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We report sulfonated hypercrosslinked polymers (SHCPs) as heterogeneous catalysts for the selective esterification of hexanoic acid with benzyl alcohol. The SHCPs demonstrate tuneable catalytic activity and selectivity, outperforming conventional acid catalysts. We also explore detrimental structural changes over multiple cycles, providing insights for optimising long-term catalyst performance.

Switchable emulsifiers are commonly studied at the macroscopic scale without significant insight into the molecular properties and processes underpinning their behaviour. This work aims to investigate on the molecular scale a switchable emulsifier comprising poly(methacrylic acid) (PMAA) and poly(ethylene glycol) methacrylate (PEGMA). This emulsifier forms stable oil/water emulsions at pH > 10, but the emulsion becomes unstable at pH < 3 due to droplet aggregation. It has been suggested that H-bonding between the MAA (methacrylic acid) and EG (ethylene glycol) groups is central for the switching behaviour. However, no detailed molecular understanding of the surface of the emulsifier coated droplets has been developed so far. Using sum frequency generation spectroscopy, we compared the spectra of the PMAA/PEGMA polymer deposited on a water surface under acidic (pH 2.5) and basic (pH 11.5) conditions. We found that at pH 2.5, both MAA-EG H-bonds and MAA = MAA cyclic dimers contribute to droplet aggregation in the emulsion. In contrast, at pH 11.5 deprotonation and solvation of the PMAA component lead to a polymer restructuring. As a result, the PMAA chains form a negative shell around the droplets, electrostatically stabilising the emulsion in alkaline conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

We explore the thermal oxidation of hyper-cross-linked polymers to enhance their hydrophilicity and efficacy in atmospheric water harvesting. Comprehensive chemical and physical characterizations are used to confirm the successful incorporation of polar oxygen moieties and the preservation of porosity upon thermal treatment. Newly introduced oxygen-based functional groups significantly improve water sorption properties, increasing total water uptake capacities by up to 400% and shifting water uptake onsets to significantly lower relative humidity. We also investigate the regeneration of oxidized hyper-cross-linked polymers after water sorption to probe their potential for multiple water harvesting cycles and reuse. Our findings outline a simple and cost-effective postsynthetic modification route for optimizing porous organic polymers for more sustainable and efficient atmospheric water harvesting.

We report a sulfonated covalent organic framework (COF) capable of atmospheric water harvesting in arid conditions. The isothermal water uptake profile of the framework was studied, and the network displayed steep water sorption at low relative humidity (RH) in temperatures of up to 45 °C, reaching a water uptake of 0.12 g g -1 at 10 % RH and even 0.08 g g -1 at just 5 % RH, representing some of the most extreme conditions on the planet. We found that the inclusion of sulfonate moieties shifted uptake in the water isotherm profiles to lower RH compared to non-sulfonated equivalents, demonstrating well the benefits of including these hydrophilic sites for water uptake in hot, arid locations. Repeated uptake and desorption cycles were performed on the material without significant detriment to its adsorption performance, demonstrating the potential of the sulfonated COF for real-world implementation., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

The synthesis and characterisation of a lignin-based elastomer system using lignin-epoxy-resins is presented. Untreated kraft black liquor was used to synthesise glycidyl lignin or black liquor-based epoxy resin (BLER), following a published procedure. A flexible, elastomeric thermoset was produced by cross-linking BLER with succinic anhydride (SA). The produced material was characterised in respect to its chemical, thermal, mechanical and swelling characteristics. In addition, vertical burning tests were performed. The obtained lignin-based elastomeric thermoset had a tensile strength of 1.0 ± 0.20 MPa and elastic moduli of 1.6 ± 1.4 and 0.44 ± 0.35 MPa at 5% and 50% elongation, respectively. A maximum elongation of 151 ± 49% was found., Competing Interests: The authors Philip Verdross and Alexander Bismarck hold a patent together with the University of Vienna based on the production of BLER resin (WO 2024/062004)., (This journal is © The Royal Society of Chemistry.)

The availability of freshwater is rapidly declining due to over-exploitation and climate change, with multiple parts of the globe already facing significant freshwater scarcity. Here, a sulfonated hypercrosslinked polymer able to repeatedly harvest significant amounts of water via direct air capture is reported. Water uptake from relative humidities as low as 10% is demonstrated, mimicking some of the harshest environments on Earth. A water harvesting device is used to show repeated uptake and harvesting without significant detriment to adsorbent performance. Desorption is triggered using simulated sunlight, presenting a low-energy route to water harvesting and adsorbent regeneration. The synthesis of sulfonated hypercrosslinked polymer requires only low-cost and readily available reagents, offering excellent potential for scale-up. Due to an almost limitless supply of water vapor from air in most regions around the globe, this approach can transform our ability to address water security concerns., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Direct air capture (DAC) using solid adsorbents has gained significant attention as a carbon dioxide removal (CDR) technology to help limit global temperature rise to below 2 °C. One large area of focus is the development of new adsorbent materials for DAC. However, the necessary data needed to employ these materials in process models for adsorbent screening are rarely available. Here, we showcase Purolite A110, a commercially available amine-functionalized polymeric resin, as a new candidate adsorbent for DAC and compare its properties to a current benchmark, Lewatit VP OC 1065. For both materials, we report their chemical features and composition, skeletal, particle, and bed density, total pore volume, particle porosity, BET area, thermal stability, and specific heat capacity. We determine their equilibrium sorption properties by measuring the volumetric CO 2 isotherms at 288, 298, 308, 333, 343, 353, and 393 K, N 2 and H 2 O isotherms at 288, 298, and 308 K, and Ar and O 2 isotherms at 298 K. For CO 2 , N 2 , and H 2 O, we also present the corresponding isotherm model fitting parameters and heats of adsorption. These data can help facilitate process modeling and optimization studies to properly assess these adsorbents at scale., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

A novel hydroxypropyl cellulose (gHPC) hydrogel with graded porosity has been fabricated, in which pore size, shape, and mechanical properties vary across the material. The graded porosity was achieved by cross-linking different parts of the hydrogel at temperatures below and above 42 °C, which was found to be the temperature of turbidity onset (lower critical solution temperature, LCST) for the HPC and divinylsulfone cross-linker mixture. Scanning electron microscopy imaging revealed a decreasing pore size along the cross-section of the HPC hydrogel from the top to the bottom layer. HPC hydrogels demonstrate graded mechanical properties whereby the top layer, Zone 1, cross-linked below LCST, can be compressed by about 50% before fracture, whereas the middle and bottom layers (Zone 2 and 3, respectively) cross-linked at 42 °C, can withstand 80% compression before failure. This work demonstrates a straightforward, yet novel, concept of exploiting a graded stimulus to incorporate a graded functionality into porous materials that can withstand mechanical stress and minor elastic deformations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The concerns about the contradiction between agricultural production and Agricultural Non-Point (ANPS) pollution has become increased with economic development in China. Government interventions are key to controlling ANPS pollution through the establishment of laws and policies. This paper uses the entropy method to calculate the emissions amount of ANPS pollution and policy strength of 31 provinces from 2010 to 2019 in China. The dynamic panel data model with system generalized moment is used to estimate the impacts of policies with different measures on ANPS pollution emission. According to our findings, China's policies have been helpful in controlling ANPS pollution though there are important regional differences. Moreover, four types of policy measures all contribute to the reduction in ANPS pollution. These findings improve our understanding of the relationship between policies and ANPS pollution in the analyzed period, thus providing support for the formulation of pollution management strategies in the next stage.

Highly active and selective heterogeneous catalysis driven by metallic nanoparticles relies on a high degree of stabilization of such nanomaterials facilitated by strong surface ligands or deposition on solid supports. In order to tackle these challenges, N-heterocyclic carbene stabilized gold nanoparticles (NHC@AuNPs) emerged as promising heterogeneous catalysts. Despite the high degree of stabilization obtained by NHCs as surface ligands, NHC@AuNPs still need to be loaded on support structures to obtain easily recyclable and reliable heterogeneous catalysts. Therefore, the combination of properties obtained by NHCs and support structures as NHC bearing "functional supports" for the stabilization of AuNPs is desirable. Here, we report the synthesis of hyper-crosslinked polymers containing benzimidazolium as NHC precursors to stabilize AuNPs. Following the successful synthesis of hyper-crosslinked polymers (HCP), a two-step procedure was developed to obtain HCP·NHC@AuNPs. Detailed characterization not only revealed the successful NHC formation but also proved that the NHC functions as a stabilizer to the AuNPs in the porous polymer network. Finally, HCP·NHC@AuNPs were evaluated in the catalytic decomposition of 4-nitrophenol. In batch reactions, a conversion of greater than 99% could be achieved in as little as 90 s. To further evaluate the catalytic capability of HCP·NHC@AuNP, the catalytic decomposition of 4-nitrophenol was also performed in a flow setup. Here the catalyst not only showed excellent catalytic conversion but also exceptional recyclability while maintaining the catalytic performance., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Numerous hyper-cross-linked polymers (HCPs) have been developed as CO 2 adsorbents and photocatalysts. Yet, little is known of the CO 2 and H 2 O adsorption mechanisms on amorphous porous polymers. Gaining a better understanding of these mechanisms and determining the adsorption sites are key to the rational design of improved adsorbents and photocatalysts. Herein, we present a unique approach that combines density functional theory (DFT), in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and multivariate spectral analysis to investigate CO 2 and H 2 O adsorption sites on a triazine-biphenyl HCP. We found that CO 2 and H 2 O adsorb on the same HCP sites albeit with different adsorption strengths. The primary amines of the triazines were identified as favoring strong CO 2 binding interactions. Given the potential use of HCPs for CO 2 photoreduction, we also investigated CO 2 and H 2 O adsorption under transient light irradiation. Under irradiation, we observed partial CO 2 and H 2 O desorption and a redistribution of interactions between the H 2 O and CO 2 molecules that remain adsorbed at HCP adsorption sites.

In semiarid agricultural regions, aquifers have watered widespread economic development. Falling water tables, however, drive up energy costs and can make the water toxic for human consumption. The study area is located in central Mexico, where arsenic and fluoride are widely present at toxic concentrations in well water. We simulated the holistic outcomes from three pumping scenarios over 100 years (2020-2120); (S1) pumping rates increase at a similar rate to the past 40 years, (S2) remain constant, or (S3) decrease. Under scenario S1, by 2120, the depth to water table increased to 426 m and energy consumption for irrigation increased to 4 × 10 9 kWh/yr. Arsenic and fluoride concentrations increased from 14 to 46 μg/L and 1.0 to 3.6 mg/L, respectively. The combined estimated IQ point decrements from drinking untreated well water lowered expected incomes in 2120 by 27% compared to what they would be with negligible exposure levels. We calculated the 100-year Net Present Value (NPV) of each scenario assuming the 2020 average crop value to water footprint ratio of 0.12 USD/m 3 . Without drinking water mitigation, S1 and S3 yielded relative NPVs of -5.96 × 10 9 and 1.51 × 10 9 USD, respectively, compared to the base case (S2). The relative NPV of providing blanket reverse osmosis treatment, while keeping pumping constant (S2), was 11.55 × 10 9 USD and this gain increased when combined with decreased pumping (S3). If a high value, low water footprint crop was substituted (broccoli, 1.51 USD/m 3 ), the net gains from increasing pumping were similar in size to those of implementing blanket drinking water treatment., Competing Interests: The authors declare no conflicts of interest relevant to this study., (© 2022 The Authors. GeoHealth published by Wiley Periodicals LLC on behalf of American Geophysical Union.)

China today has an urgent need to develop low-carbon policies that also address local air pollution. This study uses a difference-in-differences model to estimate the extent to which China's Emissions Trading Scheme (ETS), which directly addresses CO 2 emissions, has also generated cobenefits by reducing PM 2.5 . Using monthly PM 2.5 concentration and weather data for 297 Chinese cities from January 2005 to December 2017, we find that (1) China's ETS has reduced PM 2.5 concentrations by 4.8%, and this reduction effect is strongest in summer. The results are confirmed by robustness tests including propensity score matching, mahalanobis distance matching, two placebo tests, and controlling atmospheric policies. (2) The ETS pilots have positive spillovers on neighboring nonpilot cities within 300 km of the pilot cites, especially for those downwind neighboring nonpilot cities, and the ETS's cobenefits are primarily a result of firms adopting abatement activities and adjusting industrial structure. (3) The cobenefits of China's ETS pilots are greater in regions with larger carbon trading volume and higher carbon trading price. (4) The reduction in PM 2.5 concentration caused by China's ETS may have avoided 23,363 deaths and saved $41.38 billion annually in GDP.

The design of robust, high-performance photocatalysts is key for the success of solar fuel production by CO 2 conversion. In this study, hypercrosslinked polymer (HCP) photocatalysts have been developed for the selective reduction of CO 2 to CO, combining excellent CO 2 sorption capacities, good general stabilities, and low production costs. HCPs are active photocatalysts in the visible light range, significantly outperforming the benchmark material, TiO 2 P25, using only sacrificial H 2 O. It is hypothesized that superior H 2 O adsorption capacities facilitate access to photoactive sites, improving photocatalytic conversion rates when compared to sacrificial H 2 . These polymers are an intriguing set of organic photocatalysts, displaying no long-range order or extended π-conjugation. The as-synthesized networks are the sole photocatalytic component, requiring no added cocatalyst doping or photosensitizer, representing a highly versatile and exciting platform for solar-energy conversion., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Hypercrosslinked polymers were produced via the self-condensation of benzyl ether compounds, providing a one-component route to highly porous networks and significant reductions in catalyst waste compared to conventional routes. These compounds also represent a new class of external crosslinkers, able to impart improved textural properties when compared to standard aliphatic crosslinkers.

The development of graphene-polymer nanocomposite materials has been hindered by issues such as poor colloidal stability of graphene in liquid media, weak interactions between graphene and the host polymers as well as the lack of scalable and economical graphene synthesis routes. Chlorosulfonic acid (CSA) can spontaneously disperse graphene without the need for mechanical agitation, chemical functionalisation or surfactant stabilisation,1 however is incompatible with most polymers and organic materials. Here, we demonstrate how poly(p-phenylene terephthalamide) (PPTA) - the polymer which constitutes Kevlar - can be co-processed with graphene in CSA and wet-spun into nanocomposite fibres with minimal aggregation of graphene.

The effective management of fish populations requires understanding of both the biology of the species being managed and the behavior of the humans who harvest those species. For many marine fisheries, recreational harvests represent a significant portion of the total fishing mortality. For such fisheries, therefore, a model that captures the dynamics of angler choices and the fish population would be a valuable tool for fisheries management. In this study, we provide such a model, focusing on red drum and spotted seatrout, which are the two of the main recreational fishing targets in the Gulf of Mexico. The biological models are in the form of vector autoregressive models. The anglers' decision model takes the discrete choice approach, in which anglers first decide whether to go fishing and then determine the location to fish based on the distance and expected catch of two species of fish if they decide to go fishing. The coupled model predicts that, under the level of fluctuation in the abundance of the two species experienced in the past 35 years, the number of trips that might be taken by anglers fluctuates moderately. This fluctuation is magnified as the cost of travel decreases because the anglers can travel long distance to seek better fishing conditions. On the other hand, as the cost of travel increases, their preference to fish in nearby areas increases regardless of the expected catch in other locations and variation in the trips taken declines. The model demonstrates the importance of incorporating anglers' decision processes in understanding the changes in a fishing effort level. Although the model in this study still has a room for further improvement, it can be used for more effective management of fish and potentially other populations., Competing Interests: The authors have declared that no competing interests exist.

Mechanocatalytic depolymerization of lignocellulose presents a promising method for the solid-state transformation of acidified raw biomass into water-soluble products (WSPs). However, the mechanisms underlining the utilization of mechanical forces in the depolymerization are poorly understood. A kinematic model of the milling process is applied to assess the energy dose transferred to cellulose during its mechanocatalytic depolymerization under varied conditions (rotational speed, milling time, ball size, and substrate loading). The data set is compared to the apparent energy dose calculated from the kinematic model and reveals key features of the mechanocatalytic process. At low energy doses, a rapid rise in the WSP yield associated with the apparent energy dose is observed. However, at a higher energy dose obtained by extended milling duration or high milling speeds, the formation of a substrate cake layer on the mill vials appear to buffer the mechanical forces, preventing full cellulose conversion into WSPs. By contrast, for beechwood, there exists a good linear dependence between the WSP yield and the energy dose provided to the substrate over the entire range of WSP yields. As the formation of a substrate cake in depolymerization of beechwood is less severe than that for the cellulose experiments, the current results verify the hypothesis regarding the negative effect of a substrate layer formed on the mill vials upon the depolymerization process. Overall, the current findings provide valuable insight into relationships between the energy dose and the extent of cellulose depolymerization effected by the mechanocatalytic process., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Basic adsorption of hydrophobic polymers from aprotic solvents was introduced as a platform technology to modify exclusively the surfaces of cellulose nanopapers. Dynamic vapor sorption demonstrated that the water vapor uptake ability of the nanopapers remained unperturbed, despite strong repellency to liquid water caused by the adsorbed hydrophobic polymer on the surface. This was enabled by the fact that the aprotic solvents used for adsorption did not swell the nanopaper unlike water that is generally applied as the adsorption medium in such systems. As case examples, the adsorptions of polystyrene (PS) and poly(trifluoroethylene) (PF 3 E) were followed by X-ray photoelectron spectroscopy and water contact angle measurements, backed up with morphological analysis by atomic force microscopy. The resulting nanopapers are useful in applications like moisture buffers where repellence to liquid water and ability for moisture sorption are desired qualities.

Carbon foams displaying hierarchical porosity and excellent surface areas of >1400 m²/g can be produced by the activation of macroporous poly(divinylbenzene). Poly(divinylbenzene) was synthesized from the polymerization of the continuous, but minority, phase of a simple high internal phase Pickering emulsion. By the addition of KOH, chemical activation of the materials is induced during carbonization, producing Pickering-emulsion-templated carbon foams, or carboHIPEs, with tailorable macropore diameters and surface areas almost triple that of those previously reported. The retention of the customizable, macroporous open-cell structure of the poly(divinylbenzene) precursor and the production of a large degree of microporosity during activation leads to tailorable carboHIPEs with excellent surface areas.

The Public Health Service Policy on the Humane Care and Use of Laboratory Animals and sound ethical practices require institutions to provide safe working environments for personnel working with animals; this mandate is achieved in part by establishing an effective animal care Occupational Health and Safety Program (OHSP). Land-grant institutions often face unique organizational challenges in fulfilling this requirement. For example, responsibilities for providing health and safety programs often have historically been dispersed among many different divisions scattered around the campus. Here we describe how our institutional management personnel overcame organizational structure and cultural obstacles during the formation of a comprehensive campus-wide animal care OHSP. Steps toward establishing the animal care OHSP included assigning overall responsibility, identifying all stakeholders, creating a leadership group, and hiring a fulltime Animal Care OHSP Specialist. A web-based portal was developed, implemented, and refined over the past 7 y and reflected the unique organizational structures of the university and the needs of our research community. Through this web-based portal, hazards are identified, risks are assessed, and training is provided. The animal care OHSP now provides easy mandatory enrollment, supports timely feedback regarding hazards, and affords enrollees the opportunity to participate in voluntary medical surveillance. The future direction and development of the animal care OHSP will be based on the research trends of campus, identification of emerging health and safety hazards, and ongoing evaluation and refinement of the program.

Uncertainties inherent in fisheries motivate a precautionary approach to management, meaning an approach specifically intended to avoid bad outcomes. Stochastic dynamic optimization models, which have been in the fisheries literature for decades, provide a framework for decision making when uncertain outcomes have known probabilities. However, most such models incorporate population dynamics models for which the parameters are assumed known. In this paper, we apply a robust optimization approach to capture a form of uncertainty nearly universal in fisheries, uncertainty regarding the values of model parameters. Our approach, developed by Nilim and El Ghaoui (Oper Res 53(5):780-798, 2005), establishes bounds on parameter values based on the available data and the degree of precaution that the decision maker chooses. To demonstrate the applicability of the method to fisheries management problems, we use a simple example, the Skeena River sockeye salmon fishery. We show that robust optimization offers a structured and computationally tractable approach to formulating precautionary harvest policies. Moreover, as better information about the resource becomes available, less conservative management is possible without reducing the level of precaution.

To impact carbon emissions, new materials for carbon capture must be inexpensive, robust, and able to adsorb CO2 specifically from a mixture of other gases. In particular, materials must be tolerant to the water vapor and to the acidic impurities that are present in gas streams produced by using fossil fuels to generate electricity. We show that a porous organic polymer has excellent CO2 capacity and high CO2 selectivity under conditions relevant to precombustion CO2 capture. Unlike polar adsorbents, such as zeolite 13x and the metal-organic framework, HKUST-1, the CO2 adsorption capacity for the hydrophobic polymer is hardly affected by the adsorption of water vapor. The polymer is even stable to boiling in concentrated acid for extended periods, a property that is matched by few microporous adsorbents. The polymer adsorbs CO2 in a different way from rigid materials by physical swelling, much as a sponge adsorbs water. This gives rise to a higher CO2 capacities and much better CO2 selectivity than for other water-tolerant, nonswellable frameworks, such as activated carbon and ZIF-8. The polymer has superior function as a selective gas adsorbent, even though its constituent monomers are very simple organic feedstocks, as would be required for materials preparation on the large industrial scales required for carbon capture.

Subtle changes in copolymer surfactant architecture and chain-end functionality can induce diverse behaviours in pH-responsive branched copolymer-stabilized emulsions.