Surface modification using self‐assembled layers of amphiphilic cyclodextrins

In this study six amphiphilic cyclodextrin derivatives were prepared by esterification and used to coat five industrial products made from polypropylene, polyethylene, polyvinyl chloride, or polyurethane using a new, patented coating technology. This simple approach, which consists merely of dipping the material to be coated into a suspension of a given cyclodextrin derivative in an ethanol/water solution, was used to functionalize support materials with a coat that is stable in aqueous solutions and which renders the coated materials hydrophilic. The functionalization proved to be controllable in terms of amount of cyclodextrin on the surface and can be implemented in existing production lines without investment in advanced production equipment. It is hypothesized that the cyclodextrins order themselves in structured layers forming channel‐like structures preserving the very large potential for uptake and release of active compounds that is known to cyclodextrins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41047.     

Electrospun self‐assembled nanofiber yarns

A technique for making self‐assembled electrospun (E‐spun) nanofiber yarns from poly(acrylonitrile) in a single step is described. The process involved formation of the nanofiber yarn directly within the electrospinning zone and its removal before it can reach the counter‐electrode. The yarn is presumably formed due to splitting of the main jet into numerous nanojets and their reassembly into a single entity midway between the two electrodes. The process was found to occur at a particular field strength, which varied considerably with the concentration of the polymer dope. The gross morphology of yarns and the alignment of nanofibers in the yarn were evaluated by scanning electron microscopy (SEM). The rationale behind the formation of the yarn like structure has been explained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of silane‐terminated polystyrene and polymethylmethacrylate self‐assembled films on silicon wafer

End silane functionalized polystyrene and polymethylmethacrylate were prepared through radical chain‐transfer reaction and characterized with gel‐permeation chromatography. The chain‐transfer constants of mercaptopropyltrimethoxysilane for the polymerization of styrene and methylmethacrylate were determined to be 8.48 and 0.67, respectively, from the slopes of 1/DP_n versus [S]/[M] lines. The ultrathin films of the end silane–terminated polymers were prepared by self‐assembly onto hydroxylated silicon wafers. The water contact angle on the resulting ultrathin films and the film thickness were measured. The morphology and chemical features of the films were observed and investigated by means of atomic force microscopy and X‐ray photoelectron spectroscopy. Results indicated that the chain‐transfer agent played a key role in making it possible for the silane‐terminated polystyrene and polymethylmethacrylate to be self‐assembled on Si(111), whereas the thickness and surface quality of the ultrathin films were dependent on the molecular weights of the polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1695–1701, 2004     

Effects of the carboxyl‐ended hyperbranched polyester/platinum complex molecular weight on hydrosilylation activity and self‐assembled morphology

Research on platinum catalysts with high activity and long life for hydrosilylation has attracted a great deal of interest because of the increasing price of platinum metal. In this study, we examined the effect of the molecular weight of carboxyl‐ended hyperbranched polyester/platinum complexes (HTD‐n–Pt's, where n = 1, 2, 3, or 4) on hydrosilylation activity and self‐assembled morphology. Relevant parameters tuning the morphology of self‐assemblies, such as the temperature, time, concentration, and relative humidity, were examined. All of the HTD‐n–Pt's with various molecular weights had much higher hydrosilylation activities than did the conventional homogeneous Speier's catalyst, and the HTD‐n–Pt could be self‐assembled into ordered two‐dimensional treelike structures with a fractal dimension ranging from 1.48 to 1.83; this indicated perfect fractal properties. With the increase of the HTD‐n–Pt molecular weight, the size of the self‐assembled treelike structures and the catalytic activity increased first and then decreased. The self‐assembly mechanism was speculated and analyzed by dynamic light scattering, X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy; these suggested good agreement with the diffusion‐limited aggregation theory of particles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41416.     

Influence of different dopants on the adsorption,morphology, and properties of self‐assembled films of poly(o‐ethoxyaniline)

Self‐assembled films of poly(o‐ethoxyaniline)—POEA alternated with sulfonated lignin (SL)—were successfully produced, and their kinetics of formation and growth investigated for different dopants (hydrochloric acid, methanesulfonic acid, p‐toluenesulfonic acid, and camphorsulfonic acid). These films were characterized by ultraviolet‐visible spectroscopy, atomic force microscopy, surface potential, and electrical resistance measurements. It has been observed that the bulkiest dopants led to a greater time for the polymer deposition and greater amount of material adsorbed. This can be explained by the lower mobility and lower solvation of the bulkiest dopant counterions, which led to a higher screening effect of the charges present in the POEA chains and therefore to a more compact molecular conformation. The morphology of the POEA films were also greatly affected by the type of dopant used, being rougher for the bulkiest dopants. The POEA films also exhibited different electrical responses upon ethylene exposure depending on the dopant, indicating a promising use for gas sensor applications. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1309–1316, 2002     

Thermal properties and morphology of a poly(vinyl alcohol)/silica nanocomposite prepared with a self‐assembled monolayer technique

A poly(vinyl alcohol) (PVA)/silica (SiO₂) nanocomposite was prepared with a novel self‐assembled monolayer technique, and its morphology and thermal properties were studied with different material characterization instruments. The treated SiO₂ nanoparticles were dispersed in the PVA matrix homogeneously, and the thermal properties of the nanocomposite were markedly improved in comparison with those of pure PVA. Under the same isothermal heating conditions, the decomposition of the nanocomposite was delayed significantly in comparison with that of PVA. The thermal degradation of the nanocomposite was a two‐step reaction, including the degradation of the side chain and main chain. The products of side‐chain degradation were mainly carboxylic acid, whereas main‐chain degradation primarily produced carbon dioxide and low‐molecular‐weight conjugated polyene. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1436–1442, 2005     

Polyaniline self‐assembled with DTPA: Facilely tuned morphology and properties

The effects of pH profile and “soft template” during aniline chemical oxidative polymerization (COP) were investigated and evaluated simultaneously with diethylene triamine pentaacetic acid (DTPA) as a structural directing agent. Formation of PANI nanotubes and nanoparticles, smooth microspheres, and urchin‐like microspheres were illustrated by evaluating the pH profile during aniline COP while considering the “soft template” effects of DTPA. PANI nanosheets with two semicurled edges were found in the system producing nanotubes, which provides an evidence for the “curling mechanism” of PANI nanotube formation. With different pH profiles, chemical structures and aggregation structures of the as‐synthesized PANI micro/nanostructures are similar, whereas their conductivity, wettability, Cr (VI) adsorption, and electrochemical behaviors are distinct. The present study indicates that if properly conducted, pH profile adjustment is more effective than “soft template” to control the morphology and to optimize the performance of PANI micro/nanostructures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42403.     

The fabrication of full color P(St‐MAA) photonic crystal structure on polyester fabrics by vertical deposition self‐assembly

Three‐dimensional (3D) photonic crystals with face‐centered cubic structure were successfully fabricated on soft polyester fabrics via vertical deposition self‐assembly, with monodisperse P(St‐MAA) microspheres prepared by soap‐free emulsion copolymerization. The resultant polyester fabrics exhibited bright structural colors through the well‐ordered photonic crystal microstructure without any chemical dyes and pigments. The tunable structural colors across the whole visible region confirmed by reflectance spectra could be adjusted by controlling the diameters of the microspheres and viewing angles, and this was consistent with the law of the Bragg diffraction. The resultant polyester fabrics also presented some favorable properties including double‐sided coloration effect, clear fabric texture, and soft fabric handle. The structural coloration by vertical deposition self‐assembly of P(St‐MAA) photonic crystals may provide a new strategy for textile coloration without using chemical colorants, and have a potential to reduce the pollution in the current textile dyeing and printing processes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41750.     

Layer‐by‐layer assembled hydrogel nanocomposite film with a high loading capacity

The layer‐by‐layer assembly technique is a method that widely used in the preparation of nanostructured multilayer ultrathin films. We fabricated a hydrogel nanocomposite film by alternating the deposition of a core–shell poly[(dimethylimino)(2‐hydroxy‐1,3‐propanedily) chloride] (PDMIHPC)–laponite solution and poly(acrylic acid). The growth of the deposition procedure was proven by ultraviolet–visible spectroscopy and spectroscopic ellipsometry. The surface morphology of the films was observed by scanning electron microscopy. The films could reversibly load and release methylene blue (MB) dye, which was used as an indicator. It took about 4.5 h to reach loading equilibrium at pH 9.0. The loading capacity of the film for MB was as large as 4.48 μg/cm² per bilayer because of the introduction of the core–shell PDMIHPC–laponite as a film component. Nearly 90% of MB was released at pH 3.0 or in a 300 mM NaCl solution within 2.5 h. The loading and release processes were greatly influenced by the ionic strength and pH value of the MB solution. The hydrogel nanocomposite film showed good pH‐triggered loading‐release reversibility and suggested potential applications in controlled drug‐delivery systems and smart materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39352.     

An optimization‐based approach for structural design of self‐assembled DNA tiles

DNA tiles are self‐assembled nanostructures, which offer exciting opportunities for synthesis of novel materials. A challenge for structural design of DNA tiles is to identify optimal locations for so‐called crossovers, which are bridges between DNA double helices formed by pairs of single‐stranded DNA. An optimization‐based approach is presented to identify optimal locations for such crossovers. Minimization of a potential‐energy model for a given structural design demonstrates the importance of local minima. Both deterministic global optimization of a reduced model and multistart optimization of the full model are applied successfully to identify the global minimum. MINLP optimization using a branch‐and‐bound algorithm (GAMS/SBB) identifies an optimal structural design of a DNA tile successfully with significant reduction in computational load compared to exhaustive enumeration, which demonstrates the potential of the proposed method to reduce trial‐and‐error efforts for structural design of DNA tiles. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1804–1817, 2017     

Self‐assembled poly(styrene‐co‐N‐isopropylacrylamide) film induced by capillary force

The monodisperse poly(styrene‐co‐N‐isopropylacrylamide) (poly(St‐co‐NIPAAm)) particles prepared by emulsifier‐free emulsion polymerization with microwave irradiation were induced by capillary forces to self‐assemble, and formed the two‐dimensional films on the clean glassware wafer substrates. The morphologies of the two‐dimensional films were characterized by scanning electron microscopy (SEM) and atom force microscopy (AFM). The results showed that monodisperse poly(St‐co‐NIPAAm) particles could form ordered two‐dimensional films by capillary forces. With NIPAAm concentration increasing, there gradually appeared surface undulations or surface defective region on the two‐dimensional films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3514–3519, 2006     

Modification of ramie fabric with a metal‐ion‐doped flame‐retardant coating

Transition‐metal‐ion‐doped flame‐retardant coatings were constructed on the surface of ramie fabrics by a layer‐by‐layer (LbL) assembly technique to investigate possible cooperative actions that could improve the fabric's flame‐retardant efficiency. We found that these functional coatings, consisting of poly(vinylphosphonic acid) (the anionic layer) and branched polyethylenimine/cupric or zinc ions (the cationic layer), improved the fire retardancy of the ramie fabrics remarkably. Attenuated total reflectance–Fourier transform infrared (FTIR) spectroscopy and energy dispersive X‐ray spectroscopy demonstrated the successful LbL assembly process and the incorporation of metal ions into the coating. Thermogravimetric analysis coupled with FTIR spectrometry, vertical flame testing, and microscale combustion calorimetry confirmed the improved thermal stability and reduced flammability of the coated ramie fabrics. All of the results show that the metal‐ion‐doped flame‐retardant coatings not only dramatically increased the residues but also retained the original weave structure and fiber morphology of ramie fabrics well. The enhanced flame‐retardant efficiency may have been caused by the lower decomposition temperature of the flame‐retardant coating, as promoted by cupric and zinc ions, and as a result, may have helped the flame‐retardant activity to take place earlier. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and morphology of carboxylated polyether‐block‐polydimethylsiloxane and the supermolecule self‐assembled from it

In this research, hydroxyl‐terminated polyether‐block‐polydimethylsiloxane (PESO) was synthesized as an intermediate through the hydrosilylation of Si? H‐terminated polydimethylsiloxane with allyl polyoxyethylene polyoxypropylene ether. Then, carboxylated polyether‐block‐polydimethylsiloxane (CPES) was prepared through the reaction of maleic anhydride with PESO. First, the chemical structures of the synthesized polysiloxanes were characterized with IR and ¹H‐NMR spectroscopy, and then the film morphology of CPES and the supermolecule self‐assembled from CPES and N‐β‐aminoethyl‐γ‐aminopropyl polydimethylsiloxane (ASO‐1) was investigated by atomic force microscopy in detail. Experimental results indicated that the superpolysiloxane that self‐assembled from CPES and ASO‐1 showed a film morphology very different from those of CPES and ASO‐1. There were not only many small, bright dots but also some big and marvelous dots circled by dots on the film surface. The morphology of dots circled by dots was estimated to result from aggregates of CPES micelles adsorbed onto the curled ASO‐1 molecule interface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Layer‐by‐layer self‐assembled multilayer films of single‐walled carbon nanotubes and tin disulfide nanoparticles with chitosan for the fabrication of biosensors

In this study, multilayer films containing chitosan, tin disulfide (SnS₂) nanoparticles, and single‐walled carbon nanotubes were prepared on glassy carbon electrodes with the use of a layer‐by‐layer assembly technique. The resulting films were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy, and ultraviolet–visible absorption spectroscopy. The results of CV and EIS indicates that the peak currents and charge‐transfer resistance all had linear responses to the number of assembled layers. The multilayer‐film‐modified electrode showed excellent electrocatalytic properties for some species, such as dopamine hydrochloride (DA), ascorbic acid (AA), and uric acid (UA). The well‐separated voltammetric signals of DA, UA, and AA could be obtained on the assembled multilayer‐film‐modified electrode, and the peak‐to‐peak potential separations were 171, 136, and 307 mV for DA–UA, DA–AA, and UA–AA on CV, respectively. These facts showed that the multilayer‐film‐modified electrode could be used as a new sensor for the simultaneous detection of DA and UA in the presence of AA in a real sample. In addition, the multilayer films were stable, selective, and reproducible. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, and self‐assembly of cationic coumarin side‐chain polymer

In this study, the synthesis of a novel cationic coumarin‐containing polymer (C‐CPA) was presented. C‐CPA was examined optically using photoluminescence (PL) spectroscopy. The optical data suggested that they were promising blue‐emitting materials mainly due to the coumarin chromophore on the side chain. Moreover, the synthesized cationic polymer was suitable for layer‐by‐layer electrostatic self‐assembly thin film deposition from dilute polymer solution and multilayers were fully characterized by UV–vis spectroscopy, PL spectroscopy and atomic force microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effective hole‐injection characteristics of organic light‐emitting diodes due to fluorinated self‐assembled monolayer embedded as a buffer layer

The electrical and optical properties of organic light‐emitting diodes (OLEDs) are demonstrated by varying the length of the alkyl chain of a fluorinated self‐assembled monolayer (F‐nSAM). OLEDs containing F‐nSAMs that have a long alkyl chain length were found to exhibit excellent properties in terms of current density, luminance, turn‐on voltage, etc. The obtained current density at 6 V, which was the highest measurement voltage, was up to about 36 times higher for an OLED including an F‐12SAM thin film with the longest chain length than for an OLED including only an indium tin oxide (ITO) substrate. With regard to luminance characteristics depending on voltage, the luminance was about 13 times higher for the OLED including the F‐12SAM thin film than for the OLED including only the ITO substrate. Also, the turn‐on voltage of the OLED including the F‐12SAM thin film was decreased by approximately 1 V compared to that of the OLED including only the ITO substrate. Although F‐nSAMs with alkyl chains have insulating film properties, F‐nSAMs with long alkyl chains exhibited good electrical and optical properties because of an improvement in the hole‐injection barrier due to a large positive shift of the vacuum level and smooth carrier injection resulting from a high contact angle due to strong hydrophobic properties caused by the good alignment properties of F‐nSAMs resulting from strong van der Waals forces between the molecules due to the long alkyl chains. © 2019 Society of Chemical Industry     

‘Bricks and mortar’ nanoparticle self‐assembly using polymers

Developments in self‐assembly methods allow access to hierarchical materials featuring a wide range of functionality and applications. Polymer‐based self‐assembly of nanoparticles opens up new avenues for the fabrication of highly structured nanocomposites that can serve as bridges between ‘bottom‐up’ and ‘top‐down’ methods. Of various interactions leading to self‐assembly of nanocomposites, hydrogen bonding and electrostatic interactions are commonly utilized. In this review, we illustrate the design and subsequent property tuning of various self‐assembled nanocomposite materials that were developed based on these interactions. Copyright © 2007 Society of Chemical Industry     

Fire retardancy and durability of poly(N‐benzyloxycarbonyl‐3,4‐dihydroxyphenylalanine)‐montmorillonite composite film coated polyimide fabric

Polyimide (PI) fabric was coated with composite films composed of poly(N‐benzyloxycarbonyl‐3,4‐dihydroxyphenylalanine) (PNBD) and montmorillonite (MMT), prepared via layer‐by‐layer assembly. Three coating recipes (changed by altering the concentration of PNBD solution) were used to study the growth of thin films. Scanning electron microscope showed that, after 20 times standard washing, PNBD‐MMT film still coated on PI fiber, while MMT film coated on PI had been almost washed off. Thermogravimetric analysis indicated that, in nitrogen atmosphere at 900°C, the residue of uncoated PI was 36.62%, after 20 times standard washing, residue of PNBD‐MMT coated PI (53.80%) was higher than that of MMT coated PI (50.08%). Vertical flame testing showed that the burning length of PNBD‐MMT coated PI (7 mm) was much shorter than that of uncoated PI (30 mm) and MMT coated PI (17 mm) after 20 times standard washing. These results demonstrated the excellent flame retardancy and durability of PNBD‐MMT film coated PI fabric. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39608.     

Towards enhanced electrochemical capacitance with self‐assembled synthesis of poly(pyrrole‐co‐o‐toluidine) nanoparticles

Poly(pyrrole‐co‐o‐toluidine) (PPOT) nanoparticles for electrochemical capacitors are easily and productively synthesized by a chemical oxidative polymerization of pyrrole (PY) and o‐toluidine (OT) in 0.5M HCl without any external additive. The polymerization yield, electrical conductivity, and size of the copolymer nanoparticles can significantly be optimized by the oxidant/monomer molar ratio and polymerization temperature. The chemical structure of the obtained copolymer is characterized by UV–vis and FTIR. The copolymer nanoparticles synthesized at 10°C are found to generally have irregular granular morphology with a diameter of 60–100 nm and a small polydispersity index of 1.06 by laser particle‐size analyzer, FE‐SEM, and TEM, and good dispersibility in water. The formation mechanism of the nanoparticles is proposed based on the powerful amphipathicity from comonomer aggregate formed by PY and OT in the monomer solution. The PPOT nanoparticles possess a specific capacitance of 310 F g^?1 at 25 mV s^?1 as well as retain 81% of the initial specific capacitance value after 1000 cycles, while its energy density and power density are found to be 40.2 and 1196 W Kg^?1 at 2 A g^?1. The enhanced electrochemical properties can be attributed to the nanostructural advantage of the PPOT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42995.     

Recent advances and potential applications of the photo‐induced macroscopic response of self‐assembled azopolymer in aqueous media

This mini‐review highlights issues related to the photo‐triggered macroscopic response of azopolymer in supramolecular hydrogel and polymer vesicles. Cyclodextrin (CD) can form an inclusion complex with trans‐azobenzene while cis‐azobenzene is expelled out of the CD's cavity. This photo‐reversible supramolecular host ? guest interaction is used to trigger sol ? gel transitions and to induce macroscopic assembly. When substituted azobenzene is located at chain ends of linear polyethylene glycol, monodisperse vesicles are formed exhibiting a photo‐induced pulsating behavior. The macroscopic phase transition and assembly or pulsating behavior of azopolymers can be expected to have potential applications as smart biomedical materials. © 2014 Society of Chemical Industry