Development Of Functional Materials Research Articles

Biomolecular Fishing: Design, Green Synthesis, and Performance of l-Leucine-Molecularly Imprinted Polymers.

Biopurification is a challenging and growing market. Despite great efforts in the past years, current purification strategies still lack specificity, efficiency, and cost-effectiveness. The development of more sustainable functional materials and processes needs to address pressing environmental goals, efficiency, scale-up, and cost. Herein, l-leucine (LEU)-molecularly imprinted polymers (MIPs), LEU-MIPs, are presented as novel biomolecular fishing polymers for affinity sustainable biopurification. Rational design was performed using quantum mechanics calculations and molecular modeling for selecting the most appropriate monomers. LEU-MIPs were synthesized for the first time by two different green approaches, supercritical carbon dioxide (scCO2) technology and mechanochemistry. A significant imprinting factor of 12 and a binding capacity of 27 mg LEU/g polymer were obtained for the LEU-MIP synthesized in scCO2 using 2-vinylpyridine as a functional monomer, while the LEU-MIP using acrylamide as a functional monomer synthesized by mechanochemistry showed an imprinting factor of 1.4 and a binding capacity of 18 mg LEU/g polymer, both systems operating at a low binding concentration (0.5 mg LEU/mL) under physiological conditions. As expected, at a higher concentration (1.5 mg LEU/mL), the binding capacity was considerably increased. Both green technologies show high potential in obtaining ready-to-use, stable, and low-cost polymers with a molecular recognition ability for target biomolecules, being promising materials for biopurification processes.

Closed-loop recycling and degradation of guaiacol-based epoxy resin and its carbon fiber reinforced composites with S-S exchangeable bonds

The waste and desertion of petroleum-based epoxy resins have attracted increasing concerns on the damage and pollution to the environment because they are difficult to reprocess and reuse after curing. Once broken or injured, the recovery or degradation of composites is a tough challenge owing to their permanently cross-linked networks. In this paper, a novel guaiacol-based epoxy resin (BGF-EP) was prepared from renewable resources instead of conventional petroleum-based bisphenol A, curing with 4-aminophenyl disulfide (AFD). The epoxy vitrimer BGF-EP-AFD had appreciable thermal stability (Tg:143 °C, Td5%:295 °C), sufficient mechanical properties (tensile strength:55.54 MPa, elongation at break:12.23%) and stress relax from 300 min at 130 °C to 27.5 s at 200 °C. And the vitrimer could be reprocessed into a complete film. More excitingly, an efficient strategy was proposed to dissolve the cured resin and recycle its carbon fiber reinforced composites in a closed loop in an appropriate mixing solution (50%DMF/50%β-ME) at room temperature. The recovered carbon fibers are not altered and remain intact for the next utilization as confirmed by SEM. This work contributes the development of guaiacol-based renewable functional materials and provides a feasible and economical way to recycle and reprocess the carbon fiber reinforced epoxy composites.

Pruney Finger-Inspired Switchable Surface with Water-Actuated Dynamic Textures

Switchable surfaces play an important role in the development of functional materials. However, the construction of dynamic surface textures remains challenging due to the complicated structural design and surface patterning. Herein, a pruney finger-inspired switchable surface (PFISS) is developed by constructing water-sensitive surface textures on a polydimethylsiloxane substrate by taking advantage of the hygroscopicity of the inorganic salt filler and the 3D printing technology. Like human fingertips, the PFISS shows high water sensitivity with obvious surface variation in wet and dry states, which is actuated by water absorption-desorption of the hydrotropic inorganic salt filler. Besides, when the fluorescent dye is optionally added into the matrix of the surface texture, water-responsive fluorescent emitting is observed, providing a feasible surface-tracing strategy. The PFISS shows effective regulation of the surface friction and performs a good antislip effect. The reported synthetic strategy for the PFISS offers a facile way for building a wide range of switchable surfaces.

N-Rich Algal Sludge Biochar for Peroxymonosulfate Activation toward Sulfadiazine Removal

The fabrication of a green, high activity and low-cost carbon-based catalyst capable of activating new oxidant (peroxymonosulfate, PMS) for contaminants abatement is needed. In this research, we prepared novel N-doped biochars via one-step pyrolysis of algal sludge without external nitrogen sources. The obtained ASBC800 possessed the largest specific surface area (SBET = 145.596 m2 g−1) and thus it displayed the best catalytic performance, as revealed by the effective elimination of sulfadiazine (SDZ, >95% within 70 min) with 0.2 g L−1 ASBC800 and 0.5 mM PMS. Both radical species (e.g., SO4•−, and •OH), and nonradical regime (1O2 and electron-transfer) contributed to SDZ oxidation, in which ASBC800 played essential roles in activating PMS, accumulating SDZ, and regulating electron shuttle from SDZ to ASBC800-PMS*. Overall, this work not only provides a novel strategy for the synthesis of N-rich and cost-effective biochar but also promotes the development and application of carbon-based functional materials in environmental remediation.

Analyzing the Bolometric Performance of Vanadium Oxide Thin Films Modified by Carbon Nanotube Dispersions

The influence of carbon nanotube (CNT) dispersions on the electrical properties and noise signal amplitude of VOx films is investigated. For a critical range of the CNT dispersion density on VOx films, the intrinsic properties of the VOx films are modified by the CNTs. The CNT concentrations reported in this work are about 0.3 μg/cm2 and 1.6 μg/cm2, allowing for low density and high density dispersions on the VOx film surface to be investigated. These values are higher than the percolation threshold of about 0.12 μg/cm2 for these films. The composite film exhibits a significant reduction in the temperature coefficient of resistance (TCR) (from ≈3.8% K-1 to ≈0.3% K-1) for high density dispersions. In contrast, while VOx-CNT composites with low density single wall CNT dispersions exhibit no significant change in TCR values, an approximate two orders of magnitude reduction in the low frequency 1/f noise is measured. The noise signal amplitude measured at 0.1 V and at 1.0 Hz reduces from 6 × 10-5V/(Hz) for VOx films to 5 × 10-7V/(Hz) for the low density SWCNT dispersion on VOx film and to 3 × 10-6V/(Hz) for the low density MWCNT dispersion on VOx film. The CNT concentration is the critical factor for yielding the observed changes in conductivity and low frequency noise. The results presented in this work provide a better understanding of VOx-based composites, thereby enabling the development of new, versatile and functional materials for device applications.

Advanced materials engineering in historical gypsum plaster formulations

We show how historical gypsum plaster preparation methods affect the microstructure and the wettability properties of the final stucco materials. We reproduced a traditional Persian recipe (Gach-e Koshteh, ~14thcentury AD), which involves a continuous mechanical treatment during plaster hydration. These samples were compared with a laboratory-replicated historical recipe from Renaissance Italy (Gesso Sottile, ~15thcentury AD) and contemporary low-strength plaster. The Koshteh recipe induces the formation of gypsum platelets, which exhibit preferential orientation in the plaster bulk. In contrast, the Italian and low-strength plasters comprise a typical needle-like morphology of gypsum crystals. The platelets in Koshteh expose the more hydrophilic {010} face of gypsum in a much more pronounced manner than needles. Consequently, the Iranian plaster displays enhanced wettability, enabling its direct use for water-based decoration purposes, or as a fine finishing thin layer, without the need of mixing it with a binder material. Contrary, in Sottile, gypsum crystals are left to equilibrate in large excess of water, which promotes the growth of long needles at the expense of smaller crystals. Typically, such needles are several times longer than those found in a control regular plaster. For this crystal habit, the total surface of hydrophilic faces is minimized. Consequently, such plaster layers tend to repel water, which can then be used, e.g., as a substrate for oil-based panel paintings. These findings highlight the development of advanced functional materials, by tuning their microtexture, already during the premodern era.

Enhanced reversible hydrogen storage performance of Mg-decorated g-C2N: First principles calculations

The graphene-like 2D material g-C2N owns superior properties for functional materials development, for instance, its ideal porosity can easily accommodate functional metal atoms, making itself more competitive for energy storage. In this study, density functional theory (DFT) computational studies were employed to solve the electronic structure of Mg-doped g-C2N, and furthermore its potential in hydrogen storage was systematically evaluated. Within our calculations, we found that partial charges of the doped Mg atoms can be successfully transferred to pyridinic N atoms. In one aspect, the Mg atoms can display higher electropositivity, and in another aspect, the N atoms own higher electronegativity. Such a change in electronic structure is favorable to enhance its hydrogen adsorption performance, as the H2 molecules in the vicinity of Mg and N atoms can be easily polarized, and thus the electrostatic attractions can be strengthened. In addition, multiple configurations of the Mg-doped g-C2N with adsorbed H2 molecules were presented also in this study, and we found that each 2 × 2 supercell unit possesses a high gravimetric surface area of 2863 m2/g, and can accommodate at most 44 H2 molecules with the adsorption energies ranging from −0.29 eV to −0.12 eV. With the decoration of Mg, its capacity of hydrogen storage can be as high as 8.03 wt%. The theoretical analysis presented in this study provides important chemical insights for energy materials design, with profound implications for improving the performance of 2D materials’ hydrogen.

Iron Single‐Atom Catalysts on MXenes for Ultrasensitive Monitoring of Adrenal Tumor Markers and Cellular Dopamine

AbstractNeuroblastoma and pheochromocytoma are the most prevalent malignancies of the adrenal medulla. They are currently diagnosed by measuring urinary catecholamines using high‐performance liquid chromatography‐mass spectrometry, which is expensive, bulky, and tedious. Electrochemical detectors stand out as low‐cost alternatives; however, further development of functional materials with adequate sensitivity is still required to attain clinically useful diagnostic devices. Here, Ti3C2Tx MXene nanosheets stabilized with iron single‐atom catalysts (Fe‐SACs), anchored on the surface, are synthesized and utilized as efficient electrocatalysts for the determination of catecholamine (dopamine (DA)) and its end‐products (vanillylmandelic acid (VMA) and homovanillic acid (HVA)). The Fe‐SACs/Ti3C2Tx exhibits low oxidation overpotentials with high signal amplifications up to 610%, 290%, and 420%, and sensitive detection limits of 1.0, 5.0, and 10 nM for DA, VMA, and HVA, respectively. The presence of the atomic Fe elements on the Ti3C2Tx nanosheets is confirmed using high‐resolution scanning transmission electron microscopy and X‐ray photoelectron spectroscopy. The Fe‐SACs/Ti3C2Tx sensor tracks the in situ production of DA in PC12 cells and found practically useful in analyzing human urine samples. The Fe‐SACs/Ti3C2Tx stands out as a sensitive diagnostic platform for evaluating the progression of tumors and the quality of cellular DA communications

Electrostatic Heteroaggregation: Fundamentals and Applications in Interfacial Engineering.

The aggregation of oppositely charged soft materials (particles, surfactants, polyelectrolytes, etc.) that differ in one or more physical or chemical attributes, broadly referred to as electrostatic heteroaggregation, has been an active area of research for several decades now. While electrostatic heteroaggregation (EHA) is relevant to diverse fields such as environmental engineering, food technology, and pharmaceutical formulations, more recently there has been a resurgence to explore various aspects of this phenomenon in the context of interface stabilization and the development of functional materials. In this Feature Article, we provide an overview of the recent contributions of our group to this exciting field with particular emphasis on fundamental studies of electrostatic heteroaggregation between oppositely charged systems in the bulk, at interfaces, and across the bulk/interface. The influence of the size and shape of particles and the surface charge of heteroaggregates on the formation of Pickering emulsions and their utilization in the development of porous ceramics is discussed.

Machine learning and experiments: A synergy for the development of functional materials

Machine learning and experiments: A synergy for the development of functional materials

Stable Organic Radicals Participation in Charge Transfer: A New Strategy toward Molecular Functional Materials.

Charge-transfer (CT) engineering with inter-/intramolecular CT interactions by simple compositions has emerged as a universal and efficient way to construct organic functional materials. Stable organic radicals with unique physicochemical properties that cannot be realized in closed-shell molecules, have been widely demonstrated to be ideal building blocks to construct versatile organic CT materials. This concept article provides a brief overview of the advances in the design, structure and property of stable organic radicals-based CT molecular functional materials, and the strategy for the generation of these materials is also highlighted. First, radicals are introduced as open-shell donors or acceptors, with a focus on their importance and uniqueness in improving electrical, magnetic and optical properties of CT functional materials. Additionally, CT interactions in stable radical dimers and trimers are further discussed systematically. Finally, the challenges are summarized and perspectives for future development of stable organic radicals-based CT functional materials are provided.

Hierarchical Porous Monoliths of Steel with Self-Reinforcing Adaptive Properties.

Porous structures offer an attractive approach to reduce the amount of natural resources used while maintaining relatively high mechanical efficiency. However, for some applications the drop in mechanical properties resulting from the introduction of porosity is too high, which has limited the broader utilization of porous materials in industry. Here, it is shown that steel monoliths can be designed to display high mechanical efficiency and reversible self-reinforcing properties when made with porous architectures with up to three hierarchical levels. Ultralight steel structures that can float on water and autonomously adapt their stiffness are manufactured by the thermal reduction and sintering of 3D printed foam templates. Using distinct mechanical testing techniques, image analysis, and finite element simulations, the mechanisms leading to the high mechanical efficiency and self-stiffening ability of the hierarchical porous monoliths are studied. The design and fabrication of mechanically stable porous monoliths using iron as a widely available natural resource is expected to contribute to the future development of functional materials with a more sustainable footprint.

A CO2-Responsive Imidazole-Functionalized Fluorescent Material Mediates Cancer Chemotherapy.

We present a breakthrough in the synthesis and development of functional gas-responsive materials as highly potent anticancer agents suitable for applications in cancer treatment. Herein, we successfully synthesised a stimuli-responsive multifunctional material (I-R6G) consisting of a carbon dioxide (CO2)-sensitive imidazole moiety and spirolactam-containing conjugated rhodamine 6G (R6G) molecule. The resulting I-R6G is highly hydrophobic and non- or weakly fluorescent. Simple CO2 bubbling treatment induces hydrophobic I-R6G to completely dissolve in water and subsequently form self-assembled nanoparticles, which exhibit unique optical absorption and fluorescence behaviours in water and extremely low haemolytic ability against sheep red blood cells. Reversibility testing indicated that I-R6G undergoes reversible CO2/nitrogen (N2)-dependent stimulation in water, as its structural and physical properties can be reversibly and stably switched by alternating cycles of CO2 and N2 bubbling. Importantly, in vitro cellular assays clearly demonstrated that the CO2-protonated imidazole moiety promotes rapid internalisation of CO2-treated I-R6G into cancer cells, which subsequently induces massive levels of necrotic cell death. In contrast, CO2-treated I-R6G was not internalised and did not affect the viability of normal cells. Therefore, this newly created system may provide an innovative and efficient route to remarkably improve the selectivity, safety and efficacy of cancer treatment.

Cellulose-Chitosan Functional Biocomposites.

Here, we present a detailed review of recent research and achievements in the field of combining two extremely important polysaccharides; namely, cellulose and chitosan. The most important properties of the two polysaccharides are outlined, giving rise to the interest in their combination. We present various structures and forms of composite materials that have been developed recently. Thus, aerogels, hydrogels, films, foams, membranes, fibres, and nanofibres are discussed, alongside the main techniques for their fabrication, such as coextrusion, co-casting, electrospinning, coating, and adsorption. It is shown that the combination of bacterial cellulose with chitosan has recently gained increasing attention. This is particularly attractive, because both are representative of a biopolymer that is biodegradable and friendly to humans and the environment. The rising standard of living and growing environmental awareness are the driving forces for the development of these materials. In this review, we have shown that the field of combining these two extraordinary polysaccharides is an inexhaustible source of ideas and opportunities for the development of advanced functional materials.

Development and Properties of Functional Ceramic-based Photocatalytic Materials

With the rapid development of energy, information, environmental protection and biological science and technology, the material with a long history-ceramics, has also obtained a new research progress, namely, the development of functional ceramics. Functional ceramics play a key role in related scientific research and engineering project applications, with their unique thermal, electric, magnetic, acoustic and optical physical characteristics, chemical, biological and appropriate mechanics characteristics. Moreover, because the photocatalytic technology has the characteristics of mild reaction conditions, convenient operation and no secondary pollution, it is considered as the most promising environmental governance technology in the 21st century, that is, it can effectively solve the problems of fossil energy depletion and environmental pollution. In addition, photocatalytic technology also has the characteristics of low energy consumption, and has also become a necessary technology to develop new energy sources. If functional ceramics and photocatalytic technology are combined together, it will solve many problems in industrial production and life. A variety of materials with photocatalytic characteristics in functional ceramics have been developed. This paper mainly expounds the performance research and its development and application of Ti-based functional ceramic photocatalytic materials, multiple material composite ceramic photocatalytic materials and tungsten-based activated carbon-based ceramic photocatalytic materials.

Dual-Function Detoxifying Nanofabrics against Nerve Agent and Blistering Agent Simulants

The development of functional materials that can detoxify multiple chemical warfare agents (CWAs) at the same time is of great significance to cope with the uncertainty of CWA use in real-world situations. Although many catalysts capable of detoxifying CWAs have been reported, there is still a lack of effective means to integrate these catalytic-active materials on practical fibers/fabrics to achieve effective protection against coexistence of a variety of CWAs. In this work, by a combination of electrospinning and in situ solvothermal reaction, PAN@Zr(OH)4@MOF-808 nanofiber membranes were prepared for detoxification of both nerve agent and blistering agent simulants dimethyl 4-nitrophenyl phosphate (DMNP) and 2-chloroethyl ethyl sulfide (CEES). Under the catalytic effect of the MOF-808 component, DMNP hydrolysis with a half-life as short as 1.19 min was achieved. Meanwhile, an 89.3% CEES removal rate was obtained within 12 h by adsorption and catalysis of MOF-808 and Zr(OH)4 components at ambient conditions, respectively. PAN@Zr(OH)4@MOF-808 nanofiber membranes also showed a superior blocking effect on CEES compared to bare PAN and PAN@Zr(OH)4 nanofiber membranes. Simultaneous protection against DMNP and CEES showed effective inhibition of both simulants for at least 2 h. The preparation method also imparted intrinsically good interfacial adhesion between the components, contributing to the excellent recycling stability of PAN@Zr(OH)4@MOF-808 nanofiber membranes. Therefore, the prepared composite nanofabrics have great application potential, which provides a new idea for the construction of broad-spectrum protective detoxification materials.

Changes in the Electrophysical Parameters of Nanomodified Elastomers Caused by Electric Current’s Passage

The development of reliable and effective functional materials that can be used in various technological fields and environmental conditions is one of the goals of modern nanotechnology. Heating elements' manufacturing requires understanding the laws of heat transfer under conditions of different supply voltages, as this expands the possibilities of such materials' application. Elastomers based on silicon-organic compounds and polyurethane modified with multi-walled carbon nanotubes (MWCNTs) were studied at various concentrations of Ni/MgO or Co-Mo/MgO and voltages (220, 250, and 300 V). It was found that an increase in voltage from 220 to 300 V leads to an initial increase in specific power on one-third followed by a subsequent decrease in a specific power when switched on again to 220 V (for -40 °C) of up to ~44%. In turn, for a polyurethane matrix, an increase in voltage to 300 V leads to an initial peak power value of ~15% and a decrease in power when switched on again by 220 V (for -40 °C) to ~36% (Ni/MgO -MWCNT). The conducted studies have shown that the use of a polyurethane matrix reduces power degradation (associated with voltage surges above 220 V) by 2.59% for Ni/MgO-based MWCNT and by 10.42% for Co-Mo/MgO. This is due to the better heat resistance of polyurethane and the structural features of the polymer and the MWCNT. The current studies allow us to take the next step in the development of functional materials for electric heating and demonstrate the safety of using heaters at a higher voltage of up to 300 V, which does not lead to their ignition, but only causes changes in electrophysical parameters.

The Technique for Manufacturing Flexible Electromagnetic Shields Based on Resistive Materials

The article introduces the technique for manufacturing flexible electromagnetic shields based on resistive materials ( powdered charcoals and sheet foil ), as well as the results of experimental justification of the use prospects of this technique in the development of new functional materials . This justification consisted of : 1) manufacturing of the experimental samples in accordance with the presented technique ; 2) carrying out the measurements of the electromagnetic radiation reflection and transmission coefficient values in the frequency range of 0.7–17.0 GHz of the manufactured experimental samples . It was discovered that flexible electromagnetic shields based on the powdered charcoals manufactured in accordance with the presented technique are characterized by the electromagnetic radiation reflection coefficient values in the frequency range of 0.7–17.0 GHz , reaching –10.0 dB , when electromagnetic radiation reflection coefficient values reach –20.0 dB . Due to this fact it is possible to r ecommend to use them in order to ensure electromagnetic compatibility of radioelectronic equipment and to protect people from exposure to radiation , emitted by such equipment , as well as to hide ground objects from detection in the radar wavelength range .

Non-covalent interactions (NCIs) in π-conjugated functional materials: advances and perspectives.

The design and development of functional materials with real-life applications are highly demanding. Understanding and controlling inter- and intra-molecular interactions provide opportunities to design new materials. A judicious manipulation of the molecular structure significantly alters such interactions and can boost selected properties and functions of the material. There is burgeoning evidence of the beneficial effects of non-covalent interactions (NCIs), showing that manipulating NCIs may generate functional materials with a wide variety of physical properties leading to applications in catalysis, drug delivery, crystal engineering, etc. This prompted us to review the implications of NCIs on the molecular packing, optical properties, and applications of functional π-conjugated materials. To this end, this tutorial review will cover different types of interactions (electrostatic, π-interactions, metallophilic, etc.) and their impact on π-conjugated materials. Attempts have also been made to delineate the effects of weak interactions on opto-electronic (O-E) applications.

Controlled properties of perovskite oxide films by engineering oxygen octahedral rotation

Complex perovskite oxides exhibit extremely rich physical properties in terms of magnetism, electrical transport, and electrical polarization characteristics due to the competition and coupling of many degrees of freedom. The B-site ions and O ions in perovskite form six-coordinated octahedral units, which are connected at a common vertex toward the basic framework of the perovskite oxide, providing a crucial platform to tailor physical properties. The rotation or distortion of the oxygen octahedra will tip the competing balance, leading to many emergent ground states. To further clarify the subtle relationship between emergent properties and oxide octahedral behavior, this article reviews the structure of perovskite oxides, the characterization methods of oxygen octahedral rotation and the response of transport, electrical polarization and magnetism of several typical perovskite heterostructures to oxygen octahedral rotation modes. With knowledge of how to manipulate the octahedral rotation behavior and regulate the physical properties of perovskite oxides, rationally designing the sample manufacturing process can effectively guide the development and application of novel electronic functional materials and devices.