depends linearly on the work function difference. Such a linear relationship is derived from the fact that the net charge of the NG catalyst scales linearly with the work function of the substrate. Furthermore, UMax was predicted to show a volcano trend with respect to the work function difference. This is because the reaction step that determines UMax switches due to the change in the free energies of reaction intermediates by charge transfer across a vdW gap, indicating an optimal work function difference that maximizes the ORR activity of the NG catalyst supported on graphene-based substrates. The establishment of experimental techniques to control the work function difference at the substrate/NG catalyst interface will be key to achieving superior catalytic performance.
Spontaneous imbibition is a primary recovery mechanism in unconventional reservoirs. Although core-scale experiments capture the combined effects of parameters such as interfacial tension (IFT) and permeability, the individual roles of boundary conditions and gravity remain poorly understood at the pore scale. This study employed microfluidics to directly visualize and quantify these effects during chemically assisted spontaneous imbibition. Micromodels consisting of a tight matrix adjacent to a fracture were saturated with dyed kerosene. Two boundary conditions were examined: cocurrent imbibition, with two ends open, and countercurrent imbibition, with only one side open. Experiments were conducted in vertical and horizontal orientations using water and nonionic (Tween 80) and anionic (Enordet O342) surfactants. Time-lapse imaging was used to track imbibition dynamics. Quantitative metrics, including the imbibition front velocity, perimeter-area ratio, displacement efficiency, and recovery factor, were extracted to characterize the mechanics of the process. For water-only experiments, cocurrent imbibition produced smoother displacement fronts with reduced fingering and a higher displacement efficiency than countercurrent imbibition. Similar trends were observed in most of the chemical-assisted tests. Both surfactants enhanced the final recovery and displacement efficiency by stabilizing the imbibition front and reducing residual oil saturation. Horizontal experiments exhibited higher early time front velocities but more pronounced fingering and lower displacement efficiency than vertical experiments. In the absence of gravity, long unstable fingers formed rapidly and impeded the further recovery. In vertical water imbibition, a high capillary force dominated the process, which caused rapid but unstable fingering. Conversely, the application of chemical additives reduced the IFT and transitioned the system to a gravity-dominated regime, which effectively stabilized the front in the vertical orientation. The pore-scale morphologies and recovery trends were found to be governed by the interplay of the inverse Bond number, viscous coupling, and relative permeability.
IrO2 is a benchmark oxygen evolution reaction (OER) electrocatalyst, and recent studies have revealed that its OER activity can be markedly improved by the coexistence of multiple crystallographic phases. Hence, elucidating the influence of crystal phase and surface structure on OER activity is crucial for the rational design of catalysts with improved performance and reduced overpotential. In this study, first-principles calculations were performed to accurately simulate the overpotential of iridium dioxide catalysts and to clarify the surface electronic-structure factors governing the overpotential. The activity of IrO2 electrocatalysts depends on the surface index and space group. Using three density functional methods (PBE, RPBE, and optPBE-vdw), we compared the activity of stable IrO2 surfaces across the P42/mnm (tetragonal), C2/m (monoclinic), and Pbcn (orthorhombic) phases. The catalytic activity followed the order C2/m > Pbcn > P42/mnm. We explain the differences in catalytic performance among the three space groups in terms of free energy changes induced by variations in the surface-layer atomic structure. Accordingly, projected Crystal Orbital Hamilton Population analysis was employed to investigate how O-Ir-O angle variations modulate the bonding interactions of HO*, O*, and HOO* groups. The O-Ir-O angle acts as a key geometric descriptor that directly reflects the adsorption strength of these groups on the IrO2 surface. This structure-bonding interaction relationship offers valuable guidance for the rational design of highly active IrO2 OER catalysts via crystal symmetry control.
The initial dissolution of metakaolin (MK) governs the supply and stoichiometry of dissolved aluminosilicate species for subsequent geopolymerization, yet the ion-specific roles of mixed alkalis at chemically heterogeneous MK basal surfaces remain poorly understood. In this work, ReaxFF reactive molecular dynamics simulations were performed at 350 K for 2.0 ns to investigate the dissolution of Al-rich and Si-rich MK (001) basal surfaces in 5 M NaOH, 5 M KOH, and a 5 M 1:1 NaOH/KOH mixed solution, using the ReaxFF parameter sets of Aryanpour et al. and Fedkin et al. The results reveal distinct cation-specific pathways: K+ more effectively facilitates Al-O bond cleavage and promotes the formation of Al-bearing oligomers, whereas Na+ more strongly perturbs the silicate network and sustains Si release. Most importantly, the 5 M 1:1 NaOH/KOH mixed solution exhibits a synergistic effect arising from the spatiotemporal complementarity of Na+ and K+ adsorption, which suppresses premature local passivation and yields a balanced dissolved Si/Al ratio of approximately 0.9. This mixed solution also gives the lowest residual fraction of CN = 4 Al species (14.6%), indicating enhanced framework destabilization and sustained early-stage bond-breaking reactivity; the associated framework response should be understood as structural relaxation rather than true diffusion of the solid phase. These findings provide atomistic insight into cation-regulated MK dissolution and offer a mechanistic basis for designing mixed-alkali activators for alkali-activated aluminosilicate materials.
The preparation of α-hemihydrate (α-HH) from phosphogypsum (PG) is inevitably hindered by the addition of crystal modifiers, which usually inhibit the conversion of PG and drastically prolong the reaction duration. To overcome this drawback, microwave heating, a volumetric heating technique, was employed to enhance the hydrothermal conversion of PG into α-HH in the presence of Al2(SO4)3, citraconic acid (CTA), and their composite modifier. Meanwhile, the conventional contact heating was also conducted for comparison of the conversion rate. The results indicate that increasing the concentrations of Al2(SO4)3 and CTA enables effective regulation of the crystal morphology and reduces the aspect ratio of α-HH, but this is accompanied by an evident prolongation of reaction time. In the modifier-free system, microwave heating achieved a 50% reduction in reaction period compared with contact heating. For systems containing Al2(SO4)3, CTA, or their composite modifier, the reaction time was reduced by 43-78% relative to contact heating, and PG could be completely transformed into α-HH even at high modifier concentrations. These results verify that microwave heating exhibits outstanding superiority in mitigating the inhibition of crystal modifiers on PG conversion and drastically shortening the reaction time. This work provides a feasible and efficient strategy to address the inhibition issue induced by crystal modifiers during the preparation of short-column α-HH.
This work addresses the limitations of traditional sodium oleate (NaOL) collector in spodumene flotation, such as poor flotation performance and high reagent consumption, by introducing 8-hydroxyquinoline (8-HQ) to form a combined collector system. Under the condition of a combined collector dosage of 8 × 10-4 mol/L and a NaOL to 8-HQ ratio of 4:1, the recoveries of spodumene and feldspar in the single-mineral flotation tests were 81.58% and 12.15%, respectively, achieving effective separation of the two minerals. Furthermore, multiple analytical techniques demonstrated that the higher concentration of Al sites likely provided the fundamental basis for the effective collection of spodumene by the collector. The adsorption mechanism of 8-HQ involved the formation of metal chelates with Al sites on the mineral surface, thereby enhancing its surface activity. The presence of these metal chelates significantly increased the adsorption capacity of NaOL on the mineral surface. Results from molecular dynamics simulations and contact angle measurements indicated that in the combined collector system, both the collector concentration and contact angle on the feldspar surface remain relatively low. In contrast, the collector exhibited stronger adsorption on the spodumene surface, leading to a significant enhancement in surface hydrophobicity compared to the single NaOL system.
An experimental approach is presented, which enables simultaneous ultrasonic dispersion (USD) and dynamic light scattering (DLS) measurements of colloidal nanoparticle dispersions. This USD-DLS scheme combines sonotrode-based ultrasonication of nanoparticles with time-resolved DLS data collection to study deagglomeration of nanoparticles. The capabilities of this operando approach are demonstrated using two types of nanoparticle systems: monodisperse polystyrene nanospheres and agglomerated titania nanocrystals. The influence of ultrasonication on the DLS signal is investigated using polystyrene particles as probes. During ultrasonication, the recorded autocorrelation functions (ACFs) mainly probe the formation and dynamics of cavitation bubbles in the liquid medium. Upon stopping of ultrasonication, acoustic streaming dominates the particle dynamics for a few seconds (<15 s), as revealed by the transition of the ACFs to equilibrium diffusive dynamics. Then, the particle size as a function of applied ultrasound energy can be determined. The potential of the operando USD-DLS approach to probe nanoparticle deagglomeration is demonstrated for titania nanoparticles of different levels of agglomeration from two synthesis methods. The application of a sequence of ultrasound pulses results in the continuous reduction of particle size as directly probed by DLS. Detailed deagglomeration curves are determined within a single data collection sequence. These data then form the basis for studying agglomerate stability as shown using two analysis models. In addition, it is demonstrated how the USD-DLS approach can be employed to study reagglomeration of nanoparticles under destabilizing conditions in situ.
Molecular dynamics simulations were conducted to investigate the effects of constraint conditions and lubricant types on the adsorption and frictional performance of a rough gold substrate. The study compared the relative strengths of cohesion within mixed clusters and adhesion between the clusters and the substrate. The constraint condition was implemented by imposing a moving wall along the negative z-axis during the initial adsorption stage, thereby restricting the molecular motion until a designated position was reached, after which the constraint was removed. Simulation results indicate that, under constrained conditions, the adsorption film is uniformly distributed over the substrate, whereas under unconstrained conditions, the film is distributed irregularly. Compared to the unconstrained case, the constrained adsorption film exhibits improved friction and wear performance. Furthermore, using graphene nanosheets (GNSs) alone as a lubricant favors reduced substrate friction but is detrimental to wear, while perfluoropolyether (PFPE) alone results in higher friction levels but lower substrate wear. The combination of GNSs with PFPE appears to balance these effects, contributing to both lower friction and reduced wear. The same conclusion can be drawn by substituting silver and copper for gold. These findings provide theoretical guidance for the development of advanced space-lubrication technologies.
L-tryptophan (l-Trp) and 5-Hydroxytryptophan (5-HTP) are essential precursors in serotonin biosynthesis and widely used as over-the-counter dietary supplements. We hypothesize that, due to prolonged uptake and accumulation in the human body, these amino acids can spontaneously form fibrillar self-assemblies at higher concentrations, capable of interacting with model membranes, possibly constituting the underlying mechanistic basis for their cytotoxicity and associated neurodegenerative risks. The self-assemblies of l-Trp and 5-HTP were characterized using field emission scanning electron microscopy (FESEM) and fluorescence lifetime imaging microscopy (FLIM). We investigated their interfacial interactions with fatty acid model membranes, evaluating structural perturbations using fluorescence spectroscopy, molecular dynamics (MD) simulations, dynamic light scattering (DLS), and FLIM, and complementing these with in vitro cellular viability assays using SH-SY5Y cell lines. Self-assembly of l-Trp and 5-HTP formed distinct flake-like and rod-like structures, respectively, with different rigidity. Fluorescence spectroscopy and FLIM analyses demonstrated that these assemblies altered local microenvironmental polarity and significantly compromised bilayer integrity─a disruptive integration further corroborated by atomistic MD simulations. Crucially, in vitro assays linked these interfacial interactions to a marked decrease in SH-SY5Y cell viability, establishing membrane disruption as a plausible mechanism driving the neurotoxicity of these assemblies at biointerfaces.
Bi-embedded Bi2WO6 ohmic junction photocatalysts (Bi-BWO) were synthesized via a one-step direct hydrothermal route or hydrothermal method followed by in situ reduction using different reductants. The Bi(N)-BWO prepared via an in situ reduction pathway using NaBH4 showed better physicochemical and photocatalytic redox performances than the Bi-BWO via a direct hydrothermal route using glucose or ascorbic acid as a reductant. The Bi-BWO displayed an enhanced photocatalytic redox activity in Cr(VI) reduction and tetracycline (TC)/methylene blue (MB) degradation under visible light, which was ascribed to the synergy of the ohmic junction and localized surface plasmon resonance (LSPR) of Bi nanoparticles (Bi NPs). The Bi(N)-BWO provided the highest removal efficiencies with 93.4% Cr(VI) and 77.0% TC removal rates for 120 min, whose reaction rates were 4.5- and 2.5-fold higher than those of the pristine Bi2WO6, respectively. Notably, the Bi(N)-BWO exhibited a superior simultaneous removal efficiency of Cr(VI)/TC with the reaction rates of 85.4 × 10-3 for Cr(VI) and 16.4 × 10-3 min-1 for TC, which are separately 4.0- and 1.4-fold higher than those in the single Cr(VI) and TC systems, respectively. This work provides a feasible approach to improve the photocatalytic performances of bismuth-based catalysts in wastewater remediation.
Cobalt (Co) has emerged as a promising interconnect material to replace copper. Due to its susceptibility to corrosion, controlling the balance between complexing agents and inhibitors during chemical mechanical polishing (CMP) is crucial. Molecular dynamics (MD) simulation can reveal the atom removal mechanisms in CMP. However, existing force field parameters fail to accurately describe the complex interactions between Co and C/N groups in liquids. This study aims to design a closed-loop paradigm based on an active learning framework to generate the data set and optimize the ReaxFF parameters for Co CMP, and to reveal the atom removal mechanism by using the MD method. First, high-precision density functional theory (DFT) calculations for some basic configurations were performed to generate energy and force data as the training set. Systems involving key chemical groups during the Co-CMP process, and the adhesion of corrosion inhibitors triazole (TAZ) and benzotriazole (BTA), and complexing agents such as citric acid (CA) and glycine (GLY), were examined. Then, the ReaxFF parameters were optimized through machine learning within the Jax-ReaxFF framework. Inspection of the MD results was used to check the final structure, and unacceptable structures were sent back to DFT calculations for new training set generation. MD simulation results were compared with DFT analysis and experimental verification to demonstrate the reliability of the ReaxFF-MD. The adsorption geometries, charge distribution, and RDF results reveal that GLY has a stronger complexing ability, and BTA is a better corrosion inhibitor than TAZ. Both physisorption and chemisorption affect the adsorption. The "steric blocking plus stable bonding" is the key mechanism to control corrosion. This research not only provides a more accurate force field description for Co CMP but also offers a new simplified sampling scheme for the development of force field parameters.
The preservation of aging paper archives is critically challenged by the synergistic deterioration from acid hydrolysis and mechanical weakening. Traditional approaches often address deacidification or mechanical reinforcement independently, failing to reconcile the critical need for simultaneous pH neutralization and structural restoration. This study successfully overcomes the limitation of conventional single-function treatments through the rational design of a synergistic dual-function preservation system that integrates porous calcium carbonate (P-CaCO3) and cellulose nanofibrils (CNFs). The P-CaCO3 component, synthesized via a controlled process using sodium dodecyl sulfate (SDS) and polyvinylpyrrolidone (PVP) as pore-regulating agents, functions as an efficient alkaline reservoir for acid neutralization. Simultaneously, CNF serves a dual role: as a dispersant that stabilizes the P-CaCO3 suspension and promotes uniform distribution and as a reinforcing agent that enhances the mechanical integrity of the aging paper matrix. We hypothesize that this synergistic system achieves simultaneous deacidification and reinforcement in a single treatment. When this system was applied to acidified aging paper samples, it achieved a balanced enhancement of both alkaline reserve capacity and mechanical properties under optimized conditions (0.4% CNF suspension and 1% PCCs/CNF suspension), during which, the treated aging paper achieved a 22.45% increase in tensile strength, 38.42% increase in burst strength, and 17.09% increase in tear strength, alongside a pH elevation from 5.82 to 8.28 and an alkaline reserve of 305 mmol/kg. This study establishes a novel, practical approach for the long-term preventive conservation of aging paper-based cultural heritage, directly addressing the dual challenges of acid degradation and mechanical weakening in aged documents.
Receptor-mediated interactions at liquid-liquid interfaces offer a powerful strategy for detection of trace contaminants. To enable selective sensing, these methods leverage polymeric surfactants to transduce molecular recognitions into measurable changes in interfacial tension (IFT). Therefore, establishing the structure-property relationships of polymeric surfactants under relevant conditions is crucial for advancing practical implementations. To this end, we test the hypothesis that surface-activity of polymeric surfactants is governed primarily by the chemistry of the hydrophilic block. Specifically, we investigate the colloidal properties and interfacial properties of two amphiphilic diblock copolymers (BCPs), poly(styrene)-block-poly(acrylic acid) (PS-b-PAA) and poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), under different aqueous conditions. We demonstrate that postpolymerization modification of PS-b-PAA with amino acids with varying hydrophilic properties strongly influences the IFT. Our results indicate that the addition of hydrophilic and ionic amino acids leads to larger reduction of interfacial tension and reduction in aggregation but also increases sensitivity to varying pH values and nonspecific interactions with dissolved ions in complex matrices, such as synthetic groundwater (SGW). In contrast, addition of hydrophobic amino acids leads to stable IFT values, indicative of higher tolerance to the presence of dissolved ions. We anticipate that these findings will advance further design of polymeric surfactants for selective interfacial sensing and enable the development of robust sensors for environmental monitoring.
This paper investigates the interfacial forces controlling the detachment behavior of a multiphase droplet composed of immiscible liquids, an oil-coated water droplet, from a nonwetting surface, with special attention to the residue left on the surface after droplet detachment. In particular, the force required to detach a compound droplet from a spherical surface is simulated by using techniques of molecular dynamics (MD) simulations on atomistic scales. The resulting force and residual volume are then scaled up to predict the force of detachment obtained experimentally by cloaking a water droplet with an oil-based ferrofluid and detaching it from a coated glass bead by using a magnet. Using magnetic attraction and repulsion forces, it was found that a repulsive force can help reduce the amount of water residue on the surface. Good general agreement was observed between the predictions of our MD simulations and their experimental counterparts despite six orders of magnitude difference in size. The study presented in this paper can pave the way for developing a relationship between the volume of the residue on a surface and the force causing the detachment. Such information can benefit a variety of industrial applications involving multiphase droplets that interact with surfaces.
The excessive discharge of wastewater containing methylene blue (MB) has caused certain adverse effects on human health and daily life. This highlights the urgent need for the development of safe and environmentally friendly methods of degradation. In this study, two catalytic systems based on Zn-doped g-C3N4, namely, ZCN-1%/PMS and ZCN-1%/LC, were constructed for efficient activation of peroxymonosulfate (PMS) and increased laccase stability. Experimental results show that Zn-doped g-C3N4 shows much better photocatalytic activity, combined with good enzyme immobilization ability. At a catalyst dosage of 0.2 g/L, both systems were able to remove more than 97% of MB (0.2 g/L) in 30 and 60 min of irradiation, respectively. Quenching experiments and electron paramagnetic resonance (EPR) analysis further revealed singlet oxygen (1O2) and superoxide radicals (O2•-) as the main active species in the ZCN-1%/PMS and ZCN-1%/LC systems, respectively. Based on these results, the catalytic mechanisms of the two systems are systematically elucidated in this paper. This work not only proposes new methods for PMS activation and Photoenzymatic Synergistic Catalysis but also offers feasible technical strategies for treating MB-contaminated wastewater.
Adsorption of water in MOFs is central to several industrially and societally important applications. Accurate models of water adsorption are therefore essential to accelerate the computational discovery of new MOFs and to optimize existing applications. Yet, water adsorption in MOFs remains one of the most challenging problems for both experimentalists and theoreticians. In this Perspective, I discuss the origins of these challenges, highlight the fundamental insights that can be gained from molecular simulations, and argue for the need for a coherent and collaborative effort between the experimental and simulation communities to bring the computational design of MOFs for water applications closer to practical realization and impact.
Adaptive evolution has long been hypothesized to be possible in the absence of genetic molecules, but experimental evidence remains lacking. Fatty acid vesicles can spontaneously grow and divide and might therefore be capable of nongenetic inheritance, making them ideal for exploring the emergence of prebiotic evolution. In this study, we tested whether vesicle populations can respond to artificial selection for greater turbidity and, if so, whether that response can be tied to an inheritance-like mechanism. We prepared 192 independent vesicle populations, incubated them for 24 h, and then selected half of the populations to propagate into the next generation. The populations to propagate were picked either randomly, representing drift controls, or were those with the greatest turbidity, representing selection. Population propagation involved resuspension, transfer into fresh buffer, feeding with an amphiphile stock, and then incubating for the next 24 h. In three replicate experiments run for at least 10 generations, we observed consistently greater turbidity in selection compared with drift lineages. This was accompanied by a reduction in the heritability (the regression slope between parent and offspring turbidities) of the selected lineages. We conducted additional experiments to evaluate whether this response to selection is caused by a simple carryover effect or reflects cooperative dynamics where vesicles from a parental population affect newly formed vesicles in the next generation. The response to selection is much lower when the resuspension step was omitted and/or if new amphiphiles were provided as preformed vesicles. Combined with fluorescence analyses of the resuspension and feeding processes, these results suggest that cooperative vesicle dynamics occur in cases where a small number of intact vesicles from a parental generation interact with an excess of incorporated amphiphiles. Overall, this study represents the first experimental finding of a response to artificial selection in prebiotic chemistry.
The integration of nanoscale hybridization between inorganic components and biopolymers, and the formation of hierarchical porous structures capable of efficiently including and activating cells and proteins, has not yet been achieved in the design of bone substitutes for tissue regeneration. We fabricated a porous nanohybrid membrane based on hyaluronic acid (HyAc) and citric acid-coordinated apatite nanoparticles (Cit/ApNPs) and proposed a scaffold material design that integrates a dense nanohybrid structure with a hierarchical porous structure. Specifically, the network structure of HyAc molecules was utilized as a reactive field (i.e., free space) for the hybridization of Cit/ApNPs, and the high dispersibility of Cit/ApNPs effectively induced the interfacial interactions between HyAc molecules and the NPs at the nanoscale, thereby achieving nanohybridization. This nanohybridization induced the spontaneous formation of mesopores and smaller macropores (i.e., 0.05-10 μm), and additionally, larger macropores (i.e., 10-800 μm) were constructed through the freeze-drying process while maintaining the nanohybridization state. As a result, a hierarchical porous structure with three types of pores that will contribute to protein adsorption, pseudopodia interaction/extension, and cell inclusion was successfully obtained, and the membrane was confirmed to maintain its structure and shape even after immersion in simulated body fluid (SBF). Therefore, we suggest a biomaterial design concept that integrates interfacial interaction and hierarchical pore structuring, which is expected to be an effective approach for the tissue regeneration.