Chemical Functionalization Research Articles

Continuous Reactive-Roll-to-Roll Growth of Carbon Nanotubes for Fog Water Harvesting Applications

A simple method is presented for the continuous generation of carbon nanotube forests stably anchored on stainless-steel surfaces using a reactive-roll-to-roll (RR2R) configuration. No addition of catalyst nanoparticles is required for the CNT-forest generation; the stainless-steel substrate itself is tuned to generate the catalytic growth sites. The process enables very large surfaces covered with CNT forests to have individual CNT roots anchored to the metallic ground through primary bonds. Fog water harvesting is demonstrated and tested as one potential application using long CNT-covered wires. The RR2R is performed in the gas phase; no solution processing of CNT suspensions is used, contrary to usual R2R CNT-based technologies. Full or partial CNT-forest coverage provides tuning of the ratio and shape of hydrophobic and hydrophilic zones on the surface. This enables the optimization of fog water harvesters for droplet capture through the hydrophobic CNT forest and water removal from the hydrophilic SS surface. Water recovery tests using small harp-type harvesters with CNT-forest generate water capture of up to 2.2 g/cm2·h under ultrasound-generated fog flow. The strong CNT root anchoring on the stainless-steel surfaces provides opportunities for (i) robustness and easy transport of the composite structure and (ii) chemical functionalization and/or nanoparticle decoration of the structures, and it opens the road for a series of applications on large-scale surfaces, including fog harvesting.

Promising and Environmentally Friendly Removal of Copper, Zinc, Cadmium, and Lead from Wastewater Using Modified Shrimp-Based Chitosan

This study explores the potential of modified shrimp-based chitosan (MSC) as an innovative adsorbent for eliminating heavy metals (HMs) from contaminated water sources. The modifications encompassed various chemical treatments, surface functionalization, and structural optimization to enhance the chitosan’s adsorption capabilities. Comprehensive analyses using FT-IR and SEM-EDS were conducted to evaluate the properties of the chitosan. The adsorption capacity of MSC was assessed using ICP-MS before and after the adsorption process. Moreover, the study investigated the efficiency of HM removal by MSC under different conditions, including variations in pH, adsorbent dosage, and contact time. Under neutral pH conditions, the highest adsorption rates of copper, zinc, cadmium, and lead were determined as 99.72%, 84.74%, 91.35%, and 99.92%, respectively, with corresponding adsorption capacities of 20.30 mg/g for copper, 7.50 mg/g for zinc, 15.00 mg/g for cadmium, and 76.34 mg/g for lead. Analysis based on the Langmuir and Freundlich isotherm models revealed highly significant adsorption of HMs, supported by strong correlation coefficients (r2 > 0.98) obtained from the data. The pseudo-second-order kinetic model with linear coefficients (r2) greater than 0.97 effectively explained the kinetic studies of metal adsorption employing modified shrimp shells. These coefficients indicate a robust fit of the models to the experimental adsorption data for heavy metals. Further confirmation of the effectiveness of the adsorbent was obtained through FT-IR spectroscopy, which confirmed the presence of specific functional groups on the adsorbent, such as N–H joined with –COO−, H–O, C−O−C, and C–H. Additionally, the SEM-EDS analysis detected the presence of elements on the surface of MSC chitosan. The results emphasize that MSC is a highly effective and cost-efficient adsorbent for eliminating Cu, Zn, Cd, and Pb from wastewater, making it a promising eco-friendly choice.

Poly(vinylidene fluoride) ultrafiltration membranes tailored with zirconium‐based MOF‐801 for water treatment applications

AbstractHighly hydrophilic and antifouling poly(vinylidene fluoride) (PVDF) ultrafiltration membranes are developed with excellent permeation using a zirconium‐based metal–organic framework (MOF‐801). MOF‐801 is synthesized by a solvothermal method using zirconium(IV) oxychloride octahydrate (ZrOCl2⋅8H2O) and fumaric acid. The chemical functionality of MOF‐801 is studied by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) whereas surface morphology and elemental composition are probed by scanning electron microscopy (SEM)/energy‐dispersive X‐ray analysis (EDX). The PVDF/MOF‐801 membranes are characterized in terms of FTIR, XRD, FESEM/EDX and atomic force microscopy. The performance of the hybrid PVDF/MOF‐801 membranes in terms of pure water flux and antifouling ability is found to be improved compared with bare PVDF membranes. The wettability of the membranes is measured by water contact angle and found to be 76.7° for bare PVDF membrane, which decreases upon the addition of MOF‐801 to 55.1° due to the increase in surface hydrophilicity. A notable increase in roughness of 226.29 nm and a porosity of 67.91% is observed for the addition of 2 wt% MOF‐801 in PVDF membrane matrix. The flux recovery ratio of the hybrid membrane is increased from 66.4% to 89.6% and from 68.3% to 85.2% for bovine serum albumin (BSA) and humic acid (HA) separation, respectively. In addition, the reversible and irreversible fouling performance during the rejection of BSA (93%) and HA (88%) indicates the enhanced antifouling property of the PVDF/MOF‐801 membranes. A zone of inhibition test evidences the outstanding antibiofouling activity of the PVDF/MOF‐801 membranes against E. coli and S. aureus. Overall results demonstrated the suitability of hybrid PVDF/MOF‐801 membranes for water and wastewater treatment. © 2023 Society of Industrial Chemistry.

Ultrahigh-mobility semiconducting epitaxial graphene on silicon carbide.

Semiconducting graphene plays an important part in graphene nanoelectronics because of the lack of an intrinsic bandgap in graphene1. In the past two decades, attempts to modify the bandgap either by quantum confinement or by chemical functionalization failed to produce viable semiconducting graphene. Here we demonstrate that semiconducting epigraphene (SEG) on single-crystal silicon carbide substrates has a band gap of 0.6 eV and room temperature mobilities exceeding 5,000 cm2 V-1 s-1, which is 10 times larger than that of silicon and 20 times larger than that of the other two-dimensional semiconductors. It is well known that when silicon evaporates from silicon carbide crystal surfaces, the carbon-rich surface crystallizes to produce graphene multilayers2. The first graphitic layer to form on the silicon-terminated face of SiC is an insulating epigraphene layer that is partially covalently bonded to the SiC surface3. Spectroscopic measurements of this buffer layer4 demonstrated semiconducting signatures4, but the mobilities of this layer were limited because of disorder5. Here we demonstrate a quasi-equilibrium annealing method that produces SEG (that is, a well-ordered buffer layer) on macroscopic atomically flat terraces. The SEG lattice is aligned with the SiC substrate. It is chemically, mechanically and thermally robust and can be patterned and seamlessly connected to semimetallic epigraphene using conventional semiconductor fabrication techniques. These essential properties make SEG suitable for nanoelectronics.

Developing homogeneous first row early transition metal catalysts for the oxygen reduction reaction.

The oxygen reduction reaction (ORR) remains an important fixture in biological and synthetic systems for energy conversion and chemical functionalization. Late transition metals continue to dominate in the development of new catalyst systems, inspired by well-characterized metallocofactors and prior successes. By comparison, metals to the left of Fe on the periodic table are relatively understudied for the ORR. This Frontier article summarizes advancements related to the use of Mn, Cr, and V in homogeneous catalyst systems for the ORR and discusses the implications of these results for the development of catalyst systems from these metals and those earlier in the transition metal series.

Tailoring flavin-based photosensitizers for efficient photooxidative coupling of benzylic amines.

Photooxidative coupling of benzylic amines using naturally abundant O2 as an oxidant under visible light irradiation is an alternative green approach to synthesis imines and is of both fundamental and practical significance. We investigated the photophysical properties of flavin (FL) that is a naturally available sensitizer and its derivatives, i.e. 9-bromoflavin (MB-FL), 7,8-dibromoflavin (DB-FL) and 10-phenylflavin (Ph-FL), as well as the performance of these FL-based sensitizers (FLPSs) in the photooxidative coupling of benzylic amines to imines combining experimental and theoretical efforts. We showed that chemical functionalization with Br and phenyl effectively improves the photophysical properties of these FLPSs, in terms of absorption in the visible light range, singlet oxygen quantum yields, triplet lifetime, etc. Apart from nearly quantitative selectivity for the production of imines, the performance of DB-FL is superior to those of other FLPSs, and it is among the best photocatalysts for imine synthesis. Specifically, 0.5 mol% DB-FL is capable of converting 91% of 0.2 mmol benzylamine and more than 80% of 0.2 mmol fluorobenzylic amine derivatives into their corresponding imines in 5 h batch runs. Mechanistic investigation finely explained the observed photophysical properties of FLPSs and highlighted the dominant role of electron transfer in FLPS sensitized coupling of benzylic amines to imines. This work not only helps to understand the pathways for photocatalysis with FLPSs but also paves the way for the design of novel and efficient PSs to promote organic synthesis.

Control of polymer-protein interactions by tuning the composition and length of polymer chains.

Nanomoduling the 3D shape and chemical functionalities in a synthetic polymer may create recognition cavities for biomacromolecule binding, which serves as an attractive alternative to natural antibodies with much less cost. To obtain fundamental understanding and predict molecular design rules of the polymer antibody, we analyze the complex structure between the biomarker protein epithelial cell adhesion molecule (EpCAM) and a series of polymer ligands via molecular dynamics (MD) simulations. For monomeric ligands, strong enrichment of aromatic residues in protein binding sites is revealed, in line with the reported observations for natural antibodies. Yet, for linear polymers with a growing degree of polymerization, for the first time, a drastic change is revealed on the type of enriched protein residues and the location of protein binding sites, driven by the increasing steric hindrance effect that makes the adsorption of the polymer in the protein exterior feasible. Varying the polymer length and monomeric composition also significantly affects the ligand binding affinity. Here, we have captured three distinct dependences of the ligand binding free energy on the degree of polymerization: for NIPAm based hydrophilic polymers, TBAm dominated hydrophobic polymers and AAc dominated charged polymers. These results can be rationalized by the complex structure and the composition of protein residues at the binding interface. The entire analysis demonstrates unique binding features for polymer ligands and the possibility to modulate their binding sites and affinity by engineering the polymer structure.

The fabrication of robust and highly efficient oil-water separation filters via the high temperature sintering of silica micropower.

Superhydrophobic materials have been shown to have many attractive properties, however, their functionality can easily be lost due to the failure of the air layer. For long lasting air layer retention, dedicated mechanisms to maintain this layer and/or reintroduce air into the system are essential. Any air reintroduction control would allow for increased air lifetime but would require a porous material that allows air flow to be effective. Here, we prepared highly porous superhydrophobic materials, fabricated through facile sintering of silica nanoparticles followed by chemical functionalisation. Sintering temperatures were varied to maximise the material's strength and water contact angles, with angles of up to 153° achieved. Furthermore, the porous properties were demonstrated through oil/water separation experiments, where separation efficiencies of up to 98% were recorded.

Impact of hydrophilic side chains on the thin film transistor performance of a benzothieno-benzothiophene derivative.

Side-chain engineering in molecular semiconductors provides a versatile toolbox for precisely manipulating the material's processability, crystallographic properties, as well as electronic and optoelectronic characteristics. This study explores the impact of integrating hydrophilic side chains, specifically oligoethylene glycol (OEG) units, into the molecular structure of the small molecule semiconductor, 2,7-bis(2(2-methoxy ethoxy)ethoxy) benzo[b]benzo[4,5] thieno[2,3-d] thiophene (OEG-BTBT). The investigation includes a comprehensive analysis of thin film morphology and crystallographic properties, along with the optimization of deposition parameters for improving the device performance. Despite the anticipated benefits, such as enhanced processability, our investigation into OEG-BTBT-based organic field-effect transistors (OFETs) reveals suboptimal performance marked by a low effective charge carrier mobility, a low on/off ratio, and a high threshold voltage. The study unveils bias stress effects and device degradation attributed to the high ionization energy of OEG-BTBT alongside the hydrophilic nature of the ethylene-glycol moieties, which lead to charge trapping at the dielectric interface. Our findings underscore the need for a meticulous balance between electronic properties and chemical functionalities in molecular semiconductors to achieve stable and efficient performance in organic electronic devices.

Characterization of emerging 2D materials after chemical functionalization

Characterizing functionalized 2D materials is not easy. We present a critical overview of the challenges, the spectroscopic, microscopic and analytical techniques available and practical examples in the literature to illustrate their correct use.

Vertical heterostructure of graphite-MoS2 for gas sensing.

2D materials, given their form-factor, high surface-to-volume ratio, and chemical functionality have immense use in sensor design. Engineering 2D heterostructures can result in robust combinations of desirable properties but sensor design methodologies require careful considerations about material properties and orientation to maximize sensor response. This study introduces a sensor approach that combines the excellent electrical transport and transduction properties of graphite film with chemical reactivity derived from the edge sites of semiconducting molybdenum disulfide (MoS2) through a two-step chemical vapour deposition method. The resulting vertical heterostructure shows potential for high-performance hybrid chemiresistors for gas sensing. This architecture offers active sensing edge sites across the MoS2 flakes. We detail the growth of vertically oriented MoS2 over a nanoscale graphite film (NGF) cross-section, enhancing the adsorption of analytes such as NO2, NH3, and water vapor. Raman spectroscopy, density functional theory calculations and scanning probe methods elucidate the influence of chemical doping by distinguishing the role of MoS2 edge sites relative to the basal plane. High-resolution imaging techniques confirm the controlled growth of highly crystalline hybrid structures. The MoS2/NGF hybrid structure exhibits exceptional chemiresistive responses at both room and elevated temperatures compared to bare graphitic layers. Quantitative analysis reveals that the sensitivity of this hybrid sensor surpasses other 2D material hybrids, particularly in parts per billion concentrations.

Finely tuned water structure and transport in functionalized carbon nanotube membranes during desalination.

Molecular dynamics simulations were performed to tune the transport of water molecules in nanostructured membrane in a desalination process. Four armchair-type (7,7), (8,8), (9,9) and (10,10) carbon nanotubes (CNTs) with pore diameters around 1 nm were chosen, their interior surfaces were modified with -OH, -CH3 and -F groups. Simulation results show that water transport in nanochannel depends on confined water structures which could be regulated by precisely controlled channel diameter and chemical functionalization. Increasing CNT diameter changes water structures from single-file-like to be square and hexagonal-like, then into a disordered pattern, resulting in a concave-shaped trend of water permeance. The -OH functional groups promote structural ordering of water molecules in (7,7) CNT, but disrupt water structures in (8,8) and (9,9) CNTs, and reduce the order degree of water molecules in (10,10) CNT, moreover, exert an attraction to enhance surface friction inside channel. The -CH3 groups induce more strictly single-file movement of water molecules in (7,7) CNT, turning water structures in (8,8) and (9,9) CNTs into two and triangular column arrangements, improving water transport, however, causing again square-like water structure in (10,10) CNT. Fluorinations of CNT make water structure more disordered in (7,7), (9,9) and (10,10) CNTs, while enhance the square water structure in (8,8) CNT with a lower water permeance. Through changing channel diameter and functionalization, the low tetrahedral order corresponds to a more single-file-like water structure, associated with rapid water diffusion and high permeability; an increase in tetrahedrality results in more ice-like water structures, lower water diffusion coefficients, and permeability. The results of this study demonstrate that water transport could be finely regulated via a functionalized CNT membrane.

Material-specific binding peptides empower sustainable innovations in plant health, biocatalysis, medicine and microplastic quantification.

Material-binding peptides (MBPs) have emerged as a diverse and innovation-enabling class of peptides in applications such as plant-/human health, immobilization of catalysts, bioactive coatings, accelerated polymer degradation and analytics for micro-/nanoplastics quantification. Progress has been fuelled by recent advancements in protein engineering methodologies and advances in computational and analytical methodologies, which allow the design of, for instance, material-specific MBPs with fine-tuned binding strength for numerous demands in material science applications. A genetic or chemical conjugation of second (biological, chemical or physical property-changing) functionality to MBPs empowers the design of advanced (hybrid) materials, bioactive coatings and analytical tools. In this review, we provide a comprehensive overview comprising naturally occurring MBPs and their function in nature, binding properties of short man-made MBPs (<20 amino acids) mainly obtained from phage-display libraries, and medium-sized binding peptides (20-100 amino acids) that have been reported to bind to metals, polymers or other industrially produced materials. The goal of this review is to provide an in-depth understanding of molecular interactions between materials and material-specific binding peptides, and thereby empower the use of MBPs in material science applications. Protein engineering methodologies and selected examples to tailor MBPs toward applications in agriculture with a focus on plant health, biocatalysis, medicine and environmental monitoring serve as examples of the transformative power of MBPs for various industrial applications. An emphasis will be given to MBPs' role in detecting and quantifying microplastics in high throughput, distinguishing microplastics from other environmental particles, and thereby assisting to close an analytical gap in food safety and monitoring of environmental plastic pollution. In essence, this review aims to provide an overview among researchers from diverse disciplines in respect to material-(specific) binding of MBPs, protein engineering methodologies to tailor their properties to application demands, re-engineering for material science applications using MBPs, and thereby inspire researchers to employ MBPs in their research.

Genome-Wide Screen for Enhanced Noncanonical Amino Acid Incorporation in Yeast.

Expanding the genetic code beyond the 20 canonical amino acids enables access to a wide range of chemical functionality that is inaccessible within conventionally biosynthesized proteins. The vast majority of efforts to expand the genetic code have focused on the orthogonal translation systems required to achieve the genetically encoded addition of noncanonical amino acids (ncAAs) into proteins. There remain tremendous opportunities for identifying genetic and genomic factors that enhance ncAA incorporation. Here we describe genome-wide screening strategies to identify factors that enable more efficient addition of ncAAs to biosynthesized proteins. These unbiased screens can reveal previously unknown genes or mutations that can enhance ncAA incorporation and deepen our understanding of the translation apparatus.

Enhancing the oxygen evolution reaction activity of CuCo based hydroxides with V2CT x MXene.

The oxygen evolution reaction (OER) is a key reaction in the production of green hydrogen by water electrolysis. In alkaline media, the current state of the art catalysts used for the OER are based on non-noble metal oxides. However, despite their huge potential as OER catalysts, these materials exhibit various disadvantages including lack of stability and conductivity that hinder the wide-spread utilization of these materials in alkaline electrolyzer devices. This study highlights the innovative chemical functionalization of a mixed copper cobalt hydroxide with the V2CT x MXene to enhance the OER efficiency, addressing the need for effective electrocatalytic interfaces for sustainable hydrogen production. The herein synthesized CuCo@V2CT x electrocatalysts demonstrate remarkable activity, outperforming the pure CuCo catalysts for the OER and moreover show increased efficiency after 12 hours of continuous operation. This strategic integration improved the water oxidation performance of the pure oxide material by improving the composite's hydrophilicity, charge transfer properties and ability to hinder Cu leaching. The materials were characterized using an array of materials characterization techniques to help decipher both structure of the composite materials after synthesis and to elucidate the reasoning for the OER enhancement for the composites. This work demonstrates the significant potential of TMO-based nanomaterials combined with V2CT x for advanced innovative electrocatalytic interfaces in energy conversion applications.

Tailoring of bioactive glass and glass-ceramics properties for in vitro and in vivo response optimization: a review.

Bioactive glasses are inorganic biocompatible materials that can find applications in many biomedical fields. The main application is bone and dental tissue engineering. However, some applications in contact with soft tissues are emerging. It is well known that both bulk (such as composition) and surface properties (such as morphology and wettability) of an implanted material influence the response of cells in contact with the implant. This review aims to elucidate and compare the main strategies that are employed to modulate cell behavior in contact with bioactive glasses. The first part of this review is focused on the doping of bioactive glasses with ions and drugs, which can be incorporated into the bioceramic to impart several therapeutic properties, such as osteogenic, proangiogenic, or/and antibacterial ones. The second part of this review is devoted to the chemical functionalization of bioactive glasses using drugs, extra-cellular matrix proteins, vitamins, and polyphenols. In the third and final part, the physical modifications of the surfaces of bioactive glasses are reviewed. Both top-down (removing materials from the surface, for example using laser treatment and etching strategies) and bottom-up (depositing materials on the surface, for example through the deposition of coatings) strategies are discussed.

Tailoring intersystem crossing in phosphorus corroles through axial chalcogenation: a detailed theoretical study.

Intersystem crossing (ISC) of visible-light absorbing metal-free corrole macrocycles can be greatly tuned by means of suitable chemical functionalization. Axially chalcogenated phosphorus corrole derivatives (XPCs; X = O, S, Se) are expected to show large spin-orbit coupling (SOC) via the heavy-atom effect and therefore a much improved ISC. Excited-state deactivation of XPCs including PC is studied using time-dependent optimally tuned range-separated hybrid functionals combined with a polarizable continuum model with toluene as a dielectric medium to account for polar solvent effects. PC and all XPCs are dynamically stable and also show favourable thermodynamic formation feasibility as confirmed by Gibbs free energy analysis. In spite of the relatively smaller contribution of P and X to the frontier molecular orbitals compared to the tetrapyrrolic ring, SOC is considerably improved due to the heavy-atom effect. While PC shows a one-order larger ISC rate of ∼107 s-1 than fluorescence, competitive fluorescence and ISC rates of ∼107 s-1 are found for OPC. In contrast, both SPC and SePC exhibit significantly larger ISC rates of ∼109 s-1 and ∼1013 s-1, respectively, with much smaller fluorescence rates of ∼107 s-1. Importantly, the first report of anti-Kasha's emission in metal-free corroles is predicted for OPC with a radiative rate of ∼109 s-1. Furthermore, calculated phosphorescence and ISC rates from the near-degenerate lowest excited triplets to the ground-state suggest millisecond to microsecond triplet lifetimes, signalling towards long-lived excited triplet formation. Overall, all three XPCs including PC could act as triplet photosensitizers and especially both SPC and SePC are predicted to be the highly efficient ones.

Insights into Li+ storage mechanisms, kinetics, and reversibility of defect-engineered and functionalized multi-walled carbon nanotubes for enhanced energy storage

Defect engineering and chemical functionalization of MWCNTs have boosted Li+ storage capacity and enhanced Li+ diffusivity, advancing the development of high-energy and high-power LIBs.

Tandem templating strategies facilitate the assembly of calix[8]arene-supported Ln18 clusters.

Calix[n]arenes offer ideal chemical functionality through the polyphenolic lower rim to construct nano-sized coordination clusters with lanthanide (Ln) metal ions (e.g., NdIII10, GdIII8). However, the number of metal centers they can accommodate is still limited compared to that achievable with smaller ligands (e.g., GdIII140, GdIII104). Here, we exploit a combination of the "anion template strategy" and "templating ligands" to synthesise three highly symmetric (D3h, trigonal planar) LnIII18 (Ln = La, Nd, and Gd) systems, representing the largest calix[n]arene-based coordination clusters yet. The LnIII18 fragment is templated by a chloride anion located at the center of the cluster, wherefrom twelve μ3-OH- ligands bind 'internally' to the eighteen LnIII ions. 'Externally' the metallic skeleton is connected by p-tert-butylcalix[8]arene, oxo, chloro and carbonate ligands. The crystal packing in the lattice reveals large cylindrical channels of ∼26 Å in diameter, whose pore volume corresponds to ∼50% of the unit cell volume (using a 1.2 Å spherical probe radius). Magnetic measurements reveal the predominance of weak antiferromagnetic exchange in the Gd analog. Heat capacity data of GdIII18 reveal a high magnetic entropy with -ΔSm = 23.7 J K-1 kg-1, indicating potential for engineering magnetic refrigerant materials with calix[8]arenes.

Functionalized graphene-based materials for cementitious applications.

Graphene-based materials (GBM) are promising cementitious composite additives that can significantly improve the mechanical characteristics and durability of concrete due to their unique properties, such as high surface area and aspect ratio and excellent tensile strength, to name a few. To display their full potential, GBM have to be homogeneously dispersed into the aqueous environment of cement-based matrices. The present study addresses the issue of limited dispersibility in the aqueous media of GBM through the chemical functionalization of mono- and few-layer graphene structures with hydrophilic aryl sulfonate groups and shows that a series of mortar samples containing modified GBM exhibit increased flexural and compressive strength by up to 17% and 30%, respectively, compared to mortar references without additives.