Application Of Functional Materials Research Articles

Enhancing Romanian Naval Resilience to Climate Change: Advanced Functional Materials for Green Defence Strategies

Climate change poses a significant threat to European security, implicitly to Romania's naval forces in the Black Sea. Rising sea levels, extreme weather events, and ocean acidification impact maritime operations, infrastructure, and personnel, with potential ramifications for regional stability. This paper explores the implications of climate change for the Romanian Navy and proposes "Green Defence" strategies to enhance resilience and sustainability. These strategies encompass energy efficiency, renewable energy integration, sustainable procurement, and the application of advanced functional materials in naval operations and infrastructure. By adopting a proactive and multifaceted approach, the Romanian Navy can adapt to the changing climate, ensuring operational effectiveness while minimizing environmental impact. This approach aligns with broader European security concerns and contributes to a more sustainable and resilient defence posture in the face of climate-related challenges.

Recent Advances in Smart Sensing Based on Excited‐State Intramolecular Proton‐Transfer (ESIPT)‐Inspired Emitters

The optical materials based on excited state intramolecular proton transfer (ESIPT) have garnered significant attention due to their unique photophysical properties and applications in sensors and imaging agents (probes). These materials exhibit an intrinsic four‐level photocycle scheme through the enol (E)–keto (K) phototautomerization process, resulting in a large Stokes shift, environmental sensitivity, and potential for ratiometric sensing. This review primarily focuses on elucidating the luminescence mechanism and structure‐property relationships of recent ESIPT molecules, as well as exploring the sensing applications of phosphorescent functional materials.

Mechanical Motion and Color Change of Humidity-Responsive Cellulose Nanocrystal Films from Sunflower Pith.

Nanocellulose has prompted extensive exploration of its applications in advanced functional materials, especially humidity-responsive materials. However, the sunflower pith (SP), a unique agricultural by-product with high cellulose and pectin content, is always ignored and wasted. This work applied sulfuric acid hydrolysis and sonication to sunflower pith to obtain nanocellulose and construct film materials with humidity-responsive properties. The SP nanoparticle (SP-NP) suspension could form a transparent film with stacked layers of laminated structure. Due to the tightly layered structure and expansion confinement effect, when humidity increases, the SP-NP film responds rapidly in just 0.5 s and completes a full flipping cycle in 4 s, demonstrating its excellent humidity-responsive capability. After removing hemicellulose and lignin, the SP cellulose nanocrystals (SPC-NC) could self-assemble into a chiral nematic structure in the film, displaying various structural colors based on different sonication times. The color of the SPC-NC film dynamically adjusted with changes in ambient humidity, exhibiting both functionality and aesthetics. This research provides a new perspective on the high-value utilization of sunflower pith while establishing a practical foundation for developing novel responsive cellulose-based materials.

Fabrication of magnetic Cu2O nanocomposites for enhanced iodide removal: Adsorption properties, mechanism and application

The presence of iodine in water poses significant health risks to humans and aquatic ecosystems, necessitating the development of efficient and sustainable remediation strategies. Here, we present Fe3O4/Ti3C2Tx/Cu2O-Cu nanocomposites as high-performance adsorbents for iodide removal. A multistep process was utilized in the fabrication of the nanocomposite, which involved the modification of Fe3O4 nanoparticles with polydopamine (PDA) and the assembly of Ti3C2Tx nanosheets, followed by the growth of Cu2O/Cu nanoparticles. The nanocomposites showed a maximum iodide adsorption capacity of 41.34 mg/g at 25 °C, following quasi second-order adsorption kinetics and the Langmuir adsorption isotherm. A thermodynamic study revealed that the adsorption process was exothermic and spontaneous. Additionally, the nanocomposite displayed excellent selectivity for iodide despite competing anions and retained over 50 % of its adsorption capacity after two washing cycles. A mechanistic investigation indicated that the removal of iodide was primarily due to the formation of insoluble CuI under acidic conditions and surface complexation between Cu2O and iodide under neutral conditions. Owing to its high adsorption capacity, good selectivity, magnetic separability, and reusability, the Fe3O4/Ti3C2Tx/Cu2O-Cu nanocomposite offers great promise for the effective remediation of iodide-contaminated water. This study provides valuable insights into the development and application of advanced functional materials for addressing the critical issue of water pollution due to iodine.

Improvement of dispersants on nano carbon black-modified cement paste: performance, microstructure and carbon footprint

The agglomeration of nano carbon black (NCB), driven by its high specific surface energy, limits the fundamental performance of cementitious materials and hinders the broader application of functional cementitious materials in engineering domains. NCB-modified cement (NC) has a low snow-melting efficiency, resulting in high energy consumption and excessive CO2 emissions. Herein, this study innovatively proposed a method of using dispersants to overcome the above issue and systematically introduced the effects of three dispersants, polycarboxylic acid superplasticizer (PCE), tannic acid (TA), and sodium dodecyl sulfate (SDS), on NC. The dispersity of dispersant-NCB suspension was analyzed firstly, and then the performance of fresh paste, mechanical properties, resistivity, snow-melting speed and LCA of NC were explored. Experimental results indicated that, in terms of suspension stability, SDS was the most effective, followed by TA, while PCE exhibited the least efficacy. Furthermore, all three dispersants improved the fluidity of NC to varying degrees. However, PCE and TA demonstrated a retardation effect on the setting time, whereas SDS facilitated a reduction in the setting time of NC. From the point of view of mechanical properties, the use of these dispersants not only augmented the mechanical strength of the NC but also decreased its electrical resistivity. The uniform dispersion of SDS at the microstructural level of NCB had also been found. When the PCE content is 0.2%, TA content is 0.4%, and SDS content is 0.4%, the mechanical strength and resistivity of NC were the best. NC with dispersant TA melted snow three times faster than the control group, reducing snow-melting energy consumption. Moreover, LCA analysis showed that the addition of dispersants also reduced carbon emissions.

Dynamically Switchable Global Chirality in Racemic Polymer Systems.

Any polymers composed of racemic segments are obviously optically inactive and lack any chiroptical applications. Here, we present an intriguing method for precisely generating global chirality in racemic copolymer assemblies without any external asymmetrical intervention via step-wise polymerization-induced chiral self-assembly (PICSA). Global supramolecular chirality of the nanoaggregates could be dynamically switched by the two diametrically opposed chiral conflict effects: "first come, first serve" effect and "late-comer lives above" effect, which can be controlled by the precisely specified the number and sequence of enantiomeric segments. Significantly, the supramolecular stacking manners of the racemic mesogenic building units as well as the liquid crystallinity of the solvophobic core play a crucial role for the chiral communication pathway of enantiomeric mesogens. Furthermore, such switchable global chirality in racemic polymers is broadly applicable and well regulable. We propose that this research may challenge the notion that racemic systems lack optical activity while highlighting their potential applications in functional racemic polymer materials and providing insights into the evolution of racemates towards homochirality on early Earth.

Dynamically Switchable Global Chirality in Racemic Polymer Systems

Any polymers composed of racemic segments are obviously optically inactive and lack any chiroptical applications. Here, we present an intriguing method for precisely generating global chirality in racemic copolymer assemblies without any external asymmetrical intervention via step‐wise polymerization‐induced chiral self‐assembly (PICSA). Global supramolecular chirality of the nanoaggregates could be dynamically switched by the two diametrically opposed chiral conflict effects: “first come, first serve” effect and “late‐comer lives above” effect, which can be controlled by the precisely specified the number and sequence of enantiomeric segments. Significantly, the supramolecular stacking manners of the racemic mesogenic building units as well as the liquid crystallinity of the solvophobic core play a crucial role for the chiral communication pathway of enantiomeric mesogens. Furthermore, such switchable global chirality in racemic polymers is broadly applicable and well regulable. We propose that this research may challenge the notion that racemic systems lack optical activity while highlighting their potential applications in functional racemic polymer materials and providing insights into the evolution of racemates towards homochirality on early Earth.

Myrrh Oleo‐Gum Resin as a Functional Additive in Pectin and κ‐Carrageenan Composite Films for Food Packaging

ABSTRACTMyrrh oleo‐gum‐resin (MOGR) is a natural substance that has a rich history of medicinal use due to its anti‐inflammatory, antimicrobial, and antioxidant properties. The present study reports on the fabrication and assessment of pectin and K‐carrageenan composite films infused with varying proportions (0.3%, 0.5%, and 0.7%) of MOGR. Morphological analysis of the film samples was conducted using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). The results indicated that the introduction of MOGR led to a notable increase in surface roughness. The SEM micrographs of the films showed that the MOGR addition had an important effect on the microstructure of the film. The surface hydrophobicity of the MOGR‐loaded films increased, as confirmed by the rise in the contact angle. Moreover, there was an increase in the thickness (0.062 ± 0.004–0.095 ± 0.006 mm) and opacity (1.24 ± 0.07–9.41 ± 0.24) of the films with the addition of MOGR; however, tensile strength (7.30 ± 0.50–4.92 ± 0.34 MPa), elongation at break (32.41% ± 1.0%–29.70% ± 0.24%), and barrier properties decreased. Additionally, a rise in MOGR concentration corresponded to a rise in overall color difference ΔE (0.77 ± 0.03–5.09 ± 0.49) of the films. Notably, the incorporation of MOGR led to an increase in the antioxidant activity of the composite films, indicating potential applications in functional packaging materials.

Organic Photoredox-Catalyzed Hydrosilylation of Vinylboronic Esters for the Synthesis of Geminal and Vicinal Borosilanes.

Geminal and vicinal borosilanes have unique applications in functional materials and synthetic transformations. Herein, a convenient method for the synthesis of geminal and vicinal borosilanes is developed via photoredox metal-free hydrosilylation of vinylboronic esters. This strategy features the advantages of high atom economy, environmental friendliness, and excellent functional group compatibility. The mechanism studies reveal that the catalytic reaction goes through photoredox HAT catalysis and a radical addition pathway.

Efficient synthesis of highly hydrophobic lignin nanoparticles and their application as nano fillers for multifunctional composite membranes

Controlling the hydrophobic behaviors of lignin nanoparticles (LNPs) is crucial and advantageous for their application as film Nano Fillers, yet it poses a significant challenge. Herein, we successfully developed a novel method for the preparation of LNPs with highly hydrophobic behaviors using ternary deep eutectic solution (DES)-H2O systems. The resulting LNPs exhibit a significantly reduced content of hydrophilic groups on their outer surface, leading to a zeta potential value of only −4.9 mV, and up to 140.0° of water contact angle (WCA). Afterwards, a “Dissolution-Restructuration” mechanism was proposed to explain the formation of the prepared LNPs. Firstly, DES demonstrates superior H-bonding capabilities, facilitating the complete disruption of inter- and intramolecular H-bonding in lignin, and resulting in the formation of a highly homogenized lignin network. Subsequently, the DES system undergoes compromise after adding water, triggering the reformation of both inter- and intramolecular H-bonding and π-π interactions. Consequently, lignin orderly self-assembles into LNPs with highly hydrophobic characteristics. Especially, using the as-prepared LNPs as Nano fillers, a series of LNPs-containing polyvinyl alcohol (PVA) films were successfully fabricated, exhibiting exceptional hydrophobic behaviors (with contact angles reaching up to 124.0°). Furthermore, the mechanical strength, UV-shielding capabilities, and biodegradability of the PVA films are significantly enhanced. This study introduces a sustainable and efficient approach for the synthesis of hydrophobic LNPs, thereby facilitating the broadening of applications for lignin-based functional composite film materials.

Multi-diagnostic of dust growth in a capacitive Ar/C2H2 plasma

Abstract The interest in the production of nanoparticles (NPs) within Ar/C2H2 reactive plasmas is increasing, driven by their potential applications in functional materials or for their analogy to cosmic dust. The growth process of NPs has been thoroughly examined using a broad array of diagnostic tools. Significant among these tools are those that determine two-dimensional distributions of NP sizes and densities. The inherent complexity of these techniques has resulted in a limited number of works that integrate these measurements with a multitude of other diagnostic tools. Here, we show a multi-diagnostic exploration of the growing process of NPs in Ar/C2H2 plasmas. The combination of in-situ techniques, such as scattered light images, optical emission spectroscopy, light extinction, quadrupole mass signals, or self-bias voltage, with ex-situ scanning electron microscopy images and FTIR spectra of the deposited dust, provides a detailed picture of the growth process. The temporal evolution of plasma parameters, coupled with chemical composition measurements, provides a comprehensive description of the dust growth phases, and the FTIR measurements reveal an appreciable difference in chemical composition between the core and shell of the NPs. Furthermore, employing a method based on the terminal falling velocity of NPs in the afterglow, the intrinsic mass density of NPs is estimated. The asymmetries observed in the spatial distributions of NP size and density are qualitatively discussed in terms of neutral drag, ion drag, and electrostatic forces.

Gold Tripyrrindione: Redox Chemistry and Reactivity with Dichloromethane.

The identification of ligands that stabilize Au(III) centers has led to the isolation of complexes for applications in catalysis, gold-based therapeutics, and functional materials. Herein, we report the coordination of gold by tripyrrin-1,14-dione, a linear tripyrrole with the scaffold of naturally occurring metabolites of porphyrin-based protein cofactors (e.g., heme). Tripyrrindione H3TD2 binds Au(III) as a trianionic tridentate ligand to form square planar complex [Au(TD2)(H2O)], which features an adventitious aqua ligand. Two reversible ligand-based oxidations of this complex allow access to the other known redox states of the tripyrrindione framework. Conversely, (spectro)electrochemical measurements and DFT analysis indicate that the reduction of the complex is likely metal-based. The chemical reduction of [Au(TD2)(H2O)] leads to a reactive species that utilizes dichloromethane in the formation of a cyclometalated organo-Au(III) complex. Both the aqua and the organometallic Au(III) complexes were characterized in the solid state by microcrystal electron diffraction (MicroED) methods, which were critical for the analysis of the microcrystalline sample of the organo-gold species. Overall, this study illustrates the synthesis of Au(III) tripyrrindione as well as its redox profile and reactivity leading to gold alkylation chemistry.

Efficient Synthesis of Metastable Cyclodextrin-Based Polyrotaxanes with Tunable Threading Ratios.

Cyclodextrin-based polyrotaxanes (CD-PRs) are gaining attention for their dynamic sliding rings along the polymer axis, enabling various applications in molecular shuttles, drug delivery, and durable polymers with slidable cross-links. However, the conventional synthesis of CD-PRs with tunable threading ratios is typically laborious, time-consuming, and complicated, which limits their scalability and cost-effectiveness. Herein, we highlight the great potential of planetary centrifugal mixing, a process that significantly accelerates and simplifies the initial synthesis of polypseudorotaxanes (PPRs), followed by a thiol-ene click reaction as an efficient end-capping reaction for the synthesis of PRs. Notably, PRs synthesized with glutathione (GSH) as the end-capping reagent are in a metastable state, where GSH act as a molecular bumper that significantly prevent de-threading of α-CD rings at room temperature. Moreover, the rate of ring de-threading can be precisely controlled by heating, enabling the preparation of metastable PRs with tunable threading ratios over a wide range. The developed strategy is of great significance to the efficient synthesis of CD-PRs, thus marking a significant step towards their practical application in advanced functional materials and devices.

Efficient Synthesis of Metastable Cyclodextrin‐Based Polyrotaxanes with Tunable Threading Ratios

AbstractCyclodextrin‐based polyrotaxanes (CD‐PRs) are gaining attention for their dynamic sliding rings along the polymer axis, enabling various applications in molecular shuttles, drug delivery, and durable polymers with slidable cross‐links. However, the conventional synthesis of CD‐PRs with tunable threading ratios is typically laborious, time‐consuming, and complicated, which limits their scalability and cost‐effectiveness. Herein, we highlight the great potential of planetary centrifugal mixing, a process that significantly accelerates and simplifies the initial synthesis of polypseudorotaxanes (PPRs), followed by a thiol‐ene click reaction as an efficient end‐capping reaction for the synthesis of PRs. Notably, PRs synthesized with glutathione (GSH) as the end‐capping reagent are in a metastable state, where GSH act as a molecular bumper that significantly prevent de‐threading of α‐CD rings at room temperature. Moreover, the rate of ring de‐threading can be precisely controlled by heating, enabling the preparation of metastable PRs with tunable threading ratios over a wide range. The developed strategy is of great significance to the efficient synthesis of CD‐PRs, thus marking a significant step towards their practical application in advanced functional materials and devices.

Methods in molecular photocrystallography.

Over the last three decades, the technology that makes it possible to follow chemical processes in the solid state in real time has grown enormously. These studies have important implications for the design of new functional materials for applications in optoelectronics and sensors. Light-matter interactions are of particular importance, and photocrystallography has proved to be an important tool for studying these interactions. In this technique, the three-dimensional structures of light-activated molecules, in their excited states, are determined using single-crystal X-ray crystallography. With advances in the design of high-power lasers, pulsed LEDs and time-gated X-ray detectors, the increased availability of synchrotron facilities, and most recently, the development of XFELs, it is now possible to determine the structures of molecules with lifetimes ranging from minutes down to picoseconds, within a single crystal, using the photocrystallographic technique. This review discusses the procedures for conducting successful photocrystallographic studies and outlines the different methodologies that have been developed to study structures with specific lifetime ranges. The complexity of the methods required increases considerably as the lifetime of the excited state shortens. The discussion is supported by examples of successful photocrystallographic studies across a range of timescales and emphasises the importance of the use of complementary analytical techniques in order to understand the solid-state processes fully.

Enhanced luminol chemiluminescence with oxidase-like properties of prussian blue/MXene nanocomposite without H2O2 for the sensitive detection of uric acid

Novel two-dimensional MXene materials as low-cost carriers have received increasing attention in the development of nanozymes with peroxidase or oxidase-like activities. In this study, the novel materials combining Prussian blue and MXene (referred to as PB/MXene) were proposed by a facile method. In this case, MXene acted as reducing agent and nanocarrier. Compared with the single component, the obtained nanocomposites had excellent oxidase activity without foreign oxidant intervention such as hydrogen peroxide (H2O2). Furthermore, the addition of uric acid (UA) solution was able to directly burst the chemiluminescence (CL) intensity of the constructed PB/MXene-luminol platform. Based on the above process, we developed PB/MXene nanocomposites with oxidase activity as the CL biosensors for detecting UA, displaying good linearity with UA concentration (0.2–30 μM) and low detection limit (0.19 μM). This work not only provided novel biosensors for the detection of UA but also significantly expanded the potential applications of MXene-based functional materials in the fields of biological monitoring and clinical diagnosis.

High-entropy non-covalent cyclic peptide glass.

Biomolecule-based non-covalent glasses are biocompatible and biodegradable, and offer a sustainable alternative to conventional glass. Cyclic peptides (CPs) can serve as promising glass formers owing to their structural rigidity and resistance to enzymatic degradation. However, their potent crystallization tendency hinders their potential in glass construction. Here we engineered a series of CP glasses with tunable glass transition behaviours by modulating the conformational complexity of CP clusters. By incorporating multicomponent CPs, the formation of high-entropy CP glass is facilitated, which-in turn-inhibits the crystallization of individual CPs. The high-entropy CP glass demonstrates enhanced mechanical properties and enzyme tolerance compared with individual CP glass and a unique biorecycling capability that is unattainable by traditional glasses. These findings provide a promising paradigm for the design and development of stable non-covalent glasses based on naturally derived biomolecules, and advance their application in pharmaceutical formulations and smart functional materials.

Design, synthesis, and characterization of a novel pH-responsive azo dye incorporating a 1,3,4-thiadiazole ring for advanced textile applications

This study presents the synthesis and comprehensive characterization of a novel azo dye derived from 2-(5-amino-1,3,4-thiadiazol-2-yl) phenol (1a). The synthesis was initiated by reacting salicylic acid with thiosemicarbazide in the presence of phosphorus oxychloride (POCl3), yielding an 89 % conversion to compound 1a. The subsequent diazotization and coupling of 1a under alkaline conditions led to the formation of the azo dye (1b). Structural elucidation was confirmed through Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. The incorporation of the 1,3,4-thiadiazole ring is significant due to its known influence on enhancing dye stability, reactivity, and potential biological activities, while the salicylic acid moiety contributes to the dye's pH responsiveness. A notable pH-dependent color transition from yellow (pH < 6.0) to red (pH > 8.0) was observed, driven by protonation-induced resonance changes. Computational studies, including Frontier Molecular Orbital (FMO) analysis, revealed a Highest Occupied Molecular Orbital (HOMO)-Lowest Unoccupied Molecular Orbital (LUMO) gap of 1.94 eV, indicating efficient electronic transitions critical for its color properties. Molecular Electrostatic Potential (MEP) and Fukui function analyses provided further insights into the dye's reactivity and potential applications. The dyeing properties were rigorously assessed through K/S values, CIELAB color space, and fastness properties on cotton fabric, demonstrating varied color depths and hues influenced by different mordants, with copper and manganese significantly enhancing color intensity. Colorfastness tests revealed good to fair durability, with untreated fabrics showing optimal performance. This thorough characterization underscores the promising potential of this newly synthesized azo dye for applications in pH-responsive textiles and functional materials, highlighting its relevance for advanced textile and material science applications.

The Differential Impact of Resorcinarenes on Ferrocene Redox Couple: Towards Electroactive Host-Guest Systems

Alternative to complex labelling of resorcinarene hosts with redox-active probes, non-covalent complex formation offers a unique avenue towards the design of dynamic electro-active host-guest systems towards application in sensors and functional materials. Here, resorcinarene hosts were evaluated with a well-known redox probe, ferrocene (Fc). Specifically, hosts were designed based on tuning the resorcinarene rim with functional groups to allow for hydrogen bonding, pi-pi stacking, hydrophobic and electrostatic interactions. Cyclic voltammetry was used with glassy carbon electrode as a working electrode in organic solvent to evaluate interactions between hosts and Fc. Specifically, the electrochemical properties of Fc, hosts, and host-Fc mixtures were evaluated with respect to the ferrocene/ferrocenium redox couple (reversibility, current and potential). Depending on the host structure, all hosts induced a potential shift of ferrocene/ferrocenium redox couple. The reversibility of the redox couple was maintained with certain hosts, while others resulted in surface fouling. The electrochemical studies were further supplemented by non-electrochemical methods, such as nuclear magnetic resonance, spectroscopy, mass spectrometry as well as theoretical calculations using density functional theory. Data show that controlled and tunable redox host-guest systems with well-defined redox properties may be achieved through chemical modifications of hosts, which may be used to inform functional sensors and devices with a wide range of applications such as phosphate analogue detection.

Achieving high geometric fidelity in vat photopolymerization additive manufacturing through liquid surface support

The top-down vat photopolymerization (VPP) printing process, known for its extensive material adaptability and elimination of the release step between the printed object and the separation film, is widely used in 3D printing of advanced functional materials. However, for slurries that cannot achieve rapid self-leveling, edge morphology distortion in printed objects reduces geometric precision. This study investigated the issue of edge morphology distortion in the top-down VPP printing process, and proposes a liquid surface support (LSS) printing method that can be applied to general VPP printers. The results show that the protective slurry fence printed simultaneously with the object can provide excellent liquid surface support for the uncured layer above the printed object, which shifts the edge morphology distortion issue from the target object to the fence. The gap distance between the fence and the target sample is identified as the primary factor affecting edge morphology fidelity, which is influenced by surface tension. Finally, we successfully validated the application of the LSS printing method in the printing of ceramic dental prostheses and slender rod structures. This novel method significantly enhances the geometric precision of printed samples and is expected to promote the advancement of VPP printing applications for advanced functional materials.