Reinforcement learning for in silico determination of adsorbate-substrate structures.

Reinforcement learning (RL) methods have helped to define the state of the art in the field of modern artificial intelligence, mostly after the breakthrough involving AlphaGo and the discovery of novel algorithms. In this work, we present a RL method, based on Q-learning, for the structural determination of adsorbate@substrate models in silico, where the minimization of the energy landscape resulting from adsorbate interactions with a substrate is made by actions on states (translations and rotations) chosen from an agent's policy. The proposed RL method is implemented in an early version of the reinforcement learning software for materials design and discovery (RLMaterial), developed in Python3.x. RLMaterial interfaces with deMon2k, DFTB+, ORCA, and Quantum Espresso codes to compute the adsorbate@substrate energies. The RL method was applied for the structural determination of (i) the amino acid glycine and (ii) 2-amino-acetaldehyde, both interacting with a boron nitride (BN) monolayer, (iii) host-guest interactions between phenylboronic acid and ß-cyclodextrin and (iv) ammonia on naphthalene. Density functional tight binding calculations were used to build the complex search surfaces with a reasonably low computational cost for systems (i)-(iii) and DFT for system (iv). Artificial neural network and gradient boosting regression techniques were employed to approximate the Q-matrix or Q-table for better decision making (policy) on next actions. Finally, we have developed a transfer-learning protocol within the RL framework that allows learning from one chemical system and transferring the experience to another, as well as from different DFT or DFTB levels.

Aerogels based on Bacterial Nanocellulose and their Applications.

Microbial cellulose stands out for its exceptional characteristics in the form of biofilms formed by highly interlocked fibrils, namely, bacterial nanocellulose (BNC). Concurrently, bio-based aerogels are finding uses in innovative materials owing to their lightweight, high surface area, physical, mechanical, and thermal properties. In particular, bio-based aerogels based on BNC offer significant opportunities as alternatives to synthetic or mineral counterparts. BNC aerogels are proposed for diverse applications, ranging from sensors to medical devices, as well as thermal and electroactive systems. Due to the fibrous nanostructure of BNC and the micro-porosity of BNC aerogels, these materials enable the creation of tailored and specialized designs. Herein, a comprehensive review of BNC-based aerogels, their attributes, hierarchical, and multiscale features are provided. Their potential across various disciplines is highlighted, emphasizing their biocompatibility and suitability for physical and chemical modification. BNC aerogels are shown as feasible options to advance material science and foster sustainable solutions through biotechnology.

The Role of Extracellular Vesicles in the Treatment of Prostate Cancer.

Prostate cancer (PCa) has become a public health concern in elderly men due to an ever-increasing number of estimated cases. Unfortunately, the available treatments are unsatisfactory because of a lack of a durable response, especially in advanced disease states. Extracellular vesicles (EVs) are lipid-bilayer encircled nanoscale vesicles that carry numerous biomolecules (e.g., nucleic acids, proteins, and lipids), mediating the transfer of information. The past decade has witnessed a wide range of EV applications in both diagnostics and therapeutics. First, EV-based non-invasive liquid biopsies provide biomarkers in various clinical scenarios to guide treatment; EVs can facilitate the grading and staging of patients for appropriate treatment selection. Second, EVs play a pivotal role in pathophysiological processes via intercellular communication. Targeting key molecules involved in EV-mediated tumor progression (e.g., proliferation, angiogenesis, metastasis, immune escape, and drug resistance) is a potential approach for curbing PCa. Third, EVs are promising drug carriers. Naïve EVs from various sources and engineered EV-based drug delivery systems have paved the way for the development of new treatment modalities. This review discusses the recent advancements in the application of EV therapies and highlights EV-based functional materials as novel interventions for PCa.

Elucidating Structural Disorder in Ultra-Thin Bi-Rich Bismuth Oxyhalide Photocatalysts.

Advancing the field of photocatalysis requires the elucidation of structural properties that underpin the photocatalytic properties of promising materials. The focus of the present study is layered, Bi-rich bismuth oxyhalides, which are widely studied for photocatalytic applications yet poorly structurally understood, due to high levels of disorder, nano-sized domains, and the large number of structurally similar compounds. By connecting insights from multiple scattering techniques, utilizing electron-, X-ray- and neutron probes, the crystal phase of the synthesized materials is allocated as layered Bi24O31X10 (X = Cl, Br), albeit with significant deviation from the reported 3D crystalline model. The materials comprise anisotropic platelet-shaped crystalline domains, exhibiting significant in-plane ordering in two dimensions but disorder and an ultra-thin morphology in the layer stacking direction. Increased synthesis pH tailored larger, more ordered crystalline domains, leading to longer excited state lifetimes determined via femtosecond transient absorption spectroscopy (fs-TAS). Although this likely contributes to improved photocatalytic properties, assessed via the photooxidation of benzylamine, increasing the overall surface area facilitated the most significant improvement in photocatalytic performance. This study, therefore, enabled both phase allocation and a nuanced discussion of the structure-property relationship for complicated, ultra-thin photocatalysts.

Glycerol as Reaction Medium for Sonogashira Couplings: A Green Approach for the Synthesis of New Triarylamine-Based Materials with Potential Application in Optoelectronics.

This study focuses on the design, eco-friendly synthesis, and characterization of several novel three-legged triphenylamine derivatives. By performing Sonogashira couplings of functionalized aryl iodides with tris(4-ethynylphenyl)amine in glycerol, a readily available bio-derived solvent, we achieved the synthesis of target products in short times and high yields, up to 94%, with consistently lower E-factors and reduced costs compared to standard conditions using toluene as the reaction medium. The target molecules possess a D-(π-A)3 or D-(π-D)3 structure, where an electron-donating core connects to three electron-donating (D) or electron-accepting (A) peripheral aromatic subunits through an acetylene spacer. Their main optical and electronic properties have been determined experimentally and by DFT simulations and suggest a possible implementation in energy conversion technologies such as luminescent solar concentrators (LSCs) and perovskite solar cells (PSCs).

Nano-enabled smart and functional materials toward human well-being and sustainable developments.

Fabrication and operation on increasingly smaller dimensions have been highly integrated with the development of smart and functional materials, which are key to many technological innovations to meet economic and societal needs. Along with researchers worldwide, the Waterloo Institute for Nanotechnology (WIN) has long realized the synergetic interplays between nanotechnology and functional materials and designated 'Smart & Functional Materials' as one of its four major research themes. Thus far, WIN researchers have utilized the properties of smart polymers, nanoparticles, and nanocomposites to develop active materials, membranes, films, adhesives, coatings, and devices with novel and improved properties and capabilities. In this review article, we aim to highlight some of the recent developments on the subject, including our own research and key research literature, in the context of the UN Sustainability development goals.

Functional Semi-Interpenetrating Polymer Networks.

Semi-interpenetrating polymer networks (SIPNs) have garnered significant interest due to their potential applications in self-healing materials, drug delivery systems, electrolytes, functional membranes, smart gels and, toughing. SIPNs combine the characteristics of physical cross-linking with advantageous chemical properties, offering broad application prospects in materials science and engineering. This perspective introduces the history of semi-interpenetrating polymer networks and their diverse applications. Additionally, the ongoing challenges associated with traditional semi-interpenetrating polymer materials are discussed and provide an outlook on future advancements in novel functional SIPNs.

Shape Memory Polyurethane Composite With Fast Response to Near-Infrared Light Based on Tannic Acid-Iron and Dynamic Phenol-Carbamate Network.

Intelligent materials derived from green and renewable bio-based materials garner widespread attention recently. Herein, shape memory polyurethane composite (PUTA/Fe) with fast response to near-infrared (NIR) light is successfully prepared by introducing Fe3+ into the tannic acid-based polyurethane (PUTA) matrix through coordination between Fe3+ and tannic acid. The results show that the excellent NIR light response ability is due to the even distribution of Fe3+ filler with good photo-thermal conversion ability. With the increase of Fe3+ content, the NIR light response shape recovery rate of PUTA/Fe composite films is significantly improved, and the shape recovery time is reduced from over 60 s to 40 s. In addition, the mechanical properties of PUTA/Fe composite film are also improved. Importantly, owing to the dynamic phenol-carbamate network within the polymer matrix, the PUTA/Fe composite film can reshape its permanent shape through topological rearrangement and show its good NIR light response shape memory performance. Therefore, PUTA/Fe composites with high content of bio-based material (TA content of 15.1-19.4%) demonstrate the shape memory characteristics of fast response to NIR light; so, it will have great potential in the application of new intelligent materials including efficient and environmentally friendly smart photothermal responder.

Xanthan: enzymatic degradation and novel perspectives of applications.

The extracellular heteropolysaccharide xanthan, synthesized by bacteria of the genus Xanthomonas, is widely used as a thickening and stabilizing agent across the food, cosmetic, and pharmaceutical sectors. Expanding the scope of its application, current efforts target the use of xanthan to develop innovative functional materials and products, such as edible films, eco-friendly oil surfactants, and biocompatible composites for tissue engineering. Xanthan-derived oligosaccharides are useful as nutritional supplements and plant defense elicitors. Development and processing of such new functional materials and products often necessitate tuning of xanthan properties through targeted structural modification. This task can be effectively carried out with the help of xanthan-specific enzymes. However, the complex molecular structure and intricate conformational behavior of xanthan create problems with its enzymatic hydrolysis or modification. This review summarizes and analyzes data concerning xanthan-degrading enzymes originating from microorganisms and microbial consortia, with a particular focus on the dependence of enzymatic activity on the structure and conformation of xanthan. Through a comparative study of xanthan-degrading pathways found within various bacterial classes, different microbial enzyme systems for xanthan utilization have been identified. The characterization of these new enzymes opens new perspectives for modifying xanthan structure and developing innovative xanthan-based applications. KEY POINTS: • The structure and conformation of xanthan affect enzymatic degradation. • Microorganisms use diverse multienzyme systems for xanthan degradation. • Xanthan-specific enzymes can be used to develop xanthan variants for novel applications.

Strengthening nitrogen removal of rural wastewater treatment in humus biochemical system under low dissolved oxygen conditions: Sludge and microbial characteristics.

To achieve efficient and cost-effective treatment for the rural wastewater, a novel humus biochemical system (HBS) process derived from humus bio-functional material was proposed to treat rural wastewater under low dissolved oxygen (DO) conditions, and the operational performance, sludge characteristics, and microbial community in HBS were systematically investigated in this study. The results indicated that the HBS reactor could be operated stably under low DO levels of 0.2-0.8 mg/L, and maintained high removal efficiencies of 96.4%, 96.0%, and 88.2% for chemical oxygen demand, ammonia nitrogen, and total nitrogen, with corresponding effluent concentrations of 11.0, 1.7, and 5.1 mg/L, respectively. The sludge produced from HBS was characterized by relatively large particle size, complex structural morphology, and abundant humic substances, which favorably improved the system stability. Illumina sequencing demonstrated that HBS reactor possessed high microbial abundance and diversity and was enriched with plenty of nitrifying and denitrifying bacteria, which synergistically intensified the whole biological nitrogen removal process in this system. The study presented the feasibility and adaptability of HBS for energy-efficient rural wastewater treatment.

Recent Advances in Functional Materials for Optical Data Storage.

In the current data age, the fundamental research related to optical applications has been rapidly developed. Countless new-born materials equipped with distinct optical properties have been widely explored, exhibiting tremendous values in practical applications. The optical data storage technique is one of the most significant topics of the optical applications, which is considered as the prominent solution for conquering the challenge of the explosive increase in mass data, to achieve the long-life, low-energy, and super high-capacity data storage. On this basis, our review outlines the representative reports for mainly introducing the functional systems based on the newly established materials applied in the optical storage field. According to the material categories, the representative functional systems are divided into rare-earth doped nanoparticles, graphene, and diarylethene. In terms of the difference of structural features and delicate properties among the three materials, the application in optical storage is comprehensively illustrated in the review. Meanwhile, the potential opportunities and critical challenges of optical storage are also discussed in detail.

Recent Advances in Polymer Nanocomposites: Unveiling the Frontier of Shape Memory and Self-Healing Properties-A Comprehensive Review.

Shape memory and self-healing polymer nanocomposites have attracted considerable attention due to their modifiable properties and promising applications. The incorporation of nanomaterials (polypyrrole, carboxyl methyl cellulose, carbon nanotubes, titania nanotubes, graphene, graphene oxide, mesoporous silica) into these polymers has significantly enhanced their performance, opening up new avenues for diverse applications. The self-healing capability in polymer nanocomposites depends on several factors, including heat, quadruple hydrogen bonding, π-π stacking, Diels-Alder reactions, and metal-ligand coordination, which collectively govern the interactions within the composite materials. Among possible interactions, only quadruple hydrogen bonding between composite constituents has been shown to be effective in facilitating self-healing at approximately room temperature. Conversely, thermo-responsive self-healing and shape memory polymer nanocomposites require elevated temperatures to initiate the healing and recovery processes. Thermo-responsive (TRSMPs), light-actuated, magnetically actuated, and Electrically actuated Shape Memory Polymer Nanocomposite are discussed. This paper provides a comprehensive overview of the different types of interactions involved in SMP and SHP nanocomposites and examines their behavior at both room temperature and elevated temperature conditions, along with their biomedical applications. Among many applications of SMPs, special attention has been given to biomedical (drug delivery, orthodontics, tissue engineering, orthopedics, endovascular surgery), aerospace (hinges, space deployable structures, morphing aircrafts), textile (breathable fabrics, reinforced fabrics, self-healing electromagnetic interference shielding fabrics), sensor, electrical (triboelectric nanogenerators, information energy storage devices), electronic, paint and self-healing coating, and construction material (polymer cement composites) applications.

Optimization of cultivar, germination time and extraction for radish sprout extract with high sulforaphene content.

BACKGROUND: Cruciferous vegetable sprout has been highlighted as a promising functional material rich in bioactive compounds called isothiocyanates (ITCs) and it can be grown in very short periods in controlled indoor farms. However, because ITCs content depends on multiple factors such as cultivar, germination time and myrosinase activity, those variables need to be controlled during germination or extraction to produce functional materials enriched in ITCs. Sulforaphene (SFEN), an ITC found primarily in radishes (Raphanus sativus L.), exerts beneficial effects on obesity. However, the optimal germination and extraction conditions for radish sprout (RSP) to increase SFEN content remain unascertained, and the extract's anti-obesity effect has yet to be evaluated. RESULTS: The present study found that the SFEN content was highest in purple radish sprout (PRSP) among the six cultivars investigated. Optimal SFEN content occurred after 2 days of PRSP germination (2 days PRSP). To maximize the dry matter yield, total ITCs and SFEN contents in RSP extract, we found the optimal conditions for extracting PRSP [27.5 °C, 60 min, 1:75.52 solute/solvent (w/v), no ascorbic acid] using response surface methodology. Consistent with high SFEN content, 2 days PRSP extract significantly outperformed 3 days or 4 days PRSP extract in inhibiting lipid accumulation in 3T3-L1 cells. Moreover, 2 days PRSP extract suppressed adipogenesis and lipogenesis-related protein expression. CONCLUSION: Regarding the cultivar, germination time and extraction conditions, optimally produced PRSP extract contains high SFEN content and exerts anti-obesity effects. Thus, we suggest PRSP extract as a potent functional material for obesity prevention. © 2024 Society of Chemical Industry.

Aldol Condensation for the Construction of Organic Functional Materials.

Aldol condensation is a cost-effective and sustainable synthetic method, offering the advantages of low complexity, substrate universality, and high efficiency. Over the past decade, it has become popular for creating next-generation organic functional materials, particularly rigid-rod conjugated (semi)conductors. This review focuses on conjugated small molecules, oligomers, and polymeric (semi)conductors synthesized through aldol condensation, with emphasis on their remarkable features in advancing n-type organic field-effect transistors (OFETs), organic electrochemical transistors (OECTs), organic photovoltaics (OPVs), and organic thermoelectrics (OTEs) as well as NIR-II photothermal conversion. Coherence character, optical properties, microstructure, and chain conformation are investigated to understand material-property relationships. Future applications and challenges in this area are also discussed.

Spontaneous Symmetry Breaking of Achiral Molecules Leading to the Formation of Homochiral Superstructures that Exhibit Mechanoluminescence.

Chirality, with its intrinsic symmetry-breaking feature, is frequently utilized in the creation of acentric crystalline functional materials that exhibit intriguing optoelectronic properties. On the other hand, the development of chiral crystals from achiral molecules offers a solution that bypasses the need for enantiopure motifs, presenting a promising alternative and thereby expanding the possibilities of the self-assembly toolkit. Nevertheless, the rational design of achiral molecules that prefer spontaneous symmetry breaking during crystallization has so far been obscure. In this study, we present a series of six achiral molecules, demonstrating that when these conformationally flexible molecules adopt a cis-conformation and engage in multiple non-covalent interactions along a helical path, they collectively self-assemble into chiral superstructures consisting of single-handed supramolecular columns. When these homochiral supramolecular columns align in parallel, they form polar crystals that exhibit intense luminescence upon grinding or scraping. We therefore demonstrate our molecular design strategy could significantly increase the likelihood of symmetry breaking in achiral molecular synthons during self-assembly, offering a facile access to novel chiral crystalline materials with unique optoelectronic properties.

High-Throughput Exploration of Triple-Cation Perovskites via All-in-One Compositionally-Graded Films.

Many devices heavily rely on combinatorial material optimization. However, new material alloys are classically developed by studying only a fraction of giant chemical space, while many intermediate compositions remain unmade in light of the lack of methods to synthesize gapless material libraries. Here report a high-throughput all-in-one material platform to obtain and study compositionally-tunable alloys from solution is reported. This strategy is applied to make all Csx MAy FAz PbI3 perovskite alloys (MA and FA stand for methylammonium and formamidinium, respectively), in less than 10 min, on a single film, on which 520 unique alloys are then studied. Through stability mapping of all these alloys in air supersaturated with moisture, a range of targeted perovskites are found, which are then chosen to make efficient and stable solar cells in relaxed fabrication conditions, in ambient air. This all-in-one platform provides access to an unprecedented library of compositional space with no unmade alloys, and hence aids in a comprehensive accelerated discovery of efficient energy materials.

Photomechanical Laser Fragmentation of IrO2 Microparticles for the Synthesis of Active and Redox-Sensitive Colloidal Nanoclusters.

Pulsed laser fragmentation of microparticles (MPs) in liquid is a synthesis method for producing high-purity nanoparticles (NPs) from virtually any material. Compared with laser ablation in liquids (LAL), the use of MPs enables a fully continuous, single-step synthesis of colloidal NPs. Although having been employed in several studies, neither the fragmentation mechanism nor the efficiency or scalability have been described. Starting from time-resolved investigations of the single-pulse fragmentation of single IrO2 MPs in water, the contribution of stress-mediated processes to the fragmentation mechanism is highlighted. Single-pulse, multiparticle fragmentation is then performed in a continuously operated liquid jet. Here, 2 nm-sized nanoclusters (NCs) accompanied by larger fragments with sizes ranging between several ten nm and several µm are generated. For the nanosized product, an unprecedented efficiency of up to 18 µg J-1 is reached, which exceeds comparable values reported for high-power LAL by one order of magnitude. The generated NCs exhibit high catalytic activity and stability in oxygen evolution reactions while simultaneously expressing a redox-sensitive fluorescence, thus rendering them promising candidates in electrocatalytic sensing. The provided insights will pave the way for laser fragmentation of MPs to become a versatile, scalable yet simple technique for nanomaterial design and development.

Poly(Vinyl Ketones): New Directions in Photodegradable Polymers.

Poly(vinyl ketones) (PVKs) have received considerable attention over the past few decades due to their unique photochemistry and photodegradation properties under ultraviolet (UV) light. Many PVKs rapidly undergo photodegradation under UV light. The side-chain carbonyl moieties of PVKs permit photolysis through Norrish type I or Norrish type II reaction mechanisms and can also be readily modified by nucleophilic addition reactions. These unique properties lead to this class of polymers serving as versatile scaffolds for generating functional materials. This review captures the evolution of synthetic routes to access well-defined PVKs, along with their photochemistry and photo-degradation pathways, and discusses recent and potential applications of these photodegradable materials.

Carbon-Carbon Linked Organic Frameworks: An Explicit Summary and Analysis.

Organic frameworks with carbon-carbon (CC) linkage are an important class of materials owing to their outstanding chemical stability and extended π-electron delocalization resulting in unique optoelectronic properties. In the first part of this review article, the design principles for the bottom-up synthesis of 2D and 3D sp/sp2 CC linked organic frameworks are summarized. Representative reaction methodologies, such as Knoevenagel condensation, Aldol condensation, Horner-Wadsworth-Emmons reaction, Wittig reaction, and coupling reactions (Ullmann, Suzuki, Heck, Yamamoto, etc.) are included. This is discussed in the context of their reaction mechanism, reaction dynamics, and whether and why resulting in an amorphous or crystalline product. This is followed by a discussion of different state-of-the art bottom-up synthesis methodologies, like solvothermal, interfacial, and solid-state synthesis. In the second part, the structure-property relationships in CC linked organic frameworks with representative examples of organocatalysis, photo(electro)catalysis, energy storage and conversion, magnetism, and molecular storage and separation are analyzed. The importance of linkage type, building blocks, topology, and crystallinity of the framework material in connection with the structure-property relationship is highlighted. Finally, brief concluding remarks are presented based on the key development of bottom-up synthetic methods and provide perspectives for future development in this field.

Piezotronic Antimony Sulphoiodide/Polyvinylidene Composite for Strain-Sensing and Energy-Harvesting Applications.

This study investigates the piezoelectric and piezotronic properties of a novel composite material comprising polyvinylidene fluoride (PVDF) and antimony sulphoiodide (SbSI) nanowires. The material preparation method is detailed, showcasing its simplicity and reproducibility. The material's electrical resistivity, piezoelectric response, and energy-harvesting capabilities are systematically analyzed under various deflection conditions and excitation frequencies. The piezoelectric response is characterized by the generation of charge carriers in the material due to mechanical strain, resulting in voltage output. The fundamental phenomena of charge generation, along with their influence on the material's resistivity, are proposed. Dynamic strain testing reveals the composite's potential as a piezoelectric nanogenerator (PENG), converting mechanical energy into electrical energy. Comparative analyses highlight the composite's power density advantages, thereby demonstrating its potential for energy-harvesting applications. This research provides insights into the interplay between piezoelectric and piezotronic phenomena in nanocomposites and their applicability in energy-harvesting devices.