Development Of Functional Materials Research Articles

Super-Resolution Microscopy as a Versatile Tool in Probing Molecular Assembly

Molecular assembly is promising in the construction of advanced materials, obtaining structures with specific functions. In-depth investigation of the relationships between the formation, dynamics, structure, and functionality of the specific molecular assemblies is one of the greatest challenges in nanotechnology and chemistry, which is essential in the rational design and development of functional materials for a variety of applications. Super-resolution microscopy (SRM) has been used as a versatile tool for investigating and elucidating the structures of individual molecular assemblies with its nanometric resolution, multicolor ability, and minimal invasiveness, which are also complementary to conventional optical or electronic techniques that provide the direct observation. In this review, we will provide an overview of the representative studies that utilize SRM to probe molecular assemblies, mainly focusing on the imaging of biomolecular assemblies (lipid-based, peptide-based, protein-based, and DNA-based), organic–inorganic hybrid assemblies, and polymer assemblies. This review will provide guidelines for the evaluation of the dynamics of molecular assemblies, assembly and disassembly processes with distinct dynamic behaviors, and multicomponent assembly through the application of these advanced imaging techniques. We believe that this review will inspire new ideas and propel the development of structural analyses of molecular assemblies to promote the exploitation of new-generation functional materials.

Cascaded utilization of magnetite nanoparticles@onion-like carbons from wastewater purification to supercapacitive energy storage.

Developing high-performance carbon-based materials for environmental and energy-related applications produces solid waste with secondary pollution to the environment at the end of their service lives. It is still challenging to utilize these functional materials in a sustainable manner in different fields. In this study, we demonstrate a cascaded utilization of an Fe3O4@onion-like carbon (Fe3O4@OLC) structure from wastewater adsorbents to a supercapacitor electrode. The structure was formed by carbonizing Fe3O4@oleic acid monodisperse nanoparticles into interconnected Fe3O4@OLCs and subsequent insufficient acid etching. The hollow OLCs in the outside region of the hybrid structure provide high surface area and the encapsulated Fe3O4 nanoparticles in the inside region offer high ferromagnetism. The three-dimensionally interconnected graphitic layers are advantageous for efficient separation and high conductivity. As a result, the maximum saturation adsorption capacity of insufficiently etched interconnected Fe3O4@OLCs can reach up to 90.2 mg g-1 and they can be efficiently separated under a magnetic field. Furthermore, the hybrid structure is thermally transformed into N-doped HOLCs, which are demonstrated to be a high-performance supercapacitor electrode with high specific capacitance and high electrochemical stability. The cascaded utilization of the hybrid structure in this study is meaningful for eco-friendly development of functional materials for environmental and energy storage applications.

Entropically and enthalpically driven self-assembly of a naphthalimide-based luminescent organic π-amphiphile in water.

The self-assembly of π conjugated systems in water has emerged as an efficient method for the development of functional materials for biological applications. But the process is more difficult to understand and to control in water compared to organic solvents due to hydrophobic effects. For π-conjugated molecules, self-assembly in solution generally occurs due to either an enthalpic or entropic gain, but designing π systems that undergo self-assembly via both an entropically and enthalpically favorable process is challenging. Herein, we elucidate in detail the self-assembly of a luminescent naphthalene monoamide-based dipolar π-bolaamphiphile appended with a primary amine and triethylene glycol monomethyl ether (NMI-W) side chain into a vesicular nanostructure. By utilizing a detailed isothermal titration calorimetry (ITC) experiment, we have calculated the thermodynamic parameters associated with the self-assembly of NMI-W in water. Interestingly, the NMI-W shows both entropically and enthalpically favorable robust self-assembly into a vesicular structure, which can encapsulate both hydrophilic and hydrophobic guest molecules. The synergistic effect of dipole-dipole, π-π stacking and hydrophobic interactions of the NMI chromophore is found to be very crucial in driving self-assembly in an aqueous medium as revealed by various experiments and molecular dynamics.

Hollow Superhelices Based on Chiral Europium Coordination Polymers.

The construction of helical nanotubes based on chiral coordination polymers (CPs) is an intriguing but challenging task, which is important for the development of functional materials that combine macroscopic chirality with tube-related properties. Here, we selected a chiral europium phosphonate system, e.g., Eu(NO3)3/R-,S-pempH2, and carried out a systematic work. By controlling the hydrothermal reaction conditions such as the pH value of the reaction mixture, the molar ratio and concentration of the reactants, we obtained block-like crystals of R/S-1b, rod-like crystals ofR/S-3r, hollow superhelices of R/S-2hh, and solid superhelices of R/S-4sh. In the latter two cases, the chirality has been successfully transferred and amplificated from the molecular level to the macroscopic level. Interestingly, compounds R/S-2hh and R/S-4sh have the same chemical composition of Eu(R/S-pempH)3×2H2O and show identical PXRD patterns, thus can be considered as the same material except for different morphologies. We further investigatedtheir circularly polarized luminescence (CPL) properties and found that the hollow superhelix of R/S-2hh had a larger dissymmetry factor than the solid superhelix of R/S-4sh. This study not only provides the first example of hollow superhelices of chiral CPs, but also offers the possibility of modulating the chiroptical properties of CPs through morphological control.

Simultaneous Hydrogenation of an Insulated Diarylacetylene Dimer Incorporated as Axle Molecules in a Cyclodextrin-Based [c2]Daisy Chain Rotaxane.

The [c2]daisy chain rotaxane is an attractive interlocked molecule for the development of functional materials because of its unique mechanical properties that respond to various external stimuli, resulting in extension and contraction motions along the molecular axis. The synthesis of several 'impossible' [2]rotaxanes that do not exhibit obvious binding motifs between their axle and wheel moieties has been achieved through further chemical modification of their axle moieties within pre-prepared [2]rotaxanes. However, no 'impossible' [c2]daisy chain rotaxane has been synthesized using similar strategies until now. In this study, we investigated the hydrogenation of diarylacetylene moieties within a permethylated α-cyclodextrin (PM α-CD)-based [c2]daisy chain rotaxane using Pd/C or Pd/CaCO3 under hydrogen. A new [c2]daisy chain rotaxane featuring two diarylethane moieties was successfully synthesized through the simultaneous full hydrogenation of the insulated diarylacetylene moieties under optimized conditions. The new rotaxane is classified as an 'impossible' [c2]daisy chain rotaxane due to the lack of obvious binding motifs between diarylethane and the PM α-CD. This work demonstrates for the first time that the insulated axle moieties of [c2]daisy chain rotaxanes can undergo novel chemical modifications using a synthetic strategy employing transition-metal-catalyzed hydrogenation, which can potentially advance the development of nanoarchitectures with functional interlocked molecules.

E-Skin and Its Advanced Applications in Ubiquitous Health Monitoring.

E-skin is a bionic device with flexible and intelligent sensing ability that can mimic the touch, temperature, pressure, and other sensing functions of human skin. Because of its flexibility, breathability, biocompatibility, and other characteristics, it is widely used in health management, personalized medicine, disease prevention, and other pan-health fields. With the proposal of new sensing principles, the development of advanced functional materials, the development of microfabrication technology, and the integration of artificial intelligence and algorithms, e-skin has developed rapidly. This paper focuses on the characteristics, fundamentals, new principles, key technologies, and their specific applications in health management, exercise monitoring, emotion and heart monitoring, etc. that advanced e-skin needs to have in the healthcare field. In addition, its significance in infant and child care, elderly care, and assistive devices for the disabled is analyzed. Finally, the current challenges and future directions of the field are discussed. It is expected that this review will generate great interest and inspiration for the development and improvement of novel e-skins and advanced health monitoring systems.

Microgalvanic cell-mediated green synthesis of Cu2O nanocubes with (100) facets for boosting dopamine hydrochloride sensing performance

Despite numerous efforts have been made on exploring the preparation, properties and application of Cu2O nanocrystal, there is still a lack of a facile and green synthesis strategy to obtain well-defined Cu2O nanocubes (NCs). And exploration of the superior low-index lattice plane of Cu2O in electrochemical sensing is also inadequate. Herein, we proposed a Ni(OH)2-mediated in-situ synthetic strategy for the preparation of Cu2O NCs enclosed by low-index facets with simple procedure, mild temperature and low energy-consumption. The Ni(OH)2 sites not only facilitated the contact between Cu2+ and the substrate Ni foam (NF), but also can combine with the NF to act as a primary battery to regulate the nucleation and growth rate of Cu2O (100) facets. Benefiting from the high ratio of exposed electroneutral (100) lattice planes of nanocubes, the Cu2O NCs formed on Ni(OH)2-abundant Ni Foam (Cu2O NCs/NFEO) exhibited a wide linear range (3.25–1178.8 μM), a low detection limit (1.86 μM) and a high sensitivity (900 μA mM−1 cm−2) in dopamine hydrochloride (DAH) electrochemical sensing. This work expects to provide more clues about the relationship between different dominant low-index facets of Cu2O NCs and electrochemical sensing performance towards DAH, and thereby contributes to the development of functional materials based on Cu2O nanocrystals with desirable facets.

Upconversion/Downshifting Circularly Polarized Luminescence over 1200 nm in a Single Nanoparticle for Optical Anticounterfeiting and Information Encryption.

Multimodal upconversion and downshifting circularly polarized luminescent materials hold significant potential for optical anticounterfeiting applications due to their exceptional chiroptical properties. However, constructing these materials within a single emitter remains challenging. In this study, a conceptual model of multimodal up-conversion/downshifting circularly polarized luminescence (CPL) is realized within a single nanoparticle. A new type of nanoparticles with multilayer core-shell architecture is fabricated, capable of delivering upconversion/downshifting luminescence, when excited by a 980 nm laser. Utilizing a co-assembly strategy, multimodal upconversion/downshifting CPL emission, covering a broad emission range from ultraviolet (UV) to the second near-infrared (NIR-II) region, can be realized at the supramolecular level. These chiroptical properties closely follow the chirality of host matrix and are strongly dependent on the distribution mode of nanoparticles within the matrix films. The multimodal upconversion/downshifting CPL behavior enabled cutting-edge encryption applications including optical anticounterfeiting and information encryption. This work introduces a novel approach to designing multimodal upconversion/downshifting CPL materials and opens new avenues for the development of chiroptical functional materials.

Upconversion/Downshifting Circularly Polarized Luminescence over 1200 nm in a Single Nanoparticle for Optical Anticounterfeiting and Information Encryption

Multimodal upconversion and downshifting circularly polarized luminescent materials hold significant potential for optical anticounterfeiting applications due to their exceptional chiroptical properties. However, constructing these materials within a single emitter remains challenging. In this study, a conceptual model of multimodal up‐conversion/downshifting circularly polarized luminescence (CPL) is realized within a single nanoparticle. A new type of nanoparticles with multilayer core‐shell architecture is fabricated, capable of delivering upconversion/downshifting luminescence, when excited by a 980 nm laser. Utilizing a co‐assembly strategy, multimodal upconversion/downshifting CPL emission, covering a broad emission range from ultraviolet (UV) to the second near‐infrared (NIR‐II) region, can be realized at the supramolecular level. These chiroptical properties closely follow the chirality of host matrix and are strongly dependent on the distribution mode of nanoparticles within the matrix films. The multimodal upconversion/downshifting CPL behavior enabled cutting‐edge encryption applications including optical anticounterfeiting and information encryption. This work introduces a novel approach to designing multimodal upconversion/downshifting CPL materials and opens new avenues for the development of chiroptical functional materials.

Flame-Resistant Inorganic Films by Self-Assembly of Clay Nanotubes and their Conversion to Geopolymer for CO2 Capture.

Self-assembling of very long natural clay nanotubes represents a powerful strategy to fabricate thermo-stable inorganic thin films suitable for environmental applications. In this work, self-standing films with variable thicknesses (from 60 to 300µm) are prepared by the entanglement of 20-30µm length Patch halloysite clay nanotubes (PT_Hal), which interconnect into fibrosus structures. The thickness of the films is crucial to confer specific properties like transparency, mechanical resistance, and water uptake. Despite its completely inorganic composition, the thickest nanoclay film possesses elasticity comparable with polymeric materials as evidenced by its Young's modulus (ca. 1710MPa). All PT_Hal-based films are fire resistant and stable under high temperature conditions preventing flame propagation. After their direct flame exposure, produced films do not show neither deterioration effects nor macroscopic alterations. PT_Hal films are employed as precursors for the development of functional materials by alkaline activation and thermal treatment, which generate highly porous geopolymers or ceramics with a compact morphology. Due to its high porosity, geopolymer can be promising for CO2 capture. As compared to the corresponding inorganic film, the CO2 adsorption efficiency is doubled for the halloysite geopolymeric materials highlighting their potential use as a sorbent.

Cu-Atom Locations in Rocksalt SnTe Thermoelectric Alloy.

The development of functional thermoelectric materials requires direct evidence of dopants' locations to rationally design the electronic and phononic structure of the host matrix. In this study, Cs-corrected scanning transmission electron microscopy and energy dispersive X-ray spectroscopy is employed at the atomic scale to identify Cu atoms' locations in a Cu-doped SnTe thermoelectric alloy. It is revealed that Cu atoms in the rocksalt SnTe form solid solutions at both Sn and Te sites, contrary to their electronegativity order and the intentional Cu doping at Sn sites. Cu atoms are also located at the tetrahedral and crowdion sites of the face-centred cubic structure, with varying degrees of correlations. Such high flexibility of Cu atoms in the rocksalt SnTe offers diverse phonon-scattering mechanisms conducive to the ultra-low lattice thermal conductivity of singly Cu-doped SnTe. This study offers atomic-scale insights for achieving more precise dopant engineering, leading to the accelerated development of functional thermoelectric materials.

Chitosan/pre-gelatinized waxy corn starch composite edible orally disintegrating film for taurine delivery

In this study, chitosan/per-gelatinized waxy corn starch composite edible orally disintegrating films (ODFs) incorporated with taurine were prepared and the morphology, release behavior and storage stability of the ODFs were investigated. The XRD, ATR-FTIR and microscopic investigation results revealed that taurine could be uniformly dispersed in the film matrix. The optimal level of taurine addition was 1.0% (w/w). The incorporation of taurine improved the apparent morphology, mechanical properties and water holding capacity while slightly increased the film thickness, disintegration time and contact angle of the composite films. In addition, taurine exhibited a rapid release behavior in the films. The fitted results of the Ritger-Peppas model indicated that the release mechanism of taurine in the composite films was mainly Fickian diffusion with minor skeleton erosion. As a delivery carrier, the composite film had a positive effect on the preservation of taurine, increasing the retention of taurine by 8.34% ± 1.48% during storage. The study confirmed the feasibility for the development of taurine ODF carriers and provided a basis for the development of functional packaging materials.

A Review on Recent Trends in Photo-Drug Efficiency of Advanced Biomaterials in Photodynamic Therapy of Cancer.

Photodynamic Therapy (PDT) has emerged as a highly efficient and non-invasive cancer treatment, which is crucial considering the significant global mortality rates associated with cancer. The effectiveness of PDT primarily relies on the quality of the photosensitizers employed. When exposed to appropriate light irradiation, these photosensitizers absorb energy and transition to an excited state, eventually transferring energy to nearby molecules and generating Reactive Oxygen Species (ROS), including singlet oxygen [1O2]. The ability to absorb light in visible and nearinfrared wavelengths makes porphyrins and derivatives useful photosensitizers for PDT. Chemically, Porphyrins, composed of tetra-pyrrole structures connected by four methylene groups, represent the typical photosensitizers. The limited water solubility and bio-stability of porphyrin photosensitizers and their non-specific tumor-targeting properties hinder PDT effectiveness and clinical applications. Therefore, a wide range of modification and functionalization techniques have been used to maximize PDT efficiency and develop multidimensional porphyrin-based functional materials. Recent progress in porphyrin-based functional materials has been investigated in this review paper, focusing on two main aspects including the development of porphyrinic amphiphiles that improve water solubility and biocompatibility, and the design of porphyrin-based polymers, including block copolymers with covalent bonds and supramolecular polymers with noncovalent bonds, which provide versatile platforms for PDT applications. The development of porphyrin-based functional materials will allow researchers to significantly expand PDT applications for cancer therapy by opening up new opportunities. With these innovations, porphyrins will overcome their limitations and push PDT to the forefront of cancer treatment options.

Effect of pH, acid catalyst, and aging time on pore characteristics of dried silica xerogel

ABSTRACT This study investigates the impact of pH and ageing time on silica xerogel pore characteristics prepared via the sol-gel method. Using tetraethyl orthosilicate (TEOS) and HCl as a precursor and acid catalyst, respectively, tailored pore size distributions in the meso- and macroporous range were achieved. Field emission scanning electron microscopy (FESEM) revealed interconnected porous structures, with pore size increasing linearly with ageing time. pH variation yielded average pore sizes ranging from ~ 31 nm (mesoporous) to ~ 59 nm (macroporous). Higher acid catalyst concentration accelerated gelation, resulting in smaller pores. Elemental analysis confirmed silicon and oxygen as primary constituents, while X-ray diffraction (XRD) confirmed amorphous nature. Sol-gel synthesis provides versatile control over microstructure and properties, enabling customisation for applications such as liquid filters, batteries, sensors, and bio-scaffolds. It offers a cost-effective, direct synthesis of high-purity multi-component materials, emphasising its potential for functional material development.

Anti-inflammatory and antioxidant activities of Pleurotus nebrodensis extract : application in a functional tea

This study was designed to examine the nitric oxide production, hyaluronidase, and prostaglandin E2 (PGE2) inhibitory activities for the anti-inflammatory effect and DPPH and ABS radical scavenging activities for antioxidant effect using Pleurotus nebrodensis mycelium extract for a functional tea development. The cell viability was confirmed that all extracts were not cytotoxic to RAW264.7 cell within a concentration of 90 μg/mL irrespective of solvent extracts. The nitric oxide inhibitory activity in LPS-stimulated RAW264.7 cells was the highest at 43.6% using 90 μg/mL of hot water extract. The PGE2 inhibitory level was the highest 32.9% of 90 μg/mL of hot water extract. The hyaluronidase inhibitory activity as the highest 53.5% using 90 μg/mL of hot water extract. On the other hand, in the case of antioxidant activity, the maximum DPPH radical scavenging activity using 90μg/mL of ethanol extract obtained 69.6%. The maximum ABS radical scavenging activity using 90μg/mL of ethanol extract obtained 71.3%. When hot water extract was mixed in green tea, they was considered an excellent extract because the sensory evaluation showed a relatively high value. Based on the results of these experiments, it was possible to confirm the possibility of the functional material development of the tea beverage for anti-inflammatory and antioxidant agents using the hot water and ethanol extract of P. nebrodensis mycelium.

High-Value Utilization of Cellulose: Intriguing and Important Effects of Hydrogen Bonding Interactions─A Mini-Review.

Cellulose has been widely used in papermaking, textile, and chemical industries due to its diverse sources, environmental friendliness, and renewability. Recently, much more attention has been paid to converting cellulose into high-value-added products. Therefore, the extraction of nanocellulose, the dissolution of cellulose, and their applications are some of the most important research topics currently. However, cellulose's dense hydrogen bond network poses challenges for efficient extraction and dissolution, limiting its potential for functional material development. This review discusses the mechanisms of hydrogen bond disruption and weak interactions during nanocellulose extraction and cellulose dissolution. Key challenges and future research directions are highlighted, emphasizing developing efficient, ecofriendly, and cost-effective methods. Additionally, this review provides theoretical insights for constructing high-performance cellulose-based materials.

Engineering nanoparticle structure at synergistic Ru-Na interface for integrated CO2 capture and hydrogenation

The development of dual functional material for cyclic CO2 capture and hydrogenation is of great significance for converting diluted CO2 into valuable fuels, but suffers from kinetic limitation and deactivation of adsorbent and catalyst. Herein, we engineered a series of RuNa/γ-Al2O3 materials, varying the size of ruthenium from single atoms to clusters/nanoparticles. The coordination environment and structure sensitivity of ruthenium were quantitatively investigated at atomic scale. Our findings reveal that the reduced Ru nanoparticles, approximately 7.1 nm in diameter with a Ru-Ru coordination number of 5.9, exhibit high methane formation activity and selectivity at 340 °C. The Ru-Na interfacial sites facilitate CO2 migration through a deoxygenation pathway, involving carbonate dissociation, carbonyl formation, and hydrogenation. In-situ experiments and theoretical calculations show that stable carbonyl intermediates on metallic Ru nanoparticles facilitate heterolytic C–O scission and C–H bonding, significantly lowering the energy barrier for activating stored CO2.

Electroplating sludge derived CuFe2O4/MgFe2O4 metal oxide composites for highly efficient removal of Congo red.

The utilization of electroplating sludge (ES) to derive metal oxide functional materials is a key strategy, as it enables the recycling of valuable elements, mitigates environmental risks, and aligns with green, low-carbon development strategies. Nevertheless, the development of metal oxide composite functional materials with distinctive structures and properties derived from ES continues to present several challenges. Herein, we synthesized CuFe2O4/MgFe2O4 metal oxide composites from ES by one-step hydrothermal method. As-obtained CuFe2O4/MgFe2O4 metal oxide composites (MMOs) have a unique layered structure, richer mesoporous and microporous structures, activity sites. When evaluated as an adsorbent for Congo red (CR), as-synthesized CuFe2O4/MgFe2O4 with layered structure composite exhibited excellent adsorption capacity (1039.1 mg/g) and reusability (85.55% after five cycles), which was superior to most similar adsorbents reported till date. Such improvement is explored to mainly originate from two respects: the physical adsorption facilitated by the abundant pores formed through the stacking and growth of CuFe2O4 and MgFe2O4, and the chemisorption resulting from surface complexation and hydrogen bonding between the MMOs and CR. This strategy to directly transform ES into functional materials shows great promise both in waste management and preparation of robust adsorbents for wastewater treatment.

Harnessing potential of microwave-assisted ultrafast synthesis of reduced graphene oxide/Mn3O4 bioactive nanocomposite hydrogel for bone tissue engineering

The development of functional materials with the potential for bone tissue regeneration along with rapid synthesis and cost-effective approach has been challenging. In this regard, hydrogels have been explored as a potent candidate to behave as a 3D scaffold for bone repair. However, poor mechanical attributes impeded their clinical translation. Enthralling demonstration of the potential of carbon-based nanocomposites in bone tissue engineering has been constantly encouraging the fabrication of advanced nanocomposites. Here, we investigated the fabrication of reduced graphene/manganese (II, III) oxide (RGO/Mn3O4) nanocomposites by taking advantage of the microwave-assisted synthesis approach for cost effective, and ultrafast synthesis. Mn3O4 nanoparticles with uniform distribution in RGO sheets and ∼ 1.7 nm size was fabricated using the approach. Further, fine-tuning of the structural interaction and mechanical behavior of the GelMA-based hydrogels upon reinforcement with RGO/Mn3O4 nanocomposites was investigated as a function of different concentrations of the nanocomposites where upto 50 % increment in the compressive stress was observed compared to native GelMA hydrogel. The ability of these hydrogels was further investigated for their osteogenic behaviour on MC3T3-E1 preosteoblast cells where constant cell proliferation for up to 10 days was witnessed for the hybrid hydrogel with the highest concentration of the nanofillers.

Effect of entropy evolution on electromagnetic response mechanism of carbon-coated medium- and high-entropy oxides

Metal oxides have attracted much attention due to their potential in electromagnetic wave absorption. However, the inherent energy dissipation capabilities of low-entropy metal oxides pose challenges in designing materials with optimal entropy levels. The regulation of entropy structure is anticipated to facilitate the development of novel electromagnetic functional materials featuring abundant active sites, adjustable specific surface area, stable crystal structure, unique geometric compatibility, and distinctive electronic structure. This study compared the electromagnetic loss performance of low, medium, and high entropy metal oxides in carbon matrices. As entropy increases, the number of phases expands, leading to enhanced interface polarization losses and improved impedance matching. However, further increases in entropy result in performance decline due to lattice distortions and mismatches in dielectric constant and magnetic permeability. Experimental data and theoretical analysis reveal that performance enhancement in medium-to high-entropy metal oxides is attributed to their unique morphology and the synergistic effects of multiple metal components, which enhance interfacial and defect polarization mechanisms. Heterogeneous interfaces and lattice defects provide additional polarization sites, aiding in the conversion of electromagnetic energy into heat. The presence of intermediate phases effectively absorbs and dissipates electromagnetic waves, thereby enhancing the overall absorption capability.