Physicochemical Research Articles

Design of Localized High-Concentration Electrolytes from the Perspective of Physicochemical Properties.

The physicochemical properties of electrolytes profoundly impact the energy density, rate performance, and manufacturability of rechargeable lithium batteries. Localized high-concentration electrolytes (LHCEs), a novel electrolyte class, have attracted considerable interest, yet the impact of diluents on their physicochemical properties remains unclear, as most reports involve only a few samples. Here we prepared 345 electrolyte samples using 21 diluents and systematically investigated the effect of diluent type and content on the miscibility, density, viscosity, and ion conductivity of LHCEs. We found that the physicochemical properties of LHCEs are mainly affected by the diluents' density and viscosity, regardless of type. Notably, the ionic conductivity exhibits two typical variance trends, "volcano" and "descending," both correlating strongly with diluents' viscosity rather than dielectric constant, a parameter commonly employed in electrolyte design. This anomaly can be explained by the "plum pudding" solvation model, providing essential insights for developing lightweight, highly fluid, and conductive LHCEs.

Effects of interlayer spacing and applied pressure on the lanthanide transport in MoS2-based two-dimensional channels

ABSTRACT Rare-earth elements (REEs) are critical to modern industry but difficult to separate due to their subtle and monotonic changes in physicochemical properties. MoS2-based two-dimensional (2D) materials offer novel opportunities for enhancing REE separation, exhibiting a distinct volcano-shaped transport performance distribution that peaks at Sm3+. However, the specific contributions of thermodynamic and kinetic factors to ion transport within 2D confinement remain unclear. In this study, we conducted a series of non-equilibrium all-atom molecular dynamics (MD) simulations to explore the effects of interlayer spacing and external pressure on the transport of lanthanide ions in Å-scale acetate functionalized 2D MoS2 (MoS2-COOH) channels. We examined ion entry and permeation rates, water flux, dehydration, and binding modes. The simulation results reveal that the transport trends of lanthanide ions are jointly driven by the dehydration degree and the relative-binding strengths of ions to water and to the acetate within the 2D channels. Notably, the dehydration pattern of lanthanide ions during permeation is closely linked to kinetic factors. Overall, this study provides a detailed atomistic understanding of the mechanisms underlying lanthanide ion transport under confinement. These findings point to the significant potential for tuning confinement and chemical functionalization within Å-scale channels for more efficient REE separation.

Removal of proteins and lipids affects structure, in vitro digestion and physicochemical properties of rice flour modified by heat-moisture treatment.

The objective of this experiment was to investigate the role of endogenous proteins and lipids in the structural and physicochemical properties of starch in heat-moisture treatment (HMT) rice flour and to reveal their effect on starch digestibility under heat. The findings indicate that, in the absence of endogenous proteins and lipids acting as a physical barrier, especially proteins, the interaction between rice flour and endogenous proteins and lipids diminished. This reduction led to fewer starch-protein inclusion complexes and starch-lipid complexes, altering the granule aggregation structure of rice flour. It resulted in a decrease in particle size, an increase in agglomeration between starch granules, and more surface cracking on rice granules. Under HMT conditions with a moisture content of 30%, slight gelatinization of the starch granules occurred, contributing to an increased starch hydrolysis rate. In addition, the elevated thermal energy effect of HMT enhanced interactions between starch molecular chains. These resulted in a decrease in crystallinity, short-range ordering, and the content of double-helix structure within starch granules. These structural transformations led to higher pasting temperatures, improved hot and cold paste stability, and a decrease in peak viscosity, breakdown, setback, and enthalpy of pasting of the starch granules. The combined analysis of microstructure, physicochemical properties, and in vitro digestion characteristics has enabled us to further enhance our understanding of the interaction mechanisms between endogenous proteins, lipids, and starches during HMT. © 2024 Society of Chemical Industry.

Unveiling Ultrafast-Weak-Field Coherent Control of Indirect Dissociation Reactions.

Coherent control of molecular photodissociation through one-photon transitions has become a topic of interest in physical chemistry. Previous studies have shown that modulating the spectral phase of a single ultrafast laser pulse while keeping its spectral amplitude constant does not affect the dissociation yield of reactions originating from a pure eigenstate of the ground electronic state. Here, we explore the indirect photodissociation reaction of NaI molecules using theoretical and numerical methods. Our findings show that, in contrast to the outcomes achieved with negatively chirped pulses, time-dependent population of the eigenstates of the excited adiabatic potential induced by positively chirped laser pulses, acting as intermediates in the reaction, cannot be periodically restored to that caused by the unchirped pulse. This gives rise to an intriguing phenomenon: the sign of the pulse's chirp rate influences the distribution of dissociation fragments in coordinate and momentum space over extended periods. This work highlights the potential of using spectral-phase modulated pulses to manipulate indirect photodissociation reactions, offering a way to modify the transient photofragment distributions by controlling reaction intermediates.

Enhancing thermal energy storage properties of blend phase change materials using beeswax.

This study aims to use beeswax, a readily available and cost-effective organic material, as a novel phase change material (PCM) within blends of low-density polyethylene (LDPE) and styrene-b-(ethylene-co-butylene)-b-styrene (SEBS). LDPE and SEBS act as support materials to prevent beeswax leakage. The physicochemical properties of new blended phase change materials (B-PCM) were determined using an X-ray diffractometer and an infrared spectrometer, confirming the absence of a chemical reaction within the materials. A scanning electron microscope was used for microstructural analysis, indicating that the interconnection of the structure allowed better thermal conductivity. Thermal gravimetric analysis revealed enhanced thermal stability for the B-PCM when combined with SEBS, especially within its operating temperature range. Analysis of phase change temperature and latent heat with differential scanning calorimetry showed no major difference in the melting point of the various PCM blends created. During the melting/solidification process, the B-PCMs possess excellent performance as characterized by W70/P30 (112.45J.g-1) > W70/P20/S10 (94.28J.g-1) > W70/P10/S20 (96.21J.g-1) of latent heat storage. Additionally, the blends tend to reduce supercooling compared to pure beeswax. During heating and cooling cycles, the B-PCM exhibited minimal leakage and degradation, especially in blends containing SEBS. In comparison to the rapid temperature drop observed during the cooling process of W70/P30, the temperature decline of W70/P30 was slower and longer, as demonstrated by infrared thermography. The addition of LDPE to the PCM reduced melting time, indicating an improvement in the thermal energy storage reaction time to the demand. According to the obtained findings, increasing the SEBS concentration in the composite increased the thermal stability of the resulting PCM blends significantly. Despite the challenges mentioned earlier, SEBS proved to be an effective encapsulating material for beeswax, whereas LDPE served well as a supporting material. Leak tests were performed to find the ideal mass ratio, and weight loss was analyzed after multiple cycles of cooling and heating at 70°C. The morphology, thermal characteristics, and chemical composition of the beeswax/LDPE/SEBS composite were all examined. Beeswax proves to be a highly effective phase change material for storing thermal energy within LDPE/SEBS blends.

Advances in medical polyesters for vascular tissue engineering.

Blood vessels are highly dynamic and complex structures with a variety of physiological functions, including the transport of oxygen, nutrients, and metabolic wastes. Their normal functioning involves the close and coordinated cooperation of a variety of cells. However, adverse internal and external environmental factors can lead to vascular damage and the induction of various vascular diseases, including atherosclerosis and thrombosis. This can have serious consequences for patients, and there is an urgent need for innovative techniques to repair damaged blood vessels. Polyesters have been extensively researched and used in the treatment of vascular disease and repair of blood vessels due to their excellent mechanical properties, adjustable biodegradation time, and excellent biocompatibility. Given the high complexity of vascular tissues, it is still challenging to optimize the utilization of polyesters for repairing damaged blood vessels. Nevertheless, they have considerable potential for vascular tissue engineering in a range of applications. This summary reviews the physicochemical properties of polyhydroxyalkanoate (PHA), polycaprolactone (PCL), poly-lactic acid (PLA), and poly(lactide-co-glycolide) (PLGA), focusing on their unique applications in vascular tissue engineering. Polyesters can be prepared not only as 3D scaffolds to repair damage as an alternative to vascular grafts, but also in various forms such as microspheres, fibrous membranes, and nanoparticles to deliver drugs or bioactive ingredients to damaged vessels. Finally, it is anticipated that further developments in polyesters will occur in the near future, with the potential to facilitate the wider application of these materials in vascular tissue engineering.

Ultrafine Spatial Modulation of Diazapyrene-Based Two-Dimensional Conjugated Covalent Organic Frameworks.

Tailormade bottom-up synthesis of covalent organic frameworks (COFs) from various functional building blocks offer not only tunable topology and pore size but also multidimensional properties. High crystallinity is one of the prerequisites for their structures and associated physicochemical properties. Among different π-conjugated motifs for constructing COFs, pyrene-based tetragonal structures are effective in achieving highly ordered and crystalline states. In the present research, we demonstrated that the substitution of pyrene with 2,7-diazapyrene produces nearly "flat" structures of two-dimensional (2D) COF layers by controlling the torsional angle of linker molecules. Featuring finite pore diameters and excellent thermodynamic stability of ∼500 °C, ordered face-to-face (slipped AA) stacking arrangements were produced. Extended electrical conjugation spanning 2D frames with modest optical bandgaps (Eg) of ∼2.1 eV shows the planar character of diazapyrene-based COFs. The stacking of the conjugated 2D frames with small Eg values is also beneficial for the formation of highly stable conducting pathways in the crystalline state, which was confirmed by the results of the microwave conductivity measurements. Nitrogen centers in diazapyrene units also play a key role as the active sites for proton transfer, and the maximum proton conductivity of σ = 10-2 S cm-1 was achieved along the cocontinuous nanopore structures surrounded by the active sites. Results show that tetragonal COFs based on diazapyrene can be used as a highly crystalline two-dimensional material with special electrical and proton-conducting capabilities.

Influence in physicochemical, nutritional, and antioxidant properties by addition Moringa oleifera leaves in Avena sativa bread

Moringa oleifera leaves have high nutrient valor, physicochemical, and nutraceutical properties and can be used as ingredients to develop wheat-free enrich. The aim was to evaluate nutritional, chemical, and nutraceutical characterization, antioxidant capacity, along physicochemical parameters to develop four oat bread using yeast (PL), xanthan gum (PG), and 2.5% (M2) or 5.0% (M5) of moringa leaves. Morinaga leaves were a source of 23.19% protein, 12.43% ash, and 30.36% dietary fiber. The bread formulations increased the protein content by 25–50%, and decreased lipid in 52.14% compared with commercial bread. For antioxidant capacity, PLM5 had the highest with values of 11.97 mMTE/g (DPPH), 16.06 mMTE/g (ABTS), and 16.38 mMTE/g (FRAP). In the bread with MOLP were identified Epicatechin, rutin, and dihydroxybenzoic acid by HPLC. The bread with a better texture profile was PLM2. The results suggested that moringa leaves used as an oat bread ingredient can enhance the nutritional and nutraceutical content.

Solid-phase synthesis of amphiphilic cyclic peptides as a surfactin mimetic

The cyclic lipopeptide surfactin, an anionic biosurfactant, has received increased interest owing to its unique characteristics and promising applications. Although surfactin is known to exhibit distinctive surface activities and self-assembly ability, the role of the cyclic peptide moiety in its physico-chemical properties requires further investigation. Here, we report the solid-phase peptide synthesis of surfactin mimics such as cyclic heptapeptides with the same amino acid sequence as surfactin (CSF) and cyclic octapeptides with dodecyl chains (CSF12). The structure–property relationships of the cyclic peptides were then examined. The acidic forms of CSF and CSF12 were poorly soluble in water, but the addition of 1.5 or 2.0 equiv. of NaOH increased their solubility in aqueous solutions. The disodium salt of CSF (CSF-2Na) reduced the surface tension of water to 39.0 mN/m despite its absence of a long alkyl chain, indicating that the cyclic peptide moiety plays a crucial role in the surface activity of the surfactin mimic. In the case of the disodium salt of CSF12 (CSF12–2Na), the introduction of a dodecyl chain to the cyclic peptide moiety led to an increase in molecular orientation such that saturation at the air–water interface was observed. Thus, a long alkyl chain enhances the molecular assembly of the cyclic peptide at the air–water interface. The introduction of a long alkyl chain also enhanced the solubilisation of phospholipids. For instance, CSF12–1.5Na induced the solubilisation of L-α-dimyristoylphosphatidylcholine (DMPC) multilamellar vesicles in phosphate-buffered saline (PBS). These findings greatly contribute to the fundamental understanding of the broad spectrum of physico-chemical properties and biological activities of bio-derived cyclic peptides. Furthermore, these insights can also be helping design libraries for developing cyclic peptides for challenging therapeutics in skin disease or as cosmeceuticals to enhance skin appearance.

Uniform Polymeric Nanovaccine Platform for Improving the Availability and Efficacy of Neoantigen Peptides.

Personalized cancer vaccines targeting specific neoantigens have been envisioned as one of the most promising approaches in cancer immunotherapy. However, the physicochemical variability of the identified neoantigens limits their efficacy as well as vaccine manufacturing in a uniform format. Herein, we developed a uniform nanovaccine platform based on poly(2-oxazoline)s (POx) to chemically conjugate neoantigen peptides, regardless of their physicochemical properties. This vaccine system could self-assemble into nanoparticles with uniform size (around 50 nm) and improve antigen accumulation as well as infiltration in the lymph node to increase antigen presentation. In vivo vaccination using this system conjugated with three predicted peptide neoantigen peptides from the MC38 tumor cell line induced 100% robust CD8+ T cell responses and superior tumor clearance compared to free peptides. This POx-based vaccine carrier represents a generalizable approach to increase the availability and efficacy of screened neoantigen peptides for a personalized cancer vaccine.

Piplartine attenuates aminoglycoside-induced TRPV1 activity and protects from hearing loss in mice.

Hearing loss is a major health concern in our society, affecting more than 400 million people worldwide. Among the causes, aminoglycoside therapy can result in permanent hearing loss in 40% to 60% of patients receiving treatment, and despite these high numbers, no drug for preventing or treating this type of hearing loss has yet been approved by the US Food and Drug Administration. We have previously conducted high-throughput screenings of bioactive compounds, using zebrafish as our discovery platform, and identified piplartine as a potential therapeutic molecule. In the present study, we expanded this work and characterized piplartine's physicochemical and therapeutic properties. We showed that piplartine had a wide therapeutic window and neither induced nephrotoxicity in vivo in zebrafish nor interfered with aminoglycoside antibacterial activity. In addition, a fluorescence-based assay demonstrated that piplartine did not inhibit cytochrome C activity in microsomes. Coadministration of piplartine protected from kanamycin-induced hair cell loss in zebrafish and protected hearing function, outer hair cells, and presynaptic ribbons in a mouse model of kanamycin ototoxicity. Last, we investigated piplartine's mechanism of action by phospho-omics, immunoblotting, immunohistochemistry, and molecular dynamics experiments. We found an up-regulation of AKT1 signaling in the cochleas of mice cotreated with piplartine. Piplartine treatment normalized kanamycin-induced up-regulation of TRPV1 expression and modulated the gating properties of this receptor. Because aminoglycoside entrance to the inner ear is, in part, mediated by TRPV1, these results suggested that by regulating TRPV1 expression, piplartine blocked aminoglycoside's entrance, thereby preventing the long-term deleterious effects of aminoglycoside accumulation in the inner ear compartment.

Sol-gel synthesis of magnesium oxide nanoparticles and their evaluation as a therapeutic agent for the treatment of osteoarthritis.

Aim: We synthesized MgO NPs via sol-gel reaction and investigated them as carriers to deliver Mg2+ to the affected joint for osteoarthritis (OA). Materials & methods: The physicochemical properties of samples were characterized by transmission electron microscope (TEM), dynamic light scattering (DLS) and x-ray diffraction (XRD). The release of Mg2+ was monitored by ICP-MS. The potential cytotoxicity was evaluated using MTT assay. The efficacy and biosafety were evaluated in a rabbit OA model. Results: MgO NPs can prolong the Mg2+ release time from 0.5 h to 12 h. No significant cytotoxicity was observed when concentrations below 250μg/ml. Intra-articular samples could effectively alleviate the degeneration and destruction of the cartilage. Conclusion: this study demonstrates the potential of MgO NPs as a safe and effective treatment of OA. Simultaneously, the size of the particles may play a significant role in influencing the therapeutic outcome.

Sequence-encoded bioactive protein-multiblock polymer conjugates via quantitative one-pot iterative living polymerization

Protein therapeutics are essential in treating various diseases, but their inherent biological instability and short circulatory half-lives in vivo pose challenges. Herein, a quantitative one-pot iterative living polymerization technique is reported towards precision control over the molecular structure and monomer sequence of protein-polymer conjugates, aiming to maximize physicochemical properties and biological functions of proteins. Using this quantitative one-pot iterative living polymerization technique, we successfully develop a series of sequence-controlled protein-multiblock polymer conjugates, enhancing their biostability, pharmacokinetics, cellular uptake, and in vivo biodistribution. All-atom molecular dynamics simulations are performed to disclose the definite sequence-function relationship of the bioconjugates, further demonstrating their sequence-encoded cellular uptake behavior and in vivo biodistribution in mice. Overall, this work provides a robust approach for creating precision protein-polymer conjugates with defined sequences and advanced functions as a promising candidate in disease treatment.

Advances on MXene-Based Memristors for Neuromorphic Computing: A Review on Synthesis, Mechanisms, and Future Directions.

Neuromorphic computing seeks to replicate the capabilities of parallel processing, progressive learning, and inference while retaining low power consumption by drawing inspiration from the human brain. By further overcoming the constraints imposed by the traditional von Neumann architecture, this innovative approach has the potential to revolutionize modern computing systems. Memristors have emerged as a solution to implement neuromorphic computing in hardware, with research based on developing functional materials for resistive switching performance enhancement. Recently, two-dimensional MXenes, a family of transition metal carbides, nitrides, and carbonitrides, have begun to be integrated into these devices to achieve synaptic emulation. MXene-based memristors have already demonstrated diverse neuromorphic characteristics while enhancing the stability and reducing power consumption. The possibility of changing the physicochemical properties through modifications of the surface terminations, bandgap, interlayer spacing, and oxidation for each existing MXene makes them very promising. Here, recent advancements in MXene synthesis, device fabrication, and characterization of MXene-based neuromorphic artificial synapses are discussed. Then, we focus on understanding the resistive switching mechanisms and how they connect with theoretical and experimental data, along with the innovations made during the fabrication process. Additionally, we provide an in-depth review of the neuromorphic performance, making a connection with the resistive switching mechanism, along with a compendium of each relevant performance factor for nonvolatile and volatile applications. Finally, we state the remaining challenges in MXene-based devices for artificial synapses and the next steps that could be taken for future development.

Bioinspired Self-Growing Layered Hydrogel Enabled by Catechol Chemistry-Mediated Interfacial Catalytic System.

Tissue-inspired layered structural hydrogel has attracted increasing attention in artificial muscle, wound healing, wearable electronics, and soft robots. Despite numerous efforts being devoted to developing various layered hydrogels, the rapid and efficient preparation of layered hydrogels remains challenging. Herein, inspired by the self-growth concept of living organisms, an interfacial catalytic self-growth strategy based on catechol chemistry-mediated self-catalytic system of preparing layered hydrogels is demonstrated. Typically, the tannic acid-metal ion (e.g., TA-Fe3+) complex embedded in the hydrogel substrate would catalytically trigger rapid solid-liquid interfacial polymerization to grow the hydrogel layer without bulk solution polymerization. The self-growth process can be finely controlled by changing the growth time, the molar ratio of Fe3+/TA, and so on. The strategy is applicable to prepare various layered hydrogels as well as complex layered hydrogel patterns, allowing the customization of the physicochemical properties of the hydrogel. In addition, the self-adhesive layered hydrogel was prepared and can be utilized as a wearable strain sensor to monitor physiological activities and human motions. The demonstrated interfacial catalytic self-growth strategy will provide a route to design and fabricate layered hydrogel materials.

A potential toxicological risk assessment of heavy metals and pesticides in irrigated rice cultivars near industrial areas of Dhaka, Bangladesh.

Rice intake represents a significant pathway through which humans accumulate heavy metals. This study presents a comprehensive analysis of heavy metal and pesticide contamination in rice cultivars irrigated with industrial wastewater near Dhaka, Bangladesh, a region heavily influenced by industrial activities. This study employed a unique methodology that not only quantified the concentrations of heavy metals and pesticide residues in rice grains but also extended to evaluating the physicochemical properties of rice stems, husks, soil, and irrigation water. The findings revealed alarmingly high levels of heavy metals such as lead, cadmium, chromium, nickel, and mercury in the soil and irrigation water, with concentrations in some cases exceeding the World Health Organization safety thresholds by 2 to 15 times. Notably, the rice grains also exhibited significant contamination, including substantial amounts of diazinon and fenitrothion pesticides, exceeding the established safety limits. The study employed hazard quotients (HQs) and cancer risk (CR) assessments to evaluate the potential health risks associated with the consumption of contaminated rice. The results indicated HQ values were greater than 1 for rice grains across the sampled fields, suggesting a considerable non-carcinogenic health risk, particularly from lead exposure, which was found at levels twice the standard limit in all the sampling fields. Moreover, the CR values for As, Pb, Cd, Co, and Mn highlighted a significant carcinogenic risk in several instances.

Carbon quantum dots from carbohydrate-rich residue of birch obtained following lignin-first strategy

Carbon quantum dots (CQDs) were successfully synthesized from carbohydrate-rich residue of birch obtained following the lignin-first strategy. The optical and physicochemical properties of the CQDs were studied, along with their potential for photocatalytic pollutant degradation. By combining solvothermal and chemical oxidation methods, the product yield of CQDs from carbohydrate-rich residue reached 8.1 wt%. Doping nitrogen enhances the graphitization of CQDs and introduces abundant amino groups to the surface, thereby boosted the quantum yield significantly from 8.9 % to 18.7 %-19.3 %. Nitrogen-doped CQDs exhibited efficient photocatalytic degradation of methylene blue, reaching 37 % within 60 min, with a kinetic degradation rate of 0.00725 min−1. This study demonstrates that carbohydrate-rich residue obtained from lignin-first strategy are ideal precursors for synthesizing CQD with high mass yield and quantum yield by combining solvothermal treatment and chemical oxidation methods, offering a novel approach for the utilization of whole biomass components following the lignin-first strategy.

Recent advances of bone tissue engineering: carbohydrate and ceramic materials, fundamental properties and advanced biofabrication strategies ‒ a comprehensive review.

Bone is a dynamic tissue that can always regenerate itself through remodelling to maintain biofunctionality. This tissue performs several vital physiological functions. However, bone scaffoldsarerequired for critical-sizes damages and fractures and these can be addressed bybone tissue engineering. Bone tissue engineering (BTE) has the potential to develop scaffolds forrepairingcritical-size damagedbone. BTE is a multidisciplinary engineered scaffold with the desired properties for repairing damaged bone tissue. Herein, we have provided an overview of the common carbohydrate polymers, fundamental structural, physicochemical and biological properties, and fabrication techniques for bone tissue engineering. We also discussed advanced biofabrication strategies and provided the limitations and prospects by highlighting significant issues in bone tissue engineering. There are several review articles available on bone tissue engineering but we have provided a state-of-the-art review article that discussed the recent progress and trends within 3-5 years by emphasizing challenges and future perspectives.
Bone is a dynamic tissue that can always regenerate itself through remodeling to maintain biofunctionality. This tissue performs several vital physiological functions. However, bone scaffolds are required for critical-size damages and fractures, and these can be addressed by bone tissue engineering. Bone tissue engineering (BTE) has the potential to develop scaffolds for repairing critical-size damaged bone. BTE is a multidisciplinary engineered scaffold with the desired properties for repairing damaged bone tissue. Herein, we have provided an overview of the common carbohydrate polymers, fundamental structural, physicochemical, and biological properties, and fabrication techniques for bone tissue engineering. We also discussed advanced biofabrication strategies and provided the limitations and prospects by highlighting significant issues in bone tissue engineering. There are several review articles available on bone tissue engineering. However, we have provided a state-of-the-art review article that discussed recent progress and trends within the last 3-5 years by emphasizing challenges and future perspectives.

High-Efficiency Alkyl Ketene Dimer Emulsions Stabilized by Polyaluminum Chloride and Chitosan Complex.

Based on the interaction of polyaluminum chloride (PAC) and chitosan (CTS) at the molecular level, an organic/inorganic composite material was designed for the preparation of alkyl ketene dimer (AKD) emulsion. This paper aimed to explore the influence of PAC/CTS on the physicochemical properties, microstructure, and sizing efficiency of AKD emulsions. The PAC/CTS complex forms a denser adsorption layer at the oil-water interface at the microscopic level. With the increase in CTS concentration, the AKD emulsions displayed excellent stability after high-speed centrifugation. In addition, the addition of CTS can effectively improve the sizing efficiency of the emulsion. Therefore, this study proposed a strategy of PAC/CTS as an emulsifier, and the related interaction mechanism was explored, which further expands the application of inorganic/organic composites in the field of colloidal chemistry.

Electronic Structure and Functions of Carbon Nitride in Frontier Green Catalysis.

ConspectusGraphitic carbon nitride-based materials have emerged as promising photocatalysts for a variety of energy and environmental applications owing to their "earth-abundant" nature, structural versatility, tunable electronic and optical properties, and chemical stability. Optimizing carbon nitride's physicochemical properties encompasses a variety of approaches, including the regulation of inherent structural defects, morphology control, heterostructure construction, and heteroatom and metal-atom doping. These strategies are pivotal in ultimately enhancing their photocatalytic activities. Previous reviews with extensive examples have mainly focused on the synthesis, modification, and application of carbon nitride-based materials in photocatalysis. However, there has been a lack of straightforward and in-depth discussion to understand the electronic characteristics and functions of various engineered carbon nitrides as well as their precise tailoring strategies and ultimately to explain the regularity and specificity of their improved performance in targeted photocatalytic systems. In the past ten years, our group has conducted extensive investigations on carbon nitride-based materials and their application in photocatalysis. These studies demonstrate the close yet intricate relationship between the electronic structure of carbon nitride materials and their photocatalytic reactivity. Understanding the electronic structure and functions of carbon nitride, as well as different engineering strategies, is essential for the improvement of photocatalytic processes from fundamental study to practical applications.To this end, in this Account, we first delve into the nature of the electronic properties of carbon nitride, highlighting the electronic structures, including band structure, density of states, molecular orbitals, and band center, as well as its electronic functions, such as the charge distribution, internal electric field, and external electric force. Subsequently, based on recent research in our group, we present a detailed discussion of the strategic modifications of carbon nitride and the consequential impacts on the physicochemical properties, particularly the optical properties and intrinsic electronic characteristics, for enhancing the photocatalytic performance. These modifications are categorized as follows: (i) component changing, which involves intralayer and interface heterojunctions as well as homojunctions, to modulate the band-edge potentials and reactivity of photoinduced electrons and holes toward surface redox reactions; (ii) dimensional tuning, which engineers the dimensional structure of carbon nitride, to influence the electron transfer direction; (iii) defect and heteroatom modification, which introduces a symmetry break in the carbon nitride framework, to promote charge redistribution for altering the charge density and electronic structure; and (iv) anchoring of single-atom metals to facilitate orbital hybridization and charge transfer enhancement through the unique metal-N coordination configurations. Finally, we propose an appraisal of the prospects and challenges in the precise manipulation and characterization of the electronic structure and functions of carbon nitride. The integration of in situ electronic structure analysis, theoretical calculation based on machine learning, and precise mechanism study may propel its substantial development in the light-driven circular economy. We hope this Account aspires to offer novel insights and perspectives into the operational mechanisms and tailored structure of carbon nitride-based materials in photocatalysis.