Tunable Surface Properties Research Articles

A Digital‐to‐Channel Microfluidic Interface via Inkjet Printing of Silver and UV Curing of Thiol–Enes

AbstractMicrofluidic sample manipulation is a key enabler in modern chemical biology research. Both discrete droplet‐based digital microfluidic (DMF) assays and continuous flow in‐channel assays are well established, each featuring unique advantages from the viewpoint of automation and parallelization. However, there are marked differences in the applicable microfabrication materials and methods, which limit the interfacing of DMF sample preparation with in‐channel separation systems, such as the gold standard microchip electrophoresis. Simultaneously, there is an increasing demand for low‐cost and user‐friendly manufacturing techniques to foster the adaptation of microfluidic technology in routine laboratory analyses. This work demonstrates integration of DMF with in‐channel separation systems using only low‐cost and accessible (non‐cleanroom) manufacturing techniques, i.e., inkjet printing of silver for patterning of the driving electrodes and UV curing of off‐stoichiometric thiol–ene (OSTE) polymers both for dielectric coating of the electrode arrays and replica molding of the microchannel network. As a dielectric, OSTE performs similar to Parylene C (a gold standard dielectric in electrowetting), whereas its tunable surface and bulk properties facilitate straightforward bonding of the microchannel with the dielectric layer. In addition, a new chip design that facilitates efficient droplet transfer from the DMF part to the microchannel inlet solely by electrowetting is showcased.

Fabrication and Characterization of Ceftizoxime-Loaded Pectin Nanocarriers.

Ceftizoxime (C13H12N5NaO5S2) is a parenteral, third-generationcephalosporin antibiotic used to treat bacterial infections including ear, nose, and throat infections. In this work, pectin has been used as a nanocarrier for ceftizoxime due to its high biocompatibility and non-toxicity with tunable surface properties. Ceftizoxime-loaded pectin nanocarriers (CPN) were successfully synthesized by the solvent displacement method. Optimization of nanoformulation was done by response surface methodology using Design-Expert software. The optimized formulation examined various in-vitro characterizations such as particle size, morphology, and FTIR studies. TEM results revealed irregular shape nanoparticles within the range of 29–110 nm. The in-vitro drug release using the dialysis method was performed after 24 h where nanoformulation showed sustained drug release. Drug-loaded nanoparticles revealed good antimicrobial activity against Bacillus cereus, Bacillus polymyxa, Enterobacter aerogenes, and Pseudomonas aeruginosa.

Salt templated and graphene nanoplatelets draped copper (GNP-draped-Cu) composites for dramatic improvements in pool boiling heat transfer

We demonstrate a novel technique to achieve highly surface active, functional, and tunable hierarchical porous coated surfaces with high wickability using a combination of ball milling, salt-templating, and sintering techniques. Specifically, using ball-milling to obtain graphene nanoplatelets (GNP) draped copper particles followed by salt templated sintering to induce the strength and cohesiveness to the particles. The salt-templating method was specifically used to promote porosity on the coatings. A systematic study was conducted by varying size of the copper particles, ratio of GNP to copper particles, and process parameters to generate a variety of microporous coatings possessing interconnected pores and tunnels that were observed using electron microscopy. Pool boiling tests exhibited a very high critical heat flux of 289 W/cm2 at a wall superheat of just 2.2 °C for the salt templated 3 wt% GNP draped 20 µm diameter copper particles with exceedingly high wicking rates compared to non-salt-templated sintered coatings. The dramatic improvement in the pool boiling performance occurring at a very low surface temperature due to tunable surface properties is highly desirable in heat transfer and many other engineering applications.

Designable Aluminum Molecular Rings: Ring Expansion and Ligand Functionalization

AbstractPresented herein are the AlIII molecular ring architectures from 8‐ring to 16‐ring. Although there are numerous reported cyclic coordination compounds based on transition metals, gallium, or lanthanides, the Al versions are less developed due to the fast hydrolysis nature of Al3+ ion. With the assistant of monohydric alcohols, a series of atomic precisely Al molecular rings based on benzoates are synthesized. The ring expansion of these Al‐rings from 8‐ring to 16‐ring is related to the monohydric alcohol structure‐directing agents. Moreover, the organic ligands on the Al‐rings can be modified by using various benzoate derivatives, which lead to tunable surface properties of the Al‐rings from hydrophilicity to ultra‐hydrophobicity. Importantly, 4‐aminobenzoic acid bridged 16‐ring is soluble in organic solvents and exhibits high solution stability revealed by mass spectroscopy. Ligand substitution also can be performed between these Al‐rings, which reveal controllable ligand functionalization of these Al‐rings.

Designable Aluminum Molecular Rings: Ring Expansion and Ligand Functionalization.

Presented herein are the AlIII molecular ring architectures from 8-ring to 16-ring. Although there are numerous reported cyclic coordination compounds based on transition metals, gallium, or lanthanides, the Al versions are less developed due to the fast hydrolysis nature of Al3+ ion. With the assistant of monohydric alcohols, a series of atomic precisely Al molecular rings based on benzoates are synthesized. The ring expansion of these Al-rings from 8-ring to 16-ring is related to the monohydric alcohol structure-directing agents. Moreover, the organic ligands on the Al-rings can be modified by using various benzoate derivatives, which lead to tunable surface properties of the Al-rings from hydrophilicity to ultra-hydrophobicity. Importantly, 4-aminobenzoic acid bridged 16-ring is soluble in organic solvents and exhibits high solution stability revealed by mass spectroscopy. Ligand substitution also can be performed between these Al-rings, which reveal controllable ligand functionalization of these Al-rings.

Insights into the adsorption of Pb(II) over trimercapto-s-triazine trisodium salt-modified lignin in a wide pH range

A novel fabrication method for modifying alkaline lignin (AL) was reported, in which trimercapto-s-triazine trisodium salt was used as a modifier to tune surface properties of AL. Molecular structure of modified AL (FAL) was determined by 3D-EEM, synchronous fluorescence, FTIR, 13C MAS NMR and XPS. Two-dimensional correlation spectroscopy and electron localization function demonstrated that both of electrostatic and coordinate bonds formed between these functional groups and Pb(II) at higher pH of 3.0 to 6.0 while only coordinate bond at lower pH of 0.2 to 1.2. The higher the solution pH was, the stronger the adsorption capacity of FAL had. The maximum adsorption capacity (qm) of Pb(II) was 20.0, 28.2, 65.1 and 73.7 mg/g at pH of 0.2, 1.2, 3.0 and 6.0 (T = 25 °C), respectively. The adsorption performance of FAL towards Pb(II) was better by comparing with other biomass-based materials via adsorption amount, equilibrium time as well as simplicity of the synthesized steps. These results improve the understanding of FAL-Pb(II) interaction at the molecular level and facilitate a comprehensive evaluation on the treatment efficiency of FAL.

Preparation of amylose-poly(methyl methacrylate) inclusion complex as a smart nanocarrier with switchable surface hydrophilicity

Amylose, as a linear biopolymer, tends to form helical inclusion complexes with suitable guest species. This is of great importance for a variety of applications, especially in the pharmaceutical and food industry. In this study, we propose an approach for the preparation of a novel inclusion complex with switchable surface hydrophilicity. For this purpose, amylose was first conjugated to ethylene diamine hydrophilic residues. Then, the short chains of the hydrophobic poly(methyl methacrylate, PMMA) were grafted onto the cavity of amylose through atom transfer radical polymerization (ATRP). According to CD spectroscopy results, the amylose-PMMA inclusion complexes displayed solvent-directed helical chirality inversion using either DMSO or water as a solvent. Fluorescence imaging, AFM and DLS techniques revealed the solvent-dependent surface hydrophilicity of the amylose-PMMA inclusion complex. Interestingly, its morphological studies displayed a central cavity, which makes it suitable for carrying cargoes in drug delivery applications. Obtaining the amylose-polymer inclusion complexes with tailorable hydrophilicity of both the exterior surface and the interior cavity can be of paramount importance for a wide variety of bio-applications.

Phosphorus‐Modified Mesoporous Inorganic Materials for Production of Hydrocarbon Fuels and Value‐Added Chemicals

AbstractPhosphorus‐modified mesoporous inorganic materials play crucial roles in the valorization of lignocellulosic biomass materials such as syngas (CO and H2), carbohydrate sugars and lignin. This review summarizes the recent advances on the Co‐impregnated phosphorus‐modified γ‐Al2O3 and SiO2 catalysts for production of liquid hydrocarbon fuels via Fischer‐Tropsch synthesis (FTS) reaction of syngas as well as metal phosphates or precious (Pt and Ru) metals‐supported on the metal phosphates for production of furanic compounds, levulinic acid, aromatics and fuel commodities from carbohydrate sugars and lignin. These phosphorus‐modified materials play key roles in the syngas as well as biomass conversion processes due to their tunable surface properties and mesoporous structures. Phosphorus to metal ratios of inorganic materials with their porosity, calcination temperatures of metal phosphates, natures of biomass feedstocks, and reaction variables significantly affect yields of both hydrocarbon fuels and value‐added chemicals. This short review mainly focusses on the various applications of those mesoporous catalysts and supports, and strategies for effective catalytic transformations of lignocellulosic biomass‐derived feedstocks.

Self-assemblying behaviour of activated microporous carbon microspheres functionalized via water filtration process

Activated carbon spheres are truly innovative materials with their porous micro/nanostructure that gives them tunable and controllable surface properties (i.e. high surface area, size and orientation of pores etc.). They have great potential for applications as adsorbents for cleaning/purification of water, air and chemical substances, catalyst supports, energy storage and conversion, adsorption of chemical warfare agents, filtration and others. Magnetic functionalization of highly porous and high surface areas of activated carbons have received considerable attention for their more sophisticated and advanced utilization as “smart” and “self-assemblying” purposes. In this study, a novel fabrication technique was used to synthesize activated high compressive strength nanoporous carbon spheres. The functionalization via adsorption/impregnation of magnetic substances was occured during a well-known water treatment-filtering route to fill the pores with nano-sized magnetic particles. Unusually active and dynamic interactions of the magnetic phases were observed upon contacting into each other revealing self-assemblying behaviour of activated carbon microspheres. Dynamic magnetical interaction of self assemblying behaviour of these spheres may have further and advanced applications for variety of purposes.

Tunable Crystalline Phases in UV-Curable PEG-Grafted Ladder-Structured Silsesquioxane/Polyimide Composites.

A series of UV-curable hybrid composite blends containing a carboxylic acid functionalized polyimidewith varying amounts of high molecular weight (~1 K) PEG-grafted ladder-structured polysilsesquioxanes copolymerized with methacryl groups were fabricated and their structural, thermal, mechanical, and surface properties characterized. At a composite weight ratio of polyimide above 50 wt.%, a stark shift from amorphous to crystalline polyethylene glycol (PEG) phases were observed, accompanied by a drastic increase in both surface moduli and brittleness index. Moreover, fabricated composites were shown to have a wide range water contact angle, 9.8°–73.8°, attesting to the tunable surface properties of these amphiphilic hybrid polymer composites. The enhanced mechanical properties, combined with the utility of tunable surface hydrophilicity allows for the possible use of these hybrid polymer composites to be utilized as photosensitive polyimide negative photoresists for a myriad of semiconductor patterning processes.

Flax Biomass Conversion via Controlled Oxidation: Facile Tuning of Physicochemical Properties.

The role of chemical modification of pristine linen fiber (LF) on its physicochemical and adsorption properties is reported in this contribution. The surface and textural properties of the pristine LF and its peroxyacetic acid- (PAF) and chlorite-treated (CF) fiber forms were characterized by several complementary methods: spectroscopy (SEM, TEM, FT-IR, and XPS), thermal analysis (DSC and TGA), gas/water adsorption isotherms, and zeta potential (ξ). The results obtained reveal that the surface charge and textural properties (surface area and pore structure) of the LF material was modified upon chemical treatment, as indicated by changes in the biomass composition, morphology, ξ-values, and water/dye uptake properties of the fiber samples. Particularly, the pristine LF sample displays preferential removal efficiency (ER) of methylene blue (MB) dye with ER ~3-fold greater (ER~62%) as compared to the modified materials (CF or PAF; ER~21%), due to the role of surface charge of pectins and lignins present in pristine LF. At higher MB concentration, the relative ER values for LF (~19%) relative to CF or PAF (~16%) reveal the greater role of micropore adsorption sites due to the contributing effect of the textural porosity observed for the modified flax biomass at these conditions. Similar trends occur for the adsorption of water in the liquid vs. vapour phases. The chemical treatment of LF alters the polarity/charge of the surface functional groups, and pore structure properties of the chemically treated fibers, according to the variable hydration properties. The surface and textural properties of LF are altered upon chemical modification, according to the variable adsorption properties with liquid water (l) vs. water vapor (g) due to the role of surface- vs. pore-sites. This study contributes to an understanding of the structure-adsorption properties for pristine and oxidized flax fiber biomass. The chemical conversion of such biomass yields biomaterials with tunable surface and textural properties, as evidenced by the unique adsorption properties observed for pristine LF and its modified forms (CF and PAF). This study addresses knowledge gaps in the field by contributing insight on the relationship between structure and adsorption properties of such LF biomass in its pristine and chemically modified forms.

Surface-Engineered Cancer Nanomedicine: Rational Design and Recent Progress.

Cancer is highly heterogeneous in nature and characterized by abnormal, uncontrolled cells' growth. It is responsible for the second leading cause of death in the world. Nanotechnology is explored profoundly for sitespecific delivery of cancer chemotherapeutics as well as overcome multidrug-resistance (MDR) challenges in cancer. The progress in the design of various smart biocompatible materials (such as polymers, lipids and inorganic materials) has now revolutionized the area of cancer research for the rational design of nanomedicine by surface engineering with targeting ligands. The small tunable size and surface properties of nanomedicines provide the opportunity of multiple payloads and multivalent-ligand targeting to achieve drug efficacy even in MDR cancer. Furthermore, efforts are being carried out for the development of novel nano-pharmaceutical design, focusing on the delivery of therapeutic and diagnostic agents simultaneously which is called theranostics to assess the progress of therapy in cancer. This review aimed to discuss the physicochemical manipulation of cancer nanomedicine for rational design and recent progress in the area of surface engineering of nanomedicines to improve the efficacy of cancer chemotherapeutics in MDR cancer as well. Moreover, the problem of toxicity of the advanced functional materials that are used in nanomedicines and are exploited to achieve drug targeting in cancer is also addressed.

Modulation of the internal structure and surface properties of natural and synthetic polymer matrices by graphene oxide doping

Controlling the surface properties and structure of thin nanosized coatings is of primary importance in diverse engineering and medical applications. Here we report on how the nanostructure, growth mechanism, thickness, roughness, and hydrophilicity of nanocomposites composed of weak natural or strong synthetic polyelectrolytes (PE) can be tailored by graphene oxide (GO) doping. GO reverses the build‐up mechanism affecting the internal structure and the hydrophilicity in a way depending on the type of the PE‐matrix. The extent of GO‐adsorption and its impact on the surface morphology was found to be independent on the type of the underlying PE‐matrix. The nanostructure of the hybrid films is not significantly altered when a single surface‐exposed GO‐layer is deposited, while increasing the number of embedded GO‐layers leads to pronounced surface heterogeneity. These results are expected to have valuable impact on the construction strategies of coatings with tunable surface properties.

Single Chemical Sensor for Multi-Analyte Mixture Detection and Measurement: A Review

Multi-analyte chemical sensor aims to transform subtle variations in multiple analytes’ physical or chemical properties into distinct output signals. Chemically responsive nanostructure array (nanoarray) promises as a competitive sensor platform due to its robust physical properties, tunable chemical composition, and high surface area for analyte interaction. Specifically, the well-defined size, shape, and tunable surface structure and properties make it feasible to develop either new sensing modes on single device or integrated multi-modular sensors. In conjunction with the well-developed resistor-type sensors and sensor arrays, the complementary utilization of and intercorrelation with the electrochemical, optical, voltammetry modes in the multi-modular sensing strategies could provide multi-dimensional measurements to different analytes in a complex mixture form, where species information could be accurately and robustly separated from spatially collective responses. This review intends to provide a survey of the recent progress on multi-analyte sensing strategies and their unique structure design, as well as the related sensing mechanics in interaction of analytes and sensitizer and the behind mechanism for analytes’ differentiation.

Synthesis and formation mechanism of bone mineral, whitlockite nanocrystals in tri-solvent system

Whitlockite (WH, Ca18Mg2(HPO4)2(PO4)12) is the second most abundant bone mineral and has attracted attention as one of the novel bone regenerative materials. It has proven to enhance growth and promote osteogenesis of stem cells. However, investigating the mechanism of formation of pure phase WH nanocrystals remains a challenge. In this study, we introduced an interesting synthesis approach of WH nanocrystals using a tri-solvent system for the solid-liquid-solution (SLS) process. The ratio of precursor and reaction solvent composition was optimized to generate WH nanocrystals with tunable size, morphology (nanoplates, nanospheres), and surface properties (hydrophobic, hydrophilic), which is impossible to achieve using the traditional precipitation method. Molecular dynamics (MD) simulations revealed that the growth direction of nanoplates is highly related to the surfactant and its binding affinity. Finite element method (FEM) simulations elucidated that the ratio of ethanol/water plays an important role in defining the crystallinity and morphology of WH. In this study, we demonstrated that the cell proliferation of human bone marrow-derived mesenchymal stem cells (hBMSCs) is enhanced upon treatment with WH. The results of quantitative real-time polymerase chain reaction (qPCR) revealed that WH can positively accelerate the osteogenic differentiation in hBMSCs. The as-synthesized WH has a great potential in the future to be used in osteogenic tissue engineering. This study opens a new horizon for the synthesis and application of WH.

Fine tuning of surface properties of SiO2 nanoparticles for the regulation of Pickering emulsions

Pickering emulsions hold great potential in solving the mass transfer limitation in gas-liquid-solid and/or liquid-liquid-solid multiphase systems. In the present study, the surface properties of SiO2 nanoparticles were finely tuned by a novel large-scale production method, which determined the final geometry of the dispersed droplets and their stability. By controlling the amount of KH-570 grafted on the nanoparticles surface the phase inversion of Pickering emulsions was regulated. The addition of stabilizing nanoparticles, the particle size, and the amount of dispersed phase all significantly affected the geometry and stability of the dispersed droplets, mainly attributed to the varying coverage area of dispersed droplets provided by the stabilizing particles at varying grafting degrees. Mechanistic investigation suggested that estimating the value of the solid-oil intermolecular energy provided an indicator measure to predict the type of Pickering emulsions, while the estimate of interfacial tension values gave an additional measure to determine the amount of solid particles needed for forming stable Pickering emulsions.

Structure-tunable assembly of lignin sub-micro spheres by modifying the amphiphilic interfaces of lignin via n-alkane

Lignin sub-micro spheres have drawn wide attention because of their biodegradable, biocompatible and large surface area. However, the formation of stable and tunable lignin micro/nanospheres are limited by lignin source, preparation method and aggregation characteristics. Amphiphilic lignin tends to form aggregates in water under two tunable forces, including hydrophobic and hydrophilic interactions. Herein, we rationally modify the amphiphilic interface of corncob lignin (CL) with the chemical modification of four types of n-alkane to tune its amphiphilicity. Four alkylated CLs with similar chemical properties, but different interfacial interactions have been successfully synthesized. We find that n-alkane and aromatic skeleton contribute to the hydrophobic interactions to induce the aggregation of CL. The results show that modulating the hydrophobic and hydrophilic interactions can successfully promote the formation of CL sub-micro spheres (CLS) with tunable surface properties. The higher hydrophobic interactions and longer alkyl chain, the smaller size of CLS. The average diameters of CLS can be reduced from 400 nm to 100 nm by increasing the length of alkyl chain. What’s more, CLS can disperse stably in water for 60 days and in acid-base environment at pH 4–10 for 30 days.

Surface Engineering of Metal-Organic Framework Prepared on Film Bulk Acoustic Resonator for Vapor Detection.

Gravimetric resonators based on micro/nanoelectromechanical systems (M/NEMS) are potential candidates in developing smaller, less expensive, and higher-performance gas sensors. Metal-organic frameworks (MOFs) with high surface areas have recently come into focus as advanced nanoporous sensitive materials in microgravimetric gas sensors. The surface of MOFs on those sensors is critical in offering water stability and varying absorption behaviors. However, the influences of the surface on sensing performance are less explored and the strategy to tune surface properties of MOFs mounted on gravimetric resonators is still rare. In this paper, a straightforward strategy to engineer surface properties of MOFs, specifically Cu3(benzenetricarboxylate)2 (known as HKUST-1), is reported and the surface hydrophilicity/hydrophobicity of HKUST-1 is tuned by chemical vapor deposition combined with monolayer self-assembly. It was found that the hybrid inorganic and organic surface engineering strategy not only preserves the absorption capacity of inner MOFs but also significantly enhances the sensor's stability toward water.

Biodegradable Elastomers with Tunable Mechanical and Surface Properties Enhance Skeletal Muscle Regeneration

Biodegradable Elastomers with Tunable Mechanical and Surface Properties Enhance Skeletal Muscle Regeneration

Synthesis and application of tuneable carbon-silica composites from the microwave pyrolysis of waste paper for selective recovery of gold from acidic solutions.

Microwave pyrolysis bio-oil from waste paper and K60 silica gel has successfully been utilised to synthesise mesoporous carbon–silica composites with uniquely tuneable surface properties, where functionality and structural characteristics can be altered and even enhanced by curing at different temperatures. This temperature-dependence resulted in composites ranging from highly oxygenated polymerised bio-oil composites at 300 °C to aromatic carbonaceous materials covering the silica surface at 800 °C, making them attractive materials for gold recovery from mining wastewater. The composite materials exhibit exceptional ability and selectivity to recover gold from dilute solutions. Metal adsorption on the surface of these composites proceeded via both chemisorption and physisorption leading to the reduction of Au(iii) to Au(0), resulting in high recovery capacities for gold. Composite material prepared at 500 °C demonstrated the optimum combination of surface functionality and porosity, allowing for an adsorption capacity of 320 mg g−1 of gold and with 99.5% removal being achieved at concentrations mimicking those of real-life mine tailing wastes. All materials pioneered in this research display great potential as selective adsorbents for the recovery of gold from acidic media.