Effect Of Surface Functionalization Research Articles

Impact of Surface Functionalization and Deposition Method on Cu-BDC surMOF Formation, Morphology, Crystallinity, and Stability.

For direct integration into device architectures, surface-anchored metal-organic framework (surMOF) thin films are attractive systems for a wide variety of electronic, photonic, sensing, and gas storage applications. This research systematically investigates the effect of deposition method and surface functionalization on the film formation of a copper paddle-wheel-based surMOF. Solution-phase layer-by-layer (LBL) immersion and LBL spray deposition methods are employed to deposit copper benzene-1,4-dicarboxylate (Cu-BDC) on gold substrates functionalized with carboxyl- and hydroxyl-terminated alkanethiol self-assembled monolayers (SAMs). A difference in crystal orientation is observed by atomic force microscopy and X-ray diffractometry based on surface functionalization for films deposited by the LBL immersion method but not for spray-deposited films. Cu-BDC crystallites with a strong preferred orientation perpendicular to the substrate were observed for the films deposited by the LBL immersion method on carboxyl-terminated SAMs. These crystals could be removed upon testing adhesive properties, whereas all other Cu-BDC surMOF film structures demonstrated excellent adhesive properties. Additionally, film stability upon exposure to water or heat was investigated. Ellipsometric data provide insight into film formation elucidating 7 and 14 Å average thicknesses per deposition cycle for films deposited by the immersion method on 11-mercapto-1-undecanol (MUD) and 16-mercaptohexadecanoic acid (MHDA), respectively. In contrast, the films deposited by the spray method are thicker with the same average thickness per deposition cycle (21 Å) for both SAMs. While the spray method takes less time to grow thicker films, it produces similar crystallite structures, regardless of the surface functionalization. This research is fundamental to understanding the impact of deposition method and surface functionalization on surMOF film growth and to provide strategies for the preparation of high-quality surMOFs.

Theoretical study of catalytic performance of WN MXenes as cathodes for Li-O2 batteries: Effects of surface functionalization and atomic layers

Promising Li–O2 batteries suffer from high overpotentials of the oxygen evolution reaction (ηOER)/oxygen reduction reaction (ηORR) at cathodes during charging/discharging. Herein, the first-principles calculations were performed to investigate WN MXenes, including the pristine Wn+1Nn and oxygen − functionalized Wn+1NnO2 (n = 1, 2, and 3), as the potential cathode catalysts for Li − O2 batteries. Both Wn+1Nn and Wn+1NnO2 exhibit high electrical conductivity. Compared to the electrophilic W surfaces of Wn+1Nn, the nucleophilic O surfaces of Wn+1NnO2 can not only bind to Li of LixO2 to activate the Li − O bond, but also promote electron transfer to form Li+, which facilitates to the delithiation of LixO2 in the OER, thus lowering ηOER on Wn+1NnO2. Moreover, the O-functionalized surfaces can also reduce the adsorption energies of LixO2, thereby lowering ηORR and ηOER. On the other hand, reducing atomic layers of Wn+1Nn and Wn+1NnO2 can further lower ηORR and ηOER, because WN MXenes with fewer atomic layers have lower d-/p- band centers, which can weaken the adsorption of LixO2. The W2NO2 MXene not only has a high electrical conductivity but also exhibits ultra-low ORR, OER, and total overpotentials (0.12, 0.17, and 0.29 V), indicating it possesses an ultra-high catalytic performance as cathodes for Li-O2 batteries.

Amino Acid-Coated Zeolitic Imidazolate Framework for Delivery of Genetic Material in Prostate Cancer Cell.

Metal-organic frameworks (MOFs) are currently under progressive development as a tool for non-viral biomolecule delivery. Biomolecules such as proteins, lipids, carbohydrates, and nucleic acids can be encapsulated in MOFs for therapeutic purposes. The favorable physicochemical properties of MOFs make them an attractive choice for delivering a wide range of biomolecules including nucleic acids. Herein, a green fluorescence protein (GFP)-expressing plasmid DNA (pDNA) is used as a representative of a biomolecule to encapsulate within a Zn-based metal-organic framework (MOF) called a zeolitic imidazolate framework (ZIF). The synthesized biocomposites are coated with positively charged amino acids (AA) to understand the effect of surface functionalization on the delivery of pDNA to prostate cancer (PC-3) cells. FTIR and zeta potential confirm the successful preparation of positively charged amino acid-functionalized derivatives of pDNA@ZIF (i.e., pDNA@ZIFAA). Moreover, XRD and SEM data show that the functionalized derivates retain the pristine crystallinity and morphology of pDNA@ZIF. The coated biocomposites provide enhanced uptake of genetic material by PC-3 human prostate cancer cells. The AA-modulated fine-tuning of the surface charge of biocomposites results in better interaction with the cell membrane and enhances cellular uptake. These results suggest that pDNA@ZIFAA can be a promising alternative tool for non-viral gene delivery.

Effect of fiber surface functionalization on adsorption behavior of uranium from seawater desalination brine

Inspired by the easy availability and modification of fiber-like materials for water treatment and sorption applications, the functionalized natural fiber luffa cylindrica (LC) and synthetic fiber polyacrylonitrile (PAN) have been designed for the uranium adsorption. Seawater desalination brine has a significantly higher concentration of uranyl ion, so it is very meaningful to extract uranyl ions from it. In this paper, the seawater from seawater desalination plant at various treatment stages was collected to evaluate uranium adsorption performance. The effect of flocculant and scale inhibitors on uranium adsorption performance of functional fibers was also studied. The oxime/guanidine co-modified luffa cylindrica fiber (WGLC), guanidine/amidoxime co-modified polyacrylonitrile fiber (PAN-G-AO) and polyethyleneimine modified polyacrylonitrile fiber (PAN-PEI) were synthesized. PAN-G-AO showed excellent uranium capture performance with a high saturation adsorption capacity of 490.20 mg g−1 and rapid adsorption equilibrium at 15 min. Amount of uranium adsorption of three materials declined when flocculant and scale inhibitors were added. The results of adsorption experiments in various stages of seawater desalination solution for 30 days showed that adsorption materials PAN-G-AO had the largest adsorption capacity (18.6 μg g−1) in the concentrated desalinated seawater, which demonstrate promising application potential of the functionalized fiber materials for uranium adsorption from desalinated concentrated seawater.

Enhanced output performance of graphene oxide based triboelectric nanogenerators via plasmon coupling

Graphene Oxide and its derivatives continue to attract the attention of materials scientists in view of their diverse applications. In this paper, we describe the potential of graphene oxide decorated with silver nanoparticles (GO-AgNPs) in energy harvesting, a study inspired by the synergistic effects of surface functionalization of GO with metal nanoparticles. Here, we investigate the triboelectric properties of the composite by constructing the prototype of a free standing nanogenerator with the aid of GO-AgNP based paper and Teflon fabric. Studies using this protype is seen to yield a peak output power of 40 μW for a voltage of 0.2 V, which could be used for the development of sensors. According to the morphological and optical investigations done on GO and GO-AgNPs, the increased output voltage is caused by nanoparticle plasmon coupling on the GO surface.

Understanding cure and interphase effects in functionalized graphene‐epoxy nanocomposites

AbstractAgglomerations effects of graphene‐based nanofillers are often reported in the literature to be the main reason on the deterioration of the mechanical properties, especially at high filler loadings. In our study, we focused on the correlated effects of plasma‐treated graphene nanofillers on the curing reaction and mechanical properties of an epoxy matrix. Specifically, we explored the effect of dispersion state, planar size, filler content, surface functionalization and stoichiometric ratio on the epoxy curing process. The surface of the treated graphene nanofillers were studied in detail by X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy and X‐ray diffraction (XRD). The results indicated greater presence of oxygen containing groups with the crystallinity to be unaffected after the plasma process. Dynamic Mechanical Analysis (DMA) was used to assess the changes in both the Tg and the mechanical properties of graphene‐epoxy nanocomposites. Rheological and microscopic data showed that a well‐dispersed material was achieved at high filler loadings with the use of calendaring and plasma functionalization. Although, a well‐dispersed material was achieved on the bulk composite, no further mechanical reinforcement was observed at high filler loadings. The adsorption of epoxy groups onto the graphene nanofillers' surface, leading to a stoichiometric imbalance between the epoxy chains and hardener molecules, was proposed to explain the results.

The interface charge transfer induced the expanding of effective electromagnetic wave absorption band in Ti3C2/FeNi3 composites

Ti3C2/NiFe2O4 and Ti3C2/FeNi3 composites were prepared by hydrothermal and hydrazine reduction process, respectively. Effects of components and surface functionalization on dielectric/magnetic polarization of samples were studied systematically. The results indicate that the surface charge states of Ti3C2 effectively modify the dielectric performance of the corresponding samples. In Ti3C2 sheets sample, the effective absorption bandwidth (EAB) is over 2.88 GHz at thickness of 0.93 mm. In Ti3C2/NiFe2O4 composite, the EAB is about 3.92 GHz at 1.92 mm thickness. In case of Ti3C2/FeNi3 composite, its EAB exceeds 5.68 GHz at 1.59 mm thickness. Such significantly improved wave absorption performance is attributed to the additional strong interface electromagnetic loss and the optimized impedance matching. In particularly, the additional polarization induced by the charge transfer between the heterogeneous interfaces in Ti3C2/FeNi3 composite has drastic positive effects on realizing multimode synergistic attenuation of the electromagnetic energy. This work demonstrates that Ti3C2/FeNi3 composite is a novel advanced absorbent with a promising application.

Enhanced osteogenesis on proantocyanidin-loaded date palm endocarp cellulosic matrices: A novel sustainable approach for guided bone regeneration

Developing inexpensive, biocompatible natural scaffolds that can support the differentiation and proliferation of stem cells has been recently emphasized by the research community to faster obtain the FDA approvals for regenerative medicine. In this regard, plant-derived cellulose materials are a novel class of sustainable scaffolding materials with high potentials for bone tissue engineering (BTE). However, low bioactivity of the plant-derived cellulose scaffolds restricts cell proliferation and cell differentiation. This limitation can be addressed though surface-functionalization of cellulose scaffolds with natural antioxidant polyphenols, e.g., grape seed proanthocyanidin (PCA)-rich extract (GSPE). Despite the various merits of GSPE as a natural antioxidant, its impact on the proliferation and adhesion of osteoblast precursor cells, and on their osteogenic differentiation is an as-yet unknown issue. Here, we investigated the effects of GSPE surface functionalization on the physicochemical properties of decellularized date (Phoenix dactyliferous) fruit inner layer (endocarp) (DE) scaffold. In this regard, various physiochemical characteristics of the DE-GSPE scaffold such as hydrophilicity, surface roughness, mechanical stiffness, porosity, and swelling, and biodegradation behavior were compared with those of the DE scaffold. Additionally, the impact of the GSPE treatment of the DE scaffold on the osteogenic response of human mesenchymal stem cells (hMSCs) was thoroughly studied. For this purpose, cellular activities including cell adhesion, calcium deposition and mineralization, alkaline phosphatase (ALP) activity, and expression levels of bone-related genes were monitored. Taken together, the GSPE treatment enhanced the physicochemical and biological properties of the DE-GSPE scaffold, thereby raising its potentials as a promising candidate for guided bone regeneration.

Starch bio-nanocomposites based on phosphorylated and sulphated cellulose nanocrystals extracted from pepper plant residue: effect of surface functionality on property improvements

Starch bio-nanocomposites based on phosphorylated and sulphated cellulose nanocrystals extracted from pepper plant residue: effect of surface functionality on property improvements

Effect of Size, Shape and Surface Functionalization on the Antibacterial Activity of Silver Nanoparticles.

Silver nanoparticles (AgNPs) are the most investigated antibacterial agents against multidrug resistant (MDR) pathogens. They can lead to cellular death by means of different mechanisms, damaging several cell compartments, from the external membrane, to enzymes, DNA and proteins; this simultaneous attack amplifies the toxic effect on bacteria with respect to traditional antibiotics. The effectiveness of AgNPs against MDR bacteria is strongly correlated with their chemical and morphological properties, which influence the pathways involved in cellular damage. In this review, AgNPs' size, shape and modification by functional groups or other materials are reported, both to investigate the different synthetic pathways correlated with nanoparticles' modifications and to evaluate the related effect on their antibacterial activity. Indeed, understanding the synthetic conditions for obtaining performing antibacterial AgNPs could help to tailor new and improved silver-based agents to combat multidrug resistance.

Porous silica preconcentrator for selective ambient volatile organic compounds detection: Effects of surface functionalization and humidity

With the increased demand for hand-held and ambient gas sensors, it is imperative to develop sensors that can offer both selective and sensitive detection. Gas preconcentration is a widely tried and tested method to increase the sensitivity of gas detectors. While it effectively lowers the limit of detection, it does not impact the selectivity of the detector. Therefore, preconcentrator materials have mostly been used in conjunction with selective detectors. In this work, we use the preconcentration method with a nonselective small and portable photoionization detector to introduce selectivity. For this purpose, we use a relatively slow heating rate, that allows for gradual desorption and analytes from the preconcentrator material–nanoporous silica. The characteristic desorption temperature of the volatile organic compounds (VOC) from the preconcentrator allows selective detection of the VOC. In this work, we study the effect of surface functionalization, to make it hydrophobic, and observe the adsorption–desorption behavior of polar (isopropyl alcohol) and non-polar (octane) gas molecules. The hydrophobic silica surface was found to improve the adsorption of non-polar octane, while it reduced the adsorption of polar isopropyl alcohol. The desorption temperature for isopropanol remained unchanged for both functionalized and non-functionalized preconcentrators; however, the desorption temperature for octane increased by 10 °C when the functionalized hydrophobic pSiO2 was used. We also observed the presence of humidity, a known interferent, did not heavily impact the sensing performance. These results are promising evidence that functionalized porous silica integrated with a photoionization detector can be used for selective gas detection in the ambient atmosphere.

Effect of surface functionalization on the moisture stability and sorption properties of porous boron nitride

Porous boron nitride (BN) is a promising adsorbent owing to its high surface area and porosity, as well as thermal and oxidative stability. It has been explored in the past decade for applications in gas and liquid separations, such as CO2 capture and water cleaning. However, the material has displayed hydrolytic instability. Owing to the presence of moisture in most industrial settings, whether it is for storage or cyclic adsorption processes, ensuring the moisture stability of an adsorbent is crucial. While this topic has been researched for other adsorbents such as zeolites and metal organic frameworks (MOFs), little is known on controlling the hydrolytic stability of porous BN. In this study, we propose a method to enhance porous BN's hydrolytic stability via surface functionalization using a fluoroalkylsilane. We explored two different routes of functionalization: (i) functionalization of porous BN powder followed by pelletization (route 1) and (ii) coating of porous BN pellets with fluoroalkylsilane (route 2). Spectroscopic, analytical and imaging techniques confirmed the functionalization process qualitatively and quantitatively. We subjected the functionalized samples to moisture exposure at 54% RH (similar to common storage conditions) and 92% RH (similar to flue gas stream conditions with high moisture content), and characterized them to probe their resistance to moisture. We also investigated their equilibrium and kinetic sorption properties in the context of CO2/N2 separation. Both routes produced materials with enhanced moisture stability. However, we noted differences between both functionalization routes. Route 2 produced a sample with a higher grafting yield and hydrophobic nature, and therefore better resistance to moisture exposure than route 1. From a sorption point of view, despite reduced porosity, the functionalized samples maintain reasonable CO2 uptakes. The functionalization led to changes in the textural features of the samples, which caused differences in the mass transfer. This work shows that functionalization could be used to protect porous BN upon moisture exposure.

The effects of size and surface functionalization of polystyrene nanoplastics on stratum corneum model membranes: An experimental and computational study

Nanoplastics are mainly generated from the decomposition of plastic waste and artificial production and have attracted much attention due to their wide distribution in the environment and the potential risk for humans. As the largest organ of the human body, the skin is inevitably in contact with nanoplastics. Stratum corneum is the first barrier when the skin is exposed to nanoplastics. However, little is known about the interactions between nanoplastics and stratum corneum. Here, the effects of particle size and surface functionalization (amino-modified and carboxy-modified) of polystyrene nanoplastics on the stratum corneum models were studied by Langmuir monolayer and molecular dynamics simulations. An equimolar mixture of ceramide/cholesterol/free fatty acid was used to mimic stratum corneum intercellular lipids. The Langmuir monolayer studies demonstrated that the larger size and surface functionalization of polystyrene nanoplastics significantly reduced the stability of stratum corneum lipid monolayer in a concentration-dependent fashion. Simulation results elucidated that functionalized polystyrene oligomers had a stronger interaction with lipid components of the stratum corneum model membrane. The cell experiments also indicated that functionalized polystyrene nanoplastics, especially for amino-modified polystyrene nanoplastics, had significant cytotoxicity on normal human dermal fibroblast cells. Our results provide fundamental information and the basis for a deeper understanding of the health risks of nanoplastics to humans.

High-efficient laser-based bionic surface structuring for enhanced surface functionalization and self-cleaning effect

In this work, a laser-based surface functionalization method combining laser surface texturing and silicone oil-assisted heat treatment was developed to fabricate superhydrophobic surface. Two bionic surface patterns, i.e., duck feather pattern and shark skin pattern were designed and fabricated using different laser processing parameters. 3-D digital microscope, scanning electron microscope, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy were utilized to analyze the surface morphology and chemistry of the laser functionalized surface. Self-cleaning test was conducted to compare the dust removal ability between the untreated surface and laser functionalized surface. The rough hierarchical surface structure was induced by laser texturing process, and the heat treatment process with silicone oil led to the formation of low surface energy. With the combined effects of surface structure and chemistry, the fabricated surface exhibits superior superhydrophobicity. Moreover, the laser functionalized superhydrophobic surface exhibits good self-cleaning ability, and highly efficient dust removal process was observed owing to the bouncing removal of water droplets. This work is not only simple and convenient, but also significantly reduces the production cost and enhances time efficiency for fabrication of superhydrophobic surface, and thus shows strong potential for applications in diverse areas.

PCL/Gelatin/Graphene Oxide Electrospun Nanofibers: Effect of Surface Functionalization on In Vitro and Antibacterial Response.

The emergence of resistance to pathogenic bacteria has resulted from the misuse of antibiotics used in wound treatment. Therefore, nanomaterial-based agents can be used to overcome these limitations. In this study, polycaprolactone (PCL)/gelatin/graphene oxide electrospun nanofibers (PGO) are functionalized via plasma treatment with the monomeric groups diallylamine (PGO-M1), acrylic acid (PGO-M2), and tert-butyl acrylate (PGO-M3) to enhance the action against bacteria cells. The surface functionalization influences the morphology, surface wettability, mechanical properties, and thermal stability of PGO nanofibers. PGO-M1 and PGO-M2 exhibit good antibacterial activity against Staphylococcus aureus and Escherichia coli, whereas PGO-M3 tends to reduce their antibacterial properties compared to PGO nanofibers. The highest proportion of dead bacteria cells is found on the surface of hydrophilic PGO-M1, whereas live cells are colonized on the surface of hydrophobic PGO-M3. Likewise, PGO-M1 shows a good interaction with L929, which is confirmed by the high levels of adhesion and proliferation with respect to the control. All the results confirm that surface functionalization can be strategically used as a tool to engineer PGO nanofibers with controlled antibacterial properties for the fabrication of highly versatile devices suitable for different applications (e.g., health, environmental pollution).

The heteroaggregation behavior of nanoplastics on goethite: Effects of surface functionalization and solution chemistry

Nanoplastics have attracted extensive attention in recent years. However, little is known about the heteroaggregation behavior of nanoplastics on goethite (FeOOH), especially the contribution of surface functional groups. In this study, the heteroaggregation behavior between polystyrene nanoplastics (PSNPs) and FeOOH was systematically investigated under different reaction conditions. Moreover, the effect of different functional groups (-NH2, -COOH, and bare) of PSNPs and solution chemistry was evaluated. The results showed that PSNPs could heteroaggregate with FeOOH, and the heteroaggregation rate of PSNPs with surface functionalization was significantly faster. The removal of suspended PSNPs was enhanced with increasing NaCl or CaCl2 concentration. However, heteroaggregation was significantly inhibited with the increase of solution pH. The zeta potentials analysis, time-resolved dynamic light scattering (DLS) and heteroaggregation experiments suggested that the electrostatic force affected the heteroaggregation process significantly. Fourier transform infrared (FTIR) spectra proved that the adsorption affinity between PSNPs and FeOOH was stronger after surface functionalization, especially for CH, O-C=O, and -CH2- groups, indicating that chemical bonding also made a contribution during the heteroaggregation process. This work is expected to provide a theoretical basis for predicting the environmental behavior between PSNPs and FeOOH.

Surface Modification of Hetero-phase Nanoparticles for Low-Cost Solution-Processable High-k Dielectric Polymer Nanocomposites.

The surface modification of nanoparticles (NPs) is crucial for fabricating polymer nanocomposites (NCs) with high dielectric permittivity. Here, we systematically studied the effect of surface functionalization of TiO2 and BaTiO3 NPs to enhance the dielectric permittivity of polyvinylidene fluoride (PVDF) NCs by 23 and 74%, respectively, measured at a frequency of 1 kHz. To further increase the dielectric permittivity of PVDF/NPs-based NCs, we developed a new hetero-phase filler-based approach that is cost-effective and easy to implement. At a 1:3 mixing ratio of TiO2:BaTiO3 NPs, the dielectric constant of the ensuing NC is found to be 50.2, which is comparable with the functionalized BaTiO3-based NC. The highest dielectric constant value of 76.1 measured at 1 kHz was achieved using the (3-aminopropyl)triethoxysilane (APTES)-modified hetero-phase-based PVDF composite at a volume concentration of 5%. This work is an important step toward inexpensive and easy-to-process high-k nanocomposite dielectrics.

Mesoporous and microporous carbons from one-pot hydrothermal products for supercapacitor electrodes: effects of porous structures and surface functionality

Mesoporous carbons were prepared from carbon dots via physical activation. Mesoporous carbons exhibit higher Cg than high-surface-area microporous carbons, and the efficiency of the surface area for mesopores is much higher than for micropores.

Unraveling the effects of surface functionalization on the catalytic activity of ReSe2 nanostructures towards the hydrogen evolution reaction

Herein, the surface functionalization of ReSe2 nanostructures by surfactants was investigated. This was done to understand how the use of various surfactants affects the catalytic activity of ReSe2 nanostructures towards the hydrogen evolution reaction (HER), and to determine which surfactant would result in maximal exposure of the active edge sites without impeding the catalytic processes of the HER. Oleylamine (OLA), oleic acid (OA), and trioctylphosphine oxide (TOPO) were used as the surfactants. Powder X-ray diffraction confirmed the formation of ReSe2 nanostructures that crystallized in a distorted 1 T phase triclinic system with a P-1 space group. The FTIR, XPS, NMR, and computational studies revealed that the surfactants bind to the surface of the ReSe2 nanostructures through their respective head groups. The ReSe2 nanostructures synthesized using TOPO (ReSe2-TOPO) had the lowest on-set potential, Tafel slope, and overpotential at 10 mA/cm2 at 73 mV, 58 mV/dec, and 171 mV, respectively. The catalytic performance of the nanostructures was significantly affected by their interaction with the surfactants. A high degree of passivation by the surfactant resulted in poor catalytic activity, and a lower degree of passivation resulted in excellent catalytic activity towards the HER.

Effect of surface functionalization and loading on the mechanical properties of soft polymeric nanoparticles prepared by nano-emulsion templating

Drug and gene delivery systems based on polymeric nanoparticles offer a greater efficacy and a reduced toxicity compared to traditional formulations. Recent studies have evidenced that their internalization, biodistribution and efficacy can be affected, among other factors, by their mechanical properties. Here, we analyze by means of Atomic Force Microscopy force spectroscopy how composition, surface functionalization and loading affect the mechanics of nanoparticles. For this purpose, nanoparticles made of Poly(lactic-co-glycolic) (PLGA) and Ethyl cellulose (EC) with different functionalizations and loading were prepared by nano-emulsion templating using the Phase Inversion Composition method (PIC) to form the nano-emulsions. A multiparametric nanomechanical study involving the determination of the Young's modulus, maximum deformation and breakthrough force was carried out. The obtained results showed that composition, surface functionalization and loading affect the nanomechanical properties in a different way, thus requiring, in general, to consider the overall mechanical properties after the addition of a functionalization or loading. A graphical representation method has been proposed enabling to easily identify mechanically equivalent formulations, which is expected to be useful in the development of soft polymeric nanoparticles for pre-clinical and clinical use.