Search

Microbial carbon (C) use efficiency (CUE) drives soil C formation, while physical-chemical protection stabilizes subsequent microbial necromass, both shaped by soil aggregates and minerals. Soils inherit many properties from the parent material, yet the influence of lithology and associated soil geochemistry on microbial CUE and necromass stabilization remains unknow. Here, we quantified microbial CUE in well-aggregated bulk soils and crushed aggregates, as well as microbial necromass in bulk soils and the mineral-associated organic matter fraction, originating from carbonate-containing (karst) and carbonate-free (clastic rock, nonkarst) parent materials along a broad climatic gradient. We found that aggregate crushing significantly increased microbial CUE in both karst and nonkarst soils. Additionally, compared to nonkarst soils, calcium-rich karst soils increased macroaggregate stability and decreased the ratio of oligotrophic to copiotrophic microbial taxa, leading to a reduction in microbial CUE. Moreover, microbial CUE was negatively associated with iron (hydr)oxides in karst soils, attributed to the greater abundance of iron (hydr)oxides and higher soil pH. Despite the negative effects of soil aggregation and minerals on microbial CUE, particularly in karst soils, these soils concurrently showed greater microbial necromass stability through organo-mineral associations compared to nonkarst soils. Consequently, (i) bedrock lithology mediates the effects of aggregates and minerals on microbial CUE and necromass stability; and (ii) balancing minerals' dual roles in diminishing microbial CUE and enhancing microbial necromass stability is vital for optimizing soil C preservation.

Hydrogen-deuterium exchange (HDX) has become a pivotal method for investigating the structural and dynamic properties of proteins. The versatility and sensitivity of mass spectrometry (MS) made the technique the ideal companion for HDX, and today HDX-MS is addressing a growing number of applications in both academic research and industrial settings. The prolific generation of experimental data has spurred the concurrent development of numerous computational tools, designed to automate parts of the workflow while employing different strategies to achieve common objectives. Various computational methods are available to perform automated peptide searches and identification; different statistical tests have been implemented to quantify differences in the exchange pattern between two or more experimental conditions; alternative strategies have been developed to deconvolve and analyze peptides showing multimodal behavior; and different algorithms have been proposed to computationally increase the resolution of HDX-MS data, with the ultimate aim to provide information at the level of the single residue. This review delves into a comprehensive examination of the merits and drawbacks associated with the diverse strategies implemented by software tools for the analysis of HDX-MS data.

Bacterial endophthalmitis is a severe infection of the aqueous or vitreous humor of the eye that can lead to permanent vision loss. Due to the rapid emergence of antibiotic resistance and dose-limiting toxicities, the standard treatment of bacterial endophthalmitis via the intravitreal injection of broad-spectrum antibiotics remains inadequate. Membrane active cationic antimicrobial peptides (AMPs) have emerged as a promising class of effective and broad-spectrum antimicrobial agents with potential to overcome antibiotic resistance. In this work, we investigate, for the first time, the use of omiganan (IK-12), a 12-amino acid indolicidin derivative for the treatment of bacterial endophthalmitis. Additionally, IK-12 was used as a template to perform amino acid rearrangements, without altering the length or type of amino acids, to yield a series of new derivative AMPs with varying extents of secondary structure formation under membrane mimicking conditions. IK-12 and its derivatives demonstrated strong and broad-spectrum antibacterial activities against a panel of clinically isolated Gram-positive and Gram-negative bacteria, including methicillin-resistant Staphylococcus aureus commonly implicated in bacterial endophthalmitis. Interestingly, two of the new IK-12 derivatives, IP-12 and WP-12, showed lower geometric mean minimum inhibitory concentration and higher 50% hemolysis concentration values, which effectively translated into 2- to 3.4-fold higher bacterial selectivity than the parent IK-12. Furthermore, the intravitreal injection of IK-12, IP-12, and WP-12 in a rabbit model of MRSA -induced endophthalmitis led to considerably improved clinical presentation and reduced recruitment of inflammatory cells. In all, these results demonstrate the potential of IK-12 and its derivatives, IP-12 and WP-12, as promising candidates for the treatment of bacterial endophthalmitis.

Identification of bacterial lectins offers an attractive route to the development of new diagnostics, but the design of specific sensors is complicated by the low selectivity of carbohydrate-lectin interactions. Here we describe a glycopolymer-based sensor array which can identify a selection of lectins with similar carbohydrate recognition preferences through a pattern-based approach. Receptors were generated using a polymer scaffold functionalized with an environmentally sensitive fluorophore, along with simple carbohydrate motifs. Exposure to lectins induced changes in the emission profiles of the receptors, enabling the discrimination of analytes using linear discriminant analysis. The resultant algorithm was used for lectin identification across a range of concentrations and within complex mixtures of proteins. The sensor array was shown to discriminate different strains of pathogenic bacteria, demonstrating its potential application as a rapid diagnostic tool to characterize bacterial infections and identify bacterial virulence factors such as production of adhesins and antibiotic resistance.

The design of stable formulations remains a major challenge for protein therapeutics, particularly the need to minimize aggregation. Experimental formulation screens are typically based on thermal transition midpoints ( T ), and forced degradation studies at elevated temperatures. Both approaches give limited predictions of long-term storage stability, particularly at low temperatures. Better understanding of the mechanisms of action for formulation of excipients and buffers could lead to improved strategies for formulation design. Here, we identified a complex impact of glycine concentration on the experimentally determined stability of an antibody Fab fragment and then used molecular dynamics simulations to reveal mechanisms that underpin these complex behaviors. m ), and forced degradation studies at elevated temperatures. Both approaches give limited predictions of long-term storage stability, particularly at low temperatures. Better understanding of the mechanisms of action for formulation of excipients and buffers could lead to improved strategies for formulation design. Here, we identified a complex impact of glycine concentration on the experimentally determined stability of an antibody Fab fragment and then used molecular dynamics simulations to reveal mechanisms that underpin these complex behaviors. T measurements revealed more complex changes in the native ensemble dynamics, which reached a maximum at 30 mg/mL. The aggregation kinetics at 65 °C were similar at 0 and 20 mg/mL glycine, but then significantly slower at 50 mg/mL. These complex behaviors indicated changes in the dominant stabilizing mechanisms as the glycine concentration was increased. MD revealed a complex balance of glycine self-interaction, and differentially preferred interactions of glycine with the Fab as it displaced hydration-shell water, and surface-bound water and citrate buffer molecules. As a result, glycine binding to the Fab surface had different effects at different concentrations, and led from preferential interactions at low concentrations to preferential exclusion at higher concentrations. During preferential interaction, glycine displaced water from the Fab hydration shell, and a small number of water and citrate molecules from the Fab surface, which reduced the protein dynamics as measured by root-mean-square fluctuation (RMSF) on the short time scales of MD. By contrast, the native ensemble dynamics increased according to Δ m , suggesting increased conformational changes on longer time scales. The aggregation kinetics did not change at low glycine concentrations, and so the opposing dynamics effects either canceled out or were not directly relevant to aggregation. During preferential exclusion at higher glycine concentrations, glycine could only bind to the Fab surface through the displacement of citrate buffer molecules already favorably bound on the Fab surface. Displacement of citrate increased the flexibility (RMSF) of the Fab, as glycine formed fewer bridging hydrogen bonds to the Fab surface. Overall, the slowing of aggregation kinetics coincided with reduced flexibility in the Fab ensemble at the very highest glycine concentrations, as determined by both RMSF and Δ S , and occurred at a point where glycine binding displaced neither water nor citrate. These final interactions with the Fab surface were driven by mass action and were the least favorable, leading to a macromolecular crowding effect under the regime of preferential exclusion that stabilized the dynamics of Fab.vh measurements revealed more complex changes in the native ensemble dynamics, which reached a maximum at 30 mg/mL. The aggregation kinetics at 65 °C were similar at 0 and 20 mg/mL glycine, but then significantly slower at 50 mg/mL. These complex behaviors indicated changes in the dominant stabilizing mechanisms as the glycine concentration was increased. MD revealed a complex balance of glycine self-interaction, and differentially preferred interactions of glycine with the Fab as it displaced hydration-shell water, and surface-bound water and citrate buffer molecules. As a result, glycine binding to the Fab surface had different effects at different concentrations, and led from preferential interactions at low concentrations to preferential exclusion at higher concentrations. During preferential interaction, glycine displaced water from the Fab hydration shell, and a small number of water and citrate molecules from the Fab surface, which reduced the protein dynamics as measured by root-mean-square fluctuation (RMSF) on the short time scales of MD. By contrast, the native ensemble dynamics increased according to Δ S vh , suggesting increased conformational changes on longer time scales. The aggregation kinetics did not change at low glycine concentrations, and so the opposing dynamics effects either canceled out or were not directly relevant to aggregation. During preferential exclusion at higher glycine concentrations, glycine could only bind to the Fab surface through the displacement of citrate buffer molecules already favorably bound on the Fab surface. Displacement of citrate increased the flexibility (RMSF) of the Fab, as glycine formed fewer bridging hydrogen bonds to the Fab surface. Overall, the slowing of aggregation kinetics coincided with reduced flexibility in the Fab ensemble at the very highest glycine concentrations, as determined by both RMSF and Δ S vh , and occurred at a point where glycine binding displaced neither water nor citrate. These final interactions with the Fab surface were driven by mass action and were the least favorable, leading to a macromolecular crowding effect under the regime of preferential exclusion that stabilized the dynamics of Fab.

During chemotherapy treatment for cancer, often only a fraction of the administered dose reaches the tumor site, with the remaining drug spreading throughout the body, producing unwanted side-effects and restricting how much drug can be safely administered. A potential solution to reduce this problem is the use of microbubbles. The interaction between microbubbles and ultrasound generates pores in the tumor cells, permitting enhanced drug uptake. This study investigates the delivery of the ascorbic acid derivative, palmitoyl ascorbate, to KRAS-mutated colorectal cancer cells in vitro. Ultrasound-triggered microbubbles enhanced the efficacy of liposomal palmitoyl ascorbate treatments by 1.7- and 2.2-fold in LS174T and HCT116 CRC cell lines, respectively. This enhancement was achieved without increasing the drug dosage, and the therapeutic effect was shown to be localized to the area that received the ultrasound pulse, aiding in the reduction of off-site toxicity., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Fabrication of traditional 3D cell culturing scaffolds requires synthetic polymers or additives, posing a risk of poor biocompatibility and low biodegradability. Pickering emulsions stabilized by biobased nanomaterials can be used as templates to produce scaffolds with facile tunable porous structure, excellent cytocompatibility, and biodegradability. In this study, very stable high internal phase Pickering emulsions (HIPPE) with an oil content of 80% were successfully prepared by xylan hydrate nanocrystals (XNC). The HIPPE can exist stably for more than 30 days, exhibiting a high viscosity. By adding cellulose nanofibers (CNF) and removing the oil phase, scaffolds with a tuned porous structure and enhanced cell culturing ability were successfully fabricated. In the HIPPE templated scaffolds with XNC/CNF, XNC plays a major role in stabilizing the emulsions, while CNF improves the mechanical properties of the scaffolds, both of which are vital to the successful fabrication of the scaffolds. Compared with non-HIPPE templated scaffolds, the HIPPE templated scaffold had a higher porosity and a higher median pore size. The HIPPE templated scaffold was able to maintain 80% cell activity and showed an excellent cytocompatibility. The HIPPE templated scaffolds consisting of XNC and CNF demonstrate great potential in 3D cell culturing for medical purpose.

The Sustainable Development Goals emphasize coordination and integration between sectors. Solar-powered submersible water pumping systems are versatile technology that help address community drinking water, irrigation, and electricity needs. Stakeholders external to the community, particularly solar photovoltaic experts, are vital in ensuring continued system services; however, there has been no comprehensive assessment of different solar-powered water pumping system support efforts. This review is the first to systematically evaluate external support for solar-powered systems from multiple regions and implementing organizations. We reviewed solar-powered water pumping system literature to identify implemented external support and factors that affect implementation. Publication databases, organization Web sites, and citations were searched. Seventy-four studies were included and evaluated using inductive coding and thematic synthesis. We derived a framework that organized support activities and factors into three nested levels of implementation: system, program, and sector. For support efforts implemented after 2010, most support providers worked at all levels. Each provider type worked at levels aligned with their knowledge and resources and complementary to other providers' work. Drivers of support specific to solar-powered water systems were the existence of solar photovoltaic markets and infrastructure, support providers experienced with solar photovoltaics, and government and community solar advocates. We grouped support factors that study authors associated with system functionality into four categories: location and quality of support, reliability of support arrangements, frequency and timeliness of support, and policy and regulatory environment. No study outlined support for multiple uses of the systems or end-of-lifecycle care of solar panels. Solar-powered water pumping systems provide multiple community services, and their management will be bolstered by support providers collaborating to optimally apply their skill sets and create support plans that comprehensively address system versatility.

This study aims to understand the bulk and interfacial performance of potato protein microgels. Potato protein (PoP) was used to produce microgels of submicrometer diameter via a top-down approach of thermal cross-linking followed by high-shear homogenization of the bulk gel. Bulk "parent" gels were formed at protein concentrations [PoP] = 5-18 wt %, which subsequently varied in their bulk shear elastic modulus ( G ') by several orders of magnitude (1-100 kPa), G ' increasing with increasing [PoP]. The PoP microgels (PoPM) formed from these parent gels had diameters varying between 100 and 300 nm (size increasing with increasing G ' and [PoP]), as observed via dynamic light scattering and atomic force microscopy (AFM) of PoPM adsorbed onto silicon. Interfacial rheology (interfacial shear storage and loss moduli, G i ″) and interfacial tension (γ) of adsorbed films of PoP (i.e., nonheated PoP) and PoPM (both at tetradecane-water interfaces) were also studied, as well as the bulk rheology of the PoPM dispersions. The results showed that PoPM dispersions (at 50 vol %) had significantly higher bulk viscosity and shear thinning properties compared to the nonmicrogelled PoP at the same overall [PoP], but the bulk rheological behavior was in sharp contrast to the interfacial rheological performance, where G i ″ of PoP were higher than for any of the PoPM. This suggests that the deformability and size of the microgels were key in determining the interfacial rheology of the PoPM. These findings may be attributed to the limited capacity for "unfolding" and lateral interactions of the larger PoPM at the interface, which are presumed to be stiffer due to their production from the strongest PoP gels. Our study further confirmed that heating and cooling the adsorbed films of PoPM after their adsorption showed little change, highlighting that hydrogen bonding was limited between the microgel particles.G i ' and G i ″ of PoP were higher than for any of the PoPM. This suggests that the deformability and size of the microgels were key in determining the interfacial rheology of the PoPM. These findings may be attributed to the limited capacity for "unfolding" and lateral interactions of the larger PoPM at the interface, which are presumed to be stiffer due to their production from the strongest PoP gels. Our study further confirmed that heating and cooling the adsorbed films of PoPM after their adsorption showed little change, highlighting that hydrogen bonding was limited between the microgel particles.

Hydrogels, composed of hydrophilic polymer networks, have emerged as versatile materials in biomedical applications due to their high water content, biocompatibility, and tunable properties. They mimic natural tissue environments, enhancing cell viability and function. Hydrogels' tunable physical properties allow for tailored antibacterial biomaterial, wound dressings, cancer treatment, and tissue engineering scaffolds. Their ability to respond to physiological stimuli enables the controlled release of therapeutics, while their porous structure supports nutrient diffusion and waste removal, fostering tissue regeneration and repair. In wound healing, hydrogels provide a moist environment, promote cell migration, and deliver bioactive agents and antibiotics, enhancing the healing process. For cancer therapy, they offer localized drug delivery systems that target tumors, minimizing systemic toxicity and improving therapeutic efficacy. Ocular therapy benefits from hydrogels' capacity to form contact lenses and drug delivery systems that maintain prolonged contact with the eye surface, improving treatment outcomes for various eye diseases. In mucosal delivery, hydrogels facilitate the administration of therapeutics across mucosal barriers, ensuring sustained release and the improved bioavailability of drugs. Tissue regeneration sees hydrogels as scaffolds that mimic the extracellular matrix, supporting cell growth and differentiation for repairing damaged tissues. Similarly, in bone regeneration, hydrogels loaded with growth factors and stem cells promote osteogenesis and accelerate bone healing. This article highlights some of the recent advances in the use of hydrogels for various biomedical applications, driven by their ability to be engineered for specific therapeutic needs and their interactive properties with biological tissues.

Flow synthesis is becoming increasingly relevant as a sustainable and safe alternative to traditional batch processes, as reaction conditions that are not usually achievable in batch chemistry can be exploited (for example, higher temperatures and pressures). Telescoped continuous reactions have the potential to reduce waste by decreasing the number of separate unit operations (e.g., crystallization, filtration, washing, and drying), increase safety due to limiting operator interaction with potentially harmful materials that can be reacted in subsequent steps, minimize supply chain disruption, and reduce the need to store large inventories of intermediates as they can be synthesized on demand. Optimization of these flow processes leads to further efficiency when exploring new reactions, as with a higher yield comes higher purity, reduced waste, and a greener synthesis. This project explored a two-step process consisting of a three-phase heterogeneously catalyzed hydrogenation followed by a homogeneous amidation reaction. The steps were optimized individually and as a multistep telescoped process for yield using remote automated control via a Bayesian optimization algorithm and HPLC analysis to assess the performance of a reaction for a given set of experimental conditions. 2-MeTHF was selected as a green solvent throughout the process, and the heterogeneous step provided good atom economy due to the use of pure hydrogen gas as a reagent. This research highlights the benefits of using multistage automated optimization in the development of pharmaceutical syntheses. The combination of telescoping and optimization with automation allows for swift investigation of synthetic processes in a minimum number of experiments, leading to a reduction in the number of experiments performed and a large reduction in process mass intensity values., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A new method for rapid and facile fabrication of homoporous films with high volatile amine sensitivity was developed. First, red cabbage anthocyanin was encapsulated in ethyl cellulose to form water-in-organic (W/O) emulsion. Afterward, the W/O emulsion was rapidly dried using the supporting matrix Magnolia Grandiflora Linn leaf vein at 60% relative humidity and 50 °C to form a colorimetric film with regular hexagonal pores with an average side length of about 23 μm. The films exhibited good sensitivity to ammonia (NH 3 ), dimethylamine, and trimethylamine, with limit of detection of 0.26, 0.24, and 0.38 μM, respectively, and high stability when stored in high humid environments. An obvious color change of the films from pink to green was clearly observed during the freshness monitoring of pork, chicken, salmon, and shrimp. Thus, this work offered a novel and reliable method for the development of porous films for food freshness monitoring.

The knowledge of the reactivity of N -nitrosamines (NSAs) with common organic reagents in synthesis is essential in determining their presence in pharmaceutical products, if formed and retained during synthesis. In this study, we carried out a comprehensive survey of the Reaxys database for all reactions in which the NSA functional group is consumed. Very different reactivities for different classes of NSAs, e.g., N , N -dialkylnitrosamines and N , N -diphenylnitrosamine, were identified, suggesting substrates which should be included in any future reactivity screening. A classification of NSAs based on their reactivities, and corresponding reagents and transformations, was drawn up based on the data. Furthermore, the survey identified missing areas in the reported reactivities of NSAs with different reagents. This led to an experimental reactivity screening of 8 commercial NSAs with common synthetic reagents in the Mirabilis tool for purge assessment. The results showed Na 2 S 2 O 4 in 1 M aqueous NaOH at 50 °C to be highly effective at destroying NSAs without damaging other organic compounds., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

We use ab initio modeling (CASTEP) to help elucidate the crystallization phenomena and chemistry behind kidney stone composition and formation. To explore the stone formation process, we have constructed a surface model of calcium oxalate dihydrate-the mineral most commonly found in patients with hypercalciuria and modeled stone growth, by simulating further calcium oxalate adsorption onto the surface (-7.446 eV, -0.065 eV/atom). Furthermore, urine analysis of kidney stone patients has previously revealed that their urine contains higher concentrations of phospholipids compared to healthy individuals. Therefore, to investigate the interactions between urinary macromolecules and the growing crystal surfaces at an atomic level, we have performed ab initio molecular dynamics simulations of phosphocholine adsorption on calcium oxalate surfaces. We have shown that the phosphocholine headgroups become entrapped within the growing crystal and the lowest energy structures (-18.008 eV, -0.0396 eV/atom) are those where the calcium oxalate dihydrate surfaces have become disrupted, with reorganization of their crystallographic structure. Urinary calculi (kidney stones) are a common ailment affecting around 10% of the world's population and resulting in nearly 90,000 finished consultant episodes (FCE) each year in the United Kingdom [Hospital Episode Statistics, Admitted Patient Care-England, 2011-12 NHS Digital, 2021-2022. https://digital.nhs.uk/data-and-information/publications/statistical/hospital-admitted-patient-care-activity/hospital-episode-statistics-admitted-patient-care-england-2011-12]., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Lead (Pb 2+ ) is a ubiquitous pollutant. Membrane filtration represents one of the most common water treatment methods, but nanofiltration and ultrafiltration require high transmembrane pressure, while microfiltration has larger pore sizes than ions, making them unfavorable for direct ion removal at low cost. Selective and direct separation of Pb 2+ via membrane filtration at high efficiency without sacrificing the flux of clean water still remains challenging. Herein, inspired by the Pb 2+ -tolerable oleander that enriches and prevents Pb 2+ in roots from permeating the plant body, a smart Pb 2+ -adsorptive filtration membrane with a temperature- and ion-tunable water gate was prepared by loading dual-responsive poly( N -isopropylacrylamido- co -acrylamido-benzo-18-crown-6) (PNB-5-20) microgels onto a commercial membrane. The PNB-5-20 microgel exhibits pronounced temperature-responsive swelling/deswelling (hydrodynamic diameter, 650-330 nm) with a volume phase transition temperature (VPTT) at ∼33 °C. Moreover, the microgel shows a high Pb 2+ -adsorption capacity ( q max , 85.4 mg/g) and good selectivity (distribution coefficient K responsiveness, having the VPTT positively shifted to 40 °C in the presence of Pb d ∼ 1000 mL/g) thanks to its complexation with the crown ether, as well as good Pb 2+ responsiveness, having the VPTT positively shifted to 40 °C in the presence of Pb 2+ with enhanced swelling behaviors. Functionalized with PNB-5-20, the smart membrane integrates Pb 2+ with water permeation reduced. Once purified, the gates can be "re-opened" by increasing the temperature. Construction of such an intelligent membrane filtration device with a tunable water gate and excellent Pb 2+ recognition and adsorption performance will greatly simplify the remediation of Pb 2+ with water permeation reduced. Once purified, the gates can be "re-opened" by increasing the temperature. Construction of such an intelligent membrane filtration device with a tunable water gate and excellent Pb 2+ recognition and adsorption performance will greatly simplify the remediation of Pb 2+ -polluted water.

Flocculation is a type of aggregation where the surfaces of approaching droplets are still at distances no closer than a few nanometers while still remaining in close proximity. In a high internal-phase oil-in-water (O/W) emulsion, the state of flocculation affects the bulk flow behavior and viscoelasticity, which can consequently control the three-dimensional (3D)-printing process and printing performance. Herein, we present the assembly of O/W Pickering high-internal-phase emulsions (Pickering-HIPEs) as printing inks and demonstrate how depletion flocculation in such Pickering-HIPE inks can be used as a facile colloidal engineering approach to tailor a porous 3D structure suitable for drug delivery. Pickering-HIPEs were prepared using different levels of cellulose nanocrystals (CNCs), co-stabilized using "raw" submicrometer-sized sustainable particles from a biomass-processing byproduct. In the presence of this sustainable particle, the higher CNC contents facilitated particle-induced depletion flocculation, which led to the formation of a mechanically robust gel-like ink system. Nonetheless, the presence of adsorbed particles on the surface of droplets ensured their stability against coalescence, even in such a highly aggregated system. The gel structures resulting from the depletion phenomenon enabled the creation of high-performance printed objects with tunable porosity, which can be precisely controlled at two distinct levels: first, by introducing voids within the internal structure of filaments, and second, by generating cavities (pore structures) through the elimination of the water phase. In addition to printing efficacy, the HIPEs could be applied for curcumin delivery, and in vitro release kinetics demonstrated that the porous 3D scaffolds engineered for the first time using depletion-flocculated HIPE inks played an important role in 3D scaffold disintegration and curcumin release. Thus, this study offers a unique colloidal engineering approach of using depletion flocculation to template 3D printing of sustainable inks to generate next-generation porous scaffolds for personalized drug deliveries.

Thermally activated delayed fluorescence (TADF) compounds are highly attractive as sensitizing and emitting materials for organic light-emitting diodes (OLEDs). The efficiency of the OLED depends on multiple parameters, most of which rely on the properties of the emitter including those that govern the internal quantum and outcoupling efficiencies. Herein, we investigate a series of aryl substituted acridine donor derivatives of the donor-acceptor TADF emitter DMAC-TRZ , with the objective of correlating their properties, such as triplet harvesting efficiency and transition dipole moment orientation, with their corresponding device efficiency. The decoration of the DMAC donor with substituted aryl groups not only modifies the molecular weight and length of the emitter but also affects the emission color and the capacity for the emitters to efficiently harvest triplet excitons. The presence of electron-withdrawing 4-cyanophenyl and 4-trifluoromethylphenyl groups in, respectively, CNPh-DMAC-TRZ and CF3Ph-DMAC-TRZ , blue-shifts the emission spectrum but slows down the reverse intersystem crossing rate constant ( k ), while the opposite occurs in the presence of electron-donating groups in RISC ), while the opposite occurs in the presence of electron-donating groups in t BuPh-DMAC-TRZ and OMePh-DMAC-TRZ ). In contrast to our expectations, the OLED performance of the five DMAC-TRZ derivatives does not scale with their degree of horizontal emitter orientation but follows the k rates. This, in turn, demonstrates that triplet harvesting (and not horizontal emitter orientation) is the dominant effect for device efficiency using this family of emitters. Nonetheless, highly efficient OLEDs were fabricated with RISC ). In contrast to our expectations, the OLED performance of the five DMAC-TRZ derivatives does not scale with their degree of horizontal emitter orientation but follows the k RISC rates. This, in turn, demonstrates that triplet harvesting (and not horizontal emitter orientation) is the dominant effect for device efficiency using this family of emitters. Nonetheless, highly efficient OLEDs were fabricated with t BuPh-DMAC-TRZ and OMePh-DMAC-TRZ as emitters, with improved EQE max (∼28%) compared to the reference DMAC-TRZ devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

When Olga Kennard founded the Cambridge Crystallographic Data Centre in 1965, the Cambridge Structural Database was a pioneering attempt to collect scientific data in a standard format. Since then, it has evolved into an indispensable resource in contemporary molecular materials science, with over 1.25 million structures and comprehensive software tools for searching, visualizing and analyzing the data. In this perspective, we discuss the use of the CSD and CCDC tools to address the multiscale challenge of predictive materials design. We provide an overview of the core capabilities of the CSD and CCDC software and demonstrate their application to a range of materials design problems with recent case studies drawn from topical research areas, focusing in particular on the use of data mining and machine learning techniques. We also identify several challenges that can be addressed with existing capabilities or through new capabilities with varying levels of development effort., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Multivalent lectin-glycan interactions (MLGIs) are widespread and vital for biology, making them attractive therapeutic targets. Unfortunately, the structural and biophysical mechanisms of several key MLGIs remain poorly understood, limiting our ability to design spatially matched glycoconjugates as potential therapeutics against specific MLGIs. We have recently demonstrated that natural oligomannose-coated nanoparticles are powerful probes for MLGIs. They can provide not only quantitative affinity and binding thermodynamic data but also key structural information ( e.g , binding site orientation and mode) useful for designing glycoconjugate therapeutics against specific MLGIs. Despite success, how designing parameters ( e.g ., glycan type, density, and scaffold size) control their MLGI biophysical and antiviral properties remains to be elucidated. A synthetic pseudodimannose (psDiMan) ligand has been shown to selectively bind to a dendritic cell surface tetrameric lectin, DC-SIGN, over some other multimeric lectins sharing monovalent mannose specificity but having distinct cellular functions. Herein, we display psDiMan polyvalently onto gold nanoparticles (GNPs) of varying sizes ( e.g ., ∼5 and ∼13 nm, denoted as G5- and G13 psDiMan hereafter) to probe how the scaffold size and glycan display control their MLGI properties with DC-SIGN and the closely related lectin DC-SIGNR. We show that G5/13 psDiMan binds strongly to DC-SIGN, with sub-nM K d s, with affinity being enhanced with increasing scaffold size, whereas they show apparently no or only weak binding to DC-SIGNR. Interestingly, there is a minimal, GNP-size-dependent, glycan density threshold for forming strong binding with DC-SIGN. By combining temperature-dependent affinity and Van't Hoff analyses, we have developed a new GNP fluorescence quenching assay for MLGI thermodynamics, revealing that DC-SIGN-G x of ∼ -95 kJ mol H , which is ∼4-fold that of the monovalent binding and is comparable to that measured by isothermal titration calorimetry. We further reveal that the enhanced DC-SIGN affinity with G 0 of ∼ -95 kJ mol -1 -psDiMan, irrespective of the GNP size, whereas DC-SIGNR binding is dependent on GNP size, with no apparent binding with G5, and weak cross-linking with G13. Finally, we show that G x -psDiMans potently inhibit DC-SIGN-dependent augmentation of cellular entry of Ebola pseudoviruses with sub-nM EC x -psDiMan, irrespective of the GNP size, whereas DC-SIGNR binding is dependent on GNP size, with no apparent binding with G5, and weak cross-linking with G13. Finally, we show that G x -psDiMans potently inhibit DC-SIGN-dependent augmentation of cellular entry of Ebola pseudoviruses with sub-nM EC 50 values, whereas they exhibit no significant (for G5) or weak (for G13) inhibition against DC-SIGNR-augmented viral entry, consistent to their MLGI properties with DC-SIGNR in solution. These results have established G x -psDiMan as a versatile new tool for probing MLGI affinity, selectivity, and thermodynamics, as well as GNP-glycan antiviral properties., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Early detection of cancer is vital for increasing patient survivability chances. The three major techniques used to diagnose cancers are instrumental examination, tissue biopsy, and tumor biomarker detection. Circulating tumor DNA (ctDNA) has gained much attention in recent years due to advantages over traditional technology, such as high sensitivity, high specificity, and noninvasive nature. Through the mechanism of apoptosis, necrosis, and circulating exosome release in tumor cells, ctDNA can spread throughout the circulatory system and carry modifications such as methylations, mutations, gene rearrangements, and microsatellite instability. Traditional gene-detection technology struggles to achieve real-time, low-cost, and portable ctDNA measurement, whereas electrochemical biosensors offer low cost, high specificity alongside sensitivity, and portability for the detection of ctDNA. Therefore, this review focuses on describing the recent advancements in ctDNA biomarkers for various cancer types and biosensor developments for real-time, noninvasive, and rapid ctDNA detection. Further in the review, ctDNA sensors are also discussed in regards to their selections of probes for receptors based on the electrode surface recognition elements.

Hybrid organic-inorganic binders based on blast furnace slag were produced using sodium (NaAc) or potassium (KAc) acetate as the sole activator, and their properties were compared with those of sodium- or potassium hydroxide-activated slag pastes. The acetate-activated binders showed significantly lower cumulative heat release and extended setting time (∼230 h) than the hydroxide-activated binders. The main reaction products forming in all binders were calcium aluminosilicate hydrate-type gels and a hydrotalcite-like phase, independently of the activator type used. Compressive strengths of the acetate-activated pastes (∼40 MPa at 180 days) were lower than those of the hydroxide-activated binders (∼80 MPa at 180 days). However, the acetate-based binders exhibited superior impermeability and reduced wettability at 28 days, likely due to hydrophobic acetate groups. It is hypothesized that acetates dissociate in water, forming calcium acetate and alkali silicates via a reaction with species dissolving from the slag. This study demonstrates alkali acetates are effective activators for creating hybrid slag-based binders with reduced permeability., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Microencapsulation is an advanced methodology for the protection, preservation, and/or delivery of active materials in a wide range of industrial sectors, such as pharmaceuticals, cosmetics, fragrances, paints, coatings, detergents, food products, and agrochemicals. Polymeric materials have been extensively used as microcapsule shells to provide appropriate barrier properties to achieve controlled release of the encapsulated active ingredient. However, significant limitations are associated with such capsules, including undesired leaching and the nonbiodegradable nature of the typically used polymers. In addition, the energy cost of manufacturing microcapsules is an important factor to be considered when designing microcapsule systems and the corresponding production processes. Recent factors linked to UN sustainability goals are modifying how such microencapsulation systems should be designed in pursuit of "ideal" microcapsules that are efficient, safe, cost-effective and environmentally friendly. This review provides an overview of advances in microencapsulation, with emphasis on sustainable microcapsule designs. The key evaluation techniques to assess the biodegradability of microcapsules, in compliance with recently evolving European Union requirements, are also described. Moreover, the most common methodologies for the fabrication of microcapsules are presented within the framework of their energy demand. Recent promising microcapsule designs are also highlighted for their suitability toward meeting current design requirements and stringent regulations, tackling the ongoing challenges, limitations, and opportunities.

A combination of ex situ and in situ characterization techniques was used to determine the mechanism of calcium carbonate (CaCO 3 ) formation from calcium hydroxide (Ca(OH) 2 ) dispersions in methanol/water (CH 3 OH/H 2 O) systems. Mid-infrared (mid-IR) analysis shows that in the absence of carbon dioxide (CO 2 ) Ca(OH) 2 establishes a reaction equilibrium with CH 3 OH, forming calcium hydroxide methoxide (Ca(OH)(OCH 3 )) and calcium methoxide (Ca(OCH 3 ) 2 ). Combined ex situ mid-IR, thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray absorption spectroscopy and scanning electron microscopy examination of the reaction product formed in the presence of CO 2 reveals the formation of calcium dimethylcarbonate (Ca(OCOOCH 3 ) 2 ). This strongly suggests that carbonation takes place by reaction with the Ca(OCH 3 ) 2 formed from a Ca(OH) 2 and CH 3 OH reaction. Time-resolved XRD indicates that in the presence of H 2 O the Ca(OCOOCH 3 ) 2 ester releases CH 3 OH and CO 2 , forming ACC, which subsequently transforms into vaterite and then calcite. TGA reveals that thermal decomposition of Ca(OCOOCH 3 ) 2 in the absence of H 2 O mainly leads to the reformation of Ca(OCH 3 ) 2 , but this is accompanied by a significant parallel reaction that releases dimethylether (CH 3 OCH 3 ) and CO 2 . CaCO 3 is the final product in both decomposition pathways. For CH 3 OH/H 2 O mixtures containing more than 50 mol % H 2 O, direct formation of calcite from Ca(OH) 2 becomes the dominant pathway, although the formation of some Ca(OCOOCH 3 ) 2 was still evident in the in situ mid-IR spectra of 20 and 40 mol % CH 3 OH systems. In the presence of ≤20 mol % H 2 O, hydrolysis of the ester led to the formation of an ACC sol-gel. In both the 90 and 100 mol % CH 3 OH systems, diffusion-limited ACC → vaterite → calcite transformations were observed. Traces of aragonite were also detected. We believe that this is the first time that these reaction pathways during the carbonation of Ca(OH) 2 in a methanolic phase have been systematically and experimentally characterized., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Photocatalysis, a promising solution to environmental challenges, relies on the generation and utilization of photogenerated charge carriers within photocatalysts. However, the recombination of these carriers often limits efficiency. Heterostructures, especially Cu 2 O/TiO 2 , have emerged as effective solutions to enhance charge separation. This study systematically explores the effect of interfacial morphologies on the band bending within Cu 2 O/TiO 2 anatase heterostructures by employing density functional theory. Through this study, eight distinct interfaces are identified and analyzed, revealing a consistent staggered-type band alignment. Despite variations in band edge positions, systematic charge transfer from Cu 2 O to TiO 2 is observed across all interfaces. The proposed band bending configurations would suggest enhanced charge separation and photocatalytic activity under ultraviolet illumination due to a Z -scheme configuration. This theoretical investigation provides valuable insights into the interplay between interfacial morphology, band bending, and charge transfer for advancing the understanding of fundamental electronic mechanisms in heterostructures.

Carbon dioxide (CO 2 ) internal corrosion of carbon steel pipelines is a significant challenge and is typically managed by adding corrosion inhibitors. In certain operational conditions, a natural protective layer of iron carbonate (FeCO 3 ) can form on the internal walls of the pipeline, offering inhibition efficiency comparable to that of standard surfactant inhibitors. However, incomplete coverage of the FeCO 3 layer on carbon steel can sometimes trigger localized corrosion. Our previous research demonstrated that poly(allylamine hydrochloride) (PAH) can work synergistically with FeCO 3 when the corrosion product partially covers X65 carbon steel surfaces in an aqueous CO 2 corrosion environment. In this study, we utilize rotating cylinder electrode (RCE) tests along with electrochemical measurements to investigate the FeCO 3 -PAH hybrid structure in a dynamic environment. We characterize the general and localized corrosion behavior as well as the surface properties of both naturally formed FeCO 3 and FeCO 3 -PAH hybrid layers using interferometry and focused ion beam scanning electron microscopy., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Enhanced rock weathering (EW) is an emerging atmospheric carbon dioxide removal (CDR) strategy being scaled up by the commercial sector. Here, we combine multiomics analyses of belowground microbiomes, laboratory-based dissolution studies, and incubation investigations of soils from field EW trials to build the case for manipulating iron chelators in soil to increase EW efficiency and lower costs. Microbial siderophores are high-affinity, highly selective iron (Fe) chelators that enhance the uptake of Fe from soil minerals into cells. Applying RNA-seq metatranscriptomics and shotgun metagenomics to soils and basalt grains from EW field trials revealed that microbial communities on basalt grains significantly upregulate siderophore biosynthesis gene expression relative to microbiomes of the surrounding soil. Separate in vitro laboratory incubation studies showed that micromolar solutions of siderophores and high-affinity synthetic chelator (ethylenediamine- N , N '-bis-2-hydroxyphenylacetic acid, EDDHA) accelerate EW to increase CDR rates. Building on these findings, we develop a potential biotechnology pathway for accelerating EW using the synthetic Fe-chelator EDDHA that is commonly used in agronomy to alleviate the Fe deficiency in high pH soils. Incubation of EW field trial soils with potassium-EDDHA solutions increased potential CDR rates by up to 2.5-fold by promoting the abiotic dissolution of basalt and upregulating microbial siderophore production to further accelerate weathering reactions. Moreover, EDDHA may alleviate potential Fe limitation of crops due to rising soil pH with EW over time. Initial cost-benefit analysis suggests potassium-EDDHA could lower EW-CDR costs by up to U.S. $77 t CO 2 ha -1 to improve EW's competitiveness relative to other CDR strategies.

We have quantified and compared the hydration capacity (i.e., capability to incorporate water molecules) of the two surface-bound hydrophilic polymer chains, dextran (dex) and poly(ethylene glycol) (PEG), in the form of poly(l-lysine)- graft -dextran (PLL- g -dex) and poly(l-lysine)- graft -poly(ethylene glycol) (PLL- g -PEG), respectively. The copolymers were attached to a negatively charged silica-titania surface through the electrostatic interaction between the PLL backbone and the surface in neutral aqueous media. While the molecular weights of PLL and PEG were fixed, that of dex and the grafting density of PEG or dex on the PLL were varied. The hydration capacity of the polymer chains was quantified through the combined experimental approach of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation monitoring (QCM-D) to yield a value for areal solvation (Ψ), i.e., mass of associated solvent molecules within the polymer chains per unit substrate area. For the two series of copolymers with comparable stretched chain lengths of hydrophilic polymers, namely, PLL(20)- g -PEG(5) and PLL(20)- g -dex(10), the Ψ values gradually increased as the initial grafting density on the PLL backbone increased or as g decreased. However, the rate of increase in Ψ was higher for PEG than dextran chains, which was attributed to higher stiffness of the dextran chains. More importantly, the number of water molecules per hydrophilic group was clearly higher for PEG chains. Given that the -CH 2 CH 2 O- units that make up the PEG chains form a cage-like structure with 2-3 water molecules, these "strongly bound" water molecules can account for the slightly more favorable behavior of PEG compared to dextran in both aqueous lubrication and antifouling behavior of the copolymers.

The comparative crystallizability and polymorphic selectivity of ritonavir, a novel protease inhibitor for the treatment of acquired immune-deficiency syndrome, as a function of solvent selection are examined through an integrated and self-consistent experimental and computational molecular modeling study. Recrystallization at high supersaturation by rapid cooling at 283.15 K is found to produce the metastable "disappeared" polymorphic form I from acetone, ethyl acetate, acetonitrile, and toluene solutions in contrast to ethanol which produces the stable form II. Concomitant crystallization of the other known solid forms is not found under these conditions. Isothermal crystallization studies using turbidometric detection based upon classical nucleation theory reveal that, for an equal induction time, the required driving force needed to initiate solution nucleation decreases with solubility in the order of ethanol, acetone, acetonitrile, ethyl acetate, and toluene consistent with the expected desolvation behavior predicted from the calculated solute solvation free energies. Molecular dynamics simulations of the molecular and intermolecular chemistry reveal the presence of conformational interplay between intramolecular and intermolecular interactions within the solution phase. These encompass the solvent-dependent formation of intramolecular O-H...O hydrogen bonding between the hydroxyl and carbamate groups coupled with differing conformations of the hydroxyl's shielding phenyl groups. These conformational preferences and their relative interaction propensities, as a function of solvent selection, may play a rate-limiting role in the crystallization behavior by not only inhibiting to different degrees the nucleation process but also restricting the assembly of the optimal intermolecular hydrogen bonding network needed for the formation of the stable form II polymorph.

Ion mobility mass spectrometry (IM-MS) can be used to analyze native proteins according to their size and shape. By sampling individual molecules, it allows us to study mixtures of conformations, as long as they have different collision cross sections and maintain their native conformation after dehydration and vaporization in the mass spectrometer. Even though conformational heterogeneity of prolyl oligopeptidase has been demonstrated in solution, it is not detectable in IM-MS. Factors that affect the conformation in solution, binding of an active site ligand, the stabilizing Ser554Ala mutation, and acidification do not qualitatively affect the collision-induced unfolding pattern. However, measuring the protection of accessible cysteines upon ligand binding provides a principle for the development of MS-based ligand screening methods.

Increasing research efforts focus on exploiting antibodies to inhibit the amyloid formation of neurodegenerative proteins. Nevertheless, it is challenging to discover antibodies that inhibit this process in a specific manner. Using ribosome display, we screened for synthetic single-domain antibodies, i.e., sybodies, of the P1 region of α-synuclein (residues 36-42), a protein that forms amyloid in Parkinson's disease and multiple-system atrophy. Hits were assessed for direct binding to a P1 peptide and the inhibition of amyloid formation. We discovered a sybody, named αSP1, that inhibits amyloid formation of α-synuclein at substoichiometric concentrations in a specific manner, even within highly crowded heterogeneous mixtures. Fluorescence resonance energy transfer-based binding assays and seeding experiments with and without αSP1 further demonstrate the importance of the P1 region for both primary and secondary nucleation mechanisms of amyloid assembly.

Methyl esters are an important component of combustion and atmospheric systems. Reaction with the OH radical plays an important role in the removal of the simplest methyl ester, methyl formate (MF, CH 3 OCHO). In this paper, the overall rate coefficients for the reactions of OH and OD with MF isotopologues, studied under pseudo-first-order conditions, are reported using two different laser flash photolysis systems with the decay of OH monitored by laser-induced fluorescence. The room-temperature rate coefficient for OH + MF, (1.95 ± 0.34) × 10 -13 cm 3 molecule -1 s -1 , is in good agreement with the literature. The rate coefficient exhibits curved Arrhenius behavior, and our results bridge the gap between previous low-temperature and shock tube studies. In combination with the literature, the rate coefficient for the reaction of OH with MF between 230 and 1400 K can be parametrized as k OH+MF = (3.2 × 10 -13 ) × (T/300 K) 2.3 × exp(-141.4 K/ T ) cm 3 molecule -1 with an overall estimated uncertainty of ∼30%. The reactions of OD with MF isotopologues show a small enhancement (inverse secondary isotope effect) compared to the respective OH reactions. The reaction of OH/OD with MF shows a normal primary isotope effect, a decrease in the rate coefficient when MF is partially or fully deuterated. Experimental studies have been supported by -1 with an overall estimated uncertainty of ∼30%. The reactions of OD with MF isotopologues show a small enhancement (inverse secondary isotope effect) compared to the respective OH reactions. The reaction of OH/OD with MF shows a normal primary isotope effect, a decrease in the rate coefficient when MF is partially or fully deuterated. Experimental studies have been supported by ab initio /6-31+G** level of theory. The calculated, zero-point-corrected, barrier heights for abstraction at the methyl and formate sites are 1.3 and 6.0 kJ mol X /6-31+G** level of theory. The calculated, zero-point-corrected, barrier heights for abstraction at the methyl and formate sites are 1.3 and 6.0 kJ mol -1 predictions of kinetic isotope effects are in agreement with experiment. Fitting the experimental isotopologue data refines these barriers to 0.9 ± 0.6 and 4.1 ± 0.9 kJ mol ab initio . The branching ratio is approximately 50:50 at 300 K. Between 300 and 500 K, abstraction via the higher-energy, higher-entropy formate transition state becomes more favored (60:40). However, experiment and calculations suggest that as the temperature increases further, with higher energy, less constrained conformers of the methyl transition state become more significant. The implications of the experimental and theoretical results for the mechanisms of MF atmospheric oxidation and low-temperature combustion are discussed.-1 . The branching ratio is approximately 50:50 at 300 K. Between 300 and 500 K, abstraction via the higher-energy, higher-entropy formate transition state becomes more favored (60:40). However, experiment and calculations suggest that as the temperature increases further, with higher energy, less constrained conformers of the methyl transition state become more significant. The implications of the experimental and theoretical results for the mechanisms of MF atmospheric oxidation and low-temperature combustion are discussed.

This study demonstrates that the electrochemical doping of lanthanum nickelate (LNO) with cobalt ions is a promising strategy for enhancing its physical and electrochemical properties, which are critical for energy storage and conversion devices. LNO emerges as a promising hole transport layer (HTL) in solar cells due to its stability, large band gap, and high transparency. Nevertheless, its low conductivity and improperly aligned band positions are persistent problems. Here, in a pioneering endeavor, Co-doped LNO thin films were synthesized electrochemically and applied as the HTL in polymer solar cells (PSCs). Characterization revealed the impact of Co doping on the electrochemical, structural, morphological, and optical properties of LNO thin films. Depending on the Co doping level, PSCs based on 10 mol % Co-doped LNO outperformed pure LNO, achieving a champion efficiency of 6.11% with enhanced short-circuit current density (12.84 mA cm -2 ), fill factor (68%), open-circuit voltage (0.70 V), and external quantum efficiency (82.6%). This enhancement resulted from decreased series resistance, refined surface morphology, minimized trap-assisted recombination, enhanced conductivity, increased charge carrier production, favorable energy level alignment, and improved current extraction facilitated by LNC 0.10 O HTL. Moreover, the unencapsulated PSC-LNC 0.10 O long-term stability notably improved and retained 86% of its initial PCE after 450 h storage in ambient air, 82% after being continuously heated to 85 °C for 300 h, and 80% after operating at maximum power point for 300 h. These findings offer a straightforward approach to enhancing PSC performance through Co doping of LNO, supported by density functional theory (DFT) calculations that validate the experimental results and confirm the improvement in optical properties and stability of PSCs as an HTL.

Commercial perfume microcapsules are becoming popular across the globe to fulfill consumers' demands. However, most of microcapsules rely on synthetic polymers and/or animal-sourced ingredients to form the shells. Therefore, replacement of the shell materials is imperative to minimize environmental microplastic pollution, as well as to meeting peoples' needs, religious beliefs, and lifestyles. Herein, we report a methodology to fabricate environmentally benign dual-shell (fungal chitosan-SiO 2 ) microcapsules laden with fragrance oil (hexyl salicylate). Anionically stabilized oil droplets were coated with fungal chitosan via interfacial electrostatic interactions at pH 2, which were then covered by an inorganic coating of SiO 2 produced via external alkaline mineralization of sodium silicate. Core-shell microcapsules with a spherical morphology were achieved. Under compression, dual-shell chitosan-SiO 2 microcapsules yielded a mean nominal rupture stress of 3.0 ± 0.2 MPa, which was significantly higher than that of single-shell microcapsules (1.7 ± 0.2 MPa). After 20 days in neutral pH water, only ∼2.5% of the oil was released from dual-shell microcapsules, while single-shell microcapsules cumulatively released more than 10%. These findings showed that the additional SiO 2 coating significantly enhanced both mechanical and barrier properties of microcapsules, which may be appealing for multiple commercial applications, including cosmetics and detergents., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A methodology for the prediction of face-specific relative dissolution rates for single-faceted crystals accounting for inequivalent wetting by the solvent is presented. This method is an extended form of a recent binding energy model developed by the authors (Najib et al., Cryst. Growth . 2021, 21(3), 1482-1495) for predicting the face-specific dissolution rates for single-faceted crystals from the solid-state intermolecular binding energies in a vacuum. The principal modification is that the equivalent wetting of the crystal surfaces is no longer assumed, since interactions between the crystal surfaces and the solution-state molecules are incorporated. These surface interactions have been investigated by using a grid-based systematic search method. The face-specific dissolution rates predicted by the extended binding energy model for ibuprofen in a 95% v/v ethanol-water solution and furosemide in an aqueous medium have been validated against the published experimental results and are in excellent agreement. This model is a step forward toward accurate predictions of the relative face-specific dissolution rates for a wide variety of faceted crystals in any dissolution medium.& Des . 2021, 21(3), 1482-1495) for predicting the face-specific dissolution rates for single-faceted crystals from the solid-state intermolecular binding energies in a vacuum. The principal modification is that the equivalent wetting of the crystal surfaces is no longer assumed, since interactions between the crystal surfaces and the solution-state molecules are incorporated. These surface interactions have been investigated by using a grid-based systematic search method. The face-specific dissolution rates predicted by the extended binding energy model for ibuprofen in a 95% v/v ethanol-water solution and furosemide in an aqueous medium have been validated against the published experimental results and are in excellent agreement. This model is a step forward toward accurate predictions of the relative face-specific dissolution rates for a wide variety of faceted crystals in any dissolution medium., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

This review aims to provide an updated overview of the effects of protein extraction/recovery on antinutritional factors (ANFs) in plant protein ingredients, such as protein-rich fractions, protein concentrates, and isolates. ANFs mainly include lectins, trypsin inhibitors, phytic acid, phenolic compounds, oxalates, saponins, tannins, and cyanogenic glycosides. The current technologies used to recover proteins (e.g., wet extraction, dry fractionation) and novel technologies (e.g., membrane processing) are included in this review. The mechanisms involved during protein extraction/recovery that may enhance or decrease the ANF content in plant protein ingredients are discussed. However, studies on the effects of protein extraction/recovery on specific ANFs are still scarce, especially for novel technologies such as ultrasound- and microwave-assisted extraction and membrane processing. Although the negative effects of ANFs on protein digestibility and the overall absorption of plant proteins and other nutrients are a health concern, it is also important to highlight the potential positive effects of ANFs. This is particularly relevant given the rise of novel protein ingredients in the market and the potential presence or absence of these factors and their effects on consumers' health.

Inspired by the imbalance between extrinsic and intrinsic tendon healing, this study fabricated a new biofilter scaffold with a hierarchical structure based on a melt electrowriting technique. The outer multilayered fibrous structure with connected porous characteristics provides a novel passageway for vascularization and isolates the penetration of scar fibers, which can be referred to as a biofilter process. In vitro experiments found that the porous architecture in the outer layer can effectively prevent cell infiltration, whereas the aligned fibers in the inner layer can promote cell recruitment and growth, as well as the expression of tendon-associated proteins in a simulated friction condition. It was shown in vivo that the biofilter process could promote tendon healing and reduce scar invasion. Herein, this novel strategy indicates great potential to design new biomaterials for balancing extrinsic and intrinsic healing and realizing scarless tendon healing.

Liquid crystal elastomers (LCEs) are polymeric materials that are proposed for a range of applications. However, to reach their full potential, it is desirable to have as much flexibility as possible in terms of the sample dimensions, while maintaining well-defined alignment. In this work, photoinduced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization is applied to the synthesis of LCEs for the first time. An initial LCE layer (∼100 μm thickness) is partially cured before a second layer of the precursor mixture is added. The curing reaction is then resumed and is observed by FTIR to complete within 15 min of irradiation, yielding samples of increased thickness. Monodomain samples that exhibit an auxetic response and are of thickness 250-300 μm are consistently achieved. All samples are characterized thermally, mechanically, and in terms of their order parameters. The LCEs have physical properties comparable to those of analogous LCEs produced via free-radical polymerization., Competing Interests: The authors declare the following competing financial interest(s): The authors declare that patent number WO2019/077361 A1 is within the scope of this work. Additionally, H.F.G. holds a position on the board of Auxetec Ltd (Company number 12925662), and M. R. is employed by Auxetec Ltd., (© 2024 The Authors. Published by American Chemical Society.)

In this work, phase-pure Mg 1.8 (Ni 1- x Co x ) 0.2 Al 4 Si 5 O 18 (0 ≤ x ≤ 1) ceramics were synthesized by a high-temperature solid-state method. On the basis of Rietveld refinement data of X-ray powder diffraction and Phillips-Vechten-Levine theory, the atomic ionicity, lattice energy, and bond energy of the compound were calculated to explore their influence on the microwave dielectric properties of ceramics. The Mg 1.8 Ni 0.1 Co 0.1 Al 4 Si 5 O 18 ( x = 0.5) ceramic exhibited the best microwave dielectric properties: ε r = 4.44, Qf = 73 539 GHz@13 GHz, and τ f = -23.9 ppm/°C. (Ni 1- x Co x ) 2+ complex ionic doping, compared with only Ni 2+ , is beneficial for improving the symmetry of [Si 2+ , is beneficial for improving the symmetry of [Si 4 Al 2 O 18 ] hexagonal rings and reducing distortion. Subsequently, 8 wt % TiO 2 was added to Mg 1.8 Ni 0.1 Co 0.1 Al 4 Si 5 O 18 , resulting in a near-zero τ f and high Qf values for the composite ceramic, with ε = -2.06 ppm/°C. Finally, a 5G millimeter-wave antenna with a central operating frequency of 25.52 GHz was designed and fabricated using the Mg r = 5.22, Qf = 58 449 GHz@13 GHz, and τ f = -2.06 ppm/°C. Finally, a 5G millimeter-wave antenna with a central operating frequency of 25.52 GHz was designed and fabricated using the Mg 1.8 Ni 0.1 Co 0.1 Al 4 ceramics. Operating in the 24.7-26.0 GHz range, it demonstrated favorable radiation characteristics with a simulated efficiency of 85.2% and a gain of 4.58 dBi. The antenna's performance confirms the high potential of the cordierite composite for application in 5G communication systems.5 O 18 -8 wt % TiO 2 ceramics. Operating in the 24.7-26.0 GHz range, it demonstrated favorable radiation characteristics with a simulated efficiency of 85.2% and a gain of 4.58 dBi. The antenna's performance confirms the high potential of the cordierite composite for application in 5G communication systems.

This study presents new insights into the potential role of polyelectrolyte interfaces in regulating low friction and interstitial fluid pressurization of cartilage. Polymer brushes composed of hydrophilic 3-sulfopropyl methacrylate potassium salt (SPMK) tethered to a PEEK substrate (SPMK- g -PEEK) are a compelling biomimetic solution for interfacing with cartilage, inspired by the natural lubricating biopolyelectrolyte constituents of synovial fluid. These SPMK- g -PEEK surfaces exhibit a hydrated compliant layer approximately 5 μm thick, demonstrating the ability to maintain low friction coefficients (μ ∼ 0.01) across a wide speed range (0.1-200 mm/s) under physiological loads (0.75-1.2 MPa). A novel polyelectrolyte-enhanced tribological rehydration mechanism is elucidated, capable of recovering up to ∼12% cartilage strain and subsequently facilitating cartilage interstitial fluid recovery, under loads ranging from 0.25 to 2.21 MPa. This is attributed to the combined effects of fluid confinement within the contact gap and the enhanced elastohydrodynamic behavior of polymer brushes. Contrary to conventional theories that emphasize interstitial fluid pressurization in regulating cartilage lubrication, this work demonstrates that SPMK- g -PEEK's frictional behavior with cartilage is independent of these factors and provides unabating aqueous lubrication. Polyelectrolyte-enhanced tribological rehydration can occur within a static contact area and operates independently of known mechanisms of cartilage interstitial fluid recovery established for converging or migrating cartilage contacts. These findings challenge existing paradigms, proposing a novel polyelectrolyte-cartilage tribological mechanism not exclusively reliant on interstitial fluid pressurization or cartilage contact geometry. The implications of this research extend to a broader understanding of synovial joint lubrication, offering insights into the development of joint replacement materials that more accurately replicate the natural functionality of cartilage.

CMOS-compatible materials for efficient energy harvesters at temperatures characteristic for on-chip operation and body temperature are the key ingredients for sustainable green computing and ultralow power Internet of Things applications. In this context, the lattice thermal conductivity (κ) of new group IV semiconductors, namely Ge 1- x Sn x alloys, are investigated. Layers featuring Sn contents up to 14 at.% are epitaxially grown by state-of-the-art chemical-vapor deposition on Ge buffered Si wafers. An abrupt decrease of the lattice thermal conductivity (κ) from 55 W/(m·K) for Ge to 4 W/(m·K) for Ge 0.88 Sn 0.12 alloys is measured electrically by the differential 3ω-method. The thermal conductivity was verified to be independent of the layer thickness for strained relaxed alloys and confirms the Sn dependence observed by optical methods previously. The experimental κ values in conjunction with numerical estimations of the charge transport properties, able to capture the complex physics of this quasi-direct bandgap material system, are used to evaluate the thermoelectric figure of merit ZT for n- and p-type GeSn epitaxial layers. The results highlight the high potential of single-crystal GeSn alloys to achieve similar energy harvest capability as already present in SiGe alloys but in the 20 °C-100 °C temperature range where Si-compatible semiconductors are not available. This opens the possibility of monolithically integrated thermoelectric on the CMOS platform., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Oligomeric species populated during α-synuclein aggregation are considered key drivers of neurodegeneration in Parkinson's disease. However, the development of oligomer-targeting therapeutics is constrained by our limited knowledge of their structure and the molecular determinants driving their conversion to fibrils. Phenol-soluble modulin α3 (PSMα3) is a nanomolar peptide binder of α-synuclein oligomers that inhibits aggregation by blocking oligomer-to-fibril conversion. Here, we investigate the binding of PSMα3 to α-synuclein oligomers to discover the mechanistic basis of this protective activity. We find that PSMα3 selectively targets an α-synuclein N-terminal motif (residues 36-61) that populates a distinct conformation in the mono- and oligomeric states. This α-synuclein region plays a pivotal role in oligomer-to-fibril conversion as its absence renders the central NAC domain insufficient to prompt this structural transition. The hereditary mutation G51D, associated with early onset Parkinson's disease, causes a conformational fluctuation in this region, leading to delayed oligomer-to-fibril conversion and an accumulation of oligomers that are resistant to remodeling by molecular chaperones. Overall, our findings unveil a new targetable region in α-synuclein oligomers, advance our comprehension of oligomer-to-amyloid fibril conversion, and reveal a new facet of α-synuclein pathogenic mutations.

Presented here is the design and performance of a coalescing liquid-liquid filter, based on low-cost and readily available meltblown nonwoven substrates for separation of immiscible phases. The performance of the coalescer was determined across three broad classes of fluid mixtures: (i) immiscible organic/aqueous systems, (ii) a surfactant laden organic/aqueous system with modification of the type of emulsion and interfacial surface tension through the addition of sodium chloride, and (iii) a water-acetone/toluene system. The first two classes demonstrated good performance of the equipment in effecting separation, including the separation of a complex emulsion system for which a membrane separator, operating through transport of a preferentially wetting fluid through the membrane, failed entirely. The third system was used to demonstrate the performance of the separator within a multistage liquid-liquid counterflow extraction system. The performance, robust nature, and scalability of coalescing filters should mean that this approach is routinely considered for liquid-liquid separations and extractions within the fine chemical and pharmaceutical industry., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Cell-based models, such as organ-on-chips, can replace and inform in vivo (animal) studies for drug discovery, toxicology, and biomedical science, but most cannot be banked "ready to use" as they do not survive conventional cryopreservation with DMSO alone. Here, we demonstrate how macromolecular ice nucleators enable the successful cryopreservation of epithelial intestinal models supported upon the interface of transwells, allowing recovery of function in just 7 days post-thaw directly from the freezer, compared to 21 days from conventional suspension cryopreservation. Caco-2 cells and Caco-2/HT29-MTX cocultures are cryopreserved on transwell inserts, with chemically induced ice nucleation at warmer temperatures resulting in increased cell viability but crucially retaining the complex cellular adhesion on the transwell insert interfaces, which other cryoprotectants do not. Trans-epithelial electrical resistance measurements, confocal microscopy, histology, and whole-cell proteomics demonstrated the rapid recovery of differentiated cell function, including the formation of tight junctions. Lucifer yellow permeability assays confirmed that the barrier functions of the cells were intact. This work will help solve the long-standing problem of transwell tissue barrier model storage, facilitating access to advanced predictive cellular models. This is underpinned by precise control of the nucleation temperature, addressing a crucial biophysical mode of damage.