Photoresponsive Surface Research Articles

Regulating Fibroblast Shape and Mechanics through Photoresponsive Surfaces with Concentric Circular Topographic Patterns

AbstractMaterial signals in the form of surface topographies, proved to be potent regulators of cell functions and fate, through mechanotransduction pathways. While a wealth of data is related to regular topographic patterns, i.e., lines, pit, or protrusions, there are comparatively few studies addressing the effects of circular, concentric patterns. Yet, curvatures affecting cell shape dramatically alter cell contractility and behavior. Additionally, the vast majority of patterned surfaces are static in nature and this prevents to understand how cells perceive and respond to the topographic patterns. Here, a technique is exploited for dynamically embossing micrometerscale circular pattern on azopolymeric substrates using a confocal laser microscope and it is analyzed how NIH‐3T3 reacts to the underlying topography in terms of changes in shape and mechanical properties. A characteristic pattern arrangement is found which most effectively alters cell morphology and orientation. Cells perceive the concentric pattern and reconfigure as fast as 2 h after pattern inscription. The changes in morphology also reflect dramatic changes in cell mechanics and cytoskeletal arrangements. The reported method is useful to manipulate cell shape and mechanics in a facile and cost‐effective manner and most importantly enables investigate mechanotransduction events dynamically.

A photoresponsive surface molecularly imprinted polymer shell for determination of trace griseofulvin in milk

A new photoresponsive surface molecularly imprinted polymer shell (PMIPS) was developed for determination of trace griseofulvin from milk. The PMIPS was prepared by surface imprinting technique using poly(styrene-co-methacrylic acid) (PS-co-PMMA) microspheres as the sacrificial substrate, griseofulvin as the template, a photoresponsive azobenzene derivative 4-((4-(methacryloyloxy)phenyl)diazenyl)-3,5-dimethyl benzenesulfonic acid as the functional monomer, and triethanolamine trimethacrylate as the cross-linker. The PMIPS was obtained after the removal of the sacrificial PS-co-PMMA core from the surface imprinted core-shell microspheres, PS-co-PMAA@PMIP. Compared with PS-co-PMAA@PMIP, PMIPS displayed better properties such as higher surface area and pore volume, rapid photo-isomerization rate, and higher adsorption capacities, specific binding constant and binding density. The PMIPS could efficiently detect griseofulvin in complex samples such as milk.

Design, synthesis and photochromism studies of thienyl containing triarylethylene derivatives and their applications in real-time photoresponsive surfaces

Developing new photochromic materials with simple chemical structures, striking photochromic properties, real-time morphology changeable surfaces and tunable wettability.

Well-defined protein immobilization on photo-responsive phosphorylcholine polymer surfaces

In this study, we propose a new polymer substrate that is able to covalently couple intended proteins and reduce nonspecific protein fouling. Poly[2-methacryloyloxyethyl phosphorylcholine (MPC)-ran-N-methacryloyl-(L)-tyrosinemethylester (MAT)] [P(MPC/MAT)] was synthesized by free-radical polymerization. The photooxidation of the MAT unit in the copolymer was observed under ultraviolet (UV) light at 254 nm. P(MPC/MAT) was spin-coated on silicon (Si) and gold substrates. Without UV irradiation of the polymer-coated surface, P(MPC/MAT) physisorbed on the substrates, and the thickness of the polymer layer was less than 10 nm, regardless of the polymer concentration in the coating solution. In contrast, when the polymer-coated surface was irradiated with UV light, the thickness of the polymer layer could be controlled by changing the polymer concentration of the coating solution. Competitive protein adsorption on P(MPC/MAT) was studied. Bovine serum albumin was first contacted with the surface and later challenged with bovine fibrinogen. On bare gold and Si substrates, a large amount of albumin was adsorbed, and the competitive adsorption of albumin and fibronectin was observed. In contrast, the non-UV-irradiated P(MPC/MAT) surface effectively reduced protein adsorption. Interestingly, on the UV-irradiated P(MPC/MAT) surface, the primary protein preferably bonded, and significantly less secondary protein was adsorbed compared to primary protein. Cell adhesion was also tested on the substrate to clarify the effects of proteins existing on the substrates. On the bare Si surface, many adherent cells were observed, regardless of the protein pretreatment. On the non-UV-irradiated P(MPC/MAT) surface, cell adhesion was effectively reduced along with protein adsorption. Cell adhesion on the UV-irradiated P(MPC/MAT) surface depended strongly on the type of protein that was initially in contact with the surface. We concluded that the desired proteins could be immobilized on the photo-activated P(MPC/MAT) surface while preserving their function. Moreover, competitive protein exchange and multilayer adsorption hardly occurred on the surface.

Optical manipulation and defect creation in a liquid crystal on a photoresponsive surface.

Light-induced modulations of the refractive index and pattern formation are desirable to generate complex photonic structures via exposure to light. Here we show that local modulations of the effective refractive index and reconfigurable defects can be locally induced in a hybridized thin birefringent film of a nematic liquid crystal (LC) on a photoresponsive (generating photoinduced electric fields) iron doped lithium niobate surface via exposure to a focused laser beam. Samples were studied with a tailored imaging approach, which provided the ability to investigate these optically excited, field-induced responses on a microscopic level. Upon exposure with a focused laser beam, the fluent LC was expanded on the substrate's surface and localized field-induced defects were optically created. Both umbilic (central) and line defects were observed. The formation of field-induced umbilic defects was modeled in numerical simulations. In addition, line defects were experimentally studied. It was seen that line defects interconnected the centers of two central defects (field-induced defects, which were present at the upper and lower surfaces of the LC layer). In addition, line disclinations separating reverse tilt domains (caused by the inhomogeneous distribution of the photogenerated fields) were seen. These line disclinations were pinned to the central defects. By exposure with two adjacent focused laser beams two umbilic defects were created side by side and interconnected with a line defect (the line defects pinned to each umbilic defect were joined in a single defect line). An alternative technique is presented to field-induce promising photonic motives (microlenses, resonators, line defects) in a liquid crystalline, hybridized birefringent film on a microscopic scale by using a low-power laser (opposed to the high power necessary to induce optical Kerr responses in a neat LC).

The effect of ultraviolet radiation on the mild photo-responsive surface functionalization of carbon nanotubes

ABSTRACTThe effect of ultraviolet radiation on the mild photo-responsive surface functionalization of carbon nanotubes (MWCNTs) was investigated. Functional MWCNTs were prepared via standard physisorption, followed by nitrene addition using azido compounds upon ultraviolet activation. The results imply that the organic molecules involved adsorption onto the side wall of MWCNTs, then MWCNTs reacted with azido groups in organic molecules. After immersed in ethanol for 50 days, the as-obtained MWCNTs with 700 seconds ultraviolet activation remain in the good dispersion state, which can bear comparison with that of MWCNTs oxidized with mixture acids. Therefore, this approach is a more attractive than oxidation method to functionalize MWCNTs and can be used as an effective and replaceable first step for the following functionalization.

Visible light guided manipulation of liquid wettability on photoresponsive surfaces

Photoresponsive titania surfaces are of great interest due to their unique wettability change upon ultraviolet light illumination. However, their applications are often limited either by the inability to respond to visible light or the need for special treatment to recover the original wettability. Sensitizing TiO2 surfaces with visible light-absorbing materials has been utilized in photovoltaic applications. Here we demonstrate that a dye-sensitized TiO2 surface can selectively change the wettability towards contacting liquids upon visible light illumination due to a photo-induced voltage across the liquid and the underlying surface. The photo-induced wettability change of our surfaces enables external manipulation of liquid droplet motion upon illumination. We show demulsification of surfactant-stabilized brine-in-oil emulsions via coalescence of brine droplets on our dye-sensitized TiO2 surface upon visible light illumination. We anticipate that our surfaces will have a wide range of applications including microfluidic devices with customizable wettability, solar-driven oil–water clean-up and demulsification technologies.

Photoresponsive hollow molecularly imprinted polymer for trace triamterene in biological samples

This paper reports a photoresponsive hollow molecularly imprinted polymer for the determination of trace triamterene in biological sample. The photoresponsive hollow molecularly imprinted polymer was prepared on sacrificial silica microspheres via surface imprinting technique through atom transfer radical polymerization using a novel water-soluble azobenzene derivative, 4-[(4-methacryloyloxy)phenylazo]-3,5-dimethyl benzenesulfonic acid, as the functional monomer, and the sacrificial silica core was subsequently removed using HF etching method with 1.25vol.% HF ethanolic solution. The morphologies and properties of the photoresponsive hollow molecularly imprinted polymer were further characterized and compared systematically with the corresponding photoresponsive surface molecularly imprinted polymer. Compared with surface imprinted polymer, the hollow material displayed higher binding capacity, better recognition ability, faster mass-transfer rate, and larger isomerization rate constants toward triamterene. The static binding properties of the imprinted materials were investigated under three irradiation conditions. The photoresponsive hollow molecularly imprinted polymer showed better specificity toward triamterene than its structural analogues (folic acid and caffeine) as examined by UV–vis and HPLC. The photoresponsive hollow molecularly imprinted polymer was utilized for the determination of trace triamterene in biological samples (human urine and serum) with advantages of simple sample pre-treatment, good recovery and good sensitivity.

Photocontrolled extraction of uric acid from biological samples based on photoresponsive surface molecularly imprinted polymer microspheres.

We aim to develop novel photoresponsive surface molecularly imprinted polymer (SIMP) microspheres, an SiO2 -SIMP, for the photocontrolled extraction of uric acid from biological samples. The SiO2 -SMIP was prepared on silica microspheres by surface polymerization and characterized by using scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, thermogravimetric analysis, nitrogen adsorption-desorption analysis, and UV-visible spectroscopy. The SiO2 -SMIP microspheres showed a photocontrolled uptake and release of uric acid in NaH2 PO4 buffer upon alternate irradiation at 365 and 440nm. The SiO2 -SMIP microspheres were able to photocontrollably extract uric acid from complicated biological samples for concentration analysis with no significant interference encountered and it exhibited very good recognition ability and fast binding kinetics toward uric acid.

A photoresponsive soft interface reversibly controls wettability and cell adhesion by conformational changes in a spiropyran-conjugated amphiphilic block copolymer.

We developed a photoresponsive polymer soft interface, which was able to spatiotemporally control wettability and cell adhesion/detachment in a reversible manner, by introducing spiropyran into the hydrophobic block of an amphiphilic diblock copolymer. With alternating irradiation using UV and visible light, the surface exhibited unique reversible wettability changes; the direction of hydrophobicity and hydrophilicity change was opposite to the polarity change in spiropyran photo-isomerization. Light-dependent reversible control of spatiotemporal cell adhesion and detachment was also achieved with sequential UV (adhesion) and visible light irradiation (detachment). Cell detachment using noncytotoxic visible light was realized for the first time. Cell-patterning capability stably lasted for 25days. This photoresponsive surface could be applied to fabrication of engineered tissues comprised of several cellular species.

Photoresponsive Self-Assembly of Surface Active Ionic Liquid.

A novel photoresponsive surface active ionic liquid (SAIL) 1-(4-methyl azobenzene)-3-tetradecylimidazolium bromide ([C14mimAzo]Br) with azobenzene located in the headgroup was designed. Reversible vesicle formation and rupture can be finely controlled by photostimuli without any additives in the aqueous solution of the single-tailed ionic liquid. The photoisomerization of the azobenzene derivative was investigated by (1)H NMR and UV-vis spectroscopy. Density functional theory (DFT) calculations further demonstrate that trans-[C14mimAzo]Br has less negative interaction energy, which is beneficial to aggregate formation in water. The incorporation of trans-azobenzene group increases the hydrophobicity of the headgroup and reduces the electrostatic repulsion by delocalization of charge, which are beneficial to the formation of vesicles. However, the bend of cis-azobenzene makes the cis-isomers have no ability to accumulate tightly, which induces the rupture of vesicles. Our work paves a convenient way to achieve controlled topologies and self-assembly of single SAIL.

Photoresponsive surface molecularly imprinted polymer on ZnO nanorods for uric acid detection in physiological fluids

A photoresponsive surface molecularly imprinted polymer for uric acid in physiological fluids was fabricated through a facile and effective method using bio-safe and biocompatible ZnO nanorods as a support. The strategy was carried out by introducing double bonds on the surface of the ZnO nanorods with 3-methacryloxypropyltrimethoxysilane. The surface molecularly imprinted polymer on ZnO nanorods was then prepared by surface polymerization using uric acid as template, water-soluble 5-[(4-(methacryloyloxy)phenyl)diazenyl]isophthalic acid as functional monomer, and triethanolamine trimethacryl ester as cross-linker. The surface molecularly imprinted polymer on ZnO nanorods showed good photoresponsive properties, high recognition ability, and fast binding kinetics toward uric acid, with a dissociation constant of 3.22×10−5M in aqueous NaH2PO4 buffer at pH=7.0 and a maximal adsorption capacity of 1.45μmolg−1. Upon alternate irradiation at 365 and 440nm, the surface molecularly imprinted polymer on ZnO nanorods can quantitatively uptake and release uric acid.

A Photoresponsive Surface Covalent Organic Framework: Surface-Confined Synthesis, Isomerization, and Controlled Guest Capture and Release.

By introducing an azobenzene group to the backbone of diboronic acid, we have obtained a surface-confined, photoresponsive single-layer covalent organic framework with long-range order and almost entire surface coverage. Scanning tunneling microscopic characterization indicates that though the covalent linkage provides a significant locking effect, isomerization can still happen under UV irradiation, which causes destruction of the surface COF. Furthermore, the decomposed surface COF can recover upon annealing. This photoinduced decomposition provides a facile approach for the controlled capture and release of targeted objects using these nanoporous surface COFs as a host, which has been demonstrated in this work using copper phthalocyanine as a model guest.

Photoresponsive spiropyran-functionalised MOF-808: postsynthetic incorporation and light dependent gas adsorption properties

The first example of spiropyran (SP) functionalised metal–organic framework (MOF) was synthesised via a two-step post-synthesis modification of the Zr-oxo nodes in MOF-808. The resulting MOF-808-SP showed photoresponsive surface area, pore volume and CO2 uptake.

Cellulose-based nanostructures for photoresponsive surfaces

Cellulose is the main constituent of plant cell walls and can be converted into a wide range of derivatives. The derivatives are produced by a chemical reaction of the primary and two secondary hydroxyl groups available in β-d-glucopyranose units, often in heterogeneous conditions, yielding, in many cases, <3 average degrees of substitution per glucose unit. Here we profit from the richness of these systems and different assembly conditions building up from similar nanomicelles, with a characteristic length of ca. 30 nm, different nanostructures: lamellas and filaments that show dissimilar responses to UV irradiation. The chosen cellulose derivative was a thermotropic liquid crystal synthesized by the reaction of 4-(4-methoxyazobenzene-4′-yloxy)butanoyl chloride and acetoxypropylcellulose. The nanostructures were obtained from this cellulose derivative by using spin-coating as well as Langmuir–Blodgett techniques. The nanostructures with a high surface-to-volume ratio, which can be freestanding or grown off a substrate, lead to organic tunable interfacial templates with distinct wettability properties.

Photoresponsive Surface Wrinkle Morphologies in Liquid Crystalline Polymer Films

Laminated bilayer films comprised of photoresponsive azobenzene-containing liquid crystalline polymer skin layers adhered on a thick elastomeric substrate were prepared, and the wrinkle formation upon uniaxial compression was investigated. Irradiation with UV light at 365 nm led to the disappearance of the wrinkle or reduction of wrinkle wavelength, depending on the content of azobenzene unit in the polymer. Such photoresponsive modulations of wrinkle formation could be well correlated with the photoinduced changes in the Young’s modulus determined by indentation–retraction force curve measurements using an AFM cantilever. Additionally, the thickness modulation of the skin layer caused by the photoinduced mass migration can also be applied to modify the wrinkle wavelength. These photoresponsive surface wrinkle modulations are anticipated to offer new possibilities for the surface microfabrication technology.

Effects of Alkyl Chain Length and Hydrogen Bonds on the Cooperative Self-Assembly of 2-Thienyl-Type Diarylethenes at a Liquid/Highly Oriented Pyrolytic Graphite (HOPG) Interface.

An appropriate understanding of the process of self-assembly is of critical importance to tailor nanostructured order on 2D surfaces with functional molecules. Photochromic compounds are promising candidates for building blocks of advanced photoresponsive surfaces. To investigate the relationship between molecular structure and the mechanism of ordering formation, 2-thienyl-type diarylethenes with various lengths of alkyl side chains linked through an amide or ester group were synthesized. Their self-assemblies at a liquid/solid interface were investigated by scanning tunneling microscopy (STM). The concentration dependence of the surface coverage was analyzed by using a cooperative model for a 2D surface based on two characteristic parameters: the nucleation equilibrium constant (Kn) and the elongation equilibrium constant (Ke). The following conclusions can be drawn. 1) The concentration at which a stable 2D molecular ordering is observed by STM exponentially decreases with increasing length of the alkyl chain. 2) Compounds bearing amide groups have higher degrees of cooperativity in self-assembly on 2D surfaces (i.e., σ, which is defined as Kn/Ke) than compounds with ester groups. 3) The self-assembly process of the open-ring isomer of an ester derivative is close to isodesmic, whereas that of the closed-ring isomer is cooperative because of the difference in equilibrium constants for the nucleation step (i.e., Kn) between the two isomers.

"On-Off" RGD Signaling Using Azobenzene Photoswitch-Modified Surfaces.

Photoresponsive surfaces were developed by modifying glass slides with switchable Gly-Arg-Gly-Asp-Ser (GRGDS) peptides to investigate light-controlled cell adhesion. The GRGDS peptide sequence was attached to an azobenzene moiety and then "clicked" to silanized glass substrates. The photoresponsive behavior of such cell-instructive materials (CIMs) was first checked by contact angle technique and by recording local changes in wettability owing to the isomerization of the azobenzene domain upon light stimulus. "On-off" switching was observed for at least five cycles when illuminated consecutively with UV and visible-light sources. Finally, cell-adhesion studies with human umbilical vein endothelial cells (HUVECs) validated our system as an effective light-responsive CIM platform and the possibility of dynamically controlled cell adhesion in situ was envisioned.

Photoswitchable ratchet surface topographies based on self-protonating spiropyran-NIPAAM hydrogels.

In this work, self-protonating spiropyran-based poly(N-isopropylacrylamide) polymer networks are prepared. These photoresponsive hydrogel coatings can change their surface topography upon exposure with visible light in a neutral environment. Photoresponsive surface-constrained films have been fabricated for which the swelling behavior can be controlled in a reversible manner. In a first step, symmetrical switchable surface topologies with varying cross-link density are obtained by polymerization-induced diffusion. Under light exposure, the areas with low cross-link density swell more than the areas with high cross-link density, thus forming a corrugated surface. Asymmetric ratchet-like photoresponsive surfaces have been prepared on prestructured asymmetric substrates. As a result of thickness variation of the surface-confined hydrogel layer, an asymmetric swelling behavior is obtained. Depending on the cross-link density of the hydrogel, it is possible to switch between a ratchet and flat surface topography or even an inverse ratchet surface by light.

Ultrasensitive detection of bisphenol A in aqueous media using photoresponsive surface molecular imprinting polymer microspheres

A photoresponsive SMIP was prepared for photocontrolled detection of trace bisphenol A in aqueous media with simplicity and good efficiency.