Combining hydrogen-bonding complexation in solution and hydrogen-bonding-directed layer-by-layer assembly for the controlled loading of a small organic molecule into multilayer films

We have combined hydrogen-bonding complexation in solution and layer-by-layer assembly for the controlled loading of a water-insoluble small organic molecule, bis-triazine (DTA), an azobenzene derivative containing multiple hydrogen bond donors and acceptors, into layer-by-layer multilayer films of poly(acrylic acid) and diazo-resin. UV-visible spectroscopy indicates that DTA has been loaded into multilayer films, with the loading amount increasing linearly with the number of layers. The loading amount can be well tuned either by changing the concentration of DTA or the solvent composition at the complexation step. Fourier transform infrared spectroscopy has revealed that both the complexation and layer-by-layer assembly are driven by hydrogen bonding. After photo-cross-linking and immersion in dimethyl sulfoxide to release DTA, the film can serve as an absorbent for DTA. This study provides a new unconventional layer-by-layer assembly that combines hydrogen-bonding complexation in solution and hydrogen-bond-driven layer-by-layer assembly at the interface. This method provides a new route to load a variety of water-insoluble functional organic molecules into layer-by-layer films.     

Layer-by-layer fabrication of broad-band superhydrophobic antireflection coatings in near-infrared region

Broad-band superhydrophobic antireflective (AR) coatings in near infrared (NIR) region were readily fabricated on silicon or quartz substrates by a layer-by-layer (LbL) assembly technique. First, a porous poly(diallyldimethylammonium chloride) (PDDA)/SiO2 nanoparticle multilayer coating with AR property was prepared by LbL deposition of PDDA and 200 nm SiO2 nanoparticles. PDDA was then alternately assembled with sodium silicate on the PDDA/SiO2 nanoparticle coating to prepare a two-level hierarchical surface. Superhydrophobic AR coating with a water contact angle of 154 degrees was finally obtained after chemical vapor deposition of a layer of fluoroalkylsilane on the hierarchical surface. Quartz substrate with the as-fabricated superhydrophobic AR coating has a maximal transmittance above 98% of incidence light in the NIR region, which is increased by five percent compared with bare quartz substrate. Simultaneously, the superhydrophobic property endows the AR coating with water-repellent ability. Such superhydrophobic AR coatings can effectively avoid the disturbance of water vapor on their AR property and are expected to be applicable under humid environments.     

Cyto-mechanoresponsive polyelectrolyte multilayer films

Cell adhesion processes take place through mechanotransduction mechanisms where stretching of proteins results in biological responses. In this work, we present the first cyto-mechanoresponsive surface that mimics such behavior by becoming cell-adhesive through exhibition of arginine-glycine-aspartic acid (RGD) adhesion peptides under stretching. This mechanoresponsive surface is based on polyelectrolyte multilayer films built on a silicone sheet and where RGD-grafted polyelectrolytes are embedded under antifouling phosphorylcholine-grafted polyelectrolytes. The stretching of this film induces an increase in fibroblast cell viability and adhesion.     

Capillary electrochromatography using polyelectrolyte multilayer coatings

This review covers recent progress in polyelectrolyte multilayer (PEM) coatings applied to analytical separations using open-tubular capillary electrochromatography (OT-CEC). The simple preparation procedure involved in the PEM approach has provided some attractive features over other modes of capillary electrophoresis-based separations including packed column capillary electrochromatography (PC-CEC) and micellar electrokinetic chromatography (MEKC). PEM coatings have been used to alleviate the adsorption of basic analytes, to improve separations, and to improve the stability of the electroosmotic flow. Fundamental aspects of PEM coatings on surfaces and analytical separation platforms are briefly outlined in this review. In addition, applications of PEM coatings to fused-silica capillaries or microchip separation devices for the separation of small achiral or chiral analytes, as well as large biomolecules, are discussed.     

Photopatterning of multilayer n-alkylsilane films

Surface photopatterning of organosilane self-assembled monolayers (SAM) has received increasing attention since its introduction 20 years ago. Herein we report for the first time a cost-efficient soft photopatterning technique affording amplified 3D multilayer structures. The essential chemistry relies on a spatially controlled photoacid-catalyzed hydrolysis and polycondensation of n-alkyltrimethoxysilane precursors (n-C(12)H(25)Si(OCH(3))(3),). Amphiphilic siloxane species are photogenerated locally and are able to self-assemble spontaneously into a long-range-ordered lamellar mesostructure.     

Self-organized TiO2 nanorod arrays on glass substrate for self-cleaning antireflection coatings

Herein we report the direct fabrication of TiO(2) subwavelength structures with 1-dimensional TiO(2) nanorods on glass substrate through solvothermal process to form self-cleaning antireflection coatings. TiO(2) precursor solutions with different solvent constituents create TiO(2) nanorods with much different morphologies grown on glass substrates. Apiculate TiO(2) nanorods with vertical orientation are grown on the glass substrate which is solvothermally treated in the precursor solution containing ethylene glycol. This glass substrate exhibit the highest transmittance of 70-85% in the range of 520-800 nm and negligible absorption in visible light region (400-800 nm). Furthermore, the TiO(2) nanorod arrays show high hydrophobicity and photocatalytic degradation ability which offer the glass substrate self-cleaning properties for both hydrophilic and oily contaminants.     

Electrochromic properties of a metallo-supramolecular polymer derived from tetra(2-pyridyl-1,4-pyrazine) ligands integrated in thin multilayer films

The electrochromic behavior of iron complexes derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) and a hexacyanoferrate species in polyelectrolytic multilayer adsorbed films is described for the first time. This complex macromolecule was deposited onto indium-tin oxide (ITO) substrates via self-assembly, and the morphology of the modified electrodes was studied using atomic force microscopy (AFM), which indicated that the hybrid film containing the polyelectrolyte multilayer and the iron complex was highly homogeneous and was approximately 50 nm thick. The modified electrodes exhibited excellent electrochromic behavior with both intense and persistent coloration as well as a chromatic contrast of approximately 70%. In addition, this system achieved high electrochromic efficiency (over 70 cm(2) C(-1) at 630 nm) and a response time that could be measured in milliseconds. The electrode was cycled more than 10(3) times, indicating excellent stability.     

Fibronectin adsorption onto polyelectrolyte multilayer films

The Layer-by-layer deposition of positively and negatively charged macromolecular species is an ideal method for constructing thin films incorporating biological molecules. We investigate the adsorption of fibronectin onto polyelectrolyte multilayer (PEM) films using optical waveguide lightmode spectroscopy (OWLS) and atomic force microscopy (AFM). PEM films are formed by adsorption onto Si(Ti)O2 from alternately introduced flowing solutions of anionic poly(sodium 4-styrenesulfonate) (PSS) and cationic poly(allylamine hydrochloride) (PAH). Using OWLS, we find the initial rate and overall extent offibronectin adsorption to be greatest on PEM films terminated with a PAH layer. The polarizability density of the adsorbed protein layer, as measured by its refractive index, is virtually identical on both PAH- and PSS-terminated films; the higher adsorbed density on the PAH-terminated film is due to an adsorbed layer of roughly twice the thickness. The binding of monoclonal antibodies specific to the protein's cell binding site is considerably enhanced to fibronectin adsorbed to the PSS layer, indicating a more accessible adsorbed layer. With increased salt concentration, we find thicker PEM films but considerably thinner adsorbed fibronectin layers, owing to increased electrostatic screening. Using AFM, we find adsorbed fibronectin layers to contain clusters; these are more numerous and symmetric on the PSS-terminated film. By considering the electrostatic binding of a segmental model fibronectin molecule, we propose a picture of fibronectin adsorbed primarily in an end-on-oriented monolayer on a PAH-terminated film and as clusters plus side-on-oriented isolated molecules onto a PSS-terminated film.     

Photopatterned nanoporosity in polyelectrolyte multilayer films

We report on spatial control of nanoporosity in polyelectrolyte multilayer (PEM) films using photopatterning and its effects on film optical and adsorption properties. Multilayers assembled from poly(acrylic acid-ran-vinylbenzyl acrylate) (PAArVBA), a photo-cross-linking polymer, and poly(allylamine hydrochloric acid) (PAH) were patterned using ultraviolet light followed by immersion in low pH and then neutral pH solutions to induce nanoporosity in unexposed regions. Model charged small molecules rhodamine B, fluorescein, and propidium iodide and the model protein albumin exhibit increased adsorption to nanoporous regions of patterned PEM films as shown by fluorescence microscopy and radiolabeling experiments. Films assembled with alternating stacks of PAH/poly(sodium-4-styrene sulfonate) (SPS), which do not become nanoporous, and stacks of PAH/PAArVBA were patterned to create nanoporous capillary channels. Interdigitated channels demonstrated simultaneous, separate wicking of dimethyl sulfoxide-solvated fluorescein and rhodamine B. In addition, these heterostack structures exhibited patternable Bragg reflectivity of greater than 25% due to refractive index differences between the nanoporous and nonporous stacks. Finally, the PEM assembly process coupled with photo-cross-linking was used to create films with two separate stacked reflective patterns with a doubling in reflectivity where patterns overlapped. The combined adsorptive and reflective properties of these films hold promise for applications in diagnostic arrays and therapeutics delivery.     

Characterisation of tribocorrosion behaviour of multilayer PVD coatings

The effect of repassivation on tribocorrosion behaviour of two multilayer coatings of different structures is studied experimentally by measuring the variation of instantaneous open-circuit potential during friction. One coating consists of alternating Cr and CrN layers, while another consists of alternated layers of CrN and ZrN. Analysis of the results showed that friction force, i.e. the rate of the mechanical energy supplied to the material in the contact zone, has no direct influence on the tribocorrosion behaviour; however, the wear rate does strongly influence the tribocorrosion. A simple phenomenological model of repassivation of the multilayer coating is developed assuming “surface coverage” approach. This model establishes the relationship between the rate of mechanical activation of material by friction and the behaviour of the open-circuit potential.     

Biomimetic click assembled multilayer coatings exhibiting responsive properties

Stimuli-responsive polymers are capable of changing their physico-chemical properties in a dynamic way, to respond to variations on the surrounding environment. These materials have gained increasingly importance for different areas, such as drug delivery, biosensors, microelectronic systems and also for the design and modification of biomaterials to apply on tissue engineering field. In the last years, different strategies have been envisaged for the development of stimuli-responsive biomaterials. Layer-by-layer (LbL) is a promising and versatile technique to modify biomaterials' surfaces, and has allowed tailoring interactions with cells. In this study, LbL is used to construct biomimetic stimuli-responsive coatings using elastin-like recombinamers (ELRs). The recombinant nature of ELRs provides the ability to introduce specific bioactive sequences and to tune their physicochemical properties, making them attractive for biomedical and biological applications. By using complementary clickable ELRs, we were able to construct multilayer coatings stabilized by covalent bonds, resulting from the Huisgen 1,3-dipolar cycloaddition of azides and alkynes. Herein, we exploited the switchable properties of the ELRs-based coatings which are dependent on lower critical solution temperature (LCST) transition. Above LCST, the polymers collapsed and nanostructured precipitates were observed on the surface's morphology, increasing the water contact angle. Also, the influence of pH on prompting reversible responses on coatings was evaluated. Finally, in vitro cell studies using a C2C12 myoblastic cell line were performed to perceive the importance of having bioactive domains within these coatings. The effect of RGD incorporation is clearly noted not only in terms of adhesion and proliferation but also in terms of myoblast differentiation.     

Alternating bioactivity of multilayer thin films assembled from charged derivatives of chitosan

Charged derivatives of chitosan, N-sulfofurfuryl chitosan (SFC) and N-[(2-hydroxyl-3-trimethylammonium)propyl]chitosan chloride (HTACC) were prepared by reductive alkylation of amino groups of chitosan (CHI) using 5-formyl-2-furansulfonic acid, sodium salt (FFSA) as a reagent and ring opening of glycidyltrimethylammonium chloride (GTMAC) by amino groups of chitosan, respectively. The chemical structures of the charged derivatives were verified by (1)H NMR and FTIR analyses. Multilayer assembly of SFC, HTACC, CHI and the selected oppositely charged polyelectrolytes was monitored by a quartz crystal microbalance (QCM). Stratification of the multilayer film fabricated on plasma-treated poly(ethylene terephthalate) (treated PET) substrate was demonstrated by water contact angle data. The coverage of the assembled films was characterized by AFM and ATR-FTIR analyses. The bioactivity of the deposited multilayer film on the treated PET substrate was tested against selected proteins having a distinctive size and charge. This research strongly suggests that both SFC and HTACC are potential candidates for altering the surface bioactivity of materials.     

Sum frequency generation from Langmuir-Blodgett multilayer films on metal and dielectric substrates

Sum frequency generation (SFG) vibrational spectra of cadmium arachidate multilayer films adsorbed on a substrate with high nonresonant susceptibility, i.e., gold, and on a low nonresonant susceptibility substrate, i.e., fused quartz, have been investigated in the C-H stretching region in air. The films were formed by Langmuir-Blodgett (LB) deposition and their spectra recorded using SFG spectrometers employing both 532-nm nanosecond and 800-nm femtosecond lasers, with counter-propagating and co-propagating beam geometries, respectively. Both kinds of substrate were rendered hydrophobic by coating them with per-deuterated octadecanethiol (gold) or per-deuterated cadmium arachidate (fused quartz) monolayers. Single per-protonated arachidate layers in otherwise per-deuterated 10-layer films were used to show that the SFG resonances arise only from the topmost and lowermost layers in a LB film comprised of an even number of per-protonated layers, although the SFG spectra from the two hydrophobic substrates are different from each other. The differences in the spectra from the same ten-layer per-protonated films deposited on the two types of hydrophobic substrate have been explained in terms of a simple model that accounts for resonant and nonresonant contributions.     

Dimensional architecture of ferrocenyl-based oligomer honeycomb-patterned films: from monolayer to multilayer

We report a fabrication of highly ordered honeycomb-patterned films by the breath figure method from ferrocenyl-based oligomer with ferrocene units in the main chain and hydrophobic cholesteryl groups as side chains and investigate their dimensionality nature, i.e., the array of pores varying from monolayer to multilayer structure. A tentative model, including several key influencing parameters, is described to illustrate the varying layer numbers in the one film. The formation of the multilayer structure is ascribed to the Marangoni convection, thermocapillary effects, wet thickness, and evaporation speed.     

Assembly of multilayer films from polyelectrolytes containing weak and strong acid moieties

Multilayer films were assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSSMA), deposited in alternation with poly(allylamine hydrochloride) (PAH). The strongly charged groups (styrene sulfonate, SS) are expected to form electrostatic linkages (to enhance film stability), while the weakly charged groups (maleic acid, MA) can alter multilayer film properties because they are responsive to external pH changes. In this study, we varied several assembly conditions such as pH, SS/MA ratio in PSSMA, and the ionic strength of the polyelectrolyte solutions. The multilayer films were also treated by immersion into pH 2 and 11 solutions after assembly. Quartz crystal microgravimetry and UV-visible spectrophotometry showed that the thickness of PSSMA/PAH multilayers decreases with increasing assembly pH regardless of whether salt was present in the polyelectrolyte solutions. When no salt was added, the multilayers are thinner, smoother, and grow less regularly. Atomic force microscopy images indicate that the presence of salt in polyelectrolyte solutions results in rougher surface morphologies, and this effect is especially significant in multilayers assembled at pH 2 and pH 11. When both polyelectrolytes are adsorbed at conditions where they are highly charged, salt was necessary to promote regular multilayer growth. Fourier transform infrared spectroscopy studies show that the carboxylic acids in the multilayers are essentially ionized when assembled from different pHs in 0.5 M sodium chloride solutions, whereas some carboxylic acids remain protonated in the multilayers assembled from solutions with no added salt. This resulted in different pH stability regimes when the multilayers were exposed to different pH solutions, post assembly.     

Mechanically stable antireflection and antifogging coatings fabricated by the layer-by-layer deposition process and postcalcination

Complexes of poly(diallyldimethylammonium chloride) (PDDA) and sodium silicate (PDDA-silicate) are alternately deposited with poly(acrylic acid) (PAA) to fabricate PAA/PDDA-silicate multilayer films. The removal of the organic components in the PAA/PDDA-silicate mulilayer films through calcination produces highly porous silica coatings with excellent mechanical stability and good adhesion to substrates. Quartz substrates covered with such porous silica coatings exhibit both antireflection and antifogging properties because of the reduced refractive index and superhydrophilicity of the resultant films. A maximum transmittance of 99.86% in the visible spectral range is achieved for the calcinated PAA/PDDA-silicate films deposited on quartz substrates. The wavelengths of maximum transmittance could be well tailored by simply changing the deposition cycles of multilayer films. The usage of PDDA-silicate complexes allows for the introduction of high porosity to the resultant silica coatings, which favors the fabrication of antireflection and antifogging coatings with enhanced performance. Meanwhile, PDDA-silicate complexes enable rapid fabrication of thick porous silica coatings after calcination because of the large dimensions of the complexes in solution. The easy availability of the materials and simplicity of this method for film fabrication might make the mechanically stable multifunctional antireflection and antifogging coatings potentially useful in a variety of applications.     

Fabrication and characterization of multilayer films from amphiphilic poly(p-phenylene)s

Over the past two decades, considerable efforts have been devoted to the development of conjugated polymeric materials for electronic applications due to the tunability of their properties through variation of their chemical structure. The LB technique is one of the most effective and precise methods for controlling the organization and thereby the properties of polymer films at the nanoscale for device fabrication. A detailed study was performed on the Langmuir-Schaefer (LS) monolayer and Langmuir-Blodgett-Kuhn (LBK) multilayer formation of newly designed conjugated poly(p-phenylene)s (C(n)PPPOH), incorporated with alkoxy groups with different chain lengths (C(6)H(13)O-, C(12)H(25)O-, and C(18)H(37)O-) and hydroxyl groups on the polymer backbone. The monolayer formed at the air-water interface was characterized using surface pressure-area isotherms, including hysteresis measurements. The films were then transferred to different hydrophilic solid substrates and analyzed using surface plasmon resonance spectroscopy, UV-vis spectroscopy, fluorescence spectroscopy, and AFM measurements. The results showed that the polymer with a short alkoxy chain (C(6)PPPOH) forms uniform monolayers at the air-water interface and can be transferred as multilayer films compared to C(12)PPPOH and C(18)PPPOH. The observed film thicknesses measured by SPR and AFM studies were similar to the theoretical value obtained in the case of C(6)PPPOH, whereas this was not the case with the other two polymers. The present study shows that the polymer C(n)PPPOH with short alkoxy chain can be transferred onto different solid substrates for device fabrication with molecular level control.     

Polymer films derived from aligned and polymerised reactive liquid crystals

The principles and methods of fabricating thin polymer films with particular optical properties via the process of in‐situ photopolymerisation of reactive liquid crystals are described. The optical properties of these films are described in terms of their retardation profile. Some possible applications, such as compensation films for improving the viewing angle of a TN‐TFT liquid crystal display are discussed. A novel way of combining the properties of a quarter wave foil and a compensation film for a broad band cholesteric brightness enhancement film is also described.