Integrative studies of ionic liquid interface layers: bridging experiments, theoretical models and simulations.

Ionic liquids (ILs) are a class of salts existing in the liquid state below 100 °C, possessing low volatility, high thermal stability as well as many highly attractive solvent and electrochemical capabilities, etc., making them highly tunable for a great variety of applications, such as lubricants, electrolytes, and soft functional materials. In many applications, ILs are first either physi- or chemisorbed on a solid surface to successively create more functional materials. The functions of ILs at solid surfaces can differ considerably from those of bulk ILs, mainly due to distinct interfacial layers with tunable structures resulting in new ionic liquid interface layer properties and enhanced performance. Due to an almost infinite number of possible combinations among the cations and anions to form ILs, the diversity of various solid surfaces, as well as different external conditions and stimuli, a detailed molecular-level understanding of their structure-property relationship is of utmost significance for a judicious design of IL-solid interfaces with appropriate properties for task-specific applications. Many experimental techniques, such as atomic force microscopy, surface force apparatus, and so on, have been used for studying the ion structuring of the IL interface layer. Molecular Dynamics simulations have been widely used to investigate the microscopic behavior of the IL interface layer. To interpret and clarify the IL structure and dynamics as well as to predict their properties, it is always beneficial to combine both experiments and simulations as close as possible. In another theoretical model development to bridge the structure and properties of the IL interface layer with performance, thermodynamic prediction & property modeling has been demonstrated as an effective tool to add the properties and function of the studied nanomaterials. Herein, we present recent findings from applying the multiscale triangle "experiment-simulation-thermodynamic modeling" in the studies of ion structuring of ILs in the vicinity of solid surfaces, as well as how it qualitatively and quantitatively correlates to the overall ILs properties, performance, and function. We introduce the most common techniques behind "experiment-simulation-thermodynamic modeling" and how they are applied for studying the IL interface layer structuring, and we highlight the possibilities of the IL interface layer structuring in applications such as lubrication and energy storage.

Enhanced dewaterability of food waste digestate by biochar/potassium ferrate treatments: Performance and mechanisms.

The combined process of biochar (BC) and potassium ferrate (PF) offers a fascinating technique for efficient dewatering of digestate. However, the effects of BC/PF treatment on the dewaterability and mechanisms of FWD are still unknown. This study aimed to reveal the impact mechanisms of BC/PF treatment on digestate dewatering performance. Experimental results indicated that BC/PF treatment significantly enhanced the dewaterability of digestate, with the minimum specific resistance to filtration of (1.05 ± 0.02) × 1015 m·kg-1 and water content of 57.52 ± 0.51% being obtained at the concentrations of 0.018 g·g-1 total solid (TS) BC300 and 0.20 g·g-1 TS PF, which were 8.60% and 13.59% lower than PF treatment, respectively. BC/PF treatment proficiently reduced the fractal dimension, bound water content, apparent viscosity, and gel-like network structure strength of digestate, as well as increased the floc size and zeta potential of digestate. BC/PF treatment promoted the conversion of extracellular polymeric substances (EPS) fractions from inner EPS to soluble EPS, increased the fluorescence intensity of the dissolved compounds, and enhanced the hydrophobicity of proteins. Mechanisms investigations showed that BC/PF enhanced dewatering through non-reactive oxygen species pathways, i.e., via strong oxidative intermediate irons species Fe(V)/Fe(IV). BC/PF treatment enhanced the solubilization of nutrients, the inactivation of fecal coliforms, and the mitigation of heavy metal toxicity. The results suggested that BC/PF treatment is an effective digestate dewatering technology which can provide technological supports to the closed-loop treatment of FWD.

Real-world implementation of a multilevel interventions program to prevent mother-to-child transmission of HBV in China.

Reducing hepatitis B virus (HBV) mother-to-child transmission (MTCT) is a fundamental step toward the HBV elimination goal. The multicentred, multilevel SHIELD program aimed to use an intense intervention package to reduce HBV MTCT in China. This study was conducted in diverse health settings across China, encompassing 30,109 pregnant women from 178 hospitals, part of the interim analysis of stage II of the SHIELD program, and 8,642 pregnant women from 160 community-level health facilities in stage III of the SHIELD program. The study found that the overall MTCT rate was 0.23% (39 of 16,908; 95% confidence interval (CI): 0.16-0.32%) in stage II and 0.23% (12 of 5,290; 95% CI: 0.12-0.40%) in stage III. The MTCT rate was lower among participants who were compliant with the interventions (stage II: 0.16% (95% CI: 0.10-0.26%); stage III: 0.03% (95% CI: 0.00-0.19%)) than among those who were noncompliant (3.16% (95% CI: 1.94-4.85%); 1.91% (95% CI: 0.83-3.73%); P < 0.001). Our findings demonstrate that the comprehensive interventions among HBV-infected pregnant women were feasible and effective in dramatically reducing MTCT.

Natural image restoration based on multi-scale group sparsity residual constraints.

The Group Sparse Representation (GSR) model shows excellent potential in various image restoration tasks. In this study, we propose a novel Multi-Scale Group Sparse Residual Constraint Model (MS-GSRC) which can be applied to various inverse problems, including denoising, inpainting, and compressed sensing (CS). Our new method involves the following three steps: (1) finding similar patches with an overlapping scheme for the input degraded image using a multi-scale strategy, (2) performing a group sparse coding on these patches with low-rank constraints to get an initial representation vector, and (3) under the Bayesian maximum a posteriori (MAP) restoration framework, we adopt an alternating minimization scheme to solve the corresponding equation and reconstruct the target image finally. Simulation experiments demonstrate that our proposed model outperforms in terms of both objective image quality and subjective visual quality compared to several state-of-the-art methods.

Mass Transfer Enhancement in High-Solids Anaerobic Digestion of Organic Fraction of Municipal Solid Wastes: A Review.

The increasing global population and urbanization have led to a pressing need for effective solutions to manage the organic fraction of municipal solid waste (OFMSW). High-solids anaerobic digestion (HS-AD) has garnered attention as a sustainable technology that offers reduced water demand and energy consumption, and an increased biogas production rate. However, challenges such as rheology complexities and slow mass transfer hinder its widespread application. To address these limitations, this review emphasizes the importance of process optimization and the mass transfer enhancement of HS-AD, and summarizes various strategies for enhancing mass transfer in the field of HS-AD for the OFMSW, including substrate pretreatments, mixing strategies, and the addition of biochar. Additionally, the incorporation of innovative reactor designs, substrate pretreatment, the use of advanced modeling and simulation techniques, and the novel conductive materials need to be investigated in future studies to promote a better coupling between mass transfer and methane production. This review provides support and guidance to promote HS-AD technology as a more viable solution for sustainable waste management and resource recovery.

Performance of high solids enzymatic hydrolysis and bioethanol fermentation of food waste under the regulation of saponin.

Bioethanol recovery from food waste through high solids enzymatic hydrolysis (HSEH) and high solids bioethanol fermentation (HSBF) alleviate the energy crisis. However, this cause decreased glucose and bioethanol yields due to the high solids content. In this study, saponin was introduced into food waste HSEH and HSBF systems to enhance the product yields. Under the regulation of saponin, the substrate released >90% of the theoretical reducing sugar. The glucose concentration increased by 137.41 g/L after 24 h of HSEH with 2.0% saponin. The bioethanol titer reached 73.2 g/L (1.0%-saponin). Untargeted metabolomics illustrating that saponin had higher antifungal properties at lower concentrations (0.5%-saponin) that caused a decrease in bioethanol yield. The addition of saponin concentrations of 1.0%∼3.0% promoted HSEH, HSBF, and the metabolism of Saccharomyces cerevisiae; thus, 1.0% was suggested for practical use. This study deepened the understanding of saponin in enhancing HSBF and provides theoretical support for further application.

Insights into high-solids anaerobic digestion of food waste concomitant with sorbate: Performance and mechanisms.

High-solids anaerobic digestion (HS-AD) of food waste is increasingly applied commercially. Sorbate, a food preservative extensively used in the food industry, induces potential environmental risks. Results indicated sorbate at 0-10 mg/g volatile solids (VS) slightly inhibited methane production, and the cumulative methane yield suggested a negative correlation with 25 mg/g VS sorbate, with a reduction of 15.0% compared to the control (from 285.7 to 253.6 mL CH4/g VS). The reduction in methane yield could be ascribed to the promotion of solubilization and inhibition of acidogenesis and methanogenesis with sorbate addition. Excessive sorbate (25 mg/g VS) resulted in the inhibition of aceticlastic metabolism and the key enzymes activities (e.g., acetate kinase and coenzyme F420). This study deeply elucidated the response mechanism of HS-AD to sorbate, supplemented the potential ecological risk assessment of sorbate, and could provide insights to further prevent the potential risk of sorbate in anaerobic digestion of food waste.

Enhancing of pretreatment on high solids enzymatic hydrolysis of food waste: Sugar yield, trimming of substrate structure.

The development of high solids enzymatic hydrolysis (HSEH) technology is a promising way to improve the efficiency of bioenergy production from solid waste. Pretreatment methods such as ultrasound (USP), freeze-thaw (FTP), hydrothermal (HTP), and dried (DRD) were carried out to evaluate the effect and mechanism of the pretreatment methods on the HSEH of FW. The reducing sugar of HTP and DRD reached 94.75% and 94.92% of the theoretical value. HTP and DRD could reduce the crystallinity of FW. DRD resulted in lower alignment and the occurrence of fractures of the substrate and exposed the α-1,4 glycosidic bond of starch. The high destructive power of HTP and DRD reduced the obstacles caused by the high solid content. Moreover, DRD consumed only 27.62% of the total energy of HTP. DRD could be a promising pretreatment methods for glucose recovery for its high product yield, significant substrate destruction, and economic feasibility.

Treasuring industrial sulfur by-products: A review on add-value to reductive sulfide and sulfite for contaminant removal and hydrogen production.

Reductive sulfur-containing by-products (S-BPs) released from industrial process mainly exist in the simple form of sulfide and sulfite. In this study, recent advances to remove and make full use of reductive S-BPs to achieve efficient contaminant removal and hydrogen production are critically reviewed. Sulfide, serves as both reductant and nucleophile, can form intermediates with the catalyst surface functional group through chemical interaction, efficiently promoting the catalytic reduction process to remove contaminants. Sulfite assisted catalytic process could be classified to the advanced reduction processes (ARPs) and advanced oxidation processes (AOPs), mainly depending on the presence of dissolved oxygen (DO) in the solution. During ARPs, sulfite could generate reductive active species including hydrated electron (eaq-), hydrogen radical (H·), and sulfite radical (SO3•-) under the irradiation of UV light, leading to the efficient reduction removal of a variety of contaminants. During AOPs, sulfite could first produce SO3•- under the action of the catalyst or energy, initiating a series of reactions to produce oxysulfur radicals. Various contaminants could be effectively removed under the role of these oxidizing active species. Sulfides and sulfites could also be removed along with promoting hydrogen production via photocatalytic and electrocatalytic processes. Besides, the present limitations and the prospects for future practical applications of the process with these S-BPs are proposed. Overall, this review gives a comprehensive summary and aims to provide new insights and thoughts in promoting contaminant removal and hydrogen production through taking full advantage of reductive S-BPs.

Effect of optimized intermittent mixing during high-solids anaerobic co-digestion of food waste and sewage sludge: Simulation, performance, and mechanisms.

Inadequate mixing has been proven to be a major cause of anaerobic digester failure. This study revealed the mechanism of mixing intervals on high-solids anaerobic co-digestion (HS-AcoD) of food waste (FW) and sewage sludge (SS). Optimized intermittent mixing time (15 min/h) was determined through computational fluid dynamics (CFD) simulation. Experimental results indicated that the simulated intermittent mixing could shorten digestion time and increase cumulative methane output (366.8 mL/gVS) compared with continuous mixing and unmixing. Mixing could considerably accelerate substrate solubilization and hydrolysis. Maximum rates of acidogenesis (53.35 %) and methanogenesis (49.41 %) were observed with an optimized intermittent mixing (15 min/h). Vigorous mixing induced apoptosis and disrupted syntrophic metabolism, whereas intermittent mixing promoted the syntrophic metabolism between Syntrophomonas and Methanobacterium, and led to an enrichment of genes involved in acidogenic and methanogenic pathways. These findings have important implications for the development of an optimized intermittent mixing strategy for maximizing HS-AcoD efficiency of FW and SS.

Catalytic pyrolysis of lotus leaves for producing nitrogen self-doping layered graphitic biochar: Performance and mechanism for peroxydisulfate activation.

In this study, nitrogen self-doping layered graphitic biochar (Na-BC900) was prepared by catalytic pyrolysis of lotus leaves at 900 °C, in the presence of NaCl catalyst, for peroxydisulfate (PDS) activation and sulfamethoxazole (SMX) degradation. NaCl as catalyst played a crucial part in the preparation of Na-BC900 and could be reused. The SMX degradation rate in Na-BC900/PDS system was 12 times higher than that in un-modified biochar (BC900)/PDS system. The excellent performance of Na-BC900 for PDS activation was attributed to its large specific surface areas (SSAs), the enhanced graphitization structure and the high graphitic N content. The quenching and electrochemical experiments, electron paramagnetic resonance (EPR) studies inferred that the radicals included SO4•-, •OH, O2•- and the non-radical processes were driven by 1O2 and biochar mediated electron migration. Both radical and non-radical mechanisms contributed to the removal of SMX. Additionally, this catalytic pyrolysis strategy was clarified to be scalable, which can be applied to produce multiple biomass-based biochar catalysts for restoration of polluted water bodies.

Insights into high-solids anaerobic digestion of food waste enhanced by activated carbon via promoting direct interspecies electron transfer.

High-solids anaerobic digestion (HS-AD) of food waste frequently confronted the acidification and failure under high organic loading rates (OLRs). Results indicated powdered activated carbon (PAC) addition significantly enhanced methane production and process stability than granular activated carbon, and columnar activated carbon at higher OLRs via accelerating the propionate consumption. Potential direct interspecies electron transfer (DIET) partners, including various syntrophic oxidation bacteria and methanogens, were enriched with the activated carbon (AC) addition. Furthermore, DIET contribution to methane production was 35% by PAC, predicated by the modified Anaerobic Digestion Model No.1 (ADM1). This study deeply elucidated the DIET mechanism and offered the potential foundations for the selection and applications of AC-based materials in HS-AD of food waste.

Multi-Modal Image Fusion Based on Matrix Product State of Tensor.

Multi-modal image fusion integrates different images of the same scene collected by different sensors into one image, making the fused image recognizable by the computer and perceived by human vision easily. The traditional tensor decomposition is an approximate decomposition method and has been applied to image fusion. In this way, the image details may be lost in the process of fusion image reconstruction. To preserve the fine information of the images, an image fusion method based on tensor matrix product decomposition is proposed to fuse multi-modal images in this article. First, each source image is initialized into a separate third-order tensor. Then, the tensor is decomposed into a matrix product form by using singular value decomposition (SVD), and the Sigmoid function is used to fuse the features extracted in the decomposition process. Finally, the fused image is reconstructed by multiplying all the fused tensor components. Since the algorithm is based on a series of singular value decomposition, a stable closed solution can be obtained and the calculation is also simple. The experimental results show that the fusion image quality obtained by this algorithm is superior to other algorithms in both objective evaluation metrics and subjective evaluation.

Molecular Mechanistic Insights into the Ionic-Strength-Controlled Interfacial Behavior of Proteins on a TiO2 Surface.

By adjusting the ionic strengths through changing the concentration of the buffer ions, the molecular force and the interfacial behavior of cytochrome c (Cyt c) and TiO2 are systematically studied. The molecular forces determined by combining the adhesion force and adsorption capacity are found to first increase and then decrease with the increasing ionic strength, with a peak obtained at an ionic strength between 0.8 and 1.0 M. The mechanism is explained based on the dissociation and hydration of ions at the interfaces, where the buffer ions could be completely dissociated at ionic strengths of <0.8 M but were partially associated when the ionic strength increased to a high value (>1.2 M), and the strongest hydration was observed around 1.0 M. The hydrodynamic size and the zeta potential value representing the effective contact area and protein stability of the Cyt c molecule, respectively, are also affected by the hydration and are proportional to the molecular forces. The interfacial behavior of Cyt c molecules on the TiO2 surface, determined through surface-enhanced Raman scattering (SERS), is extremely affected by the ionic strength of the solution as the ion dissociation and hydration also increase the electron transfer ability, where the best SERS enhancement is observed at the ionic strength of around 1.0 M, corresponding to the largest molecular force. Our results provide a detailed understanding at the nanoscale on controlling the protein interfacial behavior with solid surfaces, adjusted by the buffer ions.

Hydrated Ionic Liquids Boost the Trace Detection Capacity of Proteins on TiO2 Support.

Trace detection based on surface-enhanced Raman scattering (SERS) has attracted considerable attention, and exploiting efficient strategies to stretch the limit of detection and understanding the mechanisms on molecular level are of utmost importance. In this work, we use ionic liquids (ILs) as trace additives in a protein-TiO2 system, allowing us to obtain an exceptionally low limit of detection down to 10-9 M. The enhancement factors (EFs) were determined to 2.30 × 104, 6.17 × 104, and 1.19 × 105, for the three systems: one without ILs, one with ILs in solutions, and one with ILs immobilized on the TiO2 substrate, respectively, corresponding to the molecular forces of 1.65, 1.32, and 1.16 nN quantified by the atomic force microscopy. The dissociation and following hydration of ILs, occurring in the SERS system, weakened the molecular forces but instead improved the electron transfer ability of ILs, which is the major contribution for the observed excellent detection. The weaker diffusion of the hydrated IL ions immobilized on the TiO2 substrate did provide a considerably greater EF value, compared to the ILs in the solution. This work clearly demonstrates the importance of the hydration of ions, causing an improved electron transfer ability of ILs and leading to an exceptional SERS performance in the field of trace detection. Our results should stimulate further development to use ILs in SERS and related applications in bioanalysis, medical diagnosis, and environmental science.

Simulation and prediction of electrooxidation removal of ammonia and its application in industrial wastewater effluent.

A FLUENT software able to predict and assess the electrooxidation of ammonia from the simulation of ammonia concentration and flow field distribution was developed in this study. The flow field-based models of ammonia removal were simulated and modified through the experimental results. The parameter of reaction constant k is corrected to 0.00195, and the modified model fitted well with experimental values, with the error less than 4%. The electrode depth of 4 cm was assessed to be optimal for ammonia removal based on the comparison of the simulation results on ammonia concentration and flow field distribution. The prediction result applied in the industrial wastewater treatment indicated that complete could be achieved at 0.27 Ah/L, and about 50% of total nitrogen was removed at 0.8 Ah/L. About 7% of chloride ions were converted into inorganic by-products, indicating low biological toxicity and risk on environment. The energy consumption increased with the promotion of removal efficiency of total nitrogen, requiring 5.4 kWh/m3 to remove 50% total nitrogen at 0.8 Ah/L. The results show the practicability and feasibility of this FLUENT software tool on the simulation and prediction of electrooxidation process, which can provide the simulation parameter settings for the subsequent application. PRACTITIONER POINTS: A FLUENT software based on the simulation of ammonia concentration and flow field distribution was able to predict and assess ammonia electrooxidation. A modified model is provided with a rate constant k of 0.00195 and the distinction of 4% with experimental results. The optimal electrode depth was predicted to be 4 cm via the obtained model. Complete ammonia and about 50% of total nitrogen could be at 0.27 Ah/L and 0.8 Ah/L, receptively. About 7% of chloride ions were converted into inorganic by-products in industrial wastewater with high chloride.

Assessment of solar-assisted electrooxidation of bisphenol AF and bisphenol A on boron-doped diamond electrodes.

Bisphenol (BP) analogues in wastewater effluent and groundwater pose a potential threat to human health due to their ability to disrupt steroidogenesis. A new solar-assisted electrochemical process (SECP) was developed and evaluated for the degradation of BP analogues. The effects of quenchers, current density, initial pH, supporting electrolyte, and aqueous matrix on the removal kinetics of bisphenol AF (BPAF) and bisphenol A (BPA) were investigated. The kinetic constants of BPAF, BPA, and bisphenol S (BPS) in the SECP with irradiation intensity of 500 mW cm-2 were 0.017 ± 0.002 min-1, 0.022 ± 0.002 min-1, and 0.012 ± 0.001 min-1, respectively. The changes in the degradation rates of BPAF, BPA, and BPS in the presence of quenchers indicated the relative contribution of hydroxyl radical (●OH) oxidation, anodic electrolysis, and singlet (1O2) oxygenation in the degradation of BPs in the SECP. The enhanced rate of generation of ●OH and 1O2 was observed in the SECP compared with those in the conventional electrochemical system. The identification of the transformation products (TPs) of BPAF demonstrated that hydroxylation, ring cleavage, ß-scission, and defluorination were the major processes during the oxidation in the SECP. The conversion to fluoride ions (76%) and mineralization of total organic carbon (72%) in the SECP indicated further degradation of TPs. The results from this study improved our understanding of the degradation of BP analogues in the electrooxidation irradiated by solar light and help to establish the application potential of the SECP for the effective degradation of emerging contaminants in wastewater.

[Rapid resolving algorithm of gas chromatographic overlapping peaks based on the asymptotic expansion of integration].

A novel algorithm, called asymptotic expansion of integration, is suggested to resolve gas chromatographic overlapping peaks. There are three steps for the algorithm. First, a valley peak or a shoulder peak is separated into two domains, and an integral equation on a subdivision and an algebraic equation on the overlapping peak domain are listed. Secondly, areas needed in two equations, are computed by a numerical integral method, then the integral equation is expended to an algebraic equation by the asymptotic formula of integration. At last, combing two equations with constraint equations of peak heights, we got a nonlinear algebraic set. The equation set can be solved rapidly by Gauss-Seidel iteration, and the maximum number of iterations is not more than 20 times. The simulation and experimental results showed that height and area errors of resolving peaks are quite small, the maximum error of area is less than 6.44%, and that of the height is about 6.80%. Because of the high accuracy and computational efficiency, the algorithm can be used in decomposition of gas chromatographic overlapping peaks and online real-time processing of general chromatographic overlapping peaks.

Effect of Adsorbed Alcohol Layers on the Behavior of Water Molecules Confined in a Graphene Nanoslit: A Molecular Dynamics Study.

With the rapid development of a two-dimensional (2D) nanomaterial, the confined liquid binary mixture has attracted increasing attention, which has significant potential in membrane separation. Alcohol/water is one of the most common systems in liquid-liquid separation. As one of the most focused systems, recent studies have found that ethanol molecules were preferentially adsorbed on the inner surface of the pore wall and formed an adsorbed ethanol layer under 2D nanoconfinement. To evaluate the effect of the alcohol adsorption layer on the mobility of water molecules, molecular simulations were performed to investigate four types of alcohol/water binary mixtures confined under a 20 Å graphene slit. Residence times of the water molecules covering the alcohol layer were in the order of methanol/water < ethanol/water < 1-propanol/water < 1-butanol/water. Detailed microstructural analysis of the hydrogen bonding (H-bond) network elucidated the underlying mechanism on the molecular scale in which a small average number of H-bonds between the preferentially adsorbed alcohol molecules and the surrounding water molecules could induce a small degree of damage to the H-bond network of the water molecules covering the alcohol layer, resulting in the long residence time of the water molecules.

Molecular Dynamics Study of Mg2+/Li+ Separation via Biomimetic Graphene-Based Nanopores: The Role of Dehydration in Second Shell.

Residual Mg2+ reduces the performance of lithium-ion batteries. However, separating Mg2+ and Li+ is difficult because of their similar ionic properties. Inspired by the high selectivity of biological Mg2+ channels, this work utilizes atomistic simulations to investigate the ability of graphene-based nanopores with diameters of 0.789, 1.024, and 1.501 nm to separate Mg2+ and Li+ under a series of transmembrane voltages. We analyzed the spatial distribution of molecules in the nanopores' vicinity, structure properties of ionic hydration, and potential of mean force of ions traveling through the nanopores. Separation was mainly caused by the difference in dehydration between the second hydration shells of Mg2+ and Li+. When ions traveled through nanopores, Li+ had to overcome a greater energy barrier than Mg2+ because it had to shed more water molecules and break more hydrogen bonds in the second hydration shell compared with Mg2+. Moreover, the ionic Coulomb blockade of Mg2+ occurred near the pore mouth, impeding Li+ transport and increasing selectivity when the pore diameter decreased to subnanometer.