Development Of Functional Materials Research Articles

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.

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.

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.

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.

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.

High-Pressure CO2 and CH4 Transport in Smooth Crystalline Silica Mesopores: A Molecular Dynamics Study.

In this study, we use molecular dynamics (MD) simulation to study pressure-driven CO2 and CH4 flows and their slippage behaviors in β-cristobalite mesopores. The result illustrates that both CO2 and CH4 have an apparent adsorption layer on pore surface. However, significant differences in gas slippage are observed: CH4 flow shows considerable slippage, while it is negligible for CO2 flow. This disparity is attributed to the collective effect of gas molecular configurations and surface structure. The linear molecular structure of CO2 allows it to align perpendicular to the surface, even penetrating into the surface. Notably, the perpendicular orientation of CO2 molecules is energetically favored near the center of the equilateral triangle formed by adjacent oxygen atoms on β-cristobalite surface. Conversely, the symmetric molecular structure of CH4, coupled with its larger size, prevents its penetration into pore surfaces. Therefore, despite smooth crystalline surfaces, CO2 topological accessible plane is much more curved than that of CH4. Consequently, CO2 displays hesitating motions undergoing rotational movements, which significantly hinders its slippage. This study highlights the collective influences of gas molecular characteristics and surface structure on gas slippage, affording important insights into gas sequestration and the development of functional materials for gas separation.

PROFiT-Net: Property-Networking Deep Learning Model for Materials.

There is a growing need to develop artificial intelligence technologies capable of accurately predicting the properties of materials. This necessitates the expansion of material databases beyond the scope of density functional theory, and also the development of deep learning (DL) models that can be effectively trained with a limited amount of high-fidelity data. We developed a DL model utilizing a crystal structure representation based on the orbital field matrix (OFM), which was modified to incorporate information on elemental properties and valence electron configurations. This model, effectively capturing the interrelation between the elemental properties in the crystal, was coined the PRoperty-networking Orbital Field maTrix-convolutional neural Network (PROFiT-Net). Remarkably, PROFiT-Net demonstrated high accuracy in predicting the dielectric constant, experimental band gaps, and formation enthalpies compared with other leading DL models. Moreover, our model accurately identifies physical patterns, such as avoiding the prediction of unphysical negative band gaps and exhibiting a Penn-model-like trend while maintaining the scalability. We envision that PROFiT-Net will accelerate the development of functional materials.

Development of functional materials based on new high content electron withdrawing groups terpolymer composites for potential applications

Development of functional materials based on new high content electron withdrawing groups terpolymer composites for potential applications

1,1'-Biolympicenyl: A Stable Non-Kekulé Diradical with a Small Singlet and Triplet Energy Gap.

Dimerization of delocalized polycyclic hydrocarbon radicals is a simple and versatile method to create diradicals with tailored electronic structures and accessible high-spin states. However, the synthesis is challenging, and the stability issue of the diradicals remains a concern. In this study, we present the synthesis of a stable non-Kekulé 1,1'-biolympicenyl diradical 1 using a protection-oxidation-protection strategy. Diradical 1 demonstrated exceptional stability, with a solution half-life time exceeding 3.5 years and a solid state thermal decomposition temperature above 300 °C. X-ray crystallographic analysis revealed its intersected molecular structure and tightly bound dimer configuration. A singlet ground state with a small singlet-triplet energy gap is consistently identified using electron paramagnetic resonance (EPR) and a superconducting quantum interference device (SQUID) in a rigid matrix, and the triplet state is thermally accessible at room temperature. The solution phase properties were systematically examined through EPR, absorption spectroscopy, and cyclic voltammetry, revealing a rotational motion in the slow-motion regime and multistage redox characteristics. This study presents an efficient synthetic and stabilization strategy for organic diradicals, enabling the development of various high-spin functional materials.

Nonequilibrium relaxation of soft responsive colloids.

Stimuli-responsive macromolecules display large conformational changes during their dynamics, sometimes switching between states. Such a multi-stability is useful for the development of soft functional materials. Here, we introduce a mean-field dynamical density functional theory for a model of responsive colloids to study the nonequilibrium dynamics of a colloidal dispersion in time-dependent external fields, with a focus on the coupling of translational and conformational dynamics during their relaxation. Specifically, we consider soft Gaussian particles with a bimodal size distribution between two confining walls with time-dependent (switching-on and off) external gravitational and osmotic fields. We find a rich relaxation behavior of the systems in excellent agreement with particle-based Brownian dynamics computer simulations. In particular, we find time-asymmetric relaxations of integrated observables (wall pressures, mean size, and liquid center-of-mass) for activation/deactivation of external potentials, respectively, which are tunable by the ratio of translational and conformational diffusion time scales. Our work thus paves the way for studying the nonequilibrium relaxation dynamics of complex soft matter with multiple degrees of freedom and hierarchical relaxations.

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.