Shell Layer Research Articles

Multifunctional Bioactivity Electrospinning Nanofibers Encapsulating Emodin Provides a Potential Postoperative Management Strategy for Skin Cancer.

Skin cancer is threatening more and more people's health; its postoperative recurrence and wound infection are still critical challenges. Therefore, specialty wound dressings with multifunctional bioactivity are urgently desired. Emodin is a natural anthraquinone compound that has anti-cancer and anti-bacterial properties. Herein, we fabricated coaxial electrospinning nanofibers loaded with emodin to exploit a multifunctional wound dressing for skin cancer postoperative management, which encapsulated emodin in a polyvinylpyrrolidone core layer, combined with chitosan-polycaprolactone as a shell layer. The nanofibers were characterized via morphology, physicochemical nature, drug load efficiency, pH-dependent drug release profiles, and biocompatibility. Meanwhile, the anti-cancer and anti-bacterial effects were evaluated in vitro. The emodin-loaded nanofibers exhibited smooth surfaces with a relatively uniform diameter distribution and a clear shell-core structure; remarkably, emodin was evenly dispersed in the nanofibers with significantly enhanced dissolution of emodin. Furthermore, they not only display good wettability, high emodin entrapment efficiency, and biphasic release profile but also present superior biocompatibility and anti-cancer properties by increasing the levels of MDA and ROS in A-375 and HSC-1 cells via apoptosis-related pathway, and long-term anti-bacterial effects in a dose-independent manner. The findings indicate that the emodin-loaded nanofiber wound dressing can provide a potential treatment strategy for skin cancer postoperative management.

Regioselective Doping into Atomically Aligned Core–Shell Structures for Electrocatalytic Reduction of Nitrate to Ammonia

AbstractThe electrochemical nitrate reduction reaction (NO3−RR) presents an environmentally friendly approach for efficient NO3− pollutant removal and ammonia (NH3) production, compared to the conventional Haber–Bosch approach. While core/shell engineering has demonstrated its potential in enhancing NO3−RR performance, significant synthetic challenges and limited shell layer modification capabilities impede the exploration of high‐performance NO3−RR core/shell catalysts. Herein, CuCoO/Co(OH)2 core/shell structure via in situ electrochemical activation is synthesized. The catalyst delivers a maximum NH3 Faradaic efficiency (FE) of 94.7% at −0.5 VRHE with excellent durability and selectivity for NH3 over a wide range of potentials in NO3−RR, surpassing the electrocatalytic performance of both undoped shell and core components. The outstanding performance Cu─CoO/Co(OH)2 is ascribed to the enhanced charge transfer, stabilization of key reaction intermediates, and regulation of hydrogen adsorption over Cu‐doped core/shell structure. Furthermore, the assembled Zn−NO3− battery device attains a peak current density exceeding 32 mA cm−2 and an NH3 yield of up to 145.4 µmol h−1 cm−2. The work offers a novel core/shell engineering strategy in electrocatalytic NO3−RR and sheds light on the doping effects on the electrochemical NH3 synthesis.

Chitosan-based bilayer shell phase change nano-capsules with excellent anti-permeability for thermal regulation dressings

Nano-encapsulated phase change materials (NEPCMs) with appropriate phase change temperature range and excellent anti-permeability have significant application value in the field of thermal regulation dressings. In this study, NEPCMs were synthesized using the microemulsion polymerization method, with eutectic fatty acids (LA-SA) as the core material and poly(methyl methacrylate) (PMMA) as the shell material. Subsequently, using the electrostatic adsorption method, chitosan (CS) was successfully coated onto the outer surface of NEPCMs, resulting in the preparation of a novel bilayer shell nano-encapsulated phase change materials (BS-NEPCMs) for thermal regulation dressings. The impact of core/shell ratio, CS acid solution concentration and cross-linking agent content on capsule properties was investigated. It was found that BS-NEPCMs exhibited excellent cyclical stability and thermal stability. In particular, the CS shell layer provided excellent interfacial impermeability effects for the capsules, achieving an anti-permeability efficiency of 96.21 %. This not only helps address the problem of high leakage rates in single wall capsules, but also ensures that the capsules maintain high phase change enthalpies of 99.32 J/g and 96.38 J/g, respectively. The dressings based on BS-NEPCMs demonstrated good thermal regulation at 33–42 °C with maximum phase change enthalpies of 39.53 J/g and 34.08 J/g, respectively. Swelling and rheological analysis showed that the dressing exhibits a gel state, with a swelling ratio of 343 %, an elastic modulus of 15 kPa and a viscous modulus of 4 kPa. This study indicated that BS-NEPCMs hold significant promise for various applications in energy storage and body thermal regulation fields.

Preparation of Al[sbnd]Si microcapsules with high latent heat and durability via control of shell thickness

Microencapsulation of the AlSi alloy is an effective approach to overcome the challenges of corrosion and oxidation during high temperature operational service when used as phase change heat storage material. Research to date has shown that the prepared microcapsules was not able retain the high latent heat of AlSi alloy and achieve excellent thermal cycling performance at the same time. In this work, AlSi alloy microcapsules with adjustable shell thickness were successfully prepared through hydrothermal reaction, in situ polymerization and heat treatment at different oxygen contents. The phase composition and microstructure of the microcapsules were characterized in detail by XRD and electron microscopy. The thermal performances were tested through thermal cycling and thermal analysis. The results demonstrated that the outer protective shell layer of microcapsules was composed of dense α-Al2O3 and the thickness was adjustable from 372 to 1504 nm by controlling the oxygen content during heat treatment. Meanwhile, the regulation mechanism of shell thickness was analyzed. According to thermal analysis, the latent heat of microcapsules could achieve 450 J·g−1, and the latent heat retention was 100 % after 5000 thermal cycles from 500 °C to 650 °C. This work provides new method of adjusting the shell thickness of AlSi microcapsules to achieve an ultra-high thermal performance in terms of latent heat and retention, which promotes the development of applications for metal-based heat storage materials.

One-pot synthesis and chiroptical activity of single Au-atom doped AuAg28 clusters protected by water-soluble chiral monothiol N‑acetyl‑(S)‑penicillamine (S-NAP)

Physicochemical properties of atomically precise metal clusters can be modulated by incorporating different metal atoms. In this article, successful one-pot synthesis of single Au-atom doped chiral AuAg28 clusters protected by water-soluble N‑acetyl‑(S)‑penicillamine (=S-NAP) is reported. The reduction of Ag and Au ions at 0 °C in the presence of S-NAP and triphenylphosphine (TPP) using tetramethylammonium borohydride (TMAB) is crucial. Importantly, upon doping of an Au atom to the monometallic Ag29 cluster, which improves the cluster stability, the chiroptical activity or maximum anisotropy factor of the bimetallic AuAg28 cluster is enhanced as compared to that of the monometallic species, which can be due to an increase in the rotatory strength that is probably brought about by the increased contribution of optical transition associated with helically-arranged surface shell layers. Such chiroptical behaviors suggest that the Au dopant position in the bimetallic cluster is not fluxional but rigid. Then the present results will help design some heteroatom-doped silver clusters with excellent chiroptical properties.

Zn-doped MnCO3 as cathode material for aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs), known for their high discharge capacity, low cost, and relatively low environmental impact, are a promising alternative for advanced energy storage. The exploration of novel electrode materials and the reaction mechanisms in AZIBs have garnered considerable attention. MnCO3, as an electrode material, is known for its safety, nontoxic nature, and widespread availability as a raw material. Nevertheless several constraints limit the use of MnCO3 cathodes, including short lifespan and reduced electrical conductivity. To resolve these shortcomings, compounds containing Zn, Co and Ni elements were added to improve the properties of the MnCO3 material. The Zn doped MnCO3 (MnCO3–Zn-0.0015 M) was successful synthesized by solvothermal, which presents a special microstructure of spherical shell. Not only does the spherical microstructure of the shell enhance the packing density, but the pore configuration within the shell layer also facilitates the insertion and extraction of Zn2+. The MnCO3–Zn-0.0015 M material, operating at a current density of 0.1 A g−1, exhibited an impressive discharge capacity of 120.4 mAh∙g−1 along with remarkable rate performance. The cathode sustained 75.29 % of its capacity following 1000th cycles at current density of 1.0 A g−1. Considering these results, the MnCO3–Zn-0.0015 M material developed in this study opens a novel avenue for optimizing the use of manganese compounds in aqueous zinc-ion batteries.

Microstructure and Mechanical Properties Evolution of W@WC/Fe Core–Shell Bar‐Reinforced Iron Matrix Composites: Effect of In‐situ Solid Diffusion Time

To improve the strength and toughness of conventional particle‐reinforced iron matrix composites, W@WC/Fe core–shell bar‐reinforced iron matrix composites (CBIMCs) are synthesized by casting and in‐situ solid‐phase diffusion method. These composites, which have an architecture similar to concrete, consist of a core of residual W bar and a shell of gradient‐structured WC‐Fe layer. The effect of in‐situ solid diffusion time on the evolution of microstructure and mechanical properties of the composites is investigated. It is observed that for in‐situ solid diffusion times ranging from 3 to 24 h, the reinforcement in the composites remained as W@WC/Fe core–shell bars. As the solid diffusion time increased, the diameter of the W core gradually decreased, and the thickness of the WC‐Fe shell layer increased. At a solid diffusion time of 30 h, the reinforcement transitioned to the WC‐Fe composite bar. Additionally, with longer solid diffusion times, the WC particles transformed from a triangular prism shape to a truncated octahedron. The composite prepared at 18 h exhibits the highest ultimate compression strength and strain, reaching values of 1100 ± 18 MPa and 35.5 ± 1.3%, respectively. This excellent ultimate compression strength is mainly due to the WC particles, which enhanced load transfer strengthening and dislocation strengthening. Moreover, the metal W core and iron matrix effectively hinder microcrack propagation, thus contributing to the enhanced toughness of the composite.

High coke resistance Ni-based CH4/CO2 reforming catalysts with strong spatial confinement effect: Effect of CeO2 shell thickness

Ni-based catalysts show promise as candidates for the dry reforming of methane (DRM), yet the susceptibility to sintering and carbon deposition is a major obstacle to industrialization. This work demonstrates a mesoporous Ni-based catalyst with a thickness-tailorable CeO2 shell for enhanced spatial confinement effect for the DRM. The Ni-MCM-41@xCeO2 catalysts are prepared at various CeO2 shell thickness through a two-step hydrothermal reaction. The kinetic studies have shown that the Ni-MCM-41@2CeO2 catalyst has the lowest activation energy, producing a high conversion of CH4 and CO2 as high as around 80 % at 700 °C. Our characterizations reveal that the Ni core is tightly confined in the mesoporous skeleton of MCM-41 and within a CeO2 shell. The Ni-MCM-41@2CeO2 catalyst is able to sustain high activity for more than 10 h of operation, with a remarkably reduced carbon deposition (0.28 %) as compared with a conventional Ni-Ce/MCM-41 catalyst (8.77 %). Furthermore, the density functional theory (DFT) calculation supports that the CeO2 shell layer significantly reduces dissociation potential barrier for CH4 and CO2, hence enhancing the catalytic activity of the DRM.

Morphology and taphonomy of the gastropod Terebralia palustris from an iron age site in the Arabian Peninsula

The Indo-Pacific gastropod Terebralia palustris is particularly suitable for comparing natural and anthropogenic induced taphonomic pathways due to its wide geographic distribution and common presence within archeological context. The present study aims to (1) correlate shell architecture and morphology with fragmentation pattern and preservation, (2) quantify taphonomic changes to differentiate between natural vs. anthropogenic preservation features, (3) provide a guideline for analyzing fragmented shell remains in archeological material. Shells and taphonomic features were studied from both recent mangrove environments from the Emirate of Sharjah, United Arab Emirates as well as archeological material within the Iron age II site (1000–600 BC) of Muweilah near the City of Sharjah. Techniques utilized include morphometry, thin sectioning, scanning electron microscopy (SEM) of recent specimens and a semi—quantitative taphonomic analysis of anthropogenic material. Thin sectioning shows a complex internal shell morphology with a tripartite subdivision of shell layers. The recent material shows better preserved features on both the exterior and internal shell surfaces than the highly fragmented material recovered from the archeological context, which shows a distinct size distribution as well as showing higher levels of surface abrasion, surface cracks and color alterations. These features are correlated to extraction techniques, cooking methods and waste disposal handling.

Control of burning rate pressure sensitivity for solid propellants by changing the interfacial contact of Al/HMX/AP with precisely located graphene-based energetic catalysts

The control of burning rate pressure sensitivity is essential for stable and reliable combustion of solid propellants. It has been proved that the combustion behavior of propellants can be effectively tuned by interfacial control of Al/oxidizers. In this work, core-shell Al-based composites, using oxidizers such as ammonium perchlorate (AP) and cyclotetramethylene tetranitramine (HMX) as the shell layer, have been prepared with a well-controlled location of graphene-based carbohydrazide complexes (GO-CHZ-M, M = Co2+ or Ni2+) as the catalysts. The catalysts can be located inside HMX or embedded on the surface of AP particles. The decomposition of AP and HMX could be greatly promoted with a trace amount of catalyst. Under the synergistic effects of Al/oxidizer interfacial control and GO-CHZ-M, the ignition delay time is shortened by >48 % with increased in flame radiation. More importantly, the burning rate (r) and pressure exponent (n) of the solid propellants are effectively regulated in a wide range. In particular, the use of Al@HMX/Co results in a lowered n of 0.29 within 1∼20 MPa compared to 0.79 for the blank reference sample. The agglomeration of Al particles during combustion was also inhibited due to the micro-explosion effect of Al@HMX composites. Novelty and Significance statementThe innovative approaches of integrating Al/HMX/AP composites and precise catalysis of graphene-based energetic catalysts in solid propellants have successfully achieved, regarding the modulation of the burning rates and pressure sensitivity. Moreover, the effect of catalyst location on the ignition delay and burning rates has also been studied thoroughly and clarified. This paper provides new insight into the regulation of combustion performance of solid propellants, with improved reaction efficiency and maintained energy density.

Preparation of thermally stable egg white protein microgel particles as assisted by differently charged polysaccharides: A comparatively study

Egg white proteins (EWP) were prone to thermal aggregation under heat sterilization conditions, thereby limiting their application in the field of protein beverages. In this study, EWP were microgel particleized via polysaccharide-protein phase separation to enhance their resistance to thermal aggregation during processing. Results indicated that the charge characteristics of polysaccharides were crucial factors influencing their interaction with EWP. Microstructural and physicochemical properties indicated that egg white protein microgel particles (EMGP) with the bilayer structure formation (polysaccharide shell layer and dense protein core) could only be formed in the phase separation system of EWP and anionic polysaccharides (carboxymethyl cellulose sodium salt (low viscosity), carboxymethyl cellulose sodium salt (high viscosity), High-methoxyl pectin). Additionally, the EMGP exhibited uniform size, high denaturation extent and dense structure that effectively prevented structural unfolding and exposure of active sites upon reheating of the EWP. The thermal denaturation temperatures of the EMGP were significantly higher (up to 155.8 °C, 163.5 °C, 165.7 °C), compared to natural proteins (88.8 °C). Thermal stability experiments confirmed that the suspension of 5% w/v microgel particles maintained good flow ability after heating at 100 °C for 30 min, demonstrating excellent thermal stability suitable for high-temperature pasteurization conditions. Moreover, its uniform particle size and adsorption of polysaccharides improved storage stability. In contrast, groups other than anionic polysaccharides exhibited aggregation and gelation upon heating. Overall, this study demonstrated that preparing heat-stable EMGP effectively reduces aggregation in EWP beverages during heat-pasteurization, enhanced product sensory attributes, extended shelf-life, and expanded the application scope of EWP.

Core-shell structured nanomembrane with sequential immune and vascular isolation effects followed by chondrogenic induction to promote stable stem cell-based subcutaneous cartilage regeneration in large animals

Bone marrow stem cell (BMSC)-regenerated cartilage (BRC) shows promising prospects for clinically repairing cartilage defects. However, when subcutaneously implanted into immunocompetent large animals, BRC is prone to ossification due to vascular invasion and inflammatory infiltration, compromising its chondrogenic stability. To address this challenge, we developed a core–shell structured KGN/Gel@Cur/PLCL nanomembrane using coaxial electrospinning technology to enhance the chondrogenic stability of BRC in subcutaneous niche. The shell layer comprises curcumin (Cur), known for its potent immunomodulatory and anti-angiogenic effects, and poly(L-lactide-co-caprolactone) (PLCL). The core layer comprises Kartogenin (KGN), a recognized chondrogenic inducer, and gelatin (Gel). This nanomembrane encapsulated BRCs induced from goat BMSCs in vitro and was subcutaneously implanted into autologous goats. The nanomembrane’s physical barrier and Cur release from the shell layer prevented vascular invasion and inflammatory infiltration. Additionally, KGN release from the core layer maintained the BRC’s chondrogenic phenotype and promoted cartilage maturation. These combined mechanisms significantly inhibited BRC ossification and preserved its chondrogenic stability. chondrogenic phenotype and promoted cartilage maturation. These combined mechanisms significantly inhibited BRC ossification and maintained its chondrogenic stability. Overall, this study highlights the effectiveness of the core–shell structured KGN/Gel@Cur/PLCL nanomembrane in providing sequential immune and vascular isolation, followed with chondrogenic induction, to prevent BRC ossification and preserve the chondrogenic stability of subcutaneously implanted BRC in large animal. This is crucial for the clinical translation of stem cell therapy into subcutaneous cartilage repair.

Core-shell nanofiber separator incorporated with PDA-PEI co-modified Li0.33La0.57TiO3 nanowires prepared by co-axial electrospinning for dendrite-free lithium metal batteries

The core-shell nanofibers containing PDA-PEI co-modified Li0.33La0.57TiO3 (LLTO) perovskite nanowires in the shell layer were fabricated by co-axial electrospinning technique to apply as separator in dendrite-free lithium metal batteries. The PVDF-HFP with good mechanical properties and polar C–F bonds was used as the core material, and polyacrylonitrile (PAN) with high thermal stability was employed as the shell layer in nanofibers. The PDA-PEI co-modified Li0.33La0.57TiO3 nanowires, reacting with PF6− anions in LiPF6 salt can not only capture free anions but also provide a lithium-ion migration pathway. Moreover, the core-shell structured nanofibers exhibited high mechanical strength (9.2 N/mm2), robust thermal stability (>0% at 200 °C for 1 h), and favorable electrolyte affinity (electrolyte uptake of 732%). Gelation of PVDF-HFP in liquid electrolyte leads to high-ionic conductivity (3.52 mS/cm), Li+ transference number (tLi+ = 0.68), uniform Li+ flux, and smooth Li deposition. The Li plating/stripping test consisting of Li–Li cells (with CS/LLTO-PDA-PEI) carried out at 0.4 mA/cm2 was conducted for 1000 h without a short circuit. NCM-Li and NCM-Gr coin cells using the CS (core-shell)/LLTO-PDA-PEI separator retained long-term cycle stability and good Coulombic efficiency (CE).

Novel design of Sn4P3@NxC electrodes and their electrochemical properties

Tin phosphide (SnxPy) is recognized as one of the most promising anode materials for lithium-ion batteries due to its exceptionally high theoretical capacity. However, its application is hampered by significant volume expansion during charge-discharge cycles and inferior electrical conductivity. Proper structural design plays a pivotal role in addressing these challenges, paving the way for high-performance anode materials. This study introduces a nitrogen-doped carbon-coated Sn4P3 nanosphere with a core-shell structure, employing dopamine as the nitrogen source. This innovative approach, utilizing template removal and solid-phase phosphorization, results in both the core and shell acting as active materials, thereby enhancing the volumetric energy density of the electrode. The internal voids within the shell layer mitigate volume expansion during charge-discharge cycles, while the presence of the nitrogen-doped carbon layer maintains the material's stability throughout cycling and improves its electrical conductivity. Electrochemical performance tests confirm this material's outstanding energy storage capability, with an initial Coulombic efficiency reaching up to 73.6 %. Furthermore, it maintains a stable capacity of 585 mAh g−1 after 1200 cycles at a current density of 2 A g−1. This research offers a design paradigm for developing novel energy storage materials.

Alleviated volume changes of germanium anode via facile chemical confinement strategy

Germanium (Ge) anode shows great promise in overcoming unsatisfied capacity and dendrite formation concerns facing conventional graphite anodes in next generation lithium ion batteries. However, volume changes during repeated alloying and de-alloying cycles seriously impair structural stability and cycle lifespan. In this work, a facile chemical confinement strategy has been firstly proposed to alleviate volume changes of Ge anode. Benefited from strong binding interaction between Ge and ZnS, discrete Ge nanoparticle can be successfully encapsulated within thin protective ZnS shell and N-doped carbon layer (Ge-ZnS@N-C) after two-step carbonization and sulfurization of polydopamine-coating Zn2GeO4 nanorod precursors. In contrast, bulk Ge aggregates and hollow N-doped carbon nanotubes can be formed without chemical confinement of ZnS. The as-prepared Ge-ZnS@N-C sample displays multifold structural merits, including nanosized Ge particles with highly electrochemical activity, sufficient pores and functional groups that facilitate ion diffusion. Besides, protective ZnS shell and N-doped carbon layer can suppress volume changes of Ge nanoparticles and guarantee high electrode reversibility, demonstrated by a series of in-situ and ex-situ experiments. The as-synthesized Ge-ZnS@N-C anodes exhibit stable long-cycle performance (1389.7 mAh/g after 450 cycles at a current density of 0.5 A/g) and excellent rate performance (548.5 and 397.8 mAh/g at 5.0 and 8.0 A/g, respectively).

(Invited) Plasmonic Yolk@Shell Nanocrystals for Photocatalytic Hydrogen Production

Plasmonic photocatalysts have garnered significant attention for hydrogen production due to their unique properties and efficiency in harnessing solar energy. This work is designed to develop yolk@shell nanocrystals as a high-efficiency photocatalyst model. The core yolk is composed of Au nanoparticles, and the shell is composed of hollow non-stoichiometric semiconductors. The compositional defects can induce a large number of free carriers, making non-stoichiometric semiconductors behave like noble metals and exhibit surface plasmon resonance (SPR) absorption. For yolk@shell nanocrystals, the core Au particles can move freely, which can effectively stir the surrounding reaction solution to increase the reaction rate. The confined space between the core particle and the shell layer can function as a nanoreactor to promote species diffusion to enhance catalysis kinetics. In addition, the core Au particles and the shell semiconductor can form metal/semiconductor heterojunction so as to exhibit remarkable photocatalytic performance. Several representative works from our lab will be introduced to demonstrate the promising potentials of plasmonic yolk@shell nanocrystals for hydrogen production applications.

Effect of Crystal Structure on Dealloying Behavior in PtCo Alloy and Its Impact on the Oxygen Reduction Reaction

The proton exchange membrane fuel cell (PEMFC) is considered ideal for power generation due to its high energy conversion efficiency, low operating temperature, and environmentally friendly features. However, the performance of PEMFC is limited by the slow oxygen reduction reaction (ORR) at the cathode, necessitating the use of catalysts such as Pt to enhance the reaction. The Pt catalyst, although effective, poses the challenge of high cost. Consequently, numerous studies have been undertaken to develop more cost-effective catalysts that can match the excellent activity of platinum while maintaining high stability. In particular, the development of alloy nano-catalysts has garnered attention, and promising results have been reported for enhancing catalyst performance through dealloying on the surface of the alloy catalyst. Alloy catalysts prepared by the dealloying method offer the advantage of improving performance by selectively dissolving less-noble metal surfaces and constructing a Pt-rich shell layer. In this study, we synthesized two PtCo alloy catalysts with distinct crystal structures: face-centered cubic (FCC) and face-centered tetragonal (FCT). To prevent particle growth during the transformation from FCC to FCT when subjected to high-temperature heat treatment for an extended duration, we employed the carbon shell encapsulation technique. Subsequently, the synthesized catalyst underwent acid treatment for dealloying. We investigated the variations in dealloying characteristics based on crystal structures and examined their impact on electrochemical performance. Various characterizations, including X-ray diffraction (XRD), High-Resolution Transmission Electron Microscopy (HR-TEM), Scanning Electron Microscopy (SEM), Thermo-Gravimetric Analysis (TGA), and Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), were conducted to validate the structure of the synthesized PtCo alloy nano-catalyst. Half-cell and unit-cell experiments were carried out to verify electrochemical properties and performance, following the testing protocol suggested by the Department of Energy (DOE) in 2020. Finally, we explored the relationship between the dealloying feature of FCC and FCT and their impact on electrochemical activity and stability.

Core-Shell Interface Engineering Strategies for Modulating Energy Transfer in Rare Earth-Doped Nanoparticles.

Rare earth-doped nanoparticles (RENPs) are promising biomaterials with substantial potential in biomedical applications. Their multilayered core-shell structure design allows for more diverse uses, such as orthogonal excitation. However, the typical synthesis strategies-one-pot successive layer-by-layer (LBL) method and seed-assisted (SA) method-for creating multilayered RENPs show notable differences in spectral performance. To clarify this issue, a thorough comparative analysis of the elemental distribution and spectral characteristics of RENPs synthesized by these two strategies was conducted. The SA strategy, which avoids the partial mixing stage of shell and core precursors inherent in the LBL strategy, produces RENPs with a distinct interface in elemental distribution. This unique elemental distribution reduces unnecessary energy loss via energy transfer between heterogeneous elements in different shell layers. Consequently, the synthesis method choice can effectively modulate the spectral properties of RENPs. This discovery has been applied to the design of orthogonal RENP biomedical probes with appropriate dimensions, where the SA strategy introduces a refined inert interface to prevent unnecessary energy loss. Notably, this strategy has exhibited a 4.3-fold enhancement in NIR-II in vivo imaging and a 2.1-fold increase in reactive oxygen species (ROS)-related photodynamic therapy (PDT) orthogonal applications.

Mechanochemical synthesis of nitrogen-modified microscale zero-valent iron for efficient Cr(VI) removal: The role of lattice strain

Lattice engineering of Fe0 based on heteroatom doping holds great promise in water purification owing to their tunable geometric and electronic structure. However, there is limited understanding of how nitrogen atom in Fe0 lattice structure affects its local microenvironment and corresponding reactivity toward target contaminants. Herein, microscale zero-valent iron with interstitial N doping (N-mZVI) was successfully prepared by a facile mechanochemical method for heavy metal pollution control. N-mZVI exhibited excellent reactivity for Cr(VI) elimination, and both removal efficiency and conversion rate could reach 100 %, which was 8.06 and 2.73 times higher than that of pristine ball milled mZVI, respectively. Besides, the rate constant of various heavy metals sequestration (Cr(VI), Ni(II), Pb(II), Cu(II), and Cd(II)) over N-mZVI was 61.3 ∼ 115.6-fold faster than that of pristine ball milled mZVI. N-mZVI was also demonstrated to be pH-universal, long-term stability, and environmental applicability. Experimental results and theoretical calculations indicated that tensile strain induced by interstitial N doping expanded Fe0 lattice and weakened the lattice Fe-Fe interaction, thus significantly accelerating electron transport dynamics in Fe0 core. Meanwhile, iron nitride species on the surface of N-mZVI promoted electron transfer from iron shell layer to heavy metals. This work comprehensively investigates the structure–property relationships of lattice engineering-based N-mZVI, and provides a new insight into rational design of modified mZVI with high reactivity.

Fast Determination of Eleven Food Additives in River Water Using C18 Functionalized Magnetic Organic Polymer Nanocomposite Followed by High-Performance Liquid Chromatography.

A novel magnetic nanomaterial with Fe3O4 as the core, PS-DVB as the shell layer, and the surface modified with C18 (C18-PS-DVB-Fe3O4) had been synthesized by seeded emulsion polymerization. C18-PS-DVB-Fe3O4 retains the advantages of the chemical stability, large porosity, and uniform morphology of organic polymers and has the magnetic properties of Fe3O4. A simple, flexible, and efficient magnetic dispersive solid phase extraction (Mag-dSPE) method for the extraction of preservatives, sweeteners, and colorants in river water was established. C18-PS-DVB-Fe3O4 was used as an adsorbent for Mag-dSPE and was coupled with high-performance liquid chromatography (HPLC) to detect 11 food additives: acesulfame, amaranth, benzoic acid, tartrazine, saccharin sodium, sorbic acid, dehydroacetic acid, sunset yellow, allura red, brilliant blue, and erythrosine. Under the optimum extraction conditions, combined with ChromCoreTMAQC18 (5 μm, 4.6 × 250 mm), 20 mmol/L ammonium acetate aqueous solution and methanol were used as mobile phases, and the detection wavelengths were 240 nm and 410 nm. The limits of detection (LODs) of 11 food additives were 0.6-3.1 μg/L with satisfactory recoveries ranging from 86.53% to 106.32%. And the material could be reused for five cycles without much sacrifice of extraction efficiency. The proposed method has been used to determine food additives in river water samples, and results demonstrate the applicability of the proposed C18-PS-DVB-Fe3O4 Mag-dSPE coupled with the HPLC method to environment monitoring analysis.