Surface Functionalization Methods Research Articles

Femtosecond Laser Fabrication of Engineered Functional Surfaces Based on Biodegradable Polymer and Biopolymer/Ceramic Composite Thin Films.

Surface functionalization introduced by precisely-defined surface structures depended on the surface texture and quality. Laser treatment is an advanced, non-contact technique for improving the biomaterials surface characteristics. In this study, femtosecond laser modification was applied to fabricate diverse structures on biodegradable polymer thin films and their ceramic blends. The influences of key laser processing parameters like laser energy and a number of applied laser pulses (N) over laser-treated surfaces were investigated. The modification of surface roughness was determined by atomic force microscopy (AFM). The surface roughness (Rrms) increased from approximately 0.5 to nearly 3 µm. The roughness changed with increasing laser energy and a number of applied laser pulses (N). The induced morphologies with different laser parameters were compared via Scanning electron microscopy (SEM) and confocal microscopy analysis. The chemical composition of exposed surfaces was examined by FTIR, X-ray photoelectron spectroscopy (XPS), and XRD analysis. This work illustrates the capacity of the laser microstructuring method for surface functionalization with possible applications in improvement of cellular attachment and orientation. Cells exhibited an extended shape along laser-modified surface zones compared to non-structured areas and demonstrated parallel alignment to the created structures. We examined laser-material interaction, microstructural outgrowth, and surface-treatment effect. By comparing the experimental results, it can be summarized that considerable processing quality can be obtained with femtosecond laser structuring.

Advances in refunctionalization of erythrocyte-based nanomedicine for enhancing cancer-targeted drug delivery.

Cancer remains a daunting and cureless disease, which is responsible for one-sixth of human deaths worldwide. These mortality rates have been expected to rise in the future due to the side effects of conventional treatments (chemotherapy, radiotherapy, and surgery), which can be addressed by applying nanomedicine. In order to escape from biological barriers, such nanomedicine should be mimicked and designed to be stealthy while navigating in the bloodstream. To achieve this, scientists take advantage of erythrocytes (red blood cells; RBCs) as drug carriers and develop RBC membrane (RBCm) coating nanotechnology. Thanks to the significant advances in nanoengineering, various facile surface functionalization methods can be applied to arm RBCm with not only targeting moieties, but also imaging agents, therapeutic agents, and nanoparticles, which are useful for theranostic nanomedicine. This review focuses on refunctionalization of erythrocyte-based nanomedicine for enhancing cancer-targeted drug delivery.

Covalent Attachment of Fibronectin onto Emulsion-Templated Porous Polymer Scaffolds Enhances Human Endometrial Stromal Cell Adhesion, Infiltration, and Function.

A novel strategy for the surface functionalization of emulsion-templated highly porous (polyHIPE) materials as well as its application to in vitro 3D cell culture is presented. A heterobifunctional linker that consists of an amine-reactive N-hydroxysuccinimide ester and a photoactivatable nitrophenyl azide, N-sulfosuccinimidyl-6-(4'-azido-2'-nitrophenylamino)hexanoate (sulfo-SANPAH), is utilized to functionalize polyHIPE surfaces. The ability to conjugate a range of compounds (6-aminofluorescein, heptafluorobutylamine, poly(ethylene glycol) bis-amine, and fibronectin) to the polyHIPE surface is demonstrated using fluorescence imaging, FTIR spectroscopy, and X-ray photoelectron spectroscopy. Compared to other existing surface functionalization methods for polyHIPE materials, this approach is facile, efficient, versatile, and benign. It can also be used to attach biomolecules to polyHIPE surfaces including cell adhesion-promoting extracellular matrix proteins. Cell culture experiments demonstrated that the fibronectin-conjugated polyHIPE scaffolds improve the adhesion and function of primary human endometrial stromal cells. It is believed that this approach can be employed to produce the next generation of polyHIPE scaffolds with tailored surface functionality, enhancing their application in 3D cell culture and tissue engineering whilst broadening the scope of applications to a wider range of cell types.

Bioinspired Surface Functionalization for Improving Osteogenesis of Electrospun Polycaprolactone Nanofibers.

Electrospun nanofibers, with a typical interconnected porous structure mimicking the extracellular matrix, are commonly used in bone tissue engineering. However, to the best of our knowledge, few studies have been reported to investigate the enhancement of osteogenesis capability of electrospun polycaprolactone (PCL) nanofibers based on bioinspired surface functionalization. In this study, a universal and versatile approach was proposed to spontaneously modify the electrospun PCL nanofibers with bioactive nano-hydroxyapatite (nHA), using dopamine as an effective bioadhesive agent. The evaluation of scanning electron microscopy, energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and surface wettability indicated that nHA was successfully coated onto electrospun nanofibers (PCL-PDHA). Furthermore, in vitro cell experiment including adhesion, proliferation, and osteogenic capability and in vitro biomineralization test in simulated body fluid revealed that the PCL-PDHA nanofibers were biocompatible to MC3T3-E1 cells, and the osteogenesis and biomineralization capabilities were greatly improved in comparison with that of PCL nanofibers. In summary, the facile bioinspired surface functionalization method introduced in the present study, due to its universality and versatility, not only can be used to improve osteogenesis of electrospun nanofibers but also can be regarded as an avenue to achieve other predesigned purposes in biomedical engineering.

Synthetic Methodologies to Gold Nanoshells: An Overview.

Gold nanostructures that can be synthetically articulated to adapt diverse morphologies, offer a versatile platform and tunable properties for applications in a variety of areas, including biomedicine and diagnostics. Among several conformational architectures, gold nanoshells provide a highly advantageous combination of properties that can be fine-tuned in designing single or multi-purpose nanomaterials, especially for applications in biology. One of the important parameters for evaluating the efficacy of gold nano-architectures is their reproducible synthesis and surface functionalization with desired moieties. A variety of methods now exist that allow fabrication and chemical manipulation of their structure and resulting properties. This review article provides an overview and a discussion of synthetic methodologies to a diverse range of gold nanoshells, and a brief summary of surface functionalization and characterization methods employed to evaluate their overall composition.

Covalent Surface Modification of Lipid Nanoparticles by Rapid Potassium Acyltrifluoroborate Amide Ligation.

Because of the recent increasing demand for the synthetic biomimetic nanoparticles as in vivo carriers of drugs and imaging probes, it is very important to develop reliable, stable, and orthogonal methods for surface functionalization of the particles. To address these issues, in this study, a recently reported chemoselective amide-forming ligation reaction [potassium acyltrifluoroborate (KAT) ligation] was employed for the first time, as a mean to provide the surface functionalization of particles for creating covalent attachments of bioactive molecules. A KAT derivative of oleic acid (OA-KAT, 1) was added to a mixture of three lipid components (triolein, phosphatidyl choline, and cholesteryl oleate), which have been commonly used as substrates for lipid nanoparticles. After sonication and extrusion in a buffer, successfully obtained lipid nanoparticles containing OA-KAT (NP-KAT) resulted to be well-dispersed with mean diameters of about 40-70 nm by dynamic light scattering. After preliminary confirmation of the fast and efficient KAT ligation in a solution phase using the identical reaction substrates, the "on-surface (on-particle)" KAT ligation on the NP-KAT was tested with an N-hydroxylamine derivative of fluorescein 2. The ligation was carried out in a phosphate buffer (10 mM, pH 5.2) at room temperature with reactant concentration ranges of 250 μM. Reaction efficiency was evaluated based on the amount of boron (determined by inductively coupled plasma mass spectrometry) and fluorescein (determined by fluorescence emission) in the particles before and after the reaction. As a result, the reaction proceeded in a significantly efficient way with ca. 40-50% conversion of the OA-KAT incorporated in the particles. Taken together with the fact that KAT ligation does not require any additional coupling reagents, these results indicated that the "on-surface" chemical functionalization of nanoparticles by KAT ligation is a useful method and represents a powerful and potentially versatile tool for the production of nanoparticles with a variety of covalently functionalized biomolecules and probes.

Synthesis and Functionalization of Stable and Bright Copper Nanoclusters by In Situ Generation of Silica Shells for Bioimaging and Biosensing

Copper nanoclusters have shown tremendous application perspective because of their outstanding luminescence properties, inherent biocompatibility, and easy accessibility; however, low emission brightness and poor resistance to ambient oxygen greatly limit their wide applications in long-term sensing and bioimaging. Herein, we develop an effective and general approach to enhancing the luminescence and stability of copper nanoclusters through in situ generation of a silica shell and further propose a versatile surface functionalization method to achieve functional copper nanoclusters via the formation of a second layer of a silica shell. The use of thiol-containing trialkoxysilane facilitates in situ generation of a silica shell on the surface of copper nanoclusters, and the existence of the first layer of a silica shell substantially improves the emission efficacy of copper nanoclusters. The introduction of a second layer of a silica shell not only greatly enhances the brightness and stability of copper na...

Phytosynthesis of gold nanoparticles: Characterization, biocompatibility, and evaluation of its osteoinductive potential for application in implant dentistry

Gold nanoparticles have been extensively used in diagnostics, biomedical imaging, and drug delivery owing to simple method of synthesis and versatile surface functionalization. Present investigation aims to evaluate the osteoinductive property of Salacia chinensis (SC) mediated gold nanoparticles (GNPs) for its application in implant dentistry. The formation of GNPs was assessed initially using the visual method and characterized analytically by using UV–visible spectroscopy, Zetasizer, X-RD, ICP-AES, AFM, and TEM. Green synthesized GNPs exhibited a remarkable stability in various blood components (0.2 M histidine, 0.2 M cysteine 2% bovine serum albumin, and 2% human serum albumin) and were found to be nontoxic when evaluated for their cytocompatibility and blood compatibility using periodontal fibroblasts and erythrocytes respectively. Exposure of GNPs to MG-63 cell lines displayed increased percent cell viability (138 ± 27.4) compared to the control group (96 ± 3.7) which confirms its osteoinductive potential. Herein, it can be concluded that the stable, biocompatible and eco-friendly GNPs can be used as an effective bone inductive agent during dental implant therapy.

Functionalization of mesoporous silica surface with carboxylic groups by Meldrum\u2019s acid and its application for sorption of proteins

A new method of silica surface functionalization with carboxyl groups is proposed based on the reaction between 2,2-dimethyl-1,3-dioxane-4,6-dione (Meldrum’s acid, MA) and the surface silanol groups. For the first time such a post-synthesis modification was successfully applied to silica materials. Although silica surface is successfully carboxylated (as evidenced by FTIR and XPS), the porosity, ordering and morphology remain practically unchanged after the proposed post-synthesis treatment (as confirmed by nitrogen sorption, XRD and electron microscopy). Adsorption study of model biomolecules (lysozyme and bovine serum albumin) shows that different surface chemistries (–OH vs. –COOH) lead to different affinities between the silica surface and sorbates.

Cleavage of Organosiloxanes with Dimethyl Carbonate: A Mild Approach To Graft-to-Surface Modification.

In this work, we explore the depolymerization of poly(dimethylsiloxane) (PDMS-100) and poly(methylphenylsiloxane) (PMPS) using dimethyl carbonate (DMC) and develop a surface functionalization method by utilizing the DMC-imparted active methoxy end groups of the partially depolymerized polysiloxanes. The efficiency of dimethyl carbonate as a reagent for organosiloxane cleavage was confirmed by means of 1H NMR spectroscopy, size-exclusion chromatography, and viscosity measurements. The reaction of fumed silica with organosiloxanes (PMPS, PDMS-50) in the presence of DMC was investigated using the ζ-potential, 29Si and 13C solid-state NMR spectroscopy, IR spectroscopy, CHN analysis, contact angle goniometry, thermogravimetric analysis, scanning and transmission electron microscopy (TEM), and rheology. It was found that the interaction of PMPS/DMC with an SiO2 surface produced hydrophobic and thermally stable moieties (up to 550 °C) with a densely packed (average 2.2 groups/nm2) alkylsiloxane network for SiO2/PMPS + DMC in comparison with SiO2/PMPS (average 1.4 groups/nm2). Surface functionalization was successfully attained at a relatively moderate temperature of 200 °C. Scanning electron microscopy data show that the average size of aggregates of PMPS/DMC-modified silica nanoparticles is smaller than that of the initial silica and silica modified with neat PMPS. TEM images reveal uniform distribution of the PMPS/DMC mixture across the SiO2 surface. Rheology studies show thixotropic behavior in industrial oil (I-40A), a fully reversible nanostructure and shorter structure recovery time for fumed silica modified in the presence of DMC.

Engineered nanomaterials and human health: Part 2. Applications and nanotoxicology (IUPAC Technical Report)

Abstract Research on engineered nanomaterials (ENM) has progressed rapidly from the very early stages of studying their unique, size-dependent physicochemical properties and commercial exploration to the development of products that influence our everyday lives. We have previously reviewed various methods for synthesis, surface functionalization, and analytical characterization of ENM in a publication titled ‘Engineered Nanomaterials: Preparation, Functionalization and Characterization’. In this second, inter-linked document, we first provide an overview of important applications of ENM in products relevant to human healthcare and consumer goods, such as food, textiles, and cosmetics. We then highlight the challenges for the design and development of new ENM for bio-applications, particularly in the rapidly developing nanomedicine sector. The second part of this document is dedicated to nanotoxicology studies of ENM in consumer products. We describe the various biological targets where toxicity may occur, summarize the four nanotoxicology principles, and discuss the need for careful consideration of the biodistribution, degradation, and elimination routes of nanosized materials before they can be safely used. Finally, we review expert opinions on the risk, regulation, and ethical aspects of using engineered nanomaterials in applications that may have direct or indirect impact on human health or our environment.

Combining Whispering-Gallery Mode Optical Biosensors with Microfluidics for Real-Time Detection of Protein Secretion from Living Cells in Complex Media.

The noninvasive monitoring of protein secretion of cells responding to drug treatment is an effective and essential tool in latest drug development and for cytotoxicity assays. In this work, a surface functionalization method is demonstrated for specific detection of protein released from cells and a platform that integrates highly sensitive optical devices, called whispering-gallery mode biosensors, with precise microfluidics control to achieve label-free and real-time detection. Cell biomarker release is measured in real time and with nanomolar sensitivity. The surface functionalization method allows for antibodies to be immobilized on the surface for specific detection, while the microfluidics system enables detection in a continuous flow with a negligible compromise between sensitivity and flow control over stabilization and mixing. Cytochrome c detection is used to illustrate the merits of the system. Jurkat cells are treated with the toxin staurosporine to trigger cell apoptosis and cytochrome c released into the cell culture medium is monitored via the newly invented optical microfluidic platform.

Mechanical Durability of Engineered Superhydrophobic Surfaces for Anti-Corrosion

Engineered superhydrophobic coating for anti-corrosion applications is a subject of great significance at present. However, the use of superhydrophobic coatings for anti-corrosion applications is hindered by the mechanical durability in many cases. There is a need for an understanding not only of how to fabricate such surfaces, but also of the corrosion resistance and mechanical durability of those coatings. This review discusses recent developments in the mechanical durability of superhydrophobic coatings primarily used for anti-corrosion. First, superhydrophobicity is introduced with an emphasis on different wetting models. After that, this review classifies the nanofabrication methods based on the material and methods of surface functionalization. Furthermore, the testing procedures used for the measurement of corrosion and mechanical durability are presented. Finally, the mechanical durability and anti-corrosion performance of the developed superhydrophobic coatings are discussed.

Reversible Immobilization of Proteins in Sensors and Solid-State Nanopores.

The controlled functionalization of surfaces with proteins is crucial for many analytical methods in life science research and biomedical applications. Here, a coating for silica-based surfaces is established which enables stable and selective immobilization of proteins with controlled orientation and tunable surface density. The coating is reusable, retains functionality upon long-term storage in air, and is applicable to surfaces of complex geometry. The protein anchoring method is validated on planar surfaces, and then a method is developed to measure the anchoring process in real time using silicon nitride solid-state nanopores. For surface attachment, polyhistidine tags that are site specifically introduced into recombinant proteins are exploited, and the yeast nucleoporin Nsp1 is used as model protein. Contrary to the commonly used covalent thiol chemistry, the anchoring of proteins via polyhistidine tag is reversible, permitting to take proteins off and replace them by other ones. Such switching in real time in experiments on individual nanopores is monitored using ion conductivity. Finally, it is demonstrated that silica and gold surfaces can be orthogonally functionalized to accommodate polyhistidine-tagged proteins on silica but prevent protein binding to gold, which extends the applicability of this surface functionalization method to even more complex sensor devices.

ZnO Q-dots as a potent therapeutic nanomedicine for in vitro cytotoxicity evaluation of mouth KB44, breast MCF7, colon HT29 and HeLa cancer cell lines, mouse ear swelling tests in vivo and its side effects using the animal model

Nanoformulations derived from fine porous ZnO quantum dot nanoparticles (QD NPs) can offer strong potential medical applications; especially in cancer therapy. ZnO QD NPs was synthesized by sol–gel hydrothermal process, fast cold quenching and further smart surface functionalization methods to obtain ultrasmall size (1–4 nm) NPs. ZnO nanopolymer, a wetting agent, PEG co-solvent and water/oil emulsion stabilizer were considered in our nanofluid formulation. The resulting nanofluid was characterized by SEM, FTIR, photoluminescence, band gap energy, zeta potential and UV–Vis spectroscopy. The cytotoxic effects on the growth of four cancer cell lines were evaluated by MTT assay. The IC50 (µg/ml) values of 30, 41, 40 and 35 for KB44, MCF-7, HT29 and HeLa cells, respectively, after 48 h of nanoformulation treatment suggested the cytotoxic effect of this nanoformulation on these cell lines in a concentration-dependent manner (p < .05). ZnO nanofluid destroyed cancer cell lines more efficiently than the normal HFF-2 (IC50 = 105 µg/ml). The reduction in cell viability in response to ZnO nanofluid treatment induced apoptosis in the cultured cells. Skin sensitization test plus antibacterial activity were also measured. Side effect tests on 70 white mice in vivo resulted in only 3–4 abnormal situations in hepatic tissue section possibly due to the idiosyncratic drug reactions.

Mechanically robust silver coatings prepared by electroless plating on thermoplastic polyurethane

A simple and low-cost surface functionalization method is proposed to activate a thermoplastic polyurethane (TPU) for the electroless deposition of a silver coating with excellent adhesion and low resistivity. The TPU surface functionalization was performed in solution and consisted in forming a physical interpenetrating network at the TPU surface, involving TPU and polyvinylpyrrolidone (PVP), a polymer displaying a strong affinity for metals. The presence of PVP on the TPU surface and its stability in aqueous solution were assessed by ATR-FTIR and contact angle measurements as a function of the PVP concentration and treatment time. A modified Tollens solution was used to grow a silver film on the TPU substrate, by using the electroless plating method. Compact silver films with an average thickness of 12.5 µm and a resistivity of 8.57 mΩ·cm were obtained for a 24 h plating time. The adhesion strength of the silver film proved to be higher than 8.5 N/cm. The resistance to fatigue of the silver films was studied by performing series of compression/stretching tests (150 cycles). It was concluded that the films kept low resistance values, although displaying a higher sensitivity to compression than to stretching. Furthermore, the films keep a good conductivity for strains up to 400%. The excellent electrical and mechanical properties of the films make them suitable candidates for the coating of multipin dry bioelectrodes. Owing to the high affinity of many metals for PVP, this activation technique has the potential to be extended to the deposition of other metals and other polymers as well, provided a suitable solvent is used.

In Situ Resonant Raman Spectroscopy to Monitor the Surface Functionalization of MoS2 and WSe2 for High-k Integration: A First-Principles Study.

Surface functionalization of the dangling-bond-free MoS2, WSe2, and other TMDs (transition metal dichalcogenides) is of large practical importance, for example, in providing nucleation sites for the subsequent high-k dielectric integration. Of the surface functionalization methods, the reversible O or N atom adsorption on top of the chalcogen atoms is most promising. However, hazards such as severe oxidation or nitridation persist when the adsorption coverage is high. An in situ characterization technique, which can be integrated with the surface functionalization and dielectric deposition chamber, becomes valuable to enable the real-time monitoring of surface adsorption conditions. Raman spectroscopy, as a nondestructive characterization method without vacuum requirement, is a strong candidate. By utilizing first-principles calculations, Raman spectra of single-layer MoS2 and WSe2 with various O/N adsorption coverages are studied. The calculations suggest that the low-coverage O/N adsorbates will act as perturbations to the periodic lattice and activate the acoustic-phonon Raman scatterings. While high-coverage adsorptions will further activate and intensify the optical-phonon Raman scatterings of previously silent A2u and E1g modes, due to the breaking of reflection symmetry in the z direction, new phonon modes associated with the adatom oscillations are also introduced. All these pieces of evidence, together with the peak shifts of previously active A1g and E2g1 modes, suggest that in situ resonant Raman spectroscopy is capable of providing important information to quantify the O/N adsorption coverage and can be used as a valuable real-time characterization technique to monitor and control the surface functionalization conditions of MoS2 and WSe2.

Quartz‐crystal Microbalance Measurements of CD19 Antibody Immobilization on Gold Surface and Capturing B Lymphoblast Cells: Effect of Surface Functionalization

AbstractWe have investigated different surface functionalization methods to immobilize CD19 antibody on gold surface to capture B lymphoblast cells associated with the acute lymphoblastic leukemia disease. Quartz Crystal Microbalance measurements were performed to analyze the binding kinetics of each layer and determine the optimum method, which results in higher cell capture rates. The random orientation of antibody and oriented antibody through protein G was investigated and protein G presence resulted in 15,2 Hz frequency shift for 104 cells/mL. The 3‐mercaptopropyltrimethoxysilane (MPS) and 11‐Mercaptoundecanoic acid (MUA) coatings of gold surface together with 4‐(N‐Maleimidomethyl)cyclohexane‐1‐carboxylic acid 3‐sulfo‐N‐hydroxysuccinimide ester sodium salt (Sulfo‐SMCC) and N‐Ethyl‐N’‐(3‐dimethylaminopropyl) carbodiimide hydrochloride (EDC)/N‐hydroxysulfosuccinimide (NHS) linker layers were tested on QCM for protein G and antibody binding. The results indicate that MUA, EDC/NHS, protein G, antibody CD19 is the optimum surface modification among the tested combinations. By using the optimum surface functionalization method, minimum 103 cell per mL was measured as 1.9 Hz frequency shift.

Substrate-Independent Epitaxial Growth of the Metal-Organic Framework MOF-508a.

Plasmachemical deposition is a substrate-independent method for the conformal surface functionalization of solid substrates. Structurally well-defined pulsed plasma deposited poly(1-allylimidazole) layers provide surface imidazole linker groups for the directed liquid-phase epitaxial (layer-by-layer) growth of metal-organic frameworks (MOFs) at room temperature. For the case of microporous [Zn (benzene-1,4-dicarboxylate)-(4,4'-bipyridine)0.5] (MOF-508), the MOF-508a polymorph containing two interpenetrating crystal lattice frameworks undergoes orientated Volmer-Weber growth and displays CO2 gas capture behavior at atmospheric concentrations in proportion to the number of epitaxially grown MOF-508 layers.

New UiO-66/CuxS Heterostructures: Surface Functionalization Synthesis and Their Application in Photocatalytic Degradation of RhB

Abstract Metal-organic frameworks (MOFs) and their heterostructures have been considered as suitable materials for photodegradation of organic pollutants in water treatment. In this work, a series of UiO-66/CuxS composites with different CuxS contents were prepared by using 3-mercaptopropionic acid as a surface-functionalizing agent to anchor CuxS nanoparticles onto UiO-66 surface. The as-synthesized UiO-66/CuxS composites were characterized by using XRD, SEM, TEM, XPS, UV-Vis, PL and the possible growth mechanism of the heterostructure composites was proposed. The UiO-66/CuxS composites were successfully used as photocatalysts for the degradation of Rhodamine B (RhB) under visible-light irradiation. Noticeably, the photocatalytic efficiency of UiO-66/CuxS composites could be tuned by changing Cu/Zr molar ratios. The enhanced photocatalytic activity could be attributed to the synergistic effect between CuxS nanoparticles and UiO-66 frameworks materials. This study provided useful information for the preparation of MOF/semiconductor heterostructure photocatalysts via the surface functionalization method.