Removal Strategies Research Articles

Engineering of HO–Zn–N2 Active Sites in Zeolitic Imidazolate Frameworks for Enhanced (Photo)Electrocatalytic Hydrogen Evolution

Currently, lack of ways to engineer specific and well‐defined active sites in zeolitic imidazolate frameworks (ZIFs) limits our fundamental knowledge with respect to the mechanistic details for (photo)electrocatalytic hydrogen evolution reaction (HER). Here, we introduce the open metal sites into ZIFs through the selective ligand removal (SeLiRe) strategy, comprehensively characterize the altered structural and electronic features, and evaluate their role in HER. In‐situ electrochemical analysis and X‐ray absorption spectroscopy reveal the formation of high‐valence HO−Zn−N2 sites through the binding of Zn−N2 with electrolyte hydroxide. The optimal OMS‐ZIF exhibits a low overpotential of 0.41 V to achieve an ampere‐level 1.0 A cm−2 with 120‐hour stability. Theoretical simulations indicate that these active sites accelerate the water molecules activation kinetics, consequently enhancing the efficiency of the Volmer step. This work demonstrates a versatile strategy to introduce highly active catalytic sites in ZIFs, providing new insights into the electrocatalytic mechanism in alkaline media.

The Global Challenge of Fluoride Contamination: A Comprehensive Review of Removal Processes and Implications for Human Health and Ecosystems

Water resources are vital for humanity, but their quality has degraded in recent years due to increasing industrial activities. One significant issue is fluoride contamination, prevalent worldwide. Fluorides exist in combined states such as calcium fluoride, fluorapatite, and cryolite, originating from industrial processes like aluminum and fertilizer manufacturing. The World Health Organization warns against fluoride levels above 1.5 mg/L in drinking water due to health risks, including dental and skeletal fluorosis. Industrial activities also release fluoride-containing wastes into the environment, endangering ecosystems and human health. Overexposure to fluoride leads to disorders affecting organs including the kidneys, liver, and nervous system. Despite fluoride’s benefits in controlled doses, excessive intake causes health problems, as evidenced by rising dental fluorosis cases in Brazil. Thus, effective and affordable fluoride removal strategies are crucial. Various methods exist, including adsorption, membrane technology, ion exchange process, electrodialysis, and electrocoagulation. Regulation of fluoride levels in drinking water is imperative to safeguard public health from its detrimental long-term effects.

Indonesia’s Handling of Terrorists’ Cyber Activities: How Repressive Measures Still Fall Short

The article examines discrepancies between the Indonesian government’s response to terrorist cyber activities and the actual activities of terrorists online. By analysing data from 55 convicted terrorists, the study reveals that while government efforts focus on censoring extremist content on social media and websites, terrorists have shifted to using messaging platforms for tactical coordination. This shift indicates that current censorship and platform removal strategies are ineffective in preventing terrorists from exploiting cyberspace. The article highlights that repressive measures, such as criminal prosecution and strict regulation, may undermine the roles of users, platform managers and tech companies in content moderation. Additionally, these measures could drive terrorists to smaller, less monitored platforms, ultimately failing to curb their online activities and compromising freedom of expression. The findings suggest that a more nuanced approach is needed to address terrorist use of cyberspace effectively.

Sustainable Pb(II) Removal and Recovery from Wastewater Using a Bioinspired Metal-Phenolic Hybrid Membrane with Efficient Regeneration.

High-performance adsorbents often require efficient selectivity in wastewater, recoverability, and ease of multiple regeneration cycles, but achieving this remains a significant challenge. We report a new strategy for the efficient removal of lead (Pb(II)) from contaminated water streams using an innovative tannic acid (TA)-Fe(III)-based metal-phenolic network (MPN) hybrid membrane (MPN-PAM). This novel membrane exploits the tunable pH-sensitive coordination structure of the MPN to achieve selective removal and recovery of Pb(II) while enabling efficient membrane regeneration by filtration. This membrane demonstrates superior selectivity for Pb(II) with a removal efficiency of up to 98 % and an adsorption capacity of approximately 117.58 mg/g, even in the presence of high salinity, as well as coexisting heavy metals. The membrane maintains high Pb(II) removal efficiency over 20 consecutive cycles and 95 % efficiency over 10 regeneration cycles. Under continuous operation, it treats approximately 85 L per m2 of membrane, reducing Pb(II) concentrations to trace levels (~40 μg/L), meeting electroplating wastewater standard (GB21900-2008). Additionally, even low concentrations of Pb(II) (<5 mg/L) are efficiently purified to below WHO drinking water standard (10 μg/L). The operational cost for treating Pb(II)-contaminated wastewater is about $0.13 per ton, highlighting the cost-effectiveness and potential for large-scale application in wastewater treatment.

Integrating complexity in population modelling: From matrix to dynamic models

Matrix models are widely used in population ecology studies and are valuable for analysing population dynamics, although they are limited in the use of time-varying parameters. This limitation can be overcome by dynamic models. In this study, we revisit a previously published study on a matrix model of a population of the box jellyfish Carybdea marsupialis (L. 1758) in the Western Mediterranean. A dynamic model integrating the transition matrix of the original model is developed in STELLA Architect with the following improvements: (1) Sensitivity study of the reliability of the methodology for calculating the transition matrix and estimation of the errors of the fitting parameters; (2) Closure of the jellyfish life cycle by adding the polyp stage. This will make it possible to simulate scenarios of ecological interest over several years such as a decline in food supply, jellyfish removal strategies, changes in drift currents and changes in substrate availability for planulae to settle. (3) The inclusion of more biological reality. In particular, a temporal pattern of strobilation is added, which improves the fit of the model to the field data.

Plasma-engineered sugarcane bagasse: a novel strategy for efficient mercury removal from aqueous solutions.

Metal ion adsorption using agro-industrial residues has shown promising results in remediating contaminated waters. However, adsorbent effectiveness relies on their properties, often necessitating processing for modification. Considering this, plasma treatment is effective in modifying material surfaces physically and chemically. This study investigated the modification of sugarcane bagasse (SB) using plasma treatment and evaluated its efficacy as a novel adsorbent for mercury removal from aqueous solutions. SB underwent low-temperature plasma treatment with sulfur hexafluoride (SF6) as the working gas, varying treatment times (2, 30, and 60min), and fixed powers (80, 190, and 300 W) at 16Pa pressure. Characterization via SEM/EDS, FTIR, XPS, and pHpzc revealed significant structural changes like increased in porosity and alteration in proportion atomic. Additionally, the successful incorporation of fluorine was confirmed in all treatment conditions, while sulfur was detected in only some samples. Amongst the tested conditions, the SB treated with 300 W for 60min demonstrated the highest mercury removal efficiency, achieving an impressive 83.67% removal rate compared to untreated SB, which yielded only 57.95%. The adsorption mechanism exhibited both physical and chemical behavior, with chemisorption being the dominant process. The Freundlich model provided the best fit to the experimental data, with an R2 value of 0.97. In conclusion, plasma treatment can be a promising alternative for improving the physical and chemical characteristics of SB adsorbents, thereby improving their efficiency in removing mercury from aqueous solutions.

Can feature removal benefit the automotive manufacturers amid supply shortages? An analytical investigation

The automotive industry has been significantly impacted by the global semiconductor shortage since 2020. Traditional strategies, such as maintaining safety stock and sourcing from backup suppliers, have been proven insufficient in mitigating supply shortages. To address the global chip shortage and build supply chain viability, leading automotive manufacturers worldwide have adopted an innovative adaptation strategy known as the feature removal strategy. This strategy involves temporarily removing non-vital features and retrofitting them once supply shortages are alleviated, thereby mitigating disruptions. Given the increasing frequency, severity, and unpredictability of global chip shortages, it is crucial to investigate the potential benefits of the feature removal strategy for automotive manufacturers. This study aims to address this gap analytically. We develop a stochastic dynamic programming model to optimize pricing and production decisions under the feature removal strategy. We reformulate the model into an equivalent convex problem and propose structural properties to manage the complexity arising from the high dimensionality of state and action spaces. Comparative analyses with benchmark strategies underscore the efficacy of the feature removal strategy in enhancing profitability and sustaining supply chain viability, especially in prolonged supply shortage scenarios.

Spontaneous Lifting and Self-Cleaning of Gas Hydrate Crystals.

Crystal fouling, which refers to the accumulation of precipitates on surfaces and the associated damage, is a common problem in many industrial processes. In deepwater oil and gas transportation, hydrate blockage poses as a considerable barrier. Consequently, modifying hydrophobicity of surfaces has become an increasingly focused strategy to mitigate hydrate. However, the design of surfaces that effectively control the hydrate remains challenging. Herein, we report a superior smooth anti-hydrate material based on silanized modification. The low-adhesion silanized silicon wafer (SSW) realizes a win-win strategy of hard formation and easy removal. Through a comprehensive study combining experimental validation with theoretical analysis, the unique characteristics of SSW in the field of anti-hydrate surfaces were deeply discussed. Various hydrate crystals exhibited a completely different hydrate growth mode at the SSW surface, in which hydrate crystals spontaneously elevated and lifted themselves off from the surface. The presence of the fluorine element on the SSW surface allowed self-lifting growth of hydrate crystals after they covered the water droplet. And the loose and porous crystal structure in this self-lifting growth could reduce the contact area between the hydrate crystals and the substrate, allowing the crystals with minimal adhesion force and removal disturbance. Furthermore, the gas enrichment on the SSW surface also reduced the contact with the substrate, thereby decreasing the adhesion and allowing self-cleaning behavior. These results indicate that the silanized surface is a promising candidate for developing anti-hydrate materials for hydrocarbon production and transportation industry.

The need for carbon-emissions-driven climate projections in CMIP7

Abstract. Previous phases of the Coupled Model Intercomparison Project (CMIP) have primarily focused on simulations driven by atmospheric concentrations of greenhouse gases (GHGs), for both idealized model experiments and climate projections of different emissions scenarios. We argue that although this approach was practical to allow parallel development of Earth system model simulations and detailed socioeconomic futures, carbon cycle uncertainty as represented by diverse, process-resolving Earth system models (ESMs) is not manifested in the scenario outcomes, thus omitting a dominant source of uncertainty in meeting the Paris Agreement. Mitigation policy is defined in terms of human activity (including emissions), with strategies varying in their timing of net-zero emissions, the balance of mitigation effort between short-lived and long-lived climate forcers, their reliance on land use strategy, and the extent and timing of carbon removals. To explore the response to these drivers, ESMs need to explicitly represent complete cycles of major GHGs, including natural processes and anthropogenic influences. Carbon removal and sequestration strategies, which rely on proposed human management of natural systems, are currently calculated in integrated assessment models (IAMs) during scenario development with only the net carbon emissions passed to the ESM. However, proper accounting of the coupled system impacts of and feedback on such interventions requires explicit process representation in ESMs to build self-consistent physical representations of their potential effectiveness and risks under climate change. We propose that CMIP7 efforts prioritize simulations driven by CO2 emissions from fossil fuel use and projected deployment of carbon dioxide removal technologies, as well as land use and management, using the process resolution allowed by state-of-the-art ESMs to resolve carbon–climate feedbacks. Post-CMIP7 ambitions should aim to incorporate modeling of non-CO2 GHGs (in particular, sources and sinks of methane and nitrous oxide) and process-based representation of carbon removal options. These developments will allow three primary benefits: (1) resources to be allocated to policy-relevant climate projections and better real-time information related to the detectability and verification of emissions reductions and their relationship to expected near-term climate impacts, (2) scenario modeling of the range of possible future climate states including Earth system processes and feedbacks that are increasingly well-represented in ESMs, and (3) optimal utilization of the strengths of ESMs in the wider context of climate modeling infrastructure (which includes simple climate models, machine learning approaches and kilometer-scale climate models).

Occurrence, Fate, and Removal of Per- and Polyfluoroalkyl Substances (PFAS) in Small- and Large-Scale Municipal Wastewater Treatment Facilities in the United States.

Wastewater treatment plants (WWTPs) could be conduits of polyfluoroalkyl substances (PFAS) contaminants in the environment. This study investigated the fate of 40 PFAS compounds across nine municipal WWTPs with varying treatment capacity and processes. High concentrations of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) were detected in wastewater, with the ratio of their total concentrations (∑PFCAs/∑PFSAs) always greater than one. Transformation of precursors by activated sludge processes significantly increased the concentrations of short-chain PFCAs (e.g., perfluoropentanoic acid (PFPeA) and perfluorohexanoic acid (PFHxA)), while further advanced treatment processes offered minimal removal of perfluoroalkyl acids. Treatment capacity and PFAS removal efficiency showed no apparent correlation. The maximum possible PFAS loads discharged from WWTPs were 340-9645 g·year-1, similar to those entering the WWTPs. Among six regulated PFAS compounds, detection frequency was 100% for five (perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorononanoic acid (PFNA), perfluorobutanesulfonic acid (PFBS), and perfluorohexanesulfonic acid (PFHxS)) and 67% for hexafluoropropylene oxide dimer acid (HFPO-DA) (Gen-X). Concentrations of PFOA and PFOS in WWTP discharges consistently exceeded 4 ng·L-1. The hazard index (HI) for mixtures containing two or more of the four PFAS (PFNA, PFBS, PFHxS, and HFPO-DA) ranged from 0.2 to 6.1. These findings indicate that wastewater discharges may pose a risk, emphasizing the need for enhanced PFAS removal strategies in wastewater treatment processes.

Exploring the Mechanism for the Photocatalytic Degradation of Oxytetracycline in Water using TiO2 and Supplementary Oxidants

The persistent presence of antibiotics in wastewater, exemplified by oxytetracycline (OTC), poses environmental risks, necessitating robust removal strategies. This study investigates the effectiveness of photocatalysis utilizing TiO2 (P25) treated at various temperatures, combined with different oxidants such as hydrogen peroxide (H2O2), potassium peroxydisulfate (PDS), potassium peroxomonosulfate (PMS) under diverse experimental conditions. The research systematically explores the impact of temperature, pH, and oxidant concentration on the efficiency of OTC degradation. Our findings reveal that the combination of P25/500, PDS, UV irradiation, and stirring demonstrates superior OTC degradation, surpassing 99% efficiency after 180 min. Optimal pH conditions are identified, emphasizing the importance of balancing acidity for enhanced performance. The study also provides insights into the optimal PDS concentration, indicating a threshold beyond which further increases yield diminishing returns. Mechanistic understanding is enhanced through scavenger experiments, elucidating the pivotal role of reactive oxygen species, particularly O2•−, in the photocatalytic process. This research offers a practical framework for TiO2-based photocatalysis in wastewater treatment, emphasizing tailored conditions for efficient antibiotic removal. The outcomes contribute valuable insights to the development of sustainable wastewater treatment protocols targeting antibiotic pollutants.

Immuno-PET/CT Imaging of Trop2 with [18F]AlF-RESCA-T4 Differentiates Lung Cancer from Inflammation.

Immuno-PET/CT imaging, a branch of molecular imaging, can noninvasively and specifically visualize biomarker expression across the body. Trophoblast cell surface antigen 2 (Trop2) is a pan-cancer biomarker and plays a crucial role in tumorigenesis through multiple signaling pathways. The study aims to develop and translate novel Trop2 single-domain antibody (sdAb) tracers for clinical use. Methods: Two sdAbs (i.e., His-tagged T4 and His-tag-free RT4) are recombinantly expressed in Chinese hamster ovary cells. The purities and binding kinetics are determined by sodium dodecyl sulfate polyacrylamide gel electrophoresis, high-performance liquid chromatography, and surface plasmon resonance assays. The AlF restrained complexing agent (RESCA) method is applied to develop 18F-labeled sdAb tracers ([18F]AlF-RESCA-T4 and [18F]AlF-RESCA-RT4), followed by thorough preclinical imaging and blocking studies on tumor-bearing mice and a pilot clinical trial evaluating the clinical imaging safety and feasibility of [18F]AlF-RESCA-T4 immuno-PET/CT. Results: [18F]AlF-RESCA-T4 and [18F]AlF-RESCA-RT4 possess high radiochemical purities. Preclinical imaging in the T3M-4 tumor model revealed prominent uptake (percentage injected dose/g) of [18F]AlF-RESCA-T4 (11.13 ± 1.53, n = 4) and [18F]AlF-RESCA-RT4 (8.83 ± 1.22, n = 4), which were significantly reduced by coinjection of unlabeled T4 and RT4 in blocking studies. The His-tag removal strategy further optimized the probe's invivo pharmacokinetics and reduced renal radioactivity accumulation without significantly decreasing tumor uptake. In a pilot clinical trial, [18F]AlF-RESCA-T4 immuno-PET/CT showed promising potency in annotating Trop2 expression and differentiating tumors from inflammatory diseases such as tuberculosis. Conclusion: [18F]AlF-RESCA-T4 and [18F]AlF-RESCA-RT4 can specifically annotate Trop2 expression. Clinical [18F]AlF-RESCA-T4 immuno-PET/CT imaging can screen patients for Trop2-targeted therapies and differentiate lung inflammation from cancer.

Thermoanalytical and Kinetic Studies for the Thermal Stability of Emerging Pharmaceutical Pollutants Under Different Heating Rates.

Emerging pharmaceutical pollutants like ciprofloxacin (CIP) and ibuprofen (IBU) are frequently detected in aquatic environments, posing risks to ecosystems and human health. Since pollutants rarely exist alone in the environment, understanding the thermal stability and degradation kinetics of these compounds, especially in mixtures, is crucial for developing effective removal strategies. This study therefore investigates the thermal stability and degradation kinetics of CIP and IBU, under different heating rates. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were employed to examine the thermal behavior of these compounds individually and in mixture (CIP + IBU) at heating rates of 10, 20, and 30 °C/min. The kinetics of thermal degradation were analyzed using both model-fitting (Coats-Redfern (CR)) and model-free (Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), and Friedman (FR)) methods. The results showed distinct degradation patterns, with CIP decomposing between 280 and 550 °C and IBU between 152 and 350 °C, while the mixture exhibited multistep decomposition in the 157-500 °C range. The CR model indicated first-order kinetics as a better fit for the degradation (except for IBU). Furthermore, CIP exhibits higher thermal stability and activation energy compared to IBU, with the KAS model yielding activation energies of 58.09 kJ/mol for CIP, 11.37 kJ/mol for IBU, and 41.09 kJ/mol for CIP + IBU mixture. The CIP + IBU mixture generally showed intermediate thermal properties, suggesting synergistic and antagonistic interactions between the compounds. Thermodynamic parameters (ΔH°, ΔG°, ΔS°) were calculated, revealing non-spontaneous, endothermic processes for all samples (except in the FWO method) with a decrease in molecular disorder and positive ΔG° values across all models and heating rates. The study found that higher heating rates led to less thermodynamically favorable conditions for degradation. These findings provide important information concerning the thermal behavior of these pharmaceutical pollutants, which can inform strategies for their removal from the environment and the development of more effective waste-treatment processes.

Eco-Friendly TiO2 Nanoparticles: Harnessing Aloe Vera for Superior Photocatalytic Degradation of Methylene Blue

In recent years, the contamination of aquatic environments by organic chemicals, including dyes such as methylene blue (MB), Congo red, and crystal violet, has become an increasing concern, as has their treatment. In this work, titanium dioxide nanoparticles (TiO2 NPs) were studied for their photocatalytic performance by measuring the degradation of MB under UV light. TiO2 NPs were synthesized using two synthetic processes optimized in this study: a green method, namely leveraging the natural properties of Aloe vera leaf extract; and a conventional approach. The resulting NPs were thoroughly characterized using X-rays Diffraction (XRD), Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Brunauer–Emmett–Teller (BET), UV–Vis and ζ-potential analysis. The TiO2 NPs synthesized by the green method demonstrated a degradation efficiency of (50 ± 3)% after 180 minutes, which was significantly higher than the (16 ± 3)% achieved by NPs synthesized through the conventional route. Moreover, the reaction rate constant for the green-synthesized TiO2 NPs was found to be approximately five times greater than that of the conventionally synthesized NPs. These results open up a new scenario in the pollution removal strategy research, using resources accessible in nature to synthesize NPs with high photocatalytic activity, which could also be useful for other applications, such as hydrogen production.

MUPPAAL: Efficient Elimination and Reduction of Useless Mutants in Real‐Time Model‐Based Systems

ABSTRACTTo assess test quality, mutation testing (MT) creates mutants by injecting artificial faults into the system and evaluates the ability of tests to distinguish these mutants. Tests distinguishing more mutants have also been proven empirically to detect more real faults. MT has been applied to many domains. We focus on MT for timed safety‐critical systems modelled as Timed Automata (TA). While powerful, MT usually yields equivalent and duplicate mutants, the former having the same behaviour as the original system and the latter other mutants. Such useless mutants bring no value, waste execution time and can be difficult to detect. We integrate useless mutant detection and removal strategies in our mutation framework MUPPAAL. MUPPAAL leverages existing equivalence‐avoiding mutation operators and focuses on detecting mutant duplicates using a scalable bisimulation algorithm and a fast approximate one based on biased simulation. We also demonstrate how to design an operator that reduces the occurrence of mutant duplicates. We evaluate MUPPAAL on six systems, demonstrating that (1) mutant duplicates account for up to 32% of all generated mutants, (2) our bisimulation approach scales effectively with these systems and (3) biased simulations further enhance performance. Our heuristic is 10 times faster than bisimulation and limits the exploration to two times the number of exact duplicates compared to up to 10 times for the baseline.

PATH-49. INTRA-OPERATIVE GENETIC ANALYSES FOR DECISION-MAKING DURING TUMOR REMOVAL OF ADULT-TYPE DIFFUSE GLIOMA USING RAPID QUANTITATIVE PCR DEVICE

Abstract BACKGROUND Recent comprehensive molecular analyses of central nervous system (CNS) tumors identified several diagnostic or prognostic markers. Especially, for adult-type diffuse glioma, IDH mutation, TERT promoter (pTERT) mutation and CDKN2A homozygous deletion are quite important markers for diagnosis and prognosis of this type of glioma. Intra-operative identification of these molecular alterations could be effective for decision-making of tumor removal strategy. METHODS In this study, we established intra-operative gene analysis method using rapid quantitative PCR device, GeneSoC, by which we could obtain genotype of these important genes for 20 minutes in an operating room. Using GeneSoC, we could perform 50 cycles of quantitative PCR for approximately 12 minutes. Results; We established rapid gene analyses of mutations of IDH1 R132H, pTERT C225T, pTERT C250T and homozygous deletion of CDKN2A for adult-type diffuse gliomas. For elution of DNA, we incubated at least 1mg of tumor tissue at 95°for 5 minutes. Combined this boiling method with GeneSoC, we could obtain those genetic alterations for 20 minutes after collection of tumor tissue. In analyses of 111 adult-type diffuse glioma cases, sensitivity and specificity for detection of IDH1 p.R132H are 98% and 98%, respectively, and those of pTERT (C225T or C250T) are 100% and 100%, respectively. In analyses of 50 cases, sensitivity and specificity for detection of CDKN2A homozygous deletion are 100% and 83%, respectively. Conclusion; In this study, we could obtain the genotype of important molecular markers intra-operatively, not only during tumor removal but even during tumor biopsy, using GeneSoC device. This rapid genetic analysis might be effective not only for intra-operative diagnosis but also for detection of boundary between tumor and normal tissue.

Effectiveness analysis of a novel rectangular tunnel boring machine with planetary transmission for box jacking

Traditional rectangular tunnel boring machines have low tunneling efficiency, poor soil mixing effects, which has hindered the construction of long-distance and large-section box jacking projects. To overcome these limitations, a new type of full-face excavation boring machine was developed based on a planetary transmission mechanism. This machine achieves full-face excavation by utilizing three eccentric cutter heads that revolve around both the central axis of the cutter plate and their individual shafts. The design methodology, feasibility, and principles of this new mechanism were introduced. Furthermore, a successful construction project of an underground highway passage in Japan was presented as a case study to demonstrate the design and application of this tunnel boring machine. The case details include the excavation face support mechanism, optimal cutter-head layout, obstacle removal strategies, and methods for reducing jacking resistance. Monitoring data from the project verified the applicability, reliability, and overall engineering performance of the rectangular shield machine developed using the planetary mechanism. This research demonstrates that the planetary transmission mechanism-based boring machine offers superior performance in terms of ground settlement and tunneling speed, potentially providing a comprehensive solution to the challenges in the development of rectangular shield machines for box jacking projects.

Interfacial Thermoconvection and Atomic Relay Catalysis Enable Equilibrium Shifting and Rapid Glucose‐to‐Fructose Isomerization

AbstractThe aqueous glucose‐to‐fructose isomerization is controlled by thermodynamics to an equilibrium limit of ~50 % fructose yield. However, here we report an in situ fructose removal strategy enabled by an interfacial local photothermal effect in combination with relay catalysis of geminal and isolated potassium single atoms (K SAs) on graphene‐type carbon (Ksg/GT) to effectively bypass the equilibrium limit and markedly speed up glucose‐to‐fructose isomerization. At 25 °C, an unprecedented fructose yield of 68.2 % was obtained over Ksg/GT in an aqueous solution without any additives under 30‐min solar‐like irradiation. Mechanistic studies expounded that the interfacial thermoconvection caused by the local photothermal effect of the graphene‐type carbon and preferable glucose adsorption on single‐atom K could facilitate the release of in situ formed fructose. The geminal K SAs were prone to form a stable metal‐glucose complex via bidentate coordination, and could significantly reduce the C−H bond electron density by light‐driven electron transfer toward K. This facilitated the hydride shift rate‐determining step and expedited glucose isomerization. In addition, isolated K SAs favored the subsequent protonation and ring‐closure process to furnish fructose. The integration of the interfacial thermoconvection‐enhanced in situ removal protocol and tailored atomic catalysis opens a prospective avenue for boosting equilibrium‐limited reactions under mild conditions.

Food and land system transformations under different societal perspectives on sustainable development

Abstract The future of food and land systems is crucial for achieving multiple UN Sustainable Development Goals, given their essential role in providing adequate nutrition and their significant impact on Earth system processes. Despite widespread consensus on the need for transformation, discussed strategies vary widely, from technology-driven to sufficiency-focused approaches, emphasizing different agents of change and policy mixes. This study assesses the implications of a new generation of target-seeking scenarios incorporating such diverse sustainability perspectives. We apply two integrated assessment models to explore food and land futures under three whole-economy Sustainable Development Pathways (SDPs): Economy-driven Innovation, Resilient Communities, and Managing the Global Commons. Our assessment shows that all SDPs align sufficient food supply with progress towards planetary integrity, halting biodiversity loss, mitigating adverse impacts from irrigation, and significantly reducing nitrogen pollution. While all pathways comply with the Paris climate target, they diverge in the timing of climate mitigation efforts and focus on different greenhouse gases and emission sources. The Economy-driven Innovation pathway rapidly achieves net-negative CO2 emissions from the land system, whereas Resilient Communities and Managing the Global Commons significantly decrease agricultural non-CO2 emissions. Moreover, sustainability interventions attenuate trade-offs associated with narrowly focused mitigation pathways and reduce reliance on carbon dioxide removal strategies like re/afforestation and bioenergy with carbon capture and storage.

Multi Targeted Therapy for Alzheimer's Disease by Guanidinium-Modified Calixarene and Cyclodextrin Co-Assembly Loaded with Insulin.

Amyloid-β (Aβ) is considered a primary therapeutic target for Alzheimer's disease (AD). However, just eliminating Aβ in patients with AD has exhibited restricted clinical efficacy, possibly failing to address the metabolic abnormalities caused by AD, such as insulin resistance. To address this concern, our research has employed two types of macrocyclic amphiphiles, guanidinium-modified calixarene and cyclodextrin coassembly (GCD), as delivery systems for insulin. This approach aimed to tackle the metabolic dysregulation characteristic of AD in an innovative manner by exploring beyond the conventional strategy of Aβ removal. As a result, GCD and insulin coassembly could effectively improve plaque deposition and insulin resistance. The coassembly could also reduce abnormal neuronal apoptosis and synaptic damage and improve cognitive impairment in 5xFAD mice. Therefore, the GCD and insulin coassembly shows promise as a viable therapeutic option for AD.