Pd(II)/LA-catalyzed acetanilide olefination with dioxygen.

Transition-metal-catalyzed aromatic olefination through direct C-H activation represents an atom and step-economic route for versatile pharmaceutical syntheses, and in many cases, different stoichiometric oxidants are frequently employed for achieving a reasonable catalytic efficiency of the transition metal ions. Herein, we report a Lewis acid promoted Pd(II)-catalyzed acetanilide olefination reaction with atmospheric dioxygen as the oxidant source. The linkage of the Lewis acid to the Pd(II) species through a diacetate bridge significantly improved its catalytic efficiency, and independent kinetic studies on the olefination step revealed that adding the Lewis acid significantly accelerated the olefination rate as well as the C-H activation step. A strong basicity of the internal base in the Pd(II) salt also benefited the olefination reaction plausibly through base-assisted ß-hydride elimination.

Deep dewatering of sludge and resource recovery of hydroxyapatite: A recyclable approach via ionic liquid biphasic system and hydrogen bonds reformation.

Deep dewatering of Waste Activated Sludge (WAS) through mechanical processes remains inefficient, primarily due to the formation of a stable hydrogen bonding network between the biopolymers and water, which consequently leads to significant water trapped by Extracellular Polymeric Substances (EPS). In this study, a novel and recyclable treatment for WAS based on Ionic Liquids (ILs) was established, named IL-biphasic aqueous system (IL-ABS) treatment. Specifically, the IL-ABS formed in WAS facilitated rapid and efficient in-situ deep dewatering while concurrently recovering hydroxyapatite. The water content decreased from an initial 98.27 % to 65.35 % with IL-ABS, formed by 1-Butyl-3-methylimidazolium bromide (BmimBr) and K3PO4 synthesized from waste H3PO4. Moreover, the recycled BmimBr maintaining the water content of the dewatered sludge consistently between 65.61 % and 67.25 % across five cycles, exhibited remarkable reproducibility. Through three-dimensional excitation-emission matrix, lactate dehydrogenase analyses and confocal laser scanning microscopy, the high concentration of BmimBr in the upper phase effectively disrupted the cells and EPS, which exposed protein and polysaccharide on the EPS surface. Subsequently, the K3PO4 in the lower phase led to an enhanced salting-out effect in WAS. Furthermore, FT-IR analysis revealed that K3PO4 disrupted the original hydrogen bonds between EPS and water. Then, BmimBr formed numerous hydrogen bonds with the sludge flocs, leading to deep dewatering and agglomeration of the sludge flocs during the unique phase separation process of IL-ABS. Notably, sludge-derived hydroxyapatite product exhibited remarkable adsorption capacity for prevalent heavy metal contaminants such as Pb2+, Cd2+ and Cu2+, with efficiencies comparable to those of commercial hydroxyapatite, thereby achieving the resource utilization of waste H3PO4. Moreover, economic calculations demonstrated the suitability of this novel treatment. This innovative treatment exhibits potential for practical applications in the non-mechanical deep dewatering of WAS.

Physical conditioning methods for sludge deep dewatering: A critical review.

Sludge is an inevitable waste product of sewage treatment with a high water content and large volume, it poses a significant threat of secondary pollution to both water and the atmosphere without proper disposal. In this regard, dewatering has emerged as an attractive method in sludge treatment, as it can reduce the sludge volume, enhance its transportability and calorific value, and even decrease the production of landfill leachate. In recent years, physical conditioning methods including non-chemical conditioners or energy input alone, have been extensively researched for their potential to enhance sludge dewatering efficiency, such as thermal treatment, freeze-thaw, microwave, ultrasonic, skeleton builders addition, and electro-dewatering, as well as combined methods. The main objective of this paper is to comprehensively evaluate the dewatering capacity of various physical conditioning methods, and identify key factors affecting sludge dewatering efficiency. In addition, future research anticipated directions and outlooks are proposed. This work is expected to provide valuable insights for developing efficient, eco-friendly, and low-energy consumption techniques for deep sludge dewatering.

Formation mechanism of persistent free radicals during pyrolysis of Fenton-conditioned sewage sludge: Influence of NOM and iron.

The present study provided an innovative insight into the formation mechanism of persistent free radicals (PFRs) during the pyrolysis of Fenton-conditioned sludge. Fenton conditioners simultaneously improve the dewatering performance of sewage sludge and catalyze the pyrolysis of sewage sludge for the formation of PFRs. In this process, PFRs with a total number of spins of 9.533×1019 spins/g DS could be generated by pyrolysis of Fenton-conditioned sludge at 400°C. The direct thermal decomposition of natural organic matter (NOM) fractions contributed to the formation of carbon-centered radicals, while the Maillard reaction produced phenols precursors. Additionally, the reaction between aromatic proteins and iron played a crucial role in the formation of phenoxyl or semiquinone-type radicals. Kinetics analysis using discrete distributed activation energy model (DAEM) demonstrated that the average activation energy for pyrolysis was reduced from 178.28 kJ/mol for raw sludge to 164.53 KJ/mol for Fenton conditioned sludge. The reaction factor (fi) indicated that the primary reaction in Fenton-conditioned sludge comprised of 27 parallel first-order reactions, resulting from pyrolysis cleavage of the NOM fractions, the Maillard reaction, and iron catalysis. These findings are significant for understanding the formation process of PFRs from NOM in Fenton-conditioned sludge and provide valuable insight for controlling PFRs formation in practical applications.

Research and application of deep learning-based sleep staging: Data, modeling, validation, and clinical practice.

Over the past few decades, researchers have attempted to simplify and accelerate the process of sleep stage classification through various approaches; however, only a few such approaches have gained widespread acceptance. Artificial intelligence technology, particularly deep learning, is promising for earning the trust of the sleep medicine community in automated sleep-staging systems, thus facilitating its application in clinical practice and integration into daily life. We aimed to comprehensively review the latest methods that are applying deep learning for enhancing sleep staging efficiency and accuracy. Starting from the requisite "data" for constructing deep learning algorithms, we elucidated the current landscape of this domain and summarized the fundamental modeling process, encompassing signal selection, data pre-processing, model architecture, classification tasks, and performance metrics. Furthermore, we reviewed the applications of automated sleep staging in scenarios such as sleep-disorder screening, diagnostic procedures, and health monitoring and management. Finally, we conducted an in-depth analysis and discussion of the challenges and future in intelligent sleep staging, particularly focusing on large-scale sleep datasets, interdisciplinary collaborations, and human-computer interactions.

Nickel(II)/Lewis acid catalysed olefin hydroamination and hydroarylation under mild conditions.

Aniline derivatives are important nitrogen-containing compounds with wide applications in chemicals, pharmaceuticals and agrochemicals. In the work described herein, nickel(II)/Lewis acid (LA) catalysed olefin hydroamination with anilines was explored for use in aniline derivative syntheses. The Ni(II)/LA catalysis proceeded smoothly under mild conditions, whereas using Ni(OAc)2 alone, the catalyst was inactive. Remarkably, the Markovnikov addition type products were obtained when substituted styrenes were used as the olefin source, while the anti-Markovnikov addition type products were obtained when the electron-deficient olefins such as acrylonitrile and acrylates were used. The mechanistic studies revealed that hydroamination of the styrene derivates proceeded via the amino-Ni(II)/LA attacking the carbocation intermediate which was generated by the protonation of the olefin, whereas for acrylonitrile and acrylates, it proceeded by a direct amino-Ni(II)/LA attack on the olefin by nucleophilic addition. In addition, the hydroarylation product was generated by the Hofmann-Martius rearrangement of the hydroamination product.

Elimination of hazardous Se(IV) through adsorption-coupled reduction by iron nanoparticles embedded on mesopores of chitin obtained from waste shrimp shells.

Selenium is an essential nutrient for biological function. However, there is a detrimental effect on the aquatic environment associated with higher concentrations of > 40 µg/L. The utilization of waste shrimp shells for the removal of high-concentrated selenium from wastewater is a commendable strategy in both the pollution control and waste management sectors. In the present study, a chitin-iron polymer complex hybrid material (Fe@SHC) was prepared from shrimp shell-derived hydrochar (SHC), and the synthesized composite was successfully employed to uptake selenium from wastewater. The highest removal performance of 79.18 mg/g was attained by Fe@SHC, whereas the capacity of SHC was 15.30 mg/g. It was found that the calcium content of Fe@SHC (1.98%) was lower than that of SHC (25.20%) and pHzpc of Fe@SHC was extended to 7.78 compared with that of SHC (2.00). The abundance of protonated hydroxyl (-OH2+) and amine (-NH3+) functional groups that developed through the iron co-precipitations resulted in the improved adsorption performance of Fe@SHC. XPS analysis demonstrated that the captured Se(IV) species were converted into less hazardous Se(0), which is accompanied by the electron transfer with both N-C = O (acetyl amine) and -NH2 (amine) functional groups. Adsorption kinetics disclosed that the adsorption process was governed by chemical sorption, and the Sips isotherm model provided the most accurate description of the isotherm equilibrium. This study proposed an inexpensive and environmentally friendly method for effective decontamination of Se from wastewater.

Unveiling the mechanisms of peracetic acid activation by iron-rich sludge biochar for sulfamethoxazole degradation with wide adaptability.

Advanced oxidation processes (AOPs) based on peracetic acid (PAA) has been extensively concerned for the degradation of organic pollutants. In this study, metallic iron-modified sludge biochar (Fe-SBC) was employed to activate PAA for the removal of sulfamethoxazole (SMX). The characterization results indicated that FeO and Fe2O3 were successfully loaded on the surface of the sludge biochar (SBC). Fe-SBC/PAA system achieved 92% SMX removal after 30 min. The pseudo-first-order kinetic reaction constant of the Fe-SBC/PAA system was 7.34 × 10-2 min-1, which was 2.4 times higher than the SBC/PAA system. The degradation of SMX was enhanced with increasing the Fe-SBC dosage and PAA concentration. Apart from Cl-, NO3- and SO42- had a negligible influence on the degradation of SMX. Quenching experiments and electron paramagnetic resonance (EPR) techniques identified the existence of reactive species, of which CH3C(O)OO•, 1O2, and O2•- were dominant reactive species in Fe-SBC/PAA system. The effect of different water matrices on the removal of SMX was investigated. The removal of SMX in tap water and lake water were 79% and 69%, respectively. Four possible pathways for the decay of SMX were presented according to the identification of oxidation products. In addition, following the ecological structure-activity relationship model (ECOSAR) procedure and the germination experiments with lettuce seeds to predict the toxicity of the intermediates. The acute and chronic ecotoxicity of SMX solution was dramatically diminished by processing with Fe-SBC/PAA system. In general, this study offered a prospective strategy for the degradation of organic pollutants.

Understanding the coordination behavior of antibiotics: Take tetracycline as an example.

Gaining insight into the occurrence states of residual antibiotics is crucial to demystify their environmental behavior. However, the complexation of heteroatoms functioned on antibiotic molecules to metal ions in the water environment is not fully understood. This study reports that a fluorescence response was unexpectedly triggered by tetracycline (TC) and Al3+, serving as solid evidence to visualize the Al3+-TC coordination reaction. Differential electron absorption spectroscopy shows a quantifiable signal of the redshifted n-π* transition with a coordination reaction, which is also proportional to the fluorescence. The occurrence of Al3+-complexed TC also caused a split in retention time in liquid chromatogram. The TC ligands were re-released in the presence of stronger ligands competing for central Al3+. The complex ratio of Al3+-TC is confirmed to be 1:1 using Job's plot with a stability constant of 1.01 × 106. Quantum chemical computations coupled with Gibbs free energy analysis simulated the formation of octahedral Al3+-TC configuration through a spontaneous bidentate chelation. This study helps convey a broad consensus and opens a new door in the mechanistic study of metal-involved antibiotic transformation process, leading to a better understanding that can ultimately be essential to reach the final goal of alleviating the antibiotic crisis.

Nitrogen-rich carbon composite fabricated from waste shrimp shells for highly efficient oxo-vanadate adsorption-coupled reduction.

Protein, calcium carbonate, and chitin are abundant in shrimp shells. In this study, chemical treatment followed by hydrothermal carbonization was used to synthesize the nitrogen-rich hydrochar (HSHC) from shrimp shells. The untreated hydrochar exhibited a higher amount of calcium (25.37%) and less amount of nitrogen (2.68%) with alkaline pH (9.1). Interestingly chemical pre-treatment on shrimp shells boosted the nitrogen content to 6.81% and eliminated the calcium while controlling the pH to 6.4, which was beneficial for oxo-vanadate removal. The HSHC achieved vanadium(V) adsorption capacity of 21.20 mg/g at an optimal solution pH of 3.0, whereas the pristine hydrochar performed poorly (0.66 mg/g). The abundance of oxygen and nitrogen-based functional groups that developed through the chemical treatment resulted in improved adsorption coupled reduction performance of HSHC. This study proposed an inexpensive and environmentally friendly method for converting waste shrimp shells into value-added adsorbent.

Study on the coordination conduct and kinetic insights within the oxo-vanadate and organic reductive nitrogen and sulfur functionalities during the reduction coupled adsorption processes: Implications in practical applications.

Vanadium(V) is arising wastewater contaminant recently. Although bio-reduction of vanadium(V) is effective, the knowledge of electron transfer pathways and coordination nature by cellular organic functionalities is seriously lacking. Herein, the coordination conduct and kinetic modes for the reduction of V(V) by organic nitrogen and sulfur functionalities in working pHs are comprehensively investigated for the first time. The kinetics follow 3 steps; (1) diffusion of V(V) species, (2) reduction of V(V) to V(IV), and (3) adsorption of existing V species. The diffusion of V(V) is controlled by the protonated =NH2+, -SH2+, -CSH+ functional groups and oxo-vanadate speciation. The reduction of V(V) to V(IV) was efficient by -SH than =NH, -NH- , because of the higher oxidation potential of sulfur and which acted as the sole electron donor in the process. The coordination of V(V)/V(IV) species interacted with oxygen, nitrogen and sulfur atoms via parallel orientation and leads to multi-docking or single-ionic interactions, revealing the previously unrecognized track. Hence, the system tested in four types of wastewaters with different pHs and resulted the comprehensive practical applicability of the system. This study proposes a novel tactic to design an efficient V(V) wastewater treatment system by considering its water parameters.

Molten-salts assisted preparation of iron-nitrogen-carbon catalyst for efficient degradation of acetaminophen by periodate activation.

Highly efficient and stable heterogeneous catalysts were desired to activate periodate (PI) for sustainable pollution control. Herein, iron-nitrogen-carbon catalyst was synthesized using a facile molten-salts mediated pyrolysis strategy (denoted as FeNC-MS) and employed to activate PI for the degradation of acetaminophen (ACE). Compared with iron-nitrogen-carbon catalyst prepared by direct pyrolysis method (marked as FeNC), FeNC-MS exhibited superior catalytic activity due to its large specific surface area (1600 m2 g-1) and the abundance of FeNx sites. The batch experiments revealed that FeNC/PI process achieved 37 % ACE removal within 20 min, while ACE removal in FeNC-MS/PI process was 98 % under the identical conditions. Integrated with electron paramagnetic resonance tests, quenching experiments, chemical probe identification, and electrochemical experiments, we demonstrated that FeNC-MS-PI complexes-mediated electron transfer was the predominant mechanism for the oxidation of ACE. Further analysis disclosed that FeNx sites in FeNC-MS were the main active sites for the activation of PI. Additionally, FeNC-MS/PI process exhibited significant resistance to humic acid and background electrolyte, and avoided the secondary pollution imposed by Fe leaching. The possible degradation pathways of ACE were proposed. The germination experiments of lettuce seeds showed that the ecotoxicity of ACE solution was significantly reduced after treatment with FeNC-MS/PI process. Overall, this study provided a facile strategy for the synthesis of efficient iron-nitrogen-carbon catalysts and gained fundamental insight into the mechanism of PI activation by iron-nitrogen-carbon catalysts for pollutants degradation.

Ball milling-assisted preparation of sludge biochar as a novel periodate activator for nonradical degradation of sulfamethoxazole: Insight into the mechanism of enhanced electron transfer.

The non-radical pathway of periodate (PI) activation for the removal of persistent organic contaminants has received increasing attention due to its higher stability and oxidative advantages. In this study, the degradation of sulfamethoxazole (SMX) by ball mill treated magnetic sludge biochar (BM-MSBC) through activation of PI by electron transfer mechanism was reported. Experimental and characterization results showed that the ball milling treatment resulted in a better pore and defect structure, which also significantly enhanced the electron transfer capacity of the sludge biochar. The BM-MSBC/PI system exhibited notable dependence of activator concentration and initial pH, while the effect of PI concentration was not significant. The coexisting substances (common anions and natural organic matters) hardly affect the degradation of SMX in the BM-MSBC/PI system. The phytotoxicity experiments suggested that the treatment of BM-MSBC/PI system could significantly reduce the biological toxicity of SMX solution. This study provides a novel, economical, and facile modification method for the application of sludge biochar in advanced oxidation processes.

Correction: Lewis acid improved dioxygen activation by a non-heme iron(II) complex towards tryptophan 2,3-dioxygenase activity for olefin oxygenation.

Correction for 'Lewis acid improved dioxygen activation by a non-heme iron(II) complex towards tryptophan 2,3-dioxygenase activity for olefin oxygenation' by Guangjian Liao et al., Dalton Trans., 2022, https://doi.org/10.1039/d2dt02769k.

Lewis acid improved dioxygen activation by a non-heme iron(II) complex towards tryptophan 2,3-dioxygenase activity for olefin oxygenation.

Dioxygen activation and catalysis around ambient temperature is a long-standing challenge in chemistry. Inspired by the significant roles of the hydrogen bond network in dioxygen activation and catalysis by redox enzymes, this work presents a Lewis acid improved dioxygen activation by an FeII(BPMEN)(OTf)2 complex towards tryptophan 2,3-dioxygenase (TDO) activity for 3-methylindole and common olefinic CC  bond oxygenation and cleavage (enzymatic Brønsted acid vs. chemical Lewis acid). It was found that the presence of a Lewis acid such as Sc3+ could substantially improve olefinic CC  bond oxygenation and cleavage activity through FeII(BPMEN)(OTf)2 catalyzed dioxygen activation. Notably, a more negative ρ value in the Hammett plot of para-substituted styrene oxygenations was observed in the presence of a stronger Lewis acid, disclosing the enhanced electrophilic oxygenation capability of the putative iron(III) superoxo species through its electrostatic interaction with a stronger Lewis acid. Thereof, this work has demonstrated a new strategy in catalyst design for dioxygen activation and catalysis for olefin oxygenation, a significant process in the chemical industry.

Observing the Agostic Hydrogen in Pd(II)-Catalyzed Aromatic C-H Activation.

Direct C-H activation and functionalization offer a convenient protocol for pharmaceutical and material syntheses. Although versatile mechanisms have been proposed to depict transition-metal-catalyzed C-H activation, to date, the shared key agostic hydrogen intermediate in several major mechanisms has not been observed yet, which apparently puzzles the mechanism-based catalyst design. This work reports the direct observations of this intermediate in Pd(II)/Sc(III)-catalyzed C-H activation of acetanilides, and its stability and reactivity in C-H activation are investigated. Remarkably, this intermediate is only observed in electron-rich acetanilides, and the meta-substituent with increased σm constant generally accelerates C-H activation, a characteristic of the base-assisted C-H activation mechanism. This study has unveiled the masks of this intermediate with an understanding of its first-hand physicochemical properties, shedding new light on mechanism-based catalyst design.

Pd(II)/Lewis Acid Catalyzed Intramolecular Annulation of Indolecarboxamides with Dioxygen through Dual C-H Activation.

Transition-metal ion catalyzed intramolecular dual C-H activation to construct polycyclic heteroarene skeletons is merited for its step and atom-economic advantages in organic synthesis. However, in most cases, stoichiometric oxidants, elevated temperature, and other harsh conditions were commonly faced for this reaction, which apparently block the synthetic applications. Herein, we report a Pd(II)/LA (LA: Lewis acid) catalyzed intramolecular dual C-H activation to construct indoloquinolinone derivatives under mild conditions with dioxygen as the sole oxidant. It was found that adding LA such as Sc3+ to Pd(OAc)2 sharply improved its catalytic efficiency, whereas Pd(OAc)2 alone was very sluggish. The activity improvement was attributed to the linkage of the Sc3+ cation to the Pd(II) species through a diacetate bridge that significantly enhanced the electrophilic properties of Pd(II) for dual C-H activation.

Understanding the nonradical activation of peroxymonosulfate by different crystallographic MnO2: The pivotal role of MnIII content on the surface.

Manganese oxide-activated persulfate plays a critical role in water purification and in situ chemical oxidation processes, but the underlying mechanism needs to be further revealed. Herein, the detailed mechanism of MnO2 with various crystallographic structures (α-, ß-, γ-, and δ-MnO2) towards peroxymonosulfate (PMS) activation was investigated. PMS activated by tunnel structured α-, ß-, and γ-MnO2 showed higher acetaminophen (ACE) removal than layer structured δ-MnO2 with the removal efficiency following an order of α-MnO2 (85%) ≈ Î³-MnO2 (84%) > ß-MnO2 (65%) > Î´-MnO2 (31%). Integrated with chemical quenching experiments, electron paramagnetic resonance, Raman spectra, X-ray photoelectron spectroscopy, and Langmuir-Hinshelwood model on kinetic data, both surface-bound PMS complexes and direct oxidation by surface manganese species (Mn(Ⅳ, Ⅲ)(s)) were disclosed as the dominant oxidation mechanism for ACE degradation in α-, ß-, and γ-MnO2/PMS, which were rarely observed in previous reports. Moreover, the catalytic activity of α-, ß-, and γ-MnO2 was positively correlated to the MnIII(s) content on the catalyst surface. Higher content of MnIII(s) would stimulate the generation of more oxygen vacancies, which was conducive to the adsorption of PMS and the formation of reactive complexes. Overall, this study might provide deeper insight into the nonradical activation mechanism of PMS over different crystallographic MnO2.

Effects of foreign metal doping on the step-by-step oxidation process in M-OMS-2 catalyzed activation of PMS.

Various metal cations M (M = Mg2+, Ca2+, Zn2+, Cu2+, Fe3+) were doped into the tunnel of manganese octahedral molecular sieve (OMS-2). Redox-inactive metal (Ca, Mg and Zn) doped OMS-2 exhibited better peroxymonosulfate (PMS) catalytic activity than redox metal-doped Cu-OMS-2 and Fe-OMS-2. Redox-inactive metals doping improves the conductivity and reducibility of the catalyst, while transition metal doping reduces the dispersion of manganese. More importantly, the degradation of ACE can be divided into two stages. In the first stage, ACE was oxidized dominantly through mediated electron transfer process. Subsequently, singlet oxygen (1O2) gradually dominated oxidative degradation in the second stage, which was derived from the reaction between superoxide radical (O2•-) and metastable manganese intermediates. The long half-life of O2•- on the surface of OMS-2 ensured the delay generation of 1O2. This study not only provides a new idea for improving the efficiency of heterogeneous catalysts activation of PMS, but also meaningful for the in-depth study of multiple reaction mechanisms in PMS activation processes.

Phosphate sequestration by lanthanum-layered rare earth hydroxides through multiple mechanisms while avoiding the attenuation effect from sediment particles in lake water.

Lanthanum-based adsorbents have been used extensively to capture phosphate from wastewater. However, the attenuation effect that arises from the coexistence of sediment and humic acid is the major drawback in practical applications. The Lanthanum-layered rare earth hydroxides (LRHs)-Cl (La-LRH-Cl) was synthesized and achieved high elemental phosphorus (P) adsorption capacity (138.9 mg-P g-1) along with a fast adsorption rate (k2 = 0.0031 g mg-1·min-1) over a wide pH range while avoiding the attenuation effect that arises from the coexistence of sediment and humic acid in lake water. The La-LRH-Cl effectively captured phosphate through multiple interactions, such as the ion exchange of Cl- and phosphate, the memory effect of LRH and the inner-sphere complexation of La-P. Moreover, physical models demonstrated that the adsorption of phosphate onto La-LRH-Cl was a monolayer endothermic process, during which PO43- interacted by multi-docking via parallel orientation at 293 K and multi-ionic interactions through pure non-parallel orientation at 303 K. Hence, 1000 L of 11.08 mg-P L-1 of the acquired lake water was decontaminated by 30 g of La-LRH-Cl to 0.09 mg-P L-1 within 7 days. In addition, over ~12,125 BV of an industrial effluent containing 3.26 mg-P L-1 was treated to below USEPA's discharge limit in fixed-bed tests. It was found that the memory effect of LRH was responsible for the stable performance and reusability. Therefore, more focus should be placed on the collective role of La and LRH layered structure as a means of preventing the attenuation effect in the real water matrix.