Development Of Functional Materials Research Articles

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; they are key to many technological innovations to meet economic and societal needs. Along with many 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.

2D Exfoliation Chemistry Towards Covalent Pseudo‐Layered Phosphate Framework Derived by Radical/Strain‐Synergistical Process

2D compounds exfoliated from weakly bonded bulk materials with van der Waals (vdW) interaction are easily accessible. However, the strong internal ionic/covalent bonding of most inorganic crystal frameworks greatly hinders 2D material exfoliation. Herein, we first proposed a radical/strain‐synergistic strategy to exfoliate non‐vdW interacting pseudo‐layered phosphate framework. Specifically, hydroxyl radicals (•OH) distort the covalent bond irreversibly, meanwhile, H2O molecules as solvents, further accelerating interlayered ionic bond breakage but mechanical expansion. The innovative 2D laminar NASICON‐type Na3V2(PO4)2O2F crystal, exfoliated by •OH/H2O synergistic strategy, exhibits enhanced sodium‐ion storage capacity, high‐rate performance (85.7 mA h g‐1 at 20 C), cyclic life (2300 cycles), and ion migration rates, compared with the bulk framework. Importantly, this chemical/physical dual driving technique realized the effective exfoliation for strongly coupled pseudo‐layered frameworks, which accelerates 2D functional material development.

Orchestrated Octuple C–H Activation: A Bottom‐Up Topology Engineering Approach toward Stimuli‐Responsive Double‐Heptagon‐Embedded Wavy Polycyclic Heteroaromatics

Curiosity‐driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties and thereby the development of novel functional organic materials. This work presents such an innovative synthetic concept of a bottom‐up molecular topology engineering through a unique orchestrated octuple C–H activation reaction, toward the rapid synthesis of a novel class of double heptagon‐incorporated nitrogen‐doped laterally‐fused polycyclic compounds with rarely reported wavy structural configuration. The profound impact of the molecular wavy structures of these compounds on their properties is manifested by weak and tunable solid‐state intermolecular interactions controlling the electronic properties of the materials, leading to reversibly switchable fluorochromism in the solid state and thin films with mechanical force and solvent vapors as external stimuli, thereby indicating their potential applicability in rewritable fluorescent optical recording media, security papers, mechanosensors, volatile organic compound (VOC) sensors etc.

Orchestrated Octuple C-H Activation: A Bottom-Up Topology Engineering Approach toward Stimuli-Responsive Double-Heptagon-Embedded Wavy Polycyclic Heteroaromatics.

Curiosity-driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties and thereby the development of novel functional organic materials. This work presents such an innovative synthetic concept of a bottom-up molecular topology engineering through a unique orchestrated octuple C-H activation reaction, toward the rapid synthesis of a novel class of double heptagon-incorporated nitrogen-doped laterally-fused polycyclic compounds with rarely reported wavy structural configuration. The profound impact of the molecular wavy structures of these compounds on their properties is manifested by weak and tunable solid-state intermolecular interactions controlling the electronic properties of the materials, leading to reversibly switchable fluorochromism in the solid state and thin films with mechanical force and solvent vapors as external stimuli, thereby indicating their potential applicability in rewritable fluorescent optical recording media, security papers, mechanosensors, volatile organic compound (VOC) sensors etc.

Interactions of Melanin with Electromagnetic Radiation: From Fundamentals to Applications.

Melanin, especially integumentary melanin, interacts in numerous ways with electromagnetic radiation, leading to a set of critical functions, including radiation protection, UV-protection, pigmentary and structural color productions, and thermoregulation. By harnessing these functions, melanin and melanin-like materials can be widely applied to diverse applications with extraordinary performance. Here we provide a unified overview of the melanin family (all melanin and melanin-like materials) and their interactions with the complete electromagnetic radiation spectrum (X-ray, Gamma-ray, UV, visible, near-infrared), which until now has been absent from the literature and is needed to establish a solid fundamental base to facilitate their future investigation and development. We begin by discussing the chemistries and morphologies of both natural and artificial melanin, then the fundamentals of melanin-radiation interactions, and finally the exciting new developments in high-performance melanin-based functional materials that exploit these interactions. This Review provides both a comprehensive overview and a discussion of future perspectives for each subfield of melanin that will help direct the future development of melanin from both fundamental and applied perspectives.

An ambipolar PEDOT-perfluorinated porphyrin electropolymer: application as an active material in energy storage systems.

The development of functional organic materials is crucial for the advancement of various fields, such as optoelectronics, energy storage, sensing, and biomedicine. In this context, we successfully prepared a stable ambipolar perfluoroporphyrin-based polymeric film by electrochemical synthesis. Our strategy involved the synthesis of a novel tetra-pentafluorophenyl porphyrin covalently linked to four 3,4-ethylenedioxythiophene (EDOT) moieties. The resulting monomer, EDOT-TPPF16, was obtained through a straightforward synthetic approach with a good overall yield. The unique molecular structure of EDOT-TPPF16 serves a dual function, with EDOT moieties allowing electropolymerization for polymeric film formation, while the electron-acceptor porphyrin core enables electrochemical reduction and electron transport. The electrochemical polymerization permits the polymer (PEDOT-TPPF16) synthesis and film formation in a reproducible and controllable manner in one step at room temperature. Spectroelectrochemical experiments confirmed that the porphyrin retained its optoelectronic properties within the polymeric matrix after the electrochemical polymerization. The obtained polymeric material exhibited stable redox capabilities. Current charge-discharge cycles and electrochemical impedance spectroscopy of the electrochemically generated organic film demonstrated that the polymer could be applied as a promising active material in the development of supercapacitor energy storage devices.

Design and Synthesis of Electrocatalysts Base on Catalysis‐Unit Engineering

AbstractIt is a pressing need to develop new energy materials to address the existing energy crisis. However, screening optimal targets out of thousands of materials candidates remains a great challenge. Herein, we propose and validate an alternative concept for highly effective materials screening based on dual‐atom salphen catalysis units. Such an approach simplifies the design of catalytic materials and reforms the trial‐and‐error experimental model into a building‐blocks‐assembly like process. Firstly, density functional theory (DFT) calculations were performed on a series of potential catalysis units which were possible to synthesize. Then, machine learning (ML) was employed to define the structure‐performance relationship and acquire chemical insights. Afterwards, the projected catalysis units were integrated into covalent organic frameworks (COFs) to validate the concept Electrochemical tests confirm that Ni‐SalphenCOF and Co‐SalphenCOF are promising conductive agent‐free oxygen evolution reaction (OER) catalysts. This work provides a fast‐tracked strategy for design and development of functional materials, which serves as a potentially workable framework for seamlessly integrating DFT calculations, ML, and experimental approaches.This article is protected by copyright. All rights reserved

Hierarchical Self-Assembly of Multidimensional Functional Materials from Sequence-Defined Peptoids.

Hierarchical self-assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular-level understanding of the hierarchical assembly of sequence-defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron-based powder X-ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence-defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Hierarchical Self‐Assembly of Multidimensional Functional Materials from Sequence‐Defined Peptoids

AbstractHierarchical self‐assembly represents a powerful strategy for the fabrication of functional materials across various length scales. However, achieving precise formation of functional hierarchical assemblies remains a significant challenge and requires a profound understanding of molecular assembly interactions. In this study, we present a molecular‐level understanding of the hierarchical assembly of sequence‐defined peptoids into multidimensional functional materials, including twisted nanotube bundles serving as a highly efficient artificial light harvesting system. By employing synchrotron‐based powder X‐ray diffraction and analyzing single crystal structures of model compounds, we elucidated the molecular packing and mechanisms underlying the assembly of peptoids into multidimensional nanostructures. Our findings demonstrate that incorporating aromatic functional groups, such as tetraphenyl ethylene (TPE), at the termini of assembling peptoid sequences promotes the formation of twisted bundles of nanotubes and nanosheets, thus enabling the creation of a highly efficient artificial light harvesting system. This research exemplifies the potential of leveraging sequence‐defined synthetic polymers to translate microscopic molecular structures into macroscopic assemblies. It holds promise for the development of functional materials with precisely controlled hierarchical structures and designed functions.

Development of Stable Water-Soluble Supratomic Silver Clusters Utilizing A Polyoxoniobate-Protected Strategy: Giant Core-Shell-Type Ag8@Nb162 Fluorescent Nanocluster.

Atomically precise low-nuclearity (n<10) silver nanoclusters (AgNCs) have garnered significant interest due to their size-dependent optical properties and diverse applications. However, their synthesis has remained challenging, primarily due to their inherent instability. The present study introduces a new feasible approach for clustering silver ions utilizing highly negative and redox-inert polyoxoniobates (PONbs) as all-inorganic ligands. This strategy not only enables the creation of novel Ag-PONb composite nanoclusters but also facilitates the synthesis of stable low-nuclearity AgNCs. Using this method, we have successfully synthesized a small octanuclear rhombic [Ag8]6+ AgNC stabilized by six highly negative [LiNb27O75]14- polyoxoanions. This marks the first PONb-protected superatomic AgNC, designated as {Ag8@(LiNb27O75)6} (Ag8@Nb162), with an aesthetically spherical core-shell structure. The crystalline Ag8@Nb162 is stable under ambient conditions, What's more, it is water-soluble and able to maintain its molecular cluster structure intact in water. Further, the stable small [Ag8]6+ AgNC has interesting temperature- and pH-dependent reversible fluorescence response, based on which a multiple optical encryption mode for anti-counterfeit technology was demonstrated. This work offers a promising avenue for the synthesis of fascinating and stable PONb-protected AgNCs and sheds light on the development of new-type optical functional materials.

Unraveling the Defect‐Induced Spectral Tuning in a Ce‐Doped Garnet Solid‐Solution Phosphor

Unraveling the Defect‐Induced Spectral Tuning in a Ce‐Doped Garnet Solid‐Solution Phosphor

Nature-Inspired Helicoidal Nanocellulose-Based Multi-Compartment Assemblies with Tunable Chiroptical Properties.

Cellulose-based nanocomposites are highly appealing for the development of next-generation sustainable functional materials. Although many advances have been made in this direction, the true potential of fibrillar nanocomposites has yet to be realized because available fabrication approaches are inadequate for achieving precise structural control at the sub-micrometer scale. Here a spray-assisted alignment methodology of cellulose nanofibrils is combined with the layer-by-layer assembly into an additive manufacturing process in which the alignment direction of each cellulose layer is rationally selected to achieve thin films with a helicoidal arrangement of the nanofibrils. The helicoidal structure of the films is verified by measuring the circular dichroism (CD) of the samples. The sign and position of the structural CD peak show that the handedness and the pitch of the chiral structures can be easily tuned by deliberately selecting simple parameters, such as the number of consecutive cellulose layers sprayed in the same direction, and the angle of rotation between successive stacks of layers. To the authors' knowledge, this approach is unique as it offers the possibility to prepare complex nanocomposite architectures with various nanoscale-controlled sub-structures from different anisometric objects, which is enabling novel designs of composite films with damage-resistant and/or optical filtering functionalities.

Recent advances in optical fiber grating sensors for detection of organic substances

The continuous development of society has led to the flourishing of environmental chemistry and biomedical fields, as well as to the research and development of novel functional materials and sensors. Some novel materials have excellent optical and biological/chemical properties and can be coupled with the optical fiber grating. The coupling between the materials and optical fiber grating can improve the performance due to the advanced materials can amplify the changing signals generated during the reaction with analytes of organic compounds. Despite the great achievements in the development of bio- and chemical-optical fiber grating sensors, there is no publicly available systematic review of the recent advances in the use of materials combined with optical fiber grating in organic substances sensing available in the literature since January 2016.Thus, we summarized the sensing principles of the bio- and chemical-optical fiber grating with and without surface plasmon resonance. We discussed the performance parameters such as sensitivity, selectivity, detection range, and low limit of detection for detection of organic substances including organic pollutants, life organics (glucose, hemoglobin, cancer markers, antibody-antigen, biotin and streptavidin, DNA, enzymes), microorganisms, and other organic substances. We analyzed the advantages and limitations of optical fiber grating sensors and presented challenges in their practical applications and future research directions.

Understanding self-assembly mechanisms in supramolecular fiber materials through multiscale simulation

Supramolecular materials, assembled through non-covalent interactions, have emerged as a versatile and tunable platform for the development of advanced functional materials with tailored properties and applications. However, comprehending the interactions between self-assembled monomers at the molecular level, particularly when organized into fibrous structures, remains a considerable challenge. In this study, we discovered that solely relying on all-atomistic molecular dynamics simulations is insufficient to reproduce the self-assembly process and the formation of fibrous supramolecular structures. Thus, we combined dissipative particle dynamics (DPD) and all-atomistic molecular dynamic simulations to accurately simulate the fibrous supramolecular structures previously observed in experiments. These structures consist of benzene-1,3,5-tricarboxamide (BTA-EG4), 2-ureido-4 [1H]-pyrimidinone-ethylene glycol molecules (UPy-EG), and glycyrrhizic acid (GA) molecules, each exhibiting varying degrees of topology and planarity. Our analyses focused on elucidating the stability mechanism of these fibrous structures. Notably, we found that hydrogen bonds, π-π interactions and nonbonded interactions, especially Coulomb interaction between monomers and water molecules, play pivotal roles in stabilizing these fibrous structures. This study significantly contributes to our understanding of self-assembly mechanism in supramolecular fiber materials and opens avenues for extending this knowledge to other fibrous supramolecular architectures.

Sub-Nanometer Mono-Layered Metal-Organic Frameworks Nanosheets for Simulated Flue Gas Photoreduction.

The dilemma between the thickness and accessible active site triggers the design of porous crystalline materials with mono-layered structure for advanced photo-catalysis applications. Here, a kind of sub-nanometer mono-layered nanosheets (Co-MOF MNSs) through the exfoliation of specifically designed Co3 cluster-based metal-organic frameworks (MOFs) is reported. The sub-nanometer thickness and inherent light-sensitivity endow Co-MOF MNSs with fully exposed Janus Co3 sites that can selectively photo-reduce CO2 into formic acid under simulated flue gas. Notably, the production efficiency of formic acid by Co-MOF MNSs (0.85mmolg-1h-1) is ≈13 times higher than that of the bulk counterpart (0.065mmolg-1h-1) under a simulated flue gas atmosphere, which is the highest in reported works up to date. Theoretical calculations prove that the exposed Janus Co3 sites with simultaneously available sites possess higher activity when compared with single Co site, validating the importance of mono-layered nanosheet morphology. These results may facilitate the development of functional nanosheet materials for CO2 photo-reduction in potential flue gas treatment.

Electrochemical sensing strategies for on‐site testing of pathogenic nucleic acids

AbstractRapid and reliable on‐site pathogen testing is crucial for diagnosing and managing human health. Nucleic acids (NAs) containing genetic information are valuable target molecules for pathogen testing, and sensitive and rapid detection of NAs using electrochemical approaches has been intensively investigated. Detection approaches for NAs are diverse and compatible with current gene amplification methods and continue to expand with the development of novel functional materials and molecules. The variety of electrochemical sensing devices also continues to expand, and more practical testing is being pursued. This review outlines the latest detection approaches and basic guidelines for NA detection. Furthermore, this review provides an overview of electrochemical sensing devices that utilize novel and unique materials and functions and comprehensively discusses their advantages.

Toward Self-Driven Autonomous Material and Device Acceleration Platforms (AMADAP) for Emerging Photovoltaics Technologies.

ConspectusIn the ever-increasing renewable-energy demand scenario, developing new photovoltaic technologies is important, even in the presence of established terawatt-scale silicon technology. Emerging photovoltaic technologies play a crucial role in diversifying material flows while expanding the photovoltaic product portfolio, thus enhancing security and competitiveness within the solar industry. They also serve as a valuable backup for silicon photovoltaic, providing resilience to the overall energy infrastructure. However, the development of functional solar materials poses intricate multiobjective optimization challenges in a large multidimensional composition and parameter space, in some cases with millions of potential candidates to be explored. Solving it necessitates reproducible, user-independent laboratory work and intelligent preselection of innovative experimental methods.Materials acceleration platforms (MAPs) seamlessly integrate robotic materials synthesis and characterization with AI-driven data analysis and experimental design, positioning them as enabling technologies for the discovery and exploration of new materials. They are proposed to revolutionize materials development away from the Edisonian trial-and-error approaches to ultrashort cycles of experiments with exceptional precision, generating a reliable and highly qualitative data situation that allows training machine learning algorithms with predictive power. MAPs are designed to assist the researcher in multidimensional aspects of materials discovery, such as material synthesis, precursor preparation, sample processing and characterization, and data analysis, and are drawing escalating attention in the field of energy materials. Device acceleration platforms (DAPs), however, are designed to optimize functional films and layer stacks. Unlike MAPs, which focus on material discovery, a central aspect of DAPs is the identification and refinement of ideal processing conditions for a predetermined set of materials. Such platforms prove especially invaluable when dealing with "disordered semiconductors," which depend heavily on the processing parameters that ultimately define the functional properties and functionality of thin film layers. By facilitating the fine-tuning of processing conditions, DAPs contribute significantly to the advancement and optimization of disordered semiconductor devices, such as emerging photovoltaics.In this Account, we review the recent advancements made by our group in automated and autonomous laboratories for advanced material discovery and device optimization with a strong focus on emerging photovoltaics, such as solution-processing perovskite solar cells and organic photovoltaics. We first introduce two MAPs and two DAPs developed in-house: a microwave-assisted high-throughput synthesis platform for the discovery of organic interface materials, a multipurpose robot-based pipetting platform for the synthesis of new semiconductors and the characterization of thin film semiconductor composites, the SPINBOT system, which is a spin-coating DAP with the potential to optimize complex device architectures, and finally, AMANDA, a fully integrated and autonomously operating DAP. Notably, we underscore the utilization of a robot-based high-throughput experimentation technique to address the common optimization challenges encountered in extensive multidimensional composition and parameter spaces pertaining to organic and perovskite photovoltaics materials. Finally, we briefly propose a holistic concept and technology, a self-driven autonomous material and device acceleration platform (AMADAP) laboratory, for autonomous functional solar materials discovery and development. We hope to discover how AMADAP can be further strengthened and universalized with advancing development of hardware and software infrastructures in the future.

Comparative Analysis of Polyphenolic Compounds in Different Amaranthus Species: Influence of Genotypes and Harvesting Year.

Amaranth is a nutritionally valuable crop, as it contains phenolic acids and flavonoids, yielding diverse plant secondary metabolites (PSMs) like phytosterol, tocopherols, and carotenoids. This study explored the variations in the contents of seventeen polyphenolic compounds within the leaves of one hundred twenty Amaranthus accessions representing nine Amaranthus species. The investigation entailed the analysis of phenolic content across nine Amaranthus species, specifically A. hypochondriacus, A. cruentus, A. caudatus, A. tricolor, A. dubius, A. blitum, A. crispus, A. hybridus, and A. viridis, utilizing ultra performance liquid chromatography with photodiode array detection (UPLC-PDA). The results revealed significant differences in polyphenolic compounds among accessions in which rutin content was predominant in all Amaranthus species in both 2018 and 2019. Among the nine Amaranthus species, the rutin content ranged from 95.72 ± 199.17 μg g-1 (A. dubius) to 1485.09 ± 679.51 μg g-1 (A. viridis) in 2018 and from 821.59 ± 709.95 μg g-1 (A. tricolor) to 3166.52 ± 1317.38 μg g-1 (A. hypochondriacus) in 2019. Correlation analysis revealed, significant positive correlations between rutin and kaempferol-3-O-β-rutinoside (r = 0.93), benzoic acid and ferulic acid (r = 0.76), and benzoic acid and kaempferol-3-O-β-rutinoside (r = 0.76), whereas gallic acid showed consistently negative correlations with each of the 16 phenolic compounds. Wide variations were identified among accessions and between plants grown in the two years. The nine species and one hundred twenty Amaranthus accessions were clustered into six groups based on their seventeen phenolic compounds in each year. These findings contribute to expanding our understanding of the phytochemical traits of accessions within nine Amaranthus species, which serve as valuable resources for Amaranthus component breeding and functional material development.

Preparation and CO2 adsorption behavior of ZIF-67-based porous liquids: A molecular dynamics study

Porous liquids (PLs) are fluids with permanent intramolecular pores, which showed high potential in CO2 capture. In this paper, novel Metal-organic Framework (MOF)-based PL has great porosity and abundant adsorption sites, achieving outstanding CO2 adsorption capacity were constructed using ZIF-67 and 18-crown-6 as dispersant. The physicochemical properties and mechanisms were studied by combining molecular dynamics simulations and quantitative calculations. ZIF-67 could be uniformly dispersed in 18-crown-6 through weak interactions, the compound has good fluidity, containing stable CO2 transmission channels and storage pores, endowing it with a high CO2 adsorption capacity than existing porous liquids. The adsorption of CO2 in ZIF-67/18-crown-6 PL is a physical adsorption through van der Waals interaction, and the recycling of the PL can be achieved by adjusting temperature and pressure. It was extra valuable that the fluidity performance of ZIF-67/18-crown-6 PL was confirmed through experimental characterizations. This work not only provides a novel PL system to achieve CO2 capture, but also gives out a new approach for the development of MOF-based functional materials.

Oligopeptide-based molecular labelling of (bio)degradable polyester biomaterials

Nowadays, a very important motivation for the development of new functional materials for medical purposes is not only their performance but also whether they are environmentally friendly. In recent years, there has been a growing interest in the possibility of labelling (bio)degradable polymers, in particular those intended for specific applications, especially in the medical sector, and the potential of information storage in such polymers, making it possible, for example, to track the ultimate environmental fate of plastics. This article presents a straightforward green approach that combines both aspects using an oligopeptide, which is an integral part of polymer material, to store binary information in a physical mixture of polymer and oligopeptide. In the proposed procedure the year of production of polymer films made of poly(l-lactide) (PLLA) and a blend of poly(1,4-butylene adipate-co-1,4-butylene terephthalate) and polylactide (PBAT/PLA) were encoded as the sequence of the appropriate amino acids in the oligopeptide (PEP) added to these polymers. The decoding of the recorded information was carried out using mass spectrometry technique as a new method of decoding, which enabled the successful retrieval and reading of the stored information. Furthermore, the properties of labelled (bio)degradable polymer films and stability during biodegradation of PLLA/PEP film under industrial composting conditions have been investigated. The labelled films exhibited good oligopeptide stability, allowing the recorded information to be retrieved from a green polymer/oligopeptide system before and after biodegradation. The MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide assay) study of the PLLA and PLLA/PBAT using the MRC-5 mammalian fibroblasts was presented for the first time.