Surface Modifier Research Articles

Ti3C2Tx MXene deposition: A simple surface engineering technique for dual enhancement of biological functions for nonbearing applications

Implant-associated complications, such as infection and poor osseointegration, present significant challenges in the field of biomedical implants. To address these issues, it is crucial to develop implant surfaces that possess both bacteriostatic and osteoconductive properties. In recent years, the field of surface modification for metallic substrates using two-dimensional materials has emerged as a highly promising strategy to enhance their biological properties. Among these materials, MXenes stand out as an excellent candidate for surface modifications due to their unique properties, such as biocompatibility, high specific surface area, and tunable chemical composition. In the present study, we introduce a simple deposition method of Ti3C2Tx MXene films on SS316L substrates to improve surface-cell interactions. The differentiation study demonstrated the alkaline phosphatase (ALP) enzyme activity on Ti3C2Tx-MXene-coated samples without osteogenic medium compared to uncoated samples in both, basic and osteogenic media. Moreover, the bacteriostatic character of the deposited MXene-coatings was confirmed against Gram-positive Staphylococcus aureus as well as Gram-negative Escherichia coli bacteria. The improved stimulation of both cell osteogenic differentiation and distinctive antimicrobial features triggered by Ti3C2Tx-MXene-coatings emphasizes their great potential as implant surface modifiers to improve integration and reduce the risk of infection in various biomedical applications.

Bioflocculant polymer reduced CuO/NiO binary transition metal oxide nanocomposite: Application as an effective non-enzymatic glucose sensor

A bimetallic copper oxide/nickel oxide nanocomposite (CuO/NiO NCs) was synthesized via direct carbonization method by using microbial polymer as reducing agent. This nanocomposite was employed as a viable non-enzymatic electrocatalyst in the glucose detection. It was completely characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopic (EDX) methods and revealed the obtained porous nanoflower morphology with particle sizes of 100–200 nm in a monoclinic face-centered cubic crystalline structure. FT-IR spectra confirmed the presence of functional groups and the purity of the nanocomposite. Electrocatalytic performance for glucose oxidation was evaluated through cyclic voltammetric (CV) and amperometric i-t techniques. The observation demonstrated that the CuO/NiO NCs exhibited a remarkable electro-oxidation activity against glucose, attributed to the synergistic effects of the bimetallic components. As an electrode surface modifier, the CuO/NiO NCs facilitated an enhanced glucose oxidation over a linear range of 1–9 mM via CV, while amperometric i-t measurements achieved a detection range from 0.04 μM to 4.86 mM in a 0.1 M NaOH (pH ∼ 13) electrolyte solution. These eco-friendly and in-expensive nanoflowers displayed excellent selectivity, stability, and reproducibility, underscoring their potential in diabetes monitoring and the subsequent scientific analysis.

Fluorescence and Colorimetric Dual-Readout Detection of Tetracycline Using Leucine-Conjugated Iron Oxide Quantum Dots.

This study developed a dual-readout system utilizing fluorescence and colorimetry based on iron oxide quantum dots (IO-QDs) for detecting tetracycline (TCy). IO-QDs were synthesized within 6 h using L-leucine as a surface modifier, achieving a more efficient route. Upon interaction with TCy, IO-QDs exhibited a significant decrease in fluorescence response and observable color changes, while fluorescence lifetime remained consistent regardless of TCy presence. Moreover, IO-QDs' fluorescence response remained stable across various temperatures. The Förster resonance energy transfer distance of less than 2 nm and a quenching constant of 2.90 × 1012 M-1s-1 indicated static quenching in the presence of TCy. Additionally, significant changes in observed and corrected fluorescence efficiency suggested the involvement of the inner filter effect in the fluorescence quenching of IO-QDs. The synthesized IO-QDs were then utilized for selective and rapid fluorescence-based TCy detection, showing a linear range of 0.5 to 80 μM. Simultaneously, a colorimetric method for TCy detection was established, demonstrating a good linear relationship within the range of 0.5 to 20 μM. The detection limits for TCy were determined as 0.539 and 0.329 μM using fluorescence and colorimetric approaches, respectively. Furthermore, IO-QDs were applied to detect real samples, and the dual-readout probe exhibited satisfactory recoveries, confirming the practical reliability of the developed method for analyzing milk and drinking water samples.

Reinvigorating Photo-Activated R-Alkoxysilanes Containing 2-Nitrobenzyl Protecting Groups as Stable Precursors for Photo-Driven Si-O Bond Formation in Polymerization and Surface Modification.

This study aimed to revitalize silicon-based sol-gel chemistry methodologies utilizing photoprotected R-alkoxysilanes to control the synthesis of unique silicon-based materials. We have investigated the synthesis, characterization, light-induced deprotection, and subsequent polymerization/surface functionalization through the use of 2-nitrobenzyloxy-based photoremovable protecting groups (PPGs) as alkoxy reactive groups on ethyl and phenyl (R x -(alkoxy) y silanes, with x = 0-3 and y = 1-3). The photochemical dynamics, relative efficiencies, and kinetics of the novel alkoxysilane-based PPGs were thoroughly investigated using UV light irradiation by NMR and UV/vis methods. We then explored the tin-catalyzed coupling of photodeprotected products (R x -silanols) to form polymers/oligomers. We have found that photoenabled removal of PPGs and conversion to silanols from all silane systems studied is achieved. Furthermore, these deprotected species are polymerizable into siloxanes and effectively used as light-controlled surface modifiers with masking techniques of which proof-of-concept examples are given, enabling promising application as photolithographic reagents.

Decoding Long-Chain Fatty Acid Ethyl Esters during the Distillation of Strong Aroma-Type Baijiu and Exploring the Adsorption Mechanism with Magnetic Nanoparticles.

Simultaneous detection of the dynamic distribution of long-chain fatty acid ethyl esters (LCFAEEs) during Baijiu distillation is crucial for optimizing its flavor and health attributes. In this study, we synthesized a simple, cost-effective Fe3O4@NH2 adsorbent to simultaneously extract eight LCFAEEs from Baijiu. Through density functional theory and adsorption experiments, we elucidated 1,6-hexanediamine as a surface modifier, with the -NH2 groups providing adsorption sites for the LCFAEEs via hydrogen-bonding interactions and van der Waals forces. Additionally, we established the magnetic solid-phase extraction-GC-MS extraction technique combined with stable isotope dilution analysis to analyze LCFAEEs. This method revealed the dynamic distribution patterns of LCFAEEs during strong aroma-type Baijiu (SAB) distillation. We observed that the concentrations of the eight LCFAEEs gradually decreased with prolonged distillation and were significantly correlated with ethanol concentration. To ensure optimal flavor and clarity in SAB, it is recommended to select the heart-stage base Baijiu with an alcohol content of 58%-63%.

Machine learning for screening and predicting the best surface modifiers for a rational optimization of efficient perovskite solar cells

The key to keep the rising slope of perovskite solar cell performances is to reduce non-radiative losses by minimizing defect density. To this end, a large variety of strategies have been adopted spanning from the use of interfacial layers, surface modifiers, to interface engineering. Although winning concepts have been demonstrated, they result from a mere trial and error approach, which is time consuming and operator-dependent. To face this challenge, in this work, we propose the use of a machine learning approach for an educated and rational material screening with optimal characteristics in terms of surface passivation. In particular, we applied Shapley additive explanation to extract the specific chemical features of the passivator, which directly impact the device parameters, specifically the open circuit voltage (Voc). By monitoring the different material parameters as input, we were able to list the most promising passivators and directly test them in working solar cells. By comparing the device performances with the results of the modeling and with additional optical and morphological characterization, we retrieved the most significant material properties linked to the highest efficiency, which are (i) the presence of chlorine and its strong binding capacity to positively charged defects on perovskite surface, reducing the non-radiative recombination and (ii) an increased flexibility of the molecule, resulting in better coverage of the surface. Finally, we tested the predictive power of the ML algorithm proposing a new passivator, which, implemented in a working device, leads to the predicted high Voc confirming the results of the modeling.

Electrochemical applications of fly ash as surface modifier: sustainable mitigation of industrial residue

Electrochemical applications of fly ash as surface modifier: sustainable mitigation of industrial residue

Advances in Immunomodulatory Mesoporous Silica Nanoparticles for Inflammatory and Cancer Therapies.

In recent decades, immunotherapy has been considered a promising treatment approach. The modulatable enhancement or attenuation of the body's immune response can effectively suppress tumors. However, challenges persist in clinical applications due to the lack of precision in antigen presentation to immune cells, immune escape mechanisms, and immunotherapy-mediated side effects. As a potential delivery system for drugs and immunomodulators, mesoporous silica has attracted extensive attention recently. Mesoporous silica nanoparticles (MSNs) possess high porosity, a large specific surface area, excellent biocompatibility, and facile surface modifiability, making them suitable as multifunctional carriers in immunotherapy. This article summarizes the latest advancements in the application of MSNs as carriers in cancer immunotherapy, aiming to stimulate further exploration of the immunomodulatory mechanisms and the development of immunotherapeutics based on MSNs.

Hydrophobic composite phase change coating: Preparation, performance and application

The utilization of composite phase change materials in energy storage and solar thermal applications is significantly restrained by their inherent non-hydrophobic surfaces and susceptibility to contamination. This study presents a novel synthesis of modified paraffin (Pa) @ silica (SiO2) nanocapsules through an efficient in situ hydrolysis and polycondensation reaction utilizing tetraethyl orthosilicate (TEOS) as the silicon source, paraffin as the phase change material, and hexamethyldisilazane (HMDS) as the surface modifier. These nanocapsules were then employed to formulate a composite phase change coating (PSC-1) by spraying onto a substrate of lithium silicate (Li2SiO3), a green inorganic binder. This coating combines self-cleaning and energy storage functionalities. The thermal characterization of PSC-1 revealed an enthalpy of phase transition of 92.95 J/g at a core-shell ratio of 1.5:1 and an HMDS to TEOS volume ratio of 1:1. Additionally, the thermal conductivity of PSC-1 was measured at 0.505 W/m∙K, which is approximately 53 % higher than that of pure paraffin. PSC-1 also demonstrated superior hydrophobicity, with a static water contact angle of 132.6°. Enhancing its practicality, the coating was subsequently dyed black and assessed for photothermal conversion efficiency, which was determined to be around 68 %. The integration of robust self-cleaning properties and high-efficiency thermal characteristics renders PSC-1 a highly promising material for broad applications in solar energy conversion and storage.

Beyond lithium-ion batteries: Are effective electrodes possible for alkaline and other alkali elements? Exploring ion intercalation in surface-modified few-layer graphene and examining layer quantity and stages

In the pursuit of reliable energy storage solutions, the significance of engineering electrodes cannot be overstated. Previous research has explored the use of surface modifiers (SMs), such as single-side fluorinated graphene, to enhance the thermodynamic stability of ion intercalation when applied atop few-layer graphene (FLG). As we seek alternatives to lithium-ion batteries (LIBs), earth-abundant elements like sodium and potassium have emerged as promising candidates. However, a comprehensive investigation into staging intercalation has been lacking thus far. By delving into staging assemblies, we have uncovered a previously unknown intercalation site that offers the most energetically favorable binding. Here, we study the first three elements in both alkali (Li, Na, K) and alkaline (Be, Mg, Ca) earth metals. Furthermore, the precise mechanism underlying this intercalation system has remained elusive in prior studies. In our work, we employed density functional theory calculations with advanced hybrid functionals to determine the electrical properties at various stages of intercalation. This approach has been proven to yield more accurate and reliable electrical information. Through the analysis of projecting density of states and Mulliken population, we have gained valuable insights into the intricate interactions among the SM, ions, and FLG as the ions progressively insert into the structures. Notably, we expanded our investigation beyond lithium and explored the effectiveness of the SM on ions with varying radii and valence, encompassing six alkali and alkaline earth metals. Additionally, we discovered that the number of graphene layers significantly influences the binding energy. Our findings present groundbreaking concepts for material design, offering diverse and economically viable alternatives to LIBs. Furthermore, they serve as a valuable reference for fine-tuning electrical properties through staging intercalation and the application of SMs.

Adsorption behavior and selective regulation of tartaric acid at solid-liquid interface: For ilmenite flotation separation

Ilmenite and its main gangue minerals (titanaugite and forsterite) are challenging to separate due to their similar surface chemical properties. The flotation process is an effective method, and the use of surface modifiers is essential. There is an urgent need to develop more effective and environmentally friendly agents to address the shortcomings of existing surface modifiers and the lack of understanding of the inhibition mechanism. In this work, sodium oleate was used as a collector to investigate the inhibitory effect of tartaric acid (TA) on gangue minerals in ilmenite flotation. This was done through micro-flotation experiments, Zeta potential measurements, x-ray photoelectron spectroscopy (XPS) analysis, solution chemical simulations, molecular dynamics (MD) simulations, and density functional theory (DFT). The results demonstrated a significant decrease in the recovery rates of titanaugite and forsterite after the addition of 1 × 10^4 mol/L TA at pH = 8. TA chemically adsorbs onto the Ca and Mg sites on the surfaces of titanaugite and forsterite through carboxylic acid groups. This impedes the adsorption of anionic collectors due to electrostatic repulsion and steric hindrance, effectively inhibiting gangue minerals and achieving separation from ilmenite.

Nanocomposites of Natural Rubber Containing Montmorillonite Modified by Poly(2-oxazolines).

Nanocomposites with a natural rubber (NR) matrix containing organomodified montmorillonite (MMT) as a precursor of nanoparticles were prepared using two different polyoxazolines as surface modifiers of the MMT. The materials were characterized by X-ray diffraction, transmission electronic microscopy and ultimate mechanical properties, and parameters obtained by DMTA method (storage and loss moduli and loss tangent) were determined. It was found that the effect of nanofillers presence has a significant effect on tensile strength as well as elongation at break, which are higher for materials with higher viscosity due to the presence of carbon blacks compared to the composites without carbon blacks. From the two modifiers, poly(2-ethyl-2-oxazoline) was identified as a prospective modifier for surface modification of MMT used as the possible additive for tyre treads exhibiting optimal balance between fuel consumption and safety of driving concerning breaking action and lateral breakaway.

Efficient Electrochemical Sensing of Chlorpromazine with a Composite of Multiwalled Carbon Nanotubes and a Thiacalix[4]arene-Based Metal-Organic Framework.

Chlorpromazine (CPMZ) is a representative drug for the treatment of psychiatric disorders. Excessive use of CPMZ could result in some serious health problems, and therefore, construction of a sensitive electrochemical sensor for CPMZ detection is greatly significant for human health. Herein, a feasible electrochemical method for the detection of CPMZ was provided. To design a suitable electrode surface modifier, a new two-dimensional (2D) thiacalix[4]arene-based metal-organic framework was designed and synthesized under solvothermal conditions, namely, [Co(TMPA)Cl2]MeOH·2EtOH·2H2O (Co-TMPA). Afterward, a series of composite materials was prepared by combining Co-TMPA with highly conductive carbon materials. Markedly, Co-TMPA/MWCNT-2@GCE (GCE = glassy carbon electrode, MWCNT = multiwalled carbon nanotube) exhibited the best electrocatalytic performance for CPMZ detection due to the synergistic effect between MWCNT and Co-TMPA. Particularly, it featured a low limit of detection (8 nM) and a wide linear range (0.05 to 1350 μM) in quantitative determination of CPMZ. Meanwhile, the sensor possessed excellent stability, selectivity, and reproducibility. Importantly, Co-TMPA/MWCNT-2@GCE was employed to analyze CPMZ in urine and serum with satisfactory recoveries (98.87-102.17%) and relative standard deviations (1.44-3.80%). Furthermore, the electrochemical detection accuracy of the Co-TMPA/MWCNT-2@GCE sensor was verified with the ultraviolet-visible spectroscopy technique. This work offers a promising sensor for the efficient analysis of drug molecules.

Elucidating the interaction between polar alkoxysilane-modified silicate glass and ionic surfactant in the obtainment of hydrophobic transparent film

Soda-lime-silicate glass is a widely used material in industry and everyday life. For some applications, it is important to have hydrophobic properties of its surface and at the same time retain the transparency in the visible spectrum. This can be achieved using fluoroalkyl silanes as surface modifiers. However, fluorine shows severe health effects and the nowadays tendency is to use more appropriate substances for surface modification. In this work, we show the possibility of obtaining a hydrophobic and transparent film on silicate glass using alkoxysilanes with alkyl groups possessing terminal -NH2 and subsequent modification of such silanized glass using an anionic surfactant. The possible mechanism of the interaction between the chemisorbed silyl group and the dodecyl sulfate ion was discussed.

Regulating coordinatively unsaturated Co active sites in TA@ZIF-L(Co) via tannic acid for efficient photoelectrochemical water oxidation

Metal-organic frameworks (MOFs) as a cocatalyst can enhance the photoelectrochemical (PEC) water oxidation performance to a certain extent, but still suffer from deficient exposure of active sites and low electron mobility. In this work, 2D Leaf-like zeolitic imidazolate frameworks (ZIF-L) were selected as a precursor for the generation of defective structures by tannic acid (TA) functionalization-assisted etching, and then coupling it with BiVO4 to prepare a novel and highly efficient TA@ZIF-L(Co)/BiVO4 photoanode by a simple impregnation method. The photocurrent density of TA@ZIF-L(Co)/BiVO4 composite photoanode achieves 4.21 mA cm−2 at 1.23 VRHE under AM 1.5 G illumination, which is superior to that of ZIF-L(Co)/BiVO4, and three times that of the bare BiVO4, with a charge injection efficiency of up to 80 %, and its stability is also remarkably improved. Experimental results and DFT calculations showed that the introduction of TA not only improved the light absorption efficiency, but also exposed more active sites, increased the electron density of the coordinatively unsaturated Co active sites, and enhanced the polarized electric field on the surface, thus accelerating electron mobility. This work demonstrates that TA as a surface modifier has great potential to activate metal sites and change the electronic environment of MOFs for BiVO4-based photoanode in PEC water oxidation, providing valuable insights into the rational design of photoanodes.

Tailoring crystal plane of short-process regenerated LiFePO4 towards enhanced rate properties

Captured by the environmental and economic value, the recycling of spent lithium iron phosphate (LFP) batteries has attracted numerous attentions. However, hydrometallurgical method still suffers from complex process, and hydrothermal method is limited by morphology control, ascribed to the strong polarity of water. Herein, supported by ethanol as crystal surface modifier, the regular (010) orientation and short b-axis are effectively tailored for regenerated LFP. As Li-storage cathode, the capacities of as-optimized LFP could reach up to 157.07 mA h g−1 at 1 C, and the stable capacity of 150.50 mA h g−1 could be remained with retention of 93.48% after 400 cycles at 1 C. Even at 10 C, their capacity could be still kept about 119.3 mA h g−1. Assisted by the detail analysis of adsorption energy, the clear growth mechanism is proposed, the lowest adsorbing energy (−4.66 eV) of ethanol on (010) crystal plane renders the ordered growth along (010) crystal plane. Given this, the work is expected to shed light on the tailoring mechanism of internal plane about regenerated materials, whilst providing effective strategies for high-performance regenerated LFP.

Parametric design and performance evaluation of TPMS porous vitrified bond diamond grinding wheel using digital light processing

Porous vitrified bond diamond grinding wheels are commonly used for grinding hard and brittle materials. However, uneven pore distribution and low porosity affect the grinding performance of the wheel significantly. In this study, three types of triply periodic minimal surface porous vitrified bond diamond grinding wheels—Gyroid, Diamond, and Lidinoid–were prepared through parametric designing and digital light processing 3D printing. The grinding wheel achieved a uniform distribution and an interconnected pore structure. The key to high-performance grinding wheel via stereolithography 3D printing lies in the preparation of the slurry with high solid loading, low viscosity and uniform stability. Hence, the effect of surface modifiers on the slurry, along with the effect of sintering temperature and the microscopic and mechanical properties, was investigated. By grinding the SiC ceramics, the material removal rate, grinding temperature, and surface roughness were compared to those achieved using a conventional solid-structure grinding wheel. The results show that the slurry with the highest solid content of 80 wt% (58 vol%) and viscosity of 4.21 Pa s (30 s−1) can be prepared using surface-modified particles. The diamond grinding wheel sintered at 680 °C exhibits the best comprehensive performance. A grinding wheel prepared using stereolithography 3D printing can achieve better surface roughness and lower the grinding temperature.

Stable aluminum-lithium alloy fuels for solid propellants by facile surface modifying

As a highly reactive metal fuel, aluminum–lithium (Al-Li) alloy is an ideal candidate for replacing Al powders in solid propellants. However, the Li solid solution and AlLi compounds on the surface of Al-Li alloy powders display high reactivity, which can react with a large number of organic and inorganic reagents. Thus, the incompatibility of Al-Li alloy with other components of propellants makes it difficult to be further applied in propellants. In this study, surface-modified Al-Li alloy powders (Li content of 5 wt%) with 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (FAS17) were prepared by a facile self-assembly method, which made the alloy powders super-hydrophobic. The results of SEM, XPS and FIB-TEM show that the surface of Al-Li alloy powder is well-coated by an evenly distributed FAS17 layer. Due to the fluoroalkyl on the surface of the powders, the water contact angle increased by 91°and the intensity of the reaction between alloy powders and water is significantly reduced, which results in improved compatibility with other components of propellants.Meanwhile, the propellant grain of surface-modified powders had fewer defects than the sample before coating, and showed original excellent combustion performance. The average combustion pressure and pressurization rate increased by ∼114 kPa and ∼8613 kPa/s, and the steady burning rate increased by 0.24 mm/s. Therefore, the surface-modified Al-Li alloy powders with FAS17 are expected to be an attractive candidate as a highly active and stable fuel in solid propellants.

Enhancing lithium titanate anode performance through surface modification with fluorine and nitrogen co-doped carbon nanotubes

In this study, we explore the efficacy of fluorine and nitrogen co-doped carbon nanotubes (F@N-CNT) as a novel surface modifier for lithium titanate (LTO) anodes in lithium-ion batteries (LIBs). The integration of F@N-CNT enhances the electrochemical properties of LTO anodes by improving electrical conductivity and facilitating lithium-ion diffusion., Electrodes modified with F@N-CNT exhibited significant improvements in capacity retention, achieving 71 % capacity retention over 200 cycles at 2 C and delivering energy capacities up to 162.9 mAh g−1 at 0.2 C, with an impressive high-rate performance of 74.8 mAh g−1 at 30 C. This study demonstrates that F@N-CNT effectively forms a conductive network within the LTO matrix, resulting in superior high-rate performance and stability. It presents a comprehensive analysis of the microstructural changes induced by co-doping and elucidates their impact on the electrochemical performance, providing valuable insights into the design of high-performance anodes for future energy storage applications. This approach not only addresses the current limitations of LTO anodes but also introduces a scalable strategy for enhancing the overall functionality of LIBs.

Strategy to Simultaneously Manipulate Direct Zn Nucleation and Hydrogen Evolution via Surface Modifier Hydrolysis for High-Performance Zn-Ion Batteries.

The demand for safer batteries is growing rapidly due to fire incidents in electronic devices that use Li-ion batteries. Zn-ion batteries are among the most promising candidates to replace Li-ion batteries because they use a water-based electrolyte and are not explosive. However, Zn-ion batteries suffer from persistent corrosion and dendritic crystal formation during the charge-discharge process, which decrease their reversibility and hinder their commercial usage. Extensive research has been conducted to address these issues, but there are significant limitations due to high process and time costs. In this study, the modulation of the Zn-electrolyte interface to overcome these challenges is attempted using acetamide-derived thioacetamide (TAA), a surface modifier used in electroplating. TAA undergoes hydrolysis in an aqueous solution and produces weakly acidic byproducts and sulfide ions. These species are adsorbed onto the Zn metal surface, which induces uniform Zn2+ deposition, facilitates the formation of a stable interfacial layer, and inhibits side reactions due to the reduced water activity. Consequently, the symmetric cell with TAA achieves a low polarization of 50 mV and stable cycling for 700 h at 1 mA cm-2. Additionally, a Zn|V6O13 full cell exhibits electrochemical reversibility, maintaining a capacity retention of 64% over 300 cycles. Therefore, this study offers useful insights into the development of a simple manufacturing process to ensure the competitiveness of Zn-ion batteries for practical applications using functional electrolyte additives.