Development Of Functional Materials Research Articles

Microcomputed Tomography for the Microstructure Evaluation of 3D Bioprinted Scaffolds.

This study implemented the application of microcomputed tomography (micro-CT) as a characterization technique for the study and investigation of the microstructure of 3D scaffold structures produced via three-dimensional bioprinting (3DBP). The study focused on the preparation, characterization, and cytotoxicity analysis of gold nanoparticles (Au-NPs) incorporated into 3DBP hydrogels for micro-CT evaluation. The Au-NPs were characterized by using various techniques, including UV-vis spectrometry, dynamic light scattering (DLS), zeta potential measurement, and transmission electron microscopy (TEM). The characterization results confirmed the successful coating of the Au-NPs with 2 kDa methoxy-PEG and revealed their spherical shape with a mean core diameter of 66 nm. Cytotoxicity analysis using live-dead fluorescent microscopy indicated that all tested Au-NP solutions were nontoxic to AC16 cardiomyocytes in both 2D and 3D culture conditions. Scanning electron microscopy (SEM) showed distinguishable differences in image contrast and intensity between samples with and without Au-NPs, with high concentrations of Au-NPs displaying nanoparticle aggregates. Micro-CT imaging demonstrated that scaffolds containing Au-NPs depicted enhanced imaging resolution and quality, allowing for visualization of the microstructure. The 3D reconstruction of scaffold structures from micro-CT imaging using Dragonfly software further supported the improved visualization. Mechanical analysis revealed that the addition of Au-NPs enhanced the mechanical properties of acellular scaffolds, including their elastic moduli and complex viscosity, but the presence of cells led to biodegradation and reduced mechanical strength. These findings highlight the successful preparation and characterization of Au-NPs, their nontoxic nature in both 2D and 3D culture conditions, their influence on imaging quality, and the impact on the mechanical properties of 3D-printed hydrogels. These results contribute to the development of functional and biocompatible materials for tissue engineering and regenerative medicine applications.

Boron-Nitrogen Lewis Pairs in the Assembly of Supramolecular Macrocycles, Molecular Cages, Polymers, and 3D Materials.

Covering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B-N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2 and acetylene, and soft polymer networks that serve as recyclable, self-healing, and responsive thermosets, gels and elastomeric materials.

Boron‐Nitrogen Lewis Pairs in the Assembly of Supramolecular Macrocycles, Molecular Cages, Polymers, and 3D Materials

AbstractCovering an exceptionally wide range of bond strengths, the dynamic nature and facile tunability of dative B−N bonds is highly attractive when it comes to the assembly of supramolecular polymers and materials. This Minireview offers an overview of advances in the development of functional materials where Lewis pairs (LPs) play a key role in their assembly and critically influence their properties. Specifically, we describe the reversible assembly of linear polymers with interesting optical, electronic and catalytic properties, discrete macrocycles and molecular cages that take up diverse guest molecules and undergo structural changes triggered by external stimuli, covalent organic frameworks (COFs) with intriguing interlocked structures that can embed and separate gases such as CO2 and acetylene, and soft polymer networks that serve as recyclable, self‐healing, and responsive thermosets, gels and elastomeric materials.

Research and application of biomimetic modified ceramics and ceramic composites: A review

AbstractCeramic materials are widely used in engineering field because of their good physical and chemical properties. The poor mechanical properties of traditional ceramics seriously limit the development of ceramic materials and have attracted extensive attention since its birth. The development of high toughness, light weight, and functional ceramic materials has long been the pursuit of materials scientists. Since ancient times, nature has been the source of all kinds of human technological ideas, engineering principles, and major inventions. The functional structure of biology provides a good research object for the bionic design and preparation of ceramic materials. Therefore, it is necessary to summarize the functional structures and mechanisms in nature and biomimetic preparation technology. The purpose of this review is to provide guidance for the functionalized biomimetic design and efficient preparation of ceramic materials. Some typical functional examples in nature are introduced in detail, and several representative biomimetic preparation methods are listed. Finally, the performance and application status of biomimetic ceramics are summarized, and the future development direction of biomimetic ceramic materials is prospected.

Recent progress in the synthesis of natural product inspired bioactive glycohybrids

Carbohydrates are a basic structural component that are indispensable to all cellular processes. In addition to being employed as chiral starting materials in the synthesis of a variety of natural products, carbohydrates are recognized as naturally occurring molecules having an enormous variety of functional, stereochemical, and structural properties. The understanding and biological roles of carbohydrate derived molecules can be greatly improved by selectively synthesizing functional carbohydrates through incorporating them with privileged scaffolds. For a deeper understanding of their roles and the development of functional materials based on sugar, it is crucial to develop new techniques for efficiently synthesizing, functionalizing, and modifying carbohydrates. Glycohybrids have a wide range of structural and functional characteristics along with protein-carbohydrate interactions that are crucial to mammalian biology and a number of disease states. This review, consisting the literature from January 2017 to July 2023 and provide an overview of recent developments in the chemical synthesis of glycohybrids based on natural product scaffolds of coumarin, quinolone, naphthalene diimide, indole, isatin, naphthoquinone, imidazole and pyrimidine. The biological activity of active glycohybrids are discussed in this review.

Disease Diagnosis with Chemosensing, Artificial Intelligence, and Prospective Contributions of Nanoarchitectonics

In modern materials research, nanotechnology will play a game-changing role, with nanoarchitectonics as an overarching integrator of the field and artificial intelligence hastening its progress as a super-accelerator. We would like to discuss how this schema can be utilized in the context of specific applications, with exemplification using disease diagnosis. In this paper, we focus on early, noninvasive disease diagnosis as a target application. In particular, recent trends in chemosensing in the detection of cancer and Parkinson’s disease are reviewed. The concept has been gaining traction as dynamic volatile metabolite profiles have been increasingly associated with disease onset, making them promising diagnostic tools in early stages of disease. We also discuss advances in nanoarchitectonic chemosensors, which are theoretically ideal form factors for diagnostic chemosensing devices. Last but not least, we shine the spotlight on the rise to prominence and emergent contributions of artificial intelligence (AI) in recent works, which have elucidated a strong synergy between chemosensing and AI. The powerful combination of nanoarchitectonic chemosensors and AI could challenge our current notions of disease diagnosis. Disease diagnosis and detection of emerging viruses are important challenges facing society. The parallel development of advanced functional materials for sensing is necessary to support and enable AI methodologies in making technological leaps in applications. The material and structural formative technologies of nanoarchitectonics are critical in meeting these challenges.

High-Entropy Oxides in the Mullite-Type Structure.

High-entropy materials (HEMs) represent a new class of solid solutions containing at least five different elements. Their compositional diversity makes them promising as platforms for the development of functional materials. We synthesized new HEMs in a mullite-type structure and present five compounds, i.e., Bi2(Al0.25Ga0.25Fe0.25Mn0.25)4O9 and A2Mn4O10 with variations of A = Nd, Sm, Y, Er, Eu, Ce, and Bi, demonstrating the vast accessible composition space. By combining scattering, microscopy, and spectroscopy techniques, we show that our materials are mixed solid solutions. Remarkably, when following their crystallization in situ using X-ray diffraction and X-ray absorption spectroscopy, we find that the HEMs form through a metastable amorphous phase without the formation of any crystalline intermediates. We expect that our synthesis is excellently suited to synthesizing diverse HEMs and therefore will have a significant impact on their future exploration.

Preparation of Strong and Thermally Conductive, Spider Silk-Inspired, Soybean Protein-Based Adhesive for Thermally Conductive Wood-Based Composites.

The development of formaldehyde-free functional wood composite materials through the preparation of strong and multifunctional soybean protein adhesives to replace formaldehyde-based resins is an important research area. However, ensuring the bonding performance of soybean protein adhesive while simultaneously developing thermally conductive adhesive and its corresponding wood composites is challenging. Taking inspiration from the microphase separation structure of spider silk, boron nitride (BN) and soy protein isolate (SPI) were mixed by ball milling to obtain a BN@SPI matrix and combined with the self-synthesized hyperbranched reactive substrates as amorphous region reinforcer and cross-linker triglycidylamine to prepare strong and thermally conductive soybean protein adhesive with cross-linked microphase separation structure. These findings indicate that mechanical ball milling can be employed to strip BN followed by combination with SPI, resulting in a tight bonded interface connection. Subsequently, the adhesive's dry and wet shear strengths increased by 14.3% and 90.5% to 1.83 and 1.05 MPa, respectively. The resultant adhesive also possesses a good thermal conductivity (0.363 W/mK). Impressively, because hot-pressing helps the resultant adhesive to establish a thermal conduction pathway, the thermal conductivity of the resulting wood-based composite is 10 times higher than that of the SPI adhesive, which shows a thermal conductivity similar to that of ceramic tile and has excellent potential for developing biothermal conductivity materials, geothermal floors, and energy storage materials. Moreover, the adhesive possessed effective flame retardancy (limit oxygen index = 36.5%) and mildew resistance (>50 days). This bionic design represents an efficient technique for developing multifunctional biomass adhesives and composites.

Nanostructured CFO@SiN-DICP-DHDA as a novel reversible magnetic gelator for the fast and effective oil–water separation: Toluene optimization by CCD approach

In the present work, a novel approach has been described for the synthesis of a durable and recyclable functionalized nanomagnetic gelator namely CoFe2O4@SiO2-NH2-1-5 di isocyanatopentane- di Hexadecylamine (CFO@SiN-DICP-DHDA). The nanocomposite was then used for efficient oil/diesel separation from water, a combination of organic solvents and oil that has rarely applied. CFO@SN-DICP-DHDA was characterized using various techniques, including Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), Vibrating sample magnetometer (VSM), X-ray diffraction (XRD), and inverted microscopic and differential scanning calorimetry (DSC). The successful gelation of the oil leads to facile isolation of the gelator by an external magnetic field. Due to the remarkable oil separation capability, as well as the great mechanical and chemical stability of CFO@SiN-DICP-DHDA, it can tightly bind the organic and inorganic layers on the CoFe2O4 nanoparticles. The gelator demonstrates reproducible application for up to seven consecutive cycles without a significant reduction in performance. These outstanding results will pave the way for the removal of oil stains from water and the development of functional super magnetic gel materials. The initial maximum toluene uptake of ∼58 % was boosted to approximately ∼97.65 % through optimization using the central composite design (CCD) approach.

A comprehensive study of Bi2Sr2Co2Oy misfit layered oxide as a supercapacitor electrode material

Recently, the development of multiple functional energy storage materials having high energy storage capacity, expanded stability, and cost-effectiveness with eco-friendly nature is primary choice. Bi2Sr2Co2Oy (BSC-222) is misfit-layered oxide having significant thermoelectric (TE) capability with high temperature stability and eco-friendly characteristics. In present work, we successfully synthesized misfit layered BSC-222 oxide by using sol–gel method. X-ray diffraction, scanning electron microscopy, and atomic force microscopy are used to describe the structure and morphology of calcined BSC-222. Average thickness of prepared oxide sheets was found to be ∼30 to ∼40 nm. By using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) in 3 M KOH, the electrochemical analysis of produced BSC-222 electrodes was carried out. The CV and GCD analysis showed that the BSC-222 oxide having high secondary cobaltite phases has better charge storage capacity (166.6C × g−1) at 2 mVs−1 and majorly charge is stored through diffusion-controlled charge storage mechanism. A chemical reactions schematic is proposed for the charge storage mechanism. Moreover, this calcined BSC-222 exhibits better cycling stability of 68.8 % up to 5000 GCD cycles at 1.5 Ag−1 current density. Hence, BSC-222 misfit layered oxide demonstrates that it has capability to store charge with its good TE ability. This present work provides the first step towards utilizing good TE misfit layered materials even after some doping or modulation in their structure to fabricate high energy density energy storage devices with multifunctional characteristics.

Alginate-based gel beads with bigel structures: Preparation, characterization and bioactive encapsulation

The current study developed novel gel beads with bigel structures based on alginate hydrogel and glycerol monostearate oleogel. Bigel beads with different structures were prepared by varying oleogel content, and the beads were also used to co-encapsulate lipophilic and hydrophilic biaoctives. All the beads had high sphericity (>0.94), and the bead size was increased with the increase in oleogel content. Beads with higher content of oleogel had lower shrinking rates and higher level of oil filling the gel pores. The oil droplets were generally acting as inactive fillers in the gel beads, as the mechanical strength (Young's modulus and hardness) was declining with the increase in oleogel content, and no interaction between the oleogel and hydrogel was detected by FTIR. Swelling studies revealed that beads in salt solution at higher temperature had higher swelling ratio, and the increase in oleogel content could inhibit the swelling. The bigel beads were able to encapsulate EGCG and curcumin simultaneously, and beads with higher oleogel content generally had lower encapsulation efficiency of EGCG but higher efficiency of curcumin. The gel structures provided good protection for curcumin, and about 70% of the original curcumin was retained after a 40-day storage test. The study provided novel information regarding the structure-function relationship of the bigel beads, which could be useful for the development of functional food materials.

Oxidation Driven Thin‐Film Solid‐State Metal Dealloying Forming Bicontinuous Nanostructures

AbstractSolid‐state metal dealloying (SSMD) is a promising method for fabricating nanoscale metallic composites and nanoporous metals across a range of materials. Thin‐film SSMD is particularly attractive due to its ability to create fine features via solid‐state interfacial reactions within a thin‐film geometry, which can be integrated into devices for various applications. This work examines a new dealloying couple, namely the Nb–Al alloy with the dealloying agent Sc, as previously predicted in the machine‐learning (ML) models. Prior ML predictions aimed to guide the design of nanoarchitectured materials through dealloying, relying on intuition‐driven discovery within a large parameter space. However, this work reveals that at the nanoscale, the involvement of oxygen in thin film processing may instead drive the dealloying process, resulting in the formation of bicontinuous nanostructures similar to those formed by metal‐agent dealloying. The phase evolution, as well as chemical and morphological changes, are closely analyzed using a combination of X‐ray absorption spectroscopy, diffraction, and scanning transmission electron microscopy to understand the mechanisms behind nanostructure formation. The findings suggest a potential pathway for utilizing oxygen to drive the formation of bicontinuous metal–metal oxide nanocomposites, paving the way for further development of functional nanoporous materials in diverse fields.

Design of hollow copper nanospheres/reduced graphene oxide nanocomposites for high performance catalytic reduction of p-nitrophenol

The development of functional materials for catalysis applications is a continuing issue, particularly in aqueous-phase catalysis. The creation of inexpensive catalysts with improved catalytic activity is still difficult. In this study, the hollow structured Cu nanospheres decorated on the reduced graphene oxide sheets (h-CuNS/rGO) nanocomposites were successfully prepared and applied in the catalytic reduction of p-nitrophenol (p-NP) in water using sodium borohydride as the reducing agent to obtain industrially useful p-aminophenol (p-AP) within a short time. The structure and morphology of h-CuNS/rGO were studied in order to get a full knowledge of the mechanism underlying the creation of its distinctive hollow structure. In the reduction of p-NP, the h-CuNS/rGO demonstrated significant catalytic activity and reusability. The catalytic hydrogenation mechanism on the surface of h-CuNS/rGO was shown to exhibit a synergistic effect between the catalytic h-CuNS and the supporting rGO. The hollow structure, abundant oxygen vacancies as well as the supported rGO worked together to enhance the catalytic activity during p-NP reduction. Therefore, this work proposes a strategy for the simple synthesis of nanocatalyst with high catalytic performance, which endows the potential applications including catalysis.

Inorganic hydrogels: synthetic strategies, properties and applications

Abstract Hydrogels are widely used in various areas of human life. The vast majority of hydrogel materials used are polymer-based. Despite a number of advantages compared to polymer-based materials, studies on inorganic hydrogels are very limited and scattered. They are rarely offered as a basis for development of new functional materials. This review is an attempt to draw attention of researches to inorganic hydrogels. It describes currently existing methods for the synthesis of such hydrogels, their properties, and shows possible applications of the hydrogel materials.

Ru(OAc)3-Catalyzed Regioselective Difunctionalization of Alkynes: Access to (E)-2-Bromo-1-alkenyl Sulfonates.

A new approach is proposed for the divergent and regioselective synthesis of (E)-2-bromo-1-phenylvinyl trifluoromethanesulfonates through alkyne difunctionalization by employing a compatible system of abundantly available alkynes, N-bromosuccinimide (NBS), and trimethylsilyl trifluoromethanesulfonate (TMSOTf) catalyzed by ruthenium(III) acetate [Ru(OAc)3]. It is a novel method for the preparation of vinyl triflate and it offers a fundamental basis for the development of advanced functional compounds, including drugs and organic functional materials. Unlike previously reported methods, the proposed protocol can tolerate a broad range of functional groups. Alkynes derived from bioactive molecules, such as l(-)-borneol, demonstrate the potential value of this new reaction in organic synthesis.

Organocatalytic Si-CAryl Bond Functionalization-Enabled Atroposelective Synthesis of Axially Chiral Biaryl Siloxanes.

Chiral organosilanes are valuable chemical entities in the development of functional organic materials, asymmetric catalysis, and medicinal chemistry. As an important strategy for constructing chiral organosilanes, the asymmetric functionalization of the Si-CAryl bond typically relies on transition-metal catalysis. Herein, we present an efficient method for atroposelective synthesis of biaryl siloxane atropisomers via organocatalytic Si-C bond functionalization of dinaphthosiloles with silanol nucleophiles. The reaction proceeds through an asymmetric protonation and simultaneous Si-C bond cleavage/silanolysis sequence in the presence of a newly developed chiral Brønsted acid catalyst. The versatile nature of the Si-C bond streamlines the derivatization of axially chiral products into other functional atropisomers, thereby expanding the applicability of this method.

2D N-doped layered mesoporous carbon sheets for high-performance electrochemical hydrogen storage

The rapid growth in energy demands and environmental concerns have drawn great attention to the development of new functional materials for sustainable energy technologies. As an emerging material, mesoporous carbon-based materials exhibit unique properties and have been considered promising candidates for electrochemical hydrogen storage applications. However, pure mesoporous carbon as electrode material may suffer from sluggish electrolyte transportation kinetic and poor hydrophilicity. Two-dimensional layered structure with high exposure area and nitrogen doping, which provides the improved accessibility of ions as well as the hydrophilicity of carbon materials, can cope with these two challenges. Here, the nitrogen-doped layered mesoporous carbon sheets, prepared by the double-hard-template route, were characterized using various technologies and investigated the electrochemically stored hydrogen energy properties. The results exhibit that hydrogen storage can be achieved around 104 mAh g−1 at 100 mA g−1, and the capacity retention was 85.4% at 2 A g−1. Moreover, it also displays superior cycling stability with a retention of 98% upon 300 cycles. According to the obtained results, the layered mesoporous carbon sheets demonstrated suitable capacity as a potential and promising active material for hydrogen-proton-related devices.

Polymer-Enabled Assembly of Au Nanoclusters with Luminescence Enhancement and Macroscopic Chirality.

The construction of macroscopic chiral luminescent aggregates with well-defined structures not only contributes to the development of functional materials but also has significant implications for analyzing chiral transfer and amplification in biological systems and self-assembly systems. Meanwhile, achieving water-soluble chiral metal nanoclusters (NCs) with high photoluminescence (PL) intensity through a convenient method remains a challenge. Herein, we reported the enhanced luminescence of gold nanoclusters stabilized by D-/L-penicillamine (D-/L-AuNCs) induced by poly(allylamine hydrochloride) (PAH) through supramolecular self-assembly strategies. FT-IR spectra and zeta potential measurements revealed that supramolecular assembly was driven by the synergistic effect of hydrogen bonds and electrostatic interactions, which effectively limited the intramolecular vibration and rotation of the ligand and reduced nonradiative relaxation, thus improving the luminescence properties of nanoclusters. Interestingly, during the slow solvent evaporation process, chiral entanglement of assemblies was enhanced, forming macroscopic wheat-shaped superstructures. This study enriches the understanding of the self-assembly mechanism of nanoclusters and provides a pathway for constructing NC-based chiroptical materials.

Challenges and interventions in developing instructional materials: Perspectives of public school teachers in basic education

This study aimed to explore the challenges faced by public school teachers in Bauko District II in developing instructional materials. The researchers used a quantitative method and distributed questionnaires to 150 teachers across the district as their primary means of data collection. This method allowed the researchers to gain insights from a substantial number of teachers, facilitating a comprehensive understanding of the challenges they faced. The results of the study highlighted two primary critical issues faced by teachers: the scarcity of time due to heavy workloads and the difficulty of keeping pace with technological advancements. Additionally, teachers reported significant challenges related to insufficient skills, knowledge and understanding of instructional materials, limited policy support and inadequate administrative assistance. In accordance with these findings, the study demonstrated some significant ways to improve the creation of instructional materials in rural communities with limited resources. The study emphasised the need for computer literacy training as a result of the expanding digitalization of instructional content. A functional instructional material development committee should be established to improve the process as well as organizing training workshops for instructional material development and encouraging partnerships with higher education institutions (HEIs) to gain access to specialized expertise. The study strongly advocates for the implementation of sustainable capacity-building mechanisms by the department of education such as regular workshops and follow-up sessions to provide continuous support to teachers in material development. Moreover, the study proposed fostering collaboration with other institutions and inviting experts as resource persons to seminars and workshops to enhance teachers' proficiency in crafting effective instructional materials.

Tunable Band Engineering Management on Perovskite MAPbBr3 /COFs Nano-Heterostructures for Efficient S-S Coupling Reactions.

Efficient artificial photosynthesis of disulfide bonds holds promises to facilitate reverse decoding of genetic codes and deciphering the secrets of protein multilevel folding, as well as the development of life science and advanced functional materials. However, the incumbent synthesis strategies encounter separation challenges arising from leaving groups in the ─S─S─ coupling reaction. In this study, according to the reaction mechanism of free-radical-triggered ─S─S─ coupling, light-driven heterojunction functional photocatalysts are tailored and constructed, enabling them to efficiently generate free radicals and trigger the coupling reaction. Specifically, perovskites and covalent organic frameworks (COFs) are screened out as target materials due to their superior light-harvesting and photoelectronic properties, as well as flexible and tunable band structure. The in situ assembled Z-scheme heterojunction MAPB-M-COF (MAPbBr3 = MAPB, MA+ = CH3 NH2 + ) demonstrates a perfect trade-off between quantum efficiency and redox chemical potential via band engineering management. The MAPB-M-COF achieves a 100% ─S─S─ coupling yield with a record photoquantum efficiency of 11.50% and outstanding cycling stability, rivaling all the incumbent similar reaction systems. It highlights the effectiveness and superiority of application-oriented band engineering management in designing efficient multifunctional photocatalysts. This study demonstrates a concept-to-proof research methodology for the development of various integrated heterojunction semiconductors for light-driven chemical reaction and energy conversion.