Long-term Stability Research Articles

Potential execution of vitiligo surgery by the most conceivable technique – which, where, and why?

While various treatment options exist for vitiligo, surgical interventions have gained significant attention due to their potential for long-lasting repigmentation. Several surgical procedures have been developed, including miniature punch grafting, thin Theirsch’s split-thickness skin grafting (STSG), suction blister technique, and ultrathin STSG. The decision-making process should also consider the potential risks and benefits associated with each technique. Factors such as graft survival, color match, post-operative complications, and long-term stability of repigmentation should be evaluated. In addition, patient factors such as comorbidities, skin type, and psychological impact should be carefully considered to ensure optimal surgical outcomes. We, hereby, aim to explore the potential execution of vitiligo surgery using the most conceivable technique, considering factors such as efficacy, safety, and patient-specific characteristics.

Suppression of Zinc Dendrite Growth by Enhanced Polyacrylamide Gel Electrolytes in Zinc-Ion Battery.

Aqueous zinc-ion batteries have become a promising energy storage battery due to high theoretical specific capacity, abundant zinc resources and low cost. However, zinc dendrite growth and hydrogen evolution reaction limit their application. This study aims to improve the cycling performance and stability of aqueous zinc-ion batteries by improving the gel electrolyte. Polyacrylamide (PAM) is selected as the base material of the gel electrolyte, which has good stability and safety, but the water retention capacity, Zn2+ migration number, and ionic conductivity of PAM are low, which affects the long-term stability of the battery. In response to these problems, we optimized PAM by chemical cross-linking method, and formed an enhanced PAM gel by adding disodium citrate dihydrate (SC). Experimental results show that the introduction of an appropriate amount of SC in the enhanced PAM gel electrolyte can significantly improve its electrochemical performance. The zinc-ion symmetric battery achieved a stable cycle of more than 2100 hours at a current density of 0.5 mA cm-2, which is mainly attributed to the inhibitory effect of the enhanced PAM gel on zinc dendrite growth and hydrogen evolution reaction. This study provides a new direction for the development and application of flexible zinc-ion batteries.

Accelerated In Vitro Oxidative Degradation Testing of Ultra-High Molecular Weight Polyethylene (UHMWPE).

Nonabsorbable polymers used in biomedical applications are assumed to be permanently stable based on short-term testing, but some may be susceptible to oxidative degradation over several years of implantation. Traditional in vitro oxidative degradation screenings employ hydrogen peroxide (H2O2) solutions. However, the inherent instability of H2O2 can compromise the consistency of oxidative conditions, especially over extended periods and at elevated temperatures used for accelerated testing. In this study, an automated reactive accelerated aging (aRAA) system, which integrates an electrochemical detection method and a feedback loop, was utilized to ensure precise control of H2O2 concentrations during polymer oxidative degradation testing. The reproducibility of the aRAA system was evaluated by comparing four identical setups. Its efficacy as an oxidation challenge was demonstrated on (i) medical-grade vitamin E (VE) blended ultra-high molecular weight polyethylene (UHMWPE) and (ii) highly crosslinked (HXL) UHMWPE as model materials. The aRAA-aged VE-UHMWPE and HXL-UHMWPE samples were also compared against samples aged via an existing accelerated aging standard, ASTM F2003-02(2022). Samples were analyzed using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to calculate their oxidation index per ASTM F2102-17. We observed that the aRAA system was more effective in oxidizing VE-UHMWPE and HXL-UHMWPE than the traditional ASTM F2003-02(2022) method. By providing a standardized and reliable approach to assess polymer oxidative degradation, the aRAA system could enhance the accuracy of long-term stability predictions for nonresorbable polymers in medical devices.

Saline based microfluidic soft pressure sensor utilizing a three-dimensional focused electric field for motion and healthcare monitoring

This paper introduces the ‘Spatially Focused Saline-based Pressure Sensor (SF-SaPS)', a novel soft microfluidic pressure sensor featuring a distinctive three-dimensional focusing structure. By critically reducing the cross-sectional area of the microchannel at the focused structure, the SF-SaPS achieves excellent sensitivity to pressure within the sensing region. With the spatially focused region, the SF-SaPS could detect a wide range of pressure from gentle touches to human weight, which is typically unachievable with low-conductivity sensing media such as saline, a medium inherently safe for human use. Beyond its sensitivity, the SF-SaPS exhibits sensing performance and stability comparable with conventional liquid metal-based pressure sensors. Our sensor demonstrated minimal signal drift, a rapid response time of 70 ms under cyclic loading, and 20-day long-term stability tests immersed in water. Additionally, the sensor possesses a transparency advantage unattainable by liquid metal sensors as we utilized transparent polymers and saline. A unique advantage of the SF-SaPS lies in its selective spatial and mechanical sensitivity; as the electrical resistance is highly dependent on changes in the cross-sectional area of the microchannels, the sensor has superior pressure sensitivity compared to bending and strain. Finally, various application examples highlight the SF-SaPS's advantages. By configuring the sensor in a two-axis array, the SF-SaPS facilitates pressure mapping across a plane. Additionally, it proves effective in healthcare monitoring, from radial pulse to finger movements. In conclusion, the SF-SaPS's combination of performance, stability, biocompatibility, and transparency positions this sensor as a versatile tool for applications extending beyond healthcare, as demonstrated in this study.

Shear creep deformation of rock fracture distrubed by dynamic loading

The long-term stability of jointed rock masses is usually dominated by fault activation, which may be triggered by the dynamic disturbance generated by blasting during mining activities, leading to the occurrence of disasters such as landslides in open-pit and rockbursts in deep mining. The initial stress and dynamic disturbance are key factors that strongly affect the shear creep behavior of rock fractures. In this work, the shear failure instability of rock fractures of sandstone under creep-impact loading was experimentally investigated by using a creep-impact test machine, which allows for applying creep loading and an additional dynamic disturbance on rock fractures. Three stages of shear creep deformation, creep strain rate, and time-to-failure are examined under different creep stress levels and impact energies. Experimental results show that the tangential and normal creep rates increase with the increase of creep stress and impact energy, but the increment of tangential creep rate is higher than that of the normal creep rate. The time-to-failure of the creeping specimen is shortened under high creep stress and large impact energy, while the time-to-failure after the last dynamic disturbance of the specimen is determined by the total impact energy and creep stress level. By using high-speed photography, it is found that the failure types of rock depend on the magnitude of impact energy and creep stress level; that is, rock mainly slides with low stress levels and shears off with high stress levels. In addition, under different impact energy and creep stress levels, the variation of height is between 0.38 and 0.52, while the defined fracture factor, which describes the degree of failure of serrations, is between 0.30 and 0.54. The findings can provide deep insight into the fault sliding mechanism caused by mining activities, which provides theoretical support for the safe mining of ore in fault fracture zones.

Do Energy Efficiency and Technology Boost Sustainable Environment: Evidence from GCC Countries

Sustainable Environment practices significantly reduce carbon emissions by ensuring the continuous use of materials and energy resources, thus making them intrinsically aligned with the underlying objectives of the decarbonization agenda. Technological advancement has the potential to contribute significantly to this shift by streamlining resource flows, enhancing waste management procedures, and allowing more efficient energy consumption. Although Gulf Cooperation Council countries have experienced robust economic growth over the decades, rising pollution emissions and low renewable energy consumption have raised concerns among policymakers about the long-term stability of this growth. In recent years, Gulf countries have paid significant concern to environmental matters and achieved carbon-free development. This study seeks to investigate the relationship between energy efficiency, technology, and sustainability, particularly emphasizing the green economy perspective. Carbon dioxide emission taken as the dependent variable. Frontier Technology Readiness Index reflects the utilization of technology within economies. Energy efficiency is also considered, symbolizing the transition from fossil fuels to green energy due to technological progression in the energy sector. The findings suggest that factors such as the Frontier Technology Readiness Index, the energy intensity level of primary energy, and medium and high-tech manufacturing significantly harm the environment, while scientific and technical journal articles and agriculture significantly improve the environment over time. To improve Gulf Cooperation Council countries' environmental quality, policymakers must understand the factors causing climate change. This study gives policymakers useful information about how to make the Gulf Cooperation Council community more sustainable by looking at energy efficiency, technology, and digital adaptation.

Unveiling the heterojunction of Fe3O4@MXene nanocatalyst for ultrafast degradation of antibiotics via non-radical pathway

The transfer of advanced oxidation processes (AOPs) to real-world applications faces several technology challenges involving oxidation performance, catalyst cost, poor reactive oxygen species (ROS) yield, and long-term stability. This work aims to develop a reactive, efficient, and stable MXene-based nanocatalyst, namely Fe3O4@Ti3C2Tx, for ultrafast removal of the selected sulfonamide antibiotics. As revealed by extensive nanocatalyst characterization, the MXene surface not only anchors Fe/Fe3O4 nanoparticles (NPs) but also prevents NP agglomeration. Notably, the conductive interface between MXene and Fe3O4 promotes the Fe(II)/Fe(III) redox cycle and accelerates peroxymonosulfate (PMS) activation. The Fe3O4@Ti3C2Tx demonstrates excellent catalytic activity by achieving complete sulfamethoxazole (SMX) degradation within 6 min and maintained its catalytic activity after 5 continuous cycles. In the Fe3O4@Ti3C2Tx/PMS system, multiple ROS (e.g., •OH, SO4•-, O2•-) are involved but 1O2 was found to be the primary ROS for SMX degradation. The presence of co-exiting inorganic impurities and pH changes may hinder SMX degradation. Finally, elucidating possible degradation pathways of SMX would greatly aid in treating antibiotic-containing wastewater.

Literature Review: Financial Management in Hospitals Using Process Improvement Methods

Financial management in hospitals faces significant challenges due to increasing healthcare costs and the demand to maintain high-quality patient care. Process Improvement methods such as Lean and Continuous Improvement have been adopted by hospitals to address these challenges. This study aims to review the literature regarding the impact of implementing Lean and Continuous Improvement methodologies on hospital financial management. The research methodology employed a systematic approach, analyzing studies published between 2018 and 2023. The results of the review showed that the implementation of Lean and Continuous Improvement methods significantly improved operational efficiency, leading to cost reductions of up to 30%, while simultaneously enhancing patient care quality and staff satisfaction. In conclusion, these methodologies offer a sustainable approach for hospitals to manage financial pressures without compromising the quality of care. Hospitals are encouraged to adopt these strategies to achieve long-term financial stability and operational excellence.

Synergistic effects of MXene and Co3O4 in composite electrodes: High-performance energy storage solutions

The development of high-performance electrode materials is crucial for advancing supercapacitor technology. The two-dimensional layered structure of MXene (Ti3C2Tx) presents high conductivity, abundant surface functional groups and accessible ion interaction between layers. However, the MXene suffers from the layer aggregation. To overcome this issue, we synthesized a composite material combining MXene with cobalt oxide (Co3O4) to enhance electrochemical performance in supercapacitors. MXene’s two-dimensional layered structure, high conductivity, and abundant surface functional groups allow for efficient ion intercalation, while Co3O4 contributes high theoretical capacitance and rich oxidation states. The resulted MXene/Co3O4 composite exhibits an impressive areal capacitance of 6.456F/cm2 at a current density of 3 mA/cm2, maintaining 90.52 % capacitance retention at 30 mA/cm2, and 81.37 % capacity after 5000 charge–discharge cycles. Additionally, the asymmetric supercapacitor (ASC) device fabricated using the MXene/Co3O4 composite achieves a power density of 6.41 mW/cm2 at an energy density of 0.37 mWh/cm2, with 82.3 % capacitance retention after 5000 cycles. These results demonstrate that the MXene/Co3O4 composite material is a promising candidate for high-performance supercapacitors, offering significant improvements in rate capability and long-term cycling stability.

Polymerization-Induced Self-Assembly Providing PEG-Gels with Dynamic Micelle-Crosslinked Hierarchical Structures and Overall Improvement of Their Comprehensive Performances.

Polymer gels are fascinating soft materials and have become excellent candidates for wearable electronics, biomedicine, sensors, etc. Synthetic gels usually suffer from poor mechanical properties, and integrating good mechanical properties, adhesiveness, stability, and self-healing performances in one gel is more difficult. Herein, polymerization-induced self-assembly (PISA) providing PEG-gels with an overall improvement in their comprehensive performances is reported. PISA synthesis is carried out in PEG (solvent) to efficiently produce various nanoparticles, which are used as the nanofillers in the subsequent synthesis of PEG-gels with dynamic micelle-crosslinked hierarchical structures. Compared to hydrogels, PEG-gels show excellent long-term stability due to the nonvolatile feature of PEG solvent. The hierarchical PEG-gels (with nanofillers) exhibit better mechanical and adhesive properties than the homogeneous-gels (without nanofillers). The energy dissipation mechanism of the PEG-gels is analyzed via stress relaxation and cyclic mechanical tests. High-density hydrogen bonds between the micelles and PAA matrix can be broken and reformed, endowing better self-healing properties of the dynamic micelle-crosslinked PEG gels. This work provides a simple strategy for producing hierarchical structural gels with enhanced properties, which offers fundamentals and inspirations for the designing of various advanced functional materials.

Palladium nanocrystals immobilized on boron and nitrogen codoped mesoporous carbon spheres as efficient methanol oxidation electrocatalysts

The development of cost-effective and high-performance electrocatalysts is crucial for the widespread application of direct methanol fuel cell. Herein, a convenient and robust method is developed to the controllable fabrication of Pd nanocrystals in situ immobilized on boron and nitrogen codoped mesoporous carbon spheres (Pd/BNMCS) as anode catalysts for the methanol oxidation reaction. The as-derived Pd/BNMCS hybrids are equipped with a series of useful structural features, such as large specific surface area, abundant mesoporous channels, presence of plentiful B and N atoms, well-dispersive Pd nanoparticles, and good electrical conductivity. As a consequence, the optimized Pd/BNMCS catalyst demonstrates superior electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area, high mass/specific activities, and reliable long-term stability, which are significantly better than those of traditional carbon black and undoped mesoporous carbon sphere supported Pd catalysts. This study highlights the potential of heteroatom codoped mesoporous carbon matrixes in the construction of advanced noble metal electrocatalysts for practical fuel cell applications.

Surface Functionalization of Gold Nanoparticles Using Alkyne Derivatives: Applications in Chemical Sensing.

Colloidal gold nanoparticles (AuNPs) are important nanomaterials for chemical sensing and therapeutics. For their application, it is vital to develop a reliable and robust surface functionalization method that can be applied to diverse functional molecules and offer better stability under harsh biological conditions. Currently, thiol (SH) is the most commonly used functional group for forming stable covalent bonds with AuNPs. However, thiolated molecules typically require complicated preparation procedures, are susceptible to oxidation, and are not compatible with many electrophiles and reducing groups. In this study, we report that surface functionalization of AuNPs can be achieved using alkyne derivatives, which exhibit several advantages over classical thiolation and peptide-bond methods, including straightforward preparation of alkyne derivatives, rapid and simple conjugation in buffers and complex media, higher conjugation efficiency, long-term stability, and resistance to decomposition under harsh conditions. Several alkynylated biotin and fluorescein derivatives are prepared, and the alkynylated-AuNPs are characterized using a lateral flow assay, gel electrophoresis, and spectroscopy techniques to investigate the conjugation efficiencies, size distributions, protein interaction properties, and binding mode of the Au-alkyne bond. We also demonstrate that alkynylated-AuNPs can be used for the sensitive detection of hydrogen peroxide and streptavidin proteins.

Amorphous AlOCl Compounds Enabling Nanocrystalline LiCl with Abnormally High Ionic Conductivity.

LiCl is a promising solid electrolyte, providing it possesses high ionic conductivity. Numerous efforts have been made to enhance its ionic conductivity through aliovalent doping. However, aliovalent substitution changes the intrinsic structure of LiCl, compromising its cost-effectiveness and electrochemical stability. Here, we report nanocrystalline LiCl embedded in amorphous AlOCl compounds with a heterogeneous structure to enhance its ionic conductivity. Nanocrystallization enlarges the LiCl unit cell, while amorphization facilitates interfacial ion transport. As a result, the amorphous AlOCl-modified LiCl nanocrystal (AlOCl-nanoLiCl) demonstrates a high ionic conductivity of 1.02 mS cm-1, which is 5 orders of magnitude higher than that of LiCl. Additionally, it exhibits high oxidative stability, low cost ($19.87 US kg-1), and low Young's modulus (2-3 GPa). When AlOCl-nanoLiCl is coupled with Li-rich cathodes (Li1.17Mn0.55Ni0.24Co0.05O2, 4.8 V vs Li+/Li), all-solid-state batteries exhibit remarkable long-term cycling stability (>1000 cycles). This work presents a novel strategy to enhance the ionic conductivity of alkaline chlorides without compromising their intrinsic advantages.

Enhanced self-biased photocatalytic fuel cell performance by dual-photoelectrode with novel graphene-based substrate for tetracycline photodegradation and electricity production

In this study, a graphene-based dual-photoelectrode photocatalytic fuel cell (PFC) system, incorporating n-type ZnO photoanode and p-type Cu2O photocathode, has been meticulously designed and fabricated to achieve concurrent organic pollutant decomposition and electricity production. The rGO-ZnO｜rGO-Cu2O PFC system displayed superior photoelectrocatalytic performance, surpassing the comparative FTO-based PFC system. Notably, it achieved power density of 22.23 μW cm−2 maximumly, tetracycline hydrochloride (TCH) degradation efficiency of 74.0 % within 120 min, and exhibited long-term stability. This enhanced performance can give the credit to the larger active areas generated by the in-situ growth of photocatalytic materials in layered microstructure of graphene films, as well as the rapid electron transfer within graphene films. This study underscores the potential application of graphene films as electrode substrate materials, and introduces a strategy for achieving the diversification and optimization of electrode substrate material selection, ultimately facilitating the development of more efficient PFC systems.

Electrical and UV-sensing performance of N-doped-Ba(Ti,Zr,Mo,Hf,Ta)O3-dielectric and ZnSnO-channel-based flexible thin-film transistors

Flexible thin-film transistors (TFTs) based on N-doped Ba(Ti,Zr,Mo,Hf,Ta)O3 dielectric and ZnSnO channel show high electrical and UV-sensing performance. The optimal N-doped Ba(Ti,Zr,Mo,Hf,Ta)O3 compositions with low equivalent oxide thicknesses (≈2 nm) and high-entropy (configurational entropy ≈ 1.59 R) are efficiently determined from a wide composition space (library). The film library is patterned to 450 metal–insulator-metal stacks, revealing dielectric constants ≈ 262–322 and loss (tan δ) ≈ 0.01–0.30 for the N-doped Ba(Ti,Zr,Mo,Hf,Ta)O3 at 1 kHz. The library is further integrated to 63 TFTs, and the promising ones exhibit the remarkable parameters: current on/off ratio of 108, threshold voltage (VT) of 0.02 V, saturation field-effect mobility of ≈76 cm2⋅V−1⋅s−1, and subthreshold swing of 0.062 V dec−1. The devices also exhibit desirable long-term stability for up to five months and perform reliably with small or negligible changes in VT and drain-source current under various gate-bias stress and temperature conditions. Furthermore, the TFT-based ultraviolet (253 nm) detector demonstrates impressive sensitivity (≈ 2 × 106) and responsibility (≈ 1171.9 A W−1). There is no substantial degradation in electrical or sensing characteristics under various levels of deformation. Charge transport in constructed energy band diagrams is used to elucidate the observed remarkable performance.

Rare-Earth Metal-Based Materials for Hydrogen Storage: Progress, Challenges, and Future Perspectives.

Rare-earth-metal-based materials have emerged as frontrunners in the quest for high-performance hydrogen storage solutions, offering a paradigm shift in clean energy technologies. This comprehensive review delves into the cutting-edge advancements, challenges, and future prospects of these materials, providing a roadmap for their development and implementation. By elucidating the fundamental principles, synthesis methods, characterization techniques, and performance enhancement strategies, we unveil the immense potential of rare-earth metals in revolutionizing hydrogen storage. The unique electronic structure and hydrogen affinity of these elements enable diverse storage mechanisms, including chemisorption, physisorption, and hydride formation. Through rational design, nanostructuring, surface modification, and catalytic doping, the hydrogen storage capacity, kinetics, and thermodynamics of rare-earth-metal-based materials can be significantly enhanced. However, challenges such as cost, scalability, and long-term stability need to be addressed for their widespread adoption. This review not only presents a critical analysis of the state-of-the-art but also highlights the opportunities for multidisciplinary research and innovation. By harnessing the synergies between materials science, nanotechnology, and computational modeling, rare-earth-metal-based hydrogen storage materials are poised to accelerate the transition towards a sustainable hydrogen economy, ushering in a new era of clean energy solutions.

Fabrication of polyoxometalate dispersed cobalt oxide nanowires for electrochemically monitoring superoxide radicals from Hela cell mitochondria

An ultrasensitive electrochemical sensor is constructed by electrostatically adsorbing negatively charged hourglass-shape Cu-Polyoxometalate (POM) onto a positively charged CoO nanowires modified carbon cloth. The petaloid CoO nanowires have a large specific surface area that can well disperse open-structured Cu-POM to form Cu-POM@CoONWs@CC, which can maximumly expose catalytic active centers (Co2+ and Cu2+) and accelerate mass/charge transfer. In addition to the above advantages, the excellent electron exchange ability of Cu-POM and good conductivity of CoONWs@CC endow the sensor with good detection capability to H2O2 including a linear detection range of 0.05–1.4 μA μM−1, a low detection limit of 0.022 μM, high sensitivity of 110.48 μA μM−1, good selectivity and long-term stability. Due to the fast transformation of superoxide anion (O2∙‐) to H2O2, the sensor can indirectly monitor the electron leakage resulting in the formation of O2∙‐ via detecting H2O2. Afterwards, Hela cell mitochondria were extracted from the living cells that cultured with different mitochondrial inhibitors and the release of O2∙‐ from the corresponding mitochondrial complexes was monitored by the sensor. Through comparing the current signals, we determined that complex I is probably the main electron leakage site. This work could provide meaningful information for the diagnosis of certain oxidative stress diseases.

Effect of surface morphology on the deformation mechanism of Cu nanocrystal under cyclic loading at different temperatures: Molecular dynamics simulations

Micro-electromechanical systems (MEMS) are often subject to mechanical vibration or temperature, the fatigue reliability of small metal parts is a potential problem for long-term operational stability. Since the MEMS packaging is performed at a high temperature of about 600 K. Therefore, in this paper, the deformation mechanisms of copper nano-single crystals with different surface morphologies under cyclic loading were investigated by molecular dynamics calculations at room temperature (300 K) and high temperature (600 K) to provide a theoretical basis for the design of copper nanomaterials. The results show that the plastic deformation modes of the models with different surface morphologies during cyclic loading are mainly Shockley partial dislocations slipping along {111}. In contrast, the fatigue damage modes are extrusion intrusion induced by high shear strain. Compared with the surface containing a pore, the damage caused by the circular and sharp recesses through the surface is more serious. The causes of stress concentration during deformation are mainly the entanglement of Shockley partial dislocations and the generation of Lomer-Corell lock fixed dislocations. The locations of these stress concentrations will produce pores in the subsequent deformation. In addition, since periodic interfaces do not cause particularly pronounced stress concentrations and shear strain concentrations on the surface compared to other models with defects, and the resulting shear strain concentration bands are split by shear strain bands in the other direction, extrusion intrusion is prevented. Therefore, at room temperature, the model with a one-dimensional sinusoidal surface has the strongest resistance to fatigue damage, while at high temperatures, the model with a two-dimensional sinusoidal surface has the optimal resistance to fatigue damage. This provides a basis for the design of NEMS/MEMS working at high temperatures.

Boosted Solar Thermochemical Low-Temperature CO2 Splitting On Pt/CeO2 by Interface Catalysis.

Solar thermochemical CO2 splitting using metal oxides is considered as a promising approach to produce solar fuels since it is capable to tap abundant sunlight directly and store solar energy in the renewable fuel. It remains a grand challenge to achieve highly efficient CO2 splitting at low temperature (<800 °C) due to insufficient activation of metal oxides for CO2. Herein, the introduction of a small amount of Pt was found to be able to greatly increase the performance of CO2 splitting with the highest peak CO production rate of about 65 mL min-1 g-1, CO productivity of about 53 mL g-1, nearly 100 % CO2 conversion and long-term stability for 0.5Pt/CeO2, which exceeded most of the state-of-the-art transition metals-based oxides even at lower temperature (700 °C). This could be attributed to the addition of Pt leading to the formation of an interface (Pt0-Ov-Ce3+) after CH4 reduction, which improved CO2 activation and dissociation due to beneficial breakage of C=O bond by the cooperation of Pt0 and oxygen vacancies in the interface.

Fully Atom-Efficient Solvent-Mediated Biopolymer Manufacturing: A Base Case Illustrated with Macromolecular Surfactants Tailored to Stable Polymer-Water Interfaces.

This work introduces a novel 1-pot, 0-waste, 0-VOC methodology for synthesizing polymeric surfactants using acrylated epoxidized soybean oil and acrylated glycerol as primary monomers. These macromolecular surfactants are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, allowing for tunable hydrophilic-lipophilic balance (HLB) and ionic properties. We characterize the copolymers' chemical composition and surface-active properties, and evaluate their effectiveness in forming and stabilizing emulsions of semiepoxidized soybean oil and poly(acrylated epoxidized high oleic soybean oil). Comprehensive analyses, including gel permeation chromatography, nuclear magnetic resonance spectroscopy, dynamic light scattering, particle size distribution, zeta potential, and critical micelle concentration, provide detailed insights into the copolymers and the emulsions they form. The results demonstrate that the RAFT-polymerized surfactants offer long-lasting stability and effectively disperse both common oil-in-water emulsions and highly viscous and hydrophobic polymer latexes. These surfactants outperform traditional small molecule surfactants by reducing particle size and preventing phase separation, even over extended storage periods. Stable polymer-water interfaces are achieved through HLB control, tailored by monomer composition, and the final product requires no additional purification since polymerization occurs in liquid surfactants. While small molecules contribute to rapid micelle formation, the polymeric components enhance long-term stability through steric repulsion and slower dynamics. This method enables even the emulsification of polymers with submicron particle size, which ordinarily requires emulsion polymerization. Integrating biobased polymeric surfactants with advanced polymer processing techniques opens new possibilities for transforming highly hydrophobic polymers into latexes, facilitating downstream applications. This innovation enhances the environmental sustainability of surfactant production and broadens the potential for polymer emulsification technologies. Additionally, the integrated solution-processing approach demonstrated here can be applied to other emerging polymers, where judiciously selected nonvolatile solvents facilitate the polymerization and play a role in the final application.