Selective Regulation Research Articles

Recent Advances in Electrochemical Carboxylation with CO2.

ConspectusCarbon dioxide (CO2) is recognized as a greenhouse gas and a common waste product. Simultaneously, it serves as an advantageous and commercially available C1 building block to generate valuable chemicals. Particularly, carboxylation with CO2 is considered a significant method for the direct and sustainable production of important carboxylic acids. However, the utilization of CO2 is challenging owing to its thermodynamic stability and kinetic inertness. Recently, organic electrosynthesis has emerged as a promising approach that utilizes electrons or holes as environmentally friendly redox reagents to produce reactive intermediates in a controlled and selective manner. This technique holds great potential for the CO2 utilization.Since 2015, our group has been dedicated to exploring the utilization of CO2 in organic synthesis with a particular focus on electrochemical carboxylation. Despite the significant advancements made in this area, there are still many challenges, including the activation of inert substrates, regulation of selectivity, diversity in electrolysis modes, and activation strategies. Over the past 7 years, our team, with many great experts, has presented findings on electrochemical carboxylation with CO2 under mild conditions. In this context, we primarily highlight our contributions to selective electrocarboxylations, encompassing new reaction systems, selectivity control methods, and activation approaches.We commenced our research by establishing a Ni-catalyzed electrochemical carboxylation of unactivated aryl halides and alkyl bromides in conjunction with a useful paired anodic reaction. This approach eliminates the need for sacrificial anodes, rendering the carboxylation process sustainable. To further utilize the widely existing yet cost-effective alkyl chlorides, we have developed a deep electroreductive system to achieve carboxylation of unactivated alkyl chlorides and poly(vinyl chloride), allowing the direct modification and upgrading of waste polymers.Through precise adjustment of the electroreductive conditions, we successfully demonstrated the dicarboxylation of both strained carbocycles and acyclic polyarylethanes with CO2 via C-C bond cleavage. Furthermore, we have realized the dicarboxylative cyclization of unactivated skipped dienes to produce the valuable ring-tethered adipic acids through single-electron reduction of CO2 to the CO2 radical anion (CO2•-). In terms of the asymmetric carboxylation, Guo's and our groups have recently achieved the nickel-catalyzed enantioselective electroreductive carboxylation reaction using racemic propargylic carbonates and CO2, paving the way for the synthesis of enantioenriched propargylic carboxylic acids.In addition to the aforementioned advancements, Lin's and our groups have also developed new electrolysis modes to achieve regiodivergent C-H carboxylation of N-heteroarenes dictated by electrochemical reactors. The choice of reactors plays a crucial role in determining whether the hydrogen atom transfer (HAT) reagents are formed anodically, consequently influencing the carboxylation pathways of N-heteroarene radical anions in the distinct electrolyzed environments.

Targeting CNS myeloid infiltrates provides neuroprotection in a progressive multiple sclerosis model

Demyelination and axonal injury in chronic-progressive Multiple Sclerosis (MS) are presumed to be driven by a neurotoxic bystander effect of meningeal-based myeloid infiltrates. There is an unmet clinical need to attenuate disease progression in such forms of CNS-compartmentalized MS. The failure of systemic immune suppressive treatments has highlighted the need for neuroprotective and repair-inducing strategies. Here, we examined whether direct targeting of CNS myeloid cells and modulating their toxicity may prevent irreversible tissue injury in chronic immune-mediated demyelinating disease. To that end, we utilized the experimental autoimmune encephalomyelitis (EAE) model in Biozzi mice, a clinically relevant MS model. We continuously delivered intracerebroventricularly (ICV) a retinoic acid receptor alpha agonist (RARα), as a potent regulator of myeloid cells, in the chronic phase of EAE. We assessed disease severity and performed pathological evaluations, functional analyses of immune cells, and single-cell RNA sequencing on isolated spinal CD11b+ cells. Although initiating treatment in the chronic phase of the disease, the RARα agonist successfully improved clinical outcomes and prevented axonal loss. ICV RARα agonist treatment inhibited pro-inflammatory pathways and shifted CNS myeloid cells toward neuroprotective phenotypes without affecting peripheral infiltrating myeloid cell phenotypes, or peripheral immunity. The treatment regulated cell-death pathways across multiple myeloid cell populations and suppressed apoptosis, resulting in paradoxically marked increased neuroinflammatory infiltrates, consisting mainly of microglia and CNS / border-associated macrophages. This work establishes the notion of bystander neurotoxicity by CNS immune infiltrates in chronic demyelinating disease. Furthermore, it shows that targeting compartmentalized neuroinflammation by selective regulation of CNS myeloid cell toxicity and survival reduces irreversible tissue injury, and may serve as a novel disease-modifying approach.

Research on compound amidohydroxysulfobetaine foamer for high-temperature and high-salinity clastic reservoirs

A high-quality foaming agent should exhibit excellent solubility in formation water and strong foaming ability, while also meeting the requirements of stability under high-temperature and high-salinity conditions, as well as low adsorption capacity. This study explores the potential of amidohydroxysulfobetaine surfactant as a foaming agent in sandstone reservoirs under specific reservoir conditions of 110 ℃ and 25.0×104 mg/L salinity. The findings indicate that compounding EHSB with a small amount of LHSB to form LA13 significantly reduces the Krafft point of EHSB. Furthermore, LA13 demonstrates outstanding solubility in 25.0×104 mg/L brine and exhibits an overall adsorption capacity on quartz sand surfaces lower than 0.6 mg/g when its concentration is below 1.0 wt%. Performance evaluation of bulk foam for LA31 at concentrations ranging from 0.05 wt% to 0.4 wt% suggests that using a foaming agent concentration of 0.05 wt% results in relatively low foaming volume and foam decay half-life; however, consistent foaming performance is observed across other concentrations, leading to highly stable foam due to the compound system's higher surface dilational modulus being the primary factor contributing to foam stability. Flow experiments reveal that the foam generated in cores with permeabilities of 46.5 mD, 185.5 mD, 632.0 mD, and 2005.3 mD exhibits a high resistance factor when the concentration of LA13 exceeds 0.1 wt%, while also demonstrating commendable gas-channeling regulation capability. Therefore, it is recommended to use LA13 as a foaming agent for field applications when its concentration surpasses 0.1 wt%. Additionally, comparing the mobility of foam formed by concentrations of 0.1 wt% and 0.2 wt% LA13 in cores with varying permeabilities shows that LA13 exhibits selective mobility regulation specifically in cores with permeabilities lower than 632.0 mD.

Adsorption behavior and selective regulation of tartaric acid at solid-liquid interface: For ilmenite flotation separation

Ilmenite and its main gangue minerals (titanaugite and forsterite) are challenging to separate due to their similar surface chemical properties. The flotation process is an effective method, and the use of surface modifiers is essential. There is an urgent need to develop more effective and environmentally friendly agents to address the shortcomings of existing surface modifiers and the lack of understanding of the inhibition mechanism. In this work, sodium oleate was used as a collector to investigate the inhibitory effect of tartaric acid (TA) on gangue minerals in ilmenite flotation. This was done through micro-flotation experiments, Zeta potential measurements, x-ray photoelectron spectroscopy (XPS) analysis, solution chemical simulations, molecular dynamics (MD) simulations, and density functional theory (DFT). The results demonstrated a significant decrease in the recovery rates of titanaugite and forsterite after the addition of 1 × 10^4 mol/L TA at pH = 8. TA chemically adsorbs onto the Ca and Mg sites on the surfaces of titanaugite and forsterite through carboxylic acid groups. This impedes the adsorption of anionic collectors due to electrostatic repulsion and steric hindrance, effectively inhibiting gangue minerals and achieving separation from ilmenite.

Hierarchical N‐doped Carbon Nanosheets Anchored Bimetallic Oxides for Selective Hydrogenation of Phenylacetylene

AbstractSelective hydrogenation of alkynes to alkenes using a low‐cost non‐noble metal catalyst is urgently desirable but challenging because of their over‐hydrogenation to undesired alkanes. Herein, a series of hierarchical N‐doped carbon nanosheets anchored bimetallic oxides were successfully fabricated. The resultant composite catalysts had advantages associated with not only two‐dimensionality (2D) nanosheets with highly active sites and fast mass transfer, but also bimetallic oxides that dissociate and transfer hydrogen with the assistance of the oxygen vacancies. Furthermore, the bimetallic oxides combined with the advantages of high activity of Ni and the selectivity regulation of Co. Benefiting from these advantages, the catalytic performance of CoNiO2−ZnCo2O4/NC NSs can reach nearly full conversion with 92 % selectivity at moderate reaction conditions and can keep excellent selectivity even prolonging the reaction time to 12 h, outperforming CoNiO2−ZnCo2O4/NC NPs, CoO−ZnCo2O4/NC NSs, and the commercial Lindlar catalysts, which demonstrate the huge potential for selective hydrogenation applications.

Neuropsychological features of somatic symptom disorder and depression/anxiety in Taiwan: An analysis based on the comorbidity status

Individuals with somatic symptom disorder (SSD) often have comorbid depression or anxiety, but whether SSD is associated with specific neuropsychological functions has yet to be fully examined. We analyzed which neuropsychological features are more closely associated with SSD, anxiety, and depression. In this case-control study, we recruited 140 individuals with SSD, 104 individuals with affective disorders without SSD, and 159 healthy controls in Taiwan. We collected DSM-5 diagnoses, questionnaire scores, and performance on eight tasks from the Cambridge Neuropsychological Test Automated Battery (CANTAB) for each participant. Several CANTAB tasks involving attention, executive function, and social cognition showed significant group differences. In the adjusted analysis, the tasks significantly associated with SSD were the Match to Sample Visual Search (MTS) and the Emotion Recognition Task (ERT). Among the questionnaires, the Cognitions about Body and Health Questionnaire showed the most significant associations with the tasks, specifically with Rapid Visual Information Processing, MTS, Paired Associates Learning, Spatial Working Memory, Intra-Extra Dimensional Set Shift, and ERT. We conclude that the MTS and ERT tasks show significant relationships with both SSD diagnosis and related questionnaires. These tasks primarily involve selective attention and negative emotion regulation.

Thermo-Switchable Enzyme@Metal-Organic Framework for Selective Biocatalysis and Biosensing.

The stimulus-responsive regulation of enzyme catalytic activity and selectivity provides a new opportunity to extend the functionality and efficiency of immobilized enzymes. This work aims to design and synthesize a thermo-switchable enzyme@MOF for size-selective biocatalysis and biosensing through the immobilization of Candida rugosa lipase (CRL) within ZIF-8 functionalized with thermally responsive polymer, poly(N-isopropylacrylamide) (PNIPAM) (CRL@ZIF-8-PNIPAM). Unlike free CRL, which does not demonstrate substrate selectivity, we can reversibly tune the pore size of the ZIF-8-PNIPAM nanostructures (open pores or blocked pores) through temperature stimulus and subsequently modulate the substrate selectivity of CRL@ZIF-8-PNIPAM. CRL@ZIF-8-PNIPAM had the highest hydrolytic activity for small molecules (12 mM p-nitrophenol/mg protein/min, 4-nitrophenyl butyrate (p-NP Be)) and the lowest hydrolytic activity for large molecules (0.16 mM p-nitrophenol/mg protein/min, 4-nitrophenyl palmitate (p-NP P)). In addition, CRL@ZIF-8-PNIPAM demonstrated thermo-switchable behavior for large molecules (p-NP P). The p-NP P hydrolytic activity of CRL@ZIF-8-PNIPAM was significantly lower at 40 °C (blocked pores) than at 27 °C (open pores). However, the transition of blocked pores and open pores is a gradual process that resulted in a delay in the "thermo-switchable" catalytic behavior of CRL@ZIF-8-PNIPAM during thermal cycling. CRL@ZIF-8-PNIPAM was also successfully used for the fabrication of electrochemical biosensors for the selective biosensing of pesticides with different molecular sizes.

Highly selective regulation of non-radical and radical mechanisms by Co cubic assembly catalysts for peroxymonosulfate activation

Peroxymonosulfate (PMS) activation on efficient catalysts is a promising strategy to produce sulfate radical (SO4−) and singlet oxygen (1O2) for the degradation of refractory organic pollutants. It is a great challenge to selectively generate these two reactive oxygen species, and the regulation mechanism from non-radical to radical pathway and vice versa is not well established. Here, we report a strategy to regulate the activation mechanism of PMS for the selective generation of SO4− and 1O2 with 100 % efficiency by sulfur-doped cobalt cubic assembly catalysts that was derived from the Co-Co Prussian blue analog precursor. This catalyst showed superior catalytic performance in activating PMS with normalized reaction rate increased by 87 times that of the commercial Co3O4 nanoparticles and had much lower activation energy barrier for the degradation of organic pollutant (e.g., p-chlorophenol) (18.32 kJ⋅mol−1). Experimental and theoretical calculation results revealed that S doping can regulate the electronic structure of Co active centers, which alters the direction of electron transfer between catalyst and PMS. This catalyst showed a strong tolerance to common organic compounds and anions in water, wide environmental applicability, and performed well in different real-water systems. This study provides new opportunities for the development of metal catalyst with metal-organic frameworks structure and good self-regeneration ability geared specifically towards PMS-based advanced oxidation processes applied for water remediation.

Cooperation of Strong Electric Field and H2O Dissociation on Co3O4-Decorated SiC Rods for Photodriven CO2 Methanation with 100% Selectivity.

Solar-driven methanation of carbon dioxide (CO2) with water (H2O) has emerged as an important strategy for achieving both carbon neutrality and fuel production. The selective methanation of CO2 was often hindered by the sluggish kinetics and the multiple competition of other C1 byproducts. To overcome this bottleneck, we utilized a biomass synthesis method to synthesize SiC rods and then constructed a direct Z-scheme heterojunction Co3O4/SiC catalyst. The substantial difference in work functions between SiC and Co3O4 served as a significant source of the charge driving force, facilitating the conversion of CO2 to CH4. The high-valent cobalt Co(IV) in Co3O4 acts as an active species to promote efficient dissociation of water. This favorable condition greatly enhanced the likelihood of a high concentration of electrons and protons around a single site on the catalyst surface for CO2 methanation. DFT calculation showed that the energy barrier of CO2 hydrogenation was significantly reduced at the Co3O4/SiC heterojunction interface, which changed the reaction pathway and completely converted the product from CO to CH4. The optimum CH4 evolution rate of Co3O4/SiC samples was 21.3 μmol g-1 h-1 with 100% selectivity. This study has an important guiding significance for the selective regulation of CO2 to CH4 products in photocatalysis applications.

Effect of the reorganization of acid sites induced by metal species on TiO2 supports on the conversion of furfural to acetals and ethers

For the catalytic hydrogenation of furfural (FFR) over supported metal catalysts, acetals and ethers were often observed as by-products when alcohols were used as solvents. The presence of specific acid sites on the catalyst led to the conversion of FFR to acetals and ethers. To understand the effect of the interaction between metal species and oxide supports on the acid properties of catalysts and the conversion of FFR to acetals and ethers, anatase TiO2 (TiO2-A), rutile TiO2 (TiO2-R) and these TiO2 supported Ni catalysts were studied as models. The relationship between the acid properties of these samples and FFR conversion pathways in isopropanol was revealed. The interaction between Ni species and TiO2 supports was found to selectively remove Brønsted acid sites on the TiO2 supports in the absence of H2, thereby inhibiting the conversion of FFR to acetals and ethers in N2. However, the presence of high-pressure H2 during the reaction induced the formation of new Brønsted acid sites on Ni/TiO2 catalysts via hydrogen spillover, promoting the acetalization of FFR to acetals and the hydrogenolysis of acetals to ethers. The Ni/TiO2-A catalyst exhibited higher activity in catalyzing the conversion of FFR to acetals and ethers compared to the Ni/TiO2-R catalyst. This work provides reference information for the selective regulation of acid-catalyzed reaction pathways of FFR in alcohols.

TDP43 autoregulation gives rise to shortened isoforms that are tightly controlled by both transcriptional and post-translational mechanisms.

The nuclear RNA-binding protein TDP43 is integrally involved in the pathogenesis of amyotrophic lateral sclerosis (ALS) and frontotemporal lobar degeneration (FTLD). Previous studies uncovered N-terminal TDP43 isoforms that are predominantly cytosolic in localization, highly prone to aggregation, and enriched in susceptible spinal motor neurons. In healthy cells, however, these shortened (s)TDP43 isoforms are difficult to detect in comparison to full-length (fl)TDP43, raising questions regarding their origin and selective regulation. Here, we show that sTDP43 is created as a byproduct of TDP43 autoregulation and cleared by nonsense mediated RNA decay (NMD). The sTDP43-encoding transcripts that escape NMD can lead to toxicity but are rapidly degraded post-translationally. Circumventing these regulatory mechanisms by overexpressing sTDP43 results in neurodegeneration in vitro and in vivo via N-terminal oligomerization and impairment of flTDP43 splicing activity, in addition to RNA binding-dependent gain-of-function toxicity. Collectively, these studies highlight endogenous mechanisms that tightly regulate sTDP43 expression and provide insight into the consequences of aberrant sTDP43 accumulation in disease.

Ion Selectivity, Current, and Water Flow Regulation in Ti3C2 MXene Nanopores.

Recent years have seen a growing interest in zero-dimensional (0D) transport phenomena occurring across two-dimensional (2D) materials for their potential applications to nanopore technology such as ion separation and molecular sensing. Herein, we investigate ion transport through 1 nm-wide nanopores in Ti3C2 MXene using molecular dynamics simulations. The high polarity and fish-bone arrangement of the Ti3C2 MXene offer a built-in potential and an atomic-scale distortion to the nanopore, causing an adsorption preference for cations. Our observation of variable cation-specific ion selectivity and Coulomb blockade highlights the complex interplay between adsorption affinity and cation size. The cation-specific ion selectivity can induce both the ion current and electro-osmotic water transmission, which can be regulated by tailoring the ions' preferential pathways through electric field tilting. Our finding underscores the pivotal role of the atomic arrangement of MXenes in 0D ion transport and provides fundamental insight into the application of 2D material in nanopores-based technologies.

Ion selectivity regulation under confinement for electromagnetic pollution management

Ionic conductors are emerging as promising candidates in the field of microwave absorption, demonstrating significant potential in absorption efficiency and practical applications. In this study, we have synthesized a series of microwave absorption clays (AC) by incorporating 2D ZIF-L with four imidazolium ionic liquids (ILs). These materials not only exhibit outstanding absorption properties but also enhance our understanding of mechanisms associated with ion-based absorbers. The selective interaction of the ZIF-L framework results in distinct dielectric properties among imidazolium ILs with varying ion sizes and polarities. Analysis of relaxation behavior and ionic conductivity reveals that smaller ions facilitate better ionic transport and longer relaxation times by accessing the interior cavities, whereas larger ions experience extended charge transport distances within the framework gaps but shorter relaxation times due to the formation of short-range ordered structures. Moreover, these clay-like ionic conductors demonstrate excellent microwave absorption capabilities, with effective bandwidths of 2.3 GHz, 7.0 GHz, 6.7 GHz, and 7.4 GHz, respectively. This work presents a promising avenue for high-performance absorbers, advancing our understanding of ion-based absorption mechanisms.

Resting-state functional connectivity of goal-directed and habitual-learning systems: The efficacy of cognitive-behavioral therapy for obsessive-compulsive disorder

BackgroundThere is an imbalance between goal-directed and habitual-learning system in patients with obsessive-compulsive disorder (OCD). At present, the relationship between cognitive behavior therapy (CBT) as a first-line therapy and goal-directed and habitual-learning disorder is still unclear. We attempted to discuss the effect of CBT treatment in patients with OCD, using abnormalities in goal-directed and habitual-learning-related brain regions at baseline as predictive factors. MethodsA total of 71 subjects, including 35 OCD patients and 36 healthy controls, were recruited. The OCD patients underwent 8 weeks of CBT. These patients were divided into two groups based on treatment response (Nresponders = 18, Nnonresponders = 17). Further subgroup analysis was conducted based on disease duration (Nshort = 17, Nlong = 18) and age of onset (Nearly = 14, Nlate = 21). We collected resting-state ROI-ROI functional connectivity data and apply repeated-measures linear mixed-effects models to investigate the differences of different subgroups. ResultsCBT led to symptom improvement in OCD patients, with varying degrees of effectiveness across subgroups. The orbitofrontal cortex (OFC) and insula, key regions for goal-directed behavior and habitual-learning, respectively, showed significant impacts on CBT efficacy in subgroups with different disease durations and ages of onset. ConclusionThe findings suggest that the goal-directed system may influence the efficacy of CBT through goal selection, maintenance, and emotion regulation. Furthermore, we found that disease duration and age of onset may affect treatment outcomes by modulating functional connectivity between goal-directed and habitual-learning brain regions.

Solar Energy-Driven Reverse Water Gas Shift Reaction: Photothermal Effect, Photoelectric Activation and Selectivity Regulation.

Excessive carbon dioxide (CO2) emissions are one of the main causes of the greenhouse effect. Thermal catalytic reverse water gas shift (RWGS) reaction, which is a pre reaction for Fischer-Tropsch synthesis, is considered an effective way to convert CO2 and synthesize high value-added chemicals in industry. However, traditional thermal catalysis requires a large amount of fossil fuels to drive reactions, which cannot achieve the true goal of carbon neutrality. Photothermal catalysis, as a novel conversion pathway, can achieve efficient CO2 conversion while significantly improving solar energy utilization. This review provides a detailed introduction of CO2 and H2 adsorption/activation and reaction pathways in thermal catalysis, as well as the catalytic mechanisms of thermal and chemical effects in photothermal catalytic RWGS to supply readers valuable insights on the mechanism of photothermal catalytic RWGS reaction and provide a reference for better catalyst design.

Selective regulation of a defined subset of inflammatory and immunoregulatory genes by an NF-κB p50-IκBζ pathway.

The five NF-κB family members and three nuclear IκB proteins play important biological roles, but the mechanisms by which distinct members of these protein families contribute to selective gene transcription remain poorly understood, especially at a genome-wide scale. Using nascent transcript RNA-seq, we observed considerable overlap between p50-dependent and IκBζ-dependent genes in Toll-like receptor 4 (TLR4)-activated macrophages. Key immunoregulatory genes, including Il6, Il1b, Nos2, Lcn2, and Batf, are among the p50-IκBζ-codependent genes. IκBζ-bound genomic sites are occupied at earlier time points by NF-κB dimers. However, p50-IκBζ codependence does not coincide with preferential binding of either p50 or IκBζ, as RelA co-occupies hundreds of genomic sites with the two proteins. A common feature of p50-IκBζ-codependent genes is a nearby p50/RelA/IκBζ-cobound site exhibiting p50-dependent binding of both RelA and IκBζ. This and other results suggest that IκBζ acts in concert with RelA:p50 heterodimers. Notably, p50-IκBζ-codependent genes comprise a high percentage of genes exhibiting the greatest differential expression between TLR4-stimulated and tumor necrosis factor receptor (TNFR)-stimulated macrophages. Thus, our genome-centric analysis reveals a defined p50-IκBζ pathway that selectively activates a set of key immunoregulatory genes and serves as an important contributor to differential TNFR and TLR4 responses.

Atomic Confinement Empowered CoZn Dual-Single-Atom Nanotubes for H2O2 Production in Sequential Dual-Cathode Electro-Fenton Process.

Single-atom catalysts (SACs) are flourishing in various fields because of their 100% atomic utilization. However, their uncontrollable selectivity, poor stability and vulnerable inactivation remain critical challenges. According to theoretical predictions and experiments, a heteronuclear CoZn dual-single-atom confined in N/O-doped hollow carbon nanotube reactors (CoZnSA@CNTs) is synthesized via spatial confinement growth. CoZnSA@CNTs exhibit superior performance for H2O2 electrosynthesis over the entire pH range due to dual-confinement of atomic sites and O2 molecule. CoZnSA@CNTs is favorable for H2O2 production mainly because the synergy of adjacent atomic sites, defect-rich feature and nanotube reactor promoted O2 enrichment and enhanced H2O2 reactivity/selectivity. The H2O2 selectivity reaches ∼100% in a range of 0.2-0.65V versus RHE and the yield achieves 7.50M gcat -1 with CoZnSA@CNTs/carbon fiber felt, exceeding most of the reported SACs in H-type cells. The obtained H2O2 is converted directly to sodium percarbonate and sodium perborate in a safe way for H2O2 storage/transportation. The sequential dual-cathode electron-Fenton process promotes the formation of reactive oxygen species (•OH, 1O2 and •O2 -) by activating the generated H2O2, enabling accelerated degradation of various pollutants and Cr(VI) detoxification in actual wastewater. This work proposes a promising confinement strategy for catalyst design and selectivity regulation of complex reactions.

Structural selective regulation of Fe3O4@C composite as adsorbent for removing different organic pollutants

ABSTRACT Many wastewater treatment methods have been developed because large amounts of organic pollutants (OPs) entered into the water bodies and adsorption is one of the classic and important technologies. Recently, magnetic adsorbents have garnered extensive attention due to the high efficiency and distinctive recyclability. The control of their structures and surface properties is crucial. Here, the magnetite@carbon (Fe3O4@C) composite was prepared by coupling microreactor and pyrolysis reactor. The structures and surface properties of the Fe3O4@C were effectively adjusted by changing the pyrolysis temperature and Na2CO3 concentration. The Fe3O4@C composite prepared at 800°C of pyrolysis temperature with 1 mol·L−1 of Na2CO3 concentration has lipophilicity and the highest adsorption capacity of 92# gasoline among those adsorbents, which is as high as 7.6 g·g−1. The Fe3O4@C synthesized at 500°C with 1 mol·L−1 of Na2CO3 concentration has hydrophilicity and the highest adsorption capacity of Rhodamine B and Methyl Blue. The saturated adsorption capacities are about 166 and 301 mg·g−1, respectively. Fe3O4@C can be easily separated from wastewater and simply regenerated with less capacity loss after five cycles. The results show that the Fe3O4@C prepared by this method could be suitable for the removal of different OPs by adjusting the preparation conditions.

Beyond the selective regulation of wetlands: towards a rights of wetlands

ABSTRACT The importance of wetlands as places worthy of protection has been recognised since at least 1975, with the passage of the global wetland treaty, the Ramsar Convention (officially the Ramsar Convention on Wetlands of International Importance Especially as Waterfowl Habitat). However, over the past 50 years wetlands have declined and at least 35% of natural wetlands have been lost with more at risk of extinction. Unfortunately, wetland habitats continue to suffer, despite the existence of protection regimes. In this context, this paper invites us to push the way we think about current wetland regulation and protection. Contemporary conceptions of wetlands that underpin dominant protection and management regimes tend to characterise wetlands in a way that overlooks all essential elements of the ecosystem. Our concern is to illuminate the plight of wetland ecosystems as interconnected waterscapes requiring more than a selective or partial regulative protection effort. We argue for a ‘rights of wetlands’ framing for a more holistic approach to regulate the management of these key ecosystems. We situate our argument using a Ramsar-listed wetland example, the Towra Point Nature Reserve, located in Botany Bay (Kamay), Sydney, Australia. Ultimately, we invite a recalibration of regulatory efforts for wetland conservation.

Carbene-catalyzed and Pnictogen Bond-assisted Access to PIII-Stereogenic Compounds.

Intermolecular pnictogen bonding (PnB) catalysis has received increased interest in non-covalent organocatalysis. It has been demonstrated that organic electron-deficient pnictogen atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral PIII compounds by combining intramolecular PnB interactions and carbene catalysis. Our design features a pre-chiral phosphorus molecules bearing two electron-withdrawing benzoyl groups, resulting in the formation of a σ-hole at the P atom. X-ray and non-covalent interaction (NCI) analysis indicate that these phosphorus substrates exhibit intrinsic PnB interactions between the oxygen atom of the formyl group and the phosphorus atom. This induces a conformational locking effect, leading to the crystallization of the phosphorus substrates in a preferred conformation (P212121 chiral group). Under the catalysis of N-heterocyclic carbene, the aldehyde moiety activated by the pnictogen bond selectively reacts with an alcohol to yield the corresponding chiral monoester/phosphorus products with excellent enantioselectivity. This Lewis acidic phosphorus center, aroused by the non-polarized intramolecular pnictogen bond interaction, assists in conformational and selective regulations, providing unique opportunities for catalysis and beyond.