Two-dimensional (2D) MoSe2 is a promising candidate for organic solvent nanofiltration (OSN) membranes. Decoding its intrinsic OSN mechanism, particularly the regulatory role of solvent polarity, is essential for advancing its applications. In this study, all-atom molecular dynamics simulations are utilized to systematically explore the OSN mechanism of 2D MoSe2 membranes. The results indicate that the permeabilities of all tested solvents increase monotonically with the enlargement of the interlayer spacing (d) in MoSe2 membranes. For nonpolar solvents, the permeabilities are hardly affected by the interfacial effect of MoSe2 nanosheets, with an exception only observed at d = 0.90 nm where benzene molecules form a upright arrangement inside the membrane due to their strong it-it interactions, which thereby inhibits the transport. For polar solvents, the permeabilities are significantly dominated by the interfacial effect of MoSe2 nanosheets when d <= 1.45 nm. As the d increases beyond 2.00 nm, the influence of interfacial effect gradually weakens. However, acetonitrile remains a layered arrangement even at d = 2.50 nm due to its strong interaction with the MoSe2 membrane. The rejection of alpha-methylstyrene dimer decreases with increasing d, and enhancing the polarity of solvents could effectively elevate its rejection rate. This work provides essential insights into the OSN mechanism of 2D MoSe2 membranes, which is of great significance for the development of 2D-based OSN membranes.
Molecularly imprinted polymer (MIP) sensors attract increasing attentions of researchers in food science, due to their low-cost, high stability, reusability, and good recognition capability, therefore many MIP sensors have been developed by integrating molecular imprinting technique with the fluorescence, Raman spectroscopy, surface plasmon resonance, chemiluminescence, resonance light scattering light, mass spectroscopy, quartz crystal microbalance, and electrochemical techniques. Among these, fluorescent MIP (FMIP) sensors exhibit outstanding performances on rapid detection of hazardous molecules, nutritional molecules, and bacteria in food samples. This review paper focuses on the development of molecular imprinting strategies for making FMIPs, synthetic approaches for preparing FMIPs, and applications of the FMIPs in food analysis targeting pesticides, antibiotics, drugs, toxins, small nutrients, proteins, lipids, and bacteria. Besides, the evaluation values on the selectivity and specificity of MIPs are proposed. In the end, perspectives of the FMIP sensors are discussed and highlighted on their current challenges and developing directions.
Bipolar membrane electrodialysis (BPMED) driven by pH gradients, combined with potassium hydroxide solvent regeneration, offers a promising strategy for atmospheric CO2 separation. One challenge lies in developing anion exchange membranes (AEMs) with selective bicarbonate (HCO3-) transport to reduce energy consumption. In this study, a monovalent selective AEM was synthesized through sulfonation of brominated 2,6-dimethyl-1,4-phenyl oxide followed by imidazole-based quaternization (SBPPO-DM). The resulting AEMs preferentially enabled the migration of HCO3-ions with high carbon loading, while restricting the permeation of divalent carbonate (CO32-) through electrostatic repulsion. The prepared AEMs exhibited a decline in monovalent selectivity with increasing current density. Under electrodialysis at 5 mA/cm2, the SBPPO-DM-0.03 membrane achieved the highest permselectivity of 4.32, surpassing the PHCO3 CO2-=1 of commercial membrane (ASE). During CO2 regeneration in the 3 BPMED, increasing current density led to a progressive increase in the CO2 regeneration ratio, accompanied by a corresponding decrease in energy consumption. At a current density of 10 mA/cm2, SBPPO-DM-0.03 delivered the highest regeneration ratio of 39.8% owing to its superior HCO3-/CO32-selectivity, whereas SBPPO-DM-0.06 exhibited the lowest energy consumption of 8.0 MJ/kg-CO2 due to its minimal surface resistance, significantly lower than ASE of 13.4 MJ/kg-CO2. By simultaneously enhancing CO2 recovery and energy efficiency, this approach offers a viable pathway toward energy efficient BPMED based CO2 regeneration and provides a foundation for future strategies aimed at further lowering process energy requirements.
Layered sodium transition-metal oxides are promising cathode materials for sodium-ion batteries but suffer from rapid air-induced degradation, particularly in Ni-rich compositions. Here, P2-type Na2/3Ni1/2Mn1/2O2 (NaNM) is employed as a model system to elucidate the coupled surface-bulk degradation pathway at the particle level. Air exposure triggers spontaneous surface Na+ loss, predominantly compensated by Ni oxidation, which propagates inward to generate a radial Ni valence gradient. Guided by this mechanistic insight, low-electronegativity Ti4+ incorporation into Na2/3Ni3/10Mn1/2Ti1/5O2 (NaNMT) limits air-induced surface Na+ depletion and mitigates the resulting bulk redox heterogeneity. Consequently, the Ti-modified NaNMT exhibits only 4.0% first-discharge capacity loss after air exposure (vs. 18.5% for NaNM) and retains 75.9% of its initial capacity after 300 cycles at 1C (vs. 58.2% for NaNM). This work establishes a particle-resolved framework for understanding air-induced degradation in layered sodium oxides and provides a rational strategy for air-stable, high-performance cathode design.
CO2 electroreduction catalyst with a broad potential range and high selectivity is important for ensuring consistent efficiency and reliability in renewable energy integration into electrocatalytic processes. In this study, we find that the addition of different the fourth elements would have different effects on the ternary AgCuAu nanoporous alloy catalyst, which is an optimized catalyst in our previous work. The addition of Mo exhibits the lightest negative effect on the intrinsic activity of AgCuAu due to the highest electronegativity of Mo among these doping elements (Mo, Ni, Ti, and Ce). Interestingly, the Mo addition in the Al2AgCuAu-based precursor alloy results in nanoporous AgCuAuMo with thin nanobelt-like ligaments and greatly enhanced specific surface area, probably due to the low surface diffusion rate of Mo and its direction-selected passivation during the dealloying. As a result, the nanoporous multicomponent AgCuAuMo alloy (NP-Ag3Cu3Au3Mo0.5) achieves a Faradaic efficiency (FE) for CO of more than 90% over a wide potential window of similar to 1.0 V, peaking at 95.7% at -0.973 V versus the reversible hydrogen electrode (RHE). A CO partial current density (j(CO)) of 202 mA/cm(2) can be achieved at -1.373 V vs RHE. This work highlights multicomponent alloys as effective catalysts for promoting the electrochemical conversion of CO2.
Photocatalytic production of hydrogen peroxide (H2O2) offers an environment-friendly and sustainable route. However, low efficiency and undesirable by-products hinder its large-scale application. A heterostructure (PDA/SCN) by in situ polymerization dopamine on edge functionalized carbon nitride (SCN) has been designed to integrate photoredox and photocatalytic production of hydrogen peroxide with revisable transformation between catechol and o-benzoquinone. Benefiting from the strong built-in electric field, efficient photoinduced charge separation is disclosed to facilitate the autoxidation of redox-active catechol moiety. In addition, functional groups (-NH2) on the heterostructure, as an interfacial H-bond modulation site, are conductive to optimize the O-2 activation and subsequent formation of the key intermediate *OO. Moreover, a homemade gas-solid-liquid triphase flow cell using PDA/SCN photocatalyst with improving mass transfer process has been constructed, which shows a high H2O2 generation of 1.32 mM h(-1) under visible light (lambda >= 420 nm) without using any sacrificial reagent. This photocatalytic system provides a new guidance of efficient photocatalyst design for the synthesis of H2O2 without using any sacrificial reagent.
This paper presents an innovative teaching approach that integrates photoelectric technology with analytical chemistry instruction through inquiry-based learning (IBL), using cerium as a selected analyte. With the advancement of science and technology, a strong foundation of basic knowledge and methodologies is crucial in analytical chemistry education. Spectrophotometry and coulometric titration are key instrumental analysis methods representing relative analysis and absolute analysis, respectively. Utilizing light and electricity, these methods provide platforms for deep exploration. To transcend traditional teaching methods, we adopted IBL, where students, stimulated by real-world problems, actively engage in the learning process. Cerium, chosen for its unique properties and wide applications, is an ideal subject for experimental analysis. Through experimental design, students use spectrophotometry and coulometric titration to measure the cerium content and explore various factors. This approach reinforces chemical equilibrium knowledge and enhances students' experimental skills, data analysis abilities, and scientific literacy. The 32 h course, spread over five sessions, promotes independent learning and teamwork. By applying IBL, we aim to ignite students' enthusiasm, deepen their understanding of foundational concepts, and prepare them for future analytical chemistry pursuits. This practice promises to enhance students' practical skills and scientific literacy, capturing the interest of chemistry educators and professionals.
Onivyde® is an intravenous irinotecan liposomal injection approved by the FDA for the treatment of gemcitabine-refractory metastatic adenocarcinoma of the pancreas in combination with fluorouracil and leucovorin. In the Onivyde® formulation, irinotecan is encapsulated in the inner compartment of the liposome using sucrose octasulfate as a trapping agent, and stabilized by a pegylated lipid membrane, resulting in prolonged circulation in the body. Due to its complex formulation design, there is limited information available regarding the critical quality attributes (CQAs) of Onivyde® and suitable methods for evaluating these attributes. In this study, we have developed a series of analytical methods to comprehensively characterize Onivyde®. These methods encompass particle size analysis, morphology and structure assessment, examination of physical and chemical properties, determination of drug and lipid contents, and evaluation of its release behavior in vitro.
The design of heterojunction and active crystal face is an effective way to promote the separation and migration of photogenerated charge in the process of photocatalytic reaction. In this work, the band gap intercalation Bi3O4Br/Bi2O2CO3/g-C3N5 (BBC) ternary photocatalyst was successfully designed by one step hydrothermal method. It is found that under alkaline conditions, the addition of g-C3N5 to Bi3O4Br leads to the preferential growth of the (0 0 1) crystal face of the third phase Bi2O2CO3, and the (0 0 1) crystal face is the active crystal face of the photocatalytic reaction. In addition, the constructed double Z-scheme heterojunction has two different electron transport pathways and bidirectional interface electric fields, which reduces the electron-hole pair recombination rate, maintains a strong redox ability, and enables the photogenerated carrier to effectively separate and transfer, thus improving the catalytic activity of the material. Under visible light irradiation, 15 % BBC presented excellent catalytic activity, the degradation rates of ARB (k = 0.0238 min-1), HCl-TC (k = 0.0183 min-1) and RHB (k = 0.0200 min-1) exceeded 90 % within 120 min. This work is not only of great significance for the purification of water pollution, but also provides a new way for further exploration of novel composite photocatalytic systems.
The development of binding gels with a fast uptake rate, high capacity, and good selectivity could be beneficial for trace Hg(II) detection based on the DGT technology. In this study, a novel PAN@MoS2/rGO-DGT was assembled by using the nanocomposite embedded in polyacrylonitrile membrane (PAN@MoS2/rGO) the binding phase. The interior regular finger-like macropore of the gel provided a convenient channel for the rapid mass diffusion of Hg(II), and the abundant sulfur offered the paramount driving force for trapping Hg(II). These endowed the PAN@MoS2/rGO with an impressive reaction rate, capacity, and selectivity toward Hg(II) and featured the PAN@MoS2/rGO-DGT with excellent diffusion rate (D) and adaptability in the complex matrixes across a wide range of pH, ion strength, common cations. However, the uptake of Hg(II) was influenced by the high content of chloride, thus a calibrated model was established based on the chloride concentration correct the accumulated mass and D . After that, the high accuracy of this method was confirmed through the good consistency between Hg(II) concentration assessed by DGT and in bulk solution when the DGT was deployed to the river water, seawater, and domestic wastewater at the static and dynamic Hg(II) concentration. Field trials in the prawn farming seawater and lake water also showed a negligible deviation of Hg(II) content from the DGT and the conventional method, acquiring actual Hg(II) level as 1.07-3.69 ng/L. The findings highlighted the application potential of macropore PAN gel hybrid with nanocomposite as a promising binding phase for trace Hg(II) or other pollutant detection.
The fabrication of well-defined, low-dimensional diamondoid-based materials is a promising approach for tailoring diamond properties such as superconductivity. On-surface self-assembly of halogenated diamondoids under ultrahigh vacuum conditions represents an effective strategy in this direction, enabling reactivity exploration and on-surface synthesis approaches. Here, we demonstrate through scanning probe microscopy, time-of-flight mass spectrometry, and X-ray photoelectron spectroscopy that self-assembled layers of dibromodiamantanes on gold can be debrominated by X-ray irradiation (Al K alpha at 8.87 & Aring; and Mg K alpha at 9.89 & Aring;) at low temperatures, without affecting their well-defined arrangement. The resulting 'in-architecture' debromination enables the fabrication of the diamantane dimer from self-assembled precursors in close proximity, which is otherwise inaccessible through annealing on metal surfaces. Our work introduces an approach for the fabrication of nanodiamond chains, with significant implications for in-architecture, layer-by-layer synthesis, and photolithography at the atomic limit.
The aim of this study was to comprehensively characterize paliperidone palmitate (PP) long-acting suspension (Invega Sustenna (R)) through reverse engineering. We developed a series of analytical methods to assess critical quality attributes of four batches of Invega Sustenna (R). The size distributions of the four batches of suspensions were measured using laser diffraction, and variations in the D50 and D90 parameters were observed. The morphology of suspension was determined through scanning electron microscope (SEM), which exhibited irregular granular shape across all batches. The size distributions determined by SEM images were similar to the laser diffraction results. Thermal characteristics were detected using differential scanning calorimetry (DSC) and crystalline properties were assessed by powder X-ray diffraction (PXRD), displaying consistency among the four batches in these two aspects. In vitro dissolution methods (sample separation and dialysis bag methods) were developed to evaluate the release behaviors of Invega Sustenna (R) and four lots showed a similar dissolution pattern. Furthermore, following a single-dose intramuscular administration to rats, two batches of Invega Sustenna (R) with the largest size differences demonstrated comparable plasma concentration-time profiles and pharmacokinetics parameters, indicative of one month long-acting release. In summary, we established a systematic quality characteristics assessment for Invega Sustenna (R), including particle size distribution, particle morphology, thermal characteristics, crystalline properties, in vitro dissolution kinetics and in vivo pharmacokinetics. Our work will assist pharmaceutical companies and regulatory agencies in the development and regulatory assessment of novel or generic products of long-acting injectable suspension.
Demand for lithium-ion batteries (LIBs) is increasing owing to the expanding use of electrical vehicles and stationary energy storage. Efficient and closed-loop battery recycling strategies are therefore needed, which will require recovering materials from spent LIBs and reintegrating them into new batteries. In this Review, we outline the current state of LIB recycling, evaluating industrial and developing technologies. Among industrial technologies, pyrometallurgy can be broadly applied to diverse electrode materials but requires operating temperatures of over 1,000 °C and therefore has high energy consumption. Hydrometallurgy can be performed at temperatures below 200 °C and has material recovery rates of up to 93
Two novel 3D bimetallic metal-organic frameworks (MOF) Cd4Zn(L1)4(DMF)2[NH2(CH3)3] (1) and [Cd4Ca(L2)2(bipy)2(H2O)4]·(NO3)2 (2) have been successfully synthesized by using organic ligands H3L1 = 4-[bis (4-carboxyphenyl) amino] benzoic acid; H4L2 = cyclopenta-1,4-diene-1,2,3,4-tetracarboxylic acid; bipy = 4-[2-(pyridin-4-yl) ethyl] pyridine; DMF: N,N-dimethylformamide under solvothermal condition, which has been fully characterized by fluorescence spectroscopy, FTIR, single-XRD, EA, SEM, etc. Fluorescence tests were conducted with an excitation wavelength at 365 nm, and the results confirm the excellent photoluminescent performance of both compounds, suggesting their potential applications as green and blue fluorescence materials. Based on the unique advantages of this novel material, we utilized composite 1 as a drug carrier to load Duhuo Jisheng Decoction. Employing non-toxic, biocompatible hydrogel encapsulation, we constructed a novel hydrogel-organic framework composite. Through analyzing the impact of metal gel particles on SW1353 cells, we elucidated the regulatory role of miRNA-27a-3P on the PI3K/Akt/mTOR signaling pathway, indicating the system’s potential in inhibiting arthritis development and offering a new avenue for knee osteoarthritis treatment.
Background: As an emerging and attractive low -dimensional functional materials, Ti 3 C 2 MXene quantum dots (QDs) enlarge the toolbox of fluorescence sensing. However, monochromatic fluorescence, which only provide one single signal, is often beset by challenges such as false -positive readouts and limitations in selectivity. Consequently, to improve the sensing accuracy by means of cross -verified dual -signal authentication, the endeavor to engineer dual -mode nanoprobes based on Ti 3 C 2 QDs, incorporating both the capability of fluorescence and an alternative sensing mechanism, emerges as a compelling avenue. Results: Here, based on the alterations in colorimetric and fluorescent signals of Ti 3 C 2 QDs with the addition of Ag + , we propose a dual -mode sensor obviating the necessity for nanoprobe labeling. Owing to the decent reducibility of Ti 3 C 2 QDs, Ag + is adsorbed and reduced, resulting in the generation of plasmonic Ag nanoparticles (NPs), which simultaneously trigger colorimetric responses of the solution and enhance the fluorescent emission of Ti 3 C 2 QDs. The confluence of colorimetry and fluorometry within this strategy optimally harnesses the modulating role of the acquired Ag NPs on the reducing capability and fluorescence characteristics of Ti 3 C 2 QDs. The equilibrium imparts versatility and promising prospects to this analyte-triggered label-free method, which enables a remarkable specificity and an excellent detecting limit (0.45 mu M) for Ag + . Significance: The balance between reducibility and fluorescence of Ti 3 C 2 QDs for dual-mode detection is inventively demonstrated. With the exemplification of a direct influence of both features of the nanoprobe via the introduction of analytes, this study opens the feasibility of the analyte-perturbed felicitous equilibrium, which endows label-free methods with versatility and promising prospects. This design may evoke more biosensing strategies with the function of double-signal mutual verification.
3D macroporous carbon‐based foams are always considered as promising candidates for high‐performance electromagnetic (EM) wave absorbing materials due to the collaborative EM contribution and salutary structure effect. However, the uneven distribution of heterogeneous EM components and the cumbersome preparation process have become key issues to hinder their performance improvement and practical popularity. Herein, the fabrication of 3D carbon foam decorated with small and highly dispersed Mo2C nanoparticles is realized by an innovative self‐foaming strategy. The foaming mechanism can be attributed to the decomposition of nitrate during the softening process of organic polymers. The good dispersion of Mo2C nanoparticles boosts interfacial polarization significantly. After regulating the content of Mo2C nanoparticles, the optimal Mo2C/CF‐x exhibits good EM absorption performance, whose minimum reflection loss intensity value can reach up to ‐72.2 dB, and effective absorption bandwidth covers 6.7 GHz with a thickness of 2.30 mm. Very importantly, the resultant Mo2C/CF‐x exhibits hydrophobicity and strong acidic anticorrosion, and a long‐time treatment in HCl solution (6.0 mol L−1) produces negligible impacts on their EM functions. It is believed that this extraordinary feature may render Mo2C/C foams as qualified and durable EM wave absorbing materials (EWAMs) under rigorous conditions.
ZIF-8 derived carbons demonstrate admirable application prospects in electrocatalytic fields, while ZnNx remaining in those materials are overlooked, crippling the validity of theoretic studies in researches. Herein, the residual Zn in ZIF-8 derived carbons are found could exceed 10 wt% even at carbonization temperatures over 900 degrees C, and Zn-NCs with various Zn contents are adopted as supports to synthesize low-platinum ORR catalysts. Substantial characterizations manifest that ZnNx in Zn-NC can not only provide Zn source for L-10-PtZn intermetallic, but act as 'spatial barriers' to prevent the formation of inactive PtNx, elevating the active Pt proportion in catalyst by similar to 104%. The resultant Zn-NC-Ar-PtZn exhibits a mass activity of 0.557 mA/g(Pt) and a peak density of 1.485 W/cm(2). DFT calculations show the strong thermodynamic tendency of forming PtN4 without the protection of ZnN4, and the superior durability and activity of Zn-NC-Ar-PtZn should be attributed to its Zn-derived ligand effects and the SMSI.
Transition metals like Au, Ag, and Cu have been reported to be quite active for CO2 reduction. In this study, we use density functional theory (DFT) calculation to investigate the electronic structure and catalytic performance of Au, Ag, Cu and their alloys for CO2 reduction reaction (CO2RR). Theoretical calculations identified the combination of Ag, Cu, and Au in a face-centered cubic (fcc) alloy as an outstanding electrocatalyst for CO2 reduction to CO, with Cu as the active site. The d-orbital projected density of state (PDOS) profile suggests that alloying alters the electronic structure of the Cu site, thereby affecting the Gibbs free energy change for the formation of *COOH intermediate (ΔG*COOH). To demonstrate the theoretical prediction experimentally, we employ a top-down dealloying approach to synthesize a nano-porous structured AgCuAu alloy (NP-Ag5Cu5Au5). Electrochemical experiments validate that the ternary alloy catalyst is clearly better than unary and binary catalysts, showing a Faradaic efficiency (FE) for CO over 90% across a broad potential range of 0.6 V, with a peak of approximately 96% at −0.573 V vs. RHE. This study underscores the potential of multi-component alloys in CO2RR and establishes a theoretical basis for designing efficient catalysts for CO2 utilization.