Photoresponsive Surface Research Articles

Photo and temperature responsive novel surface active ionic liquid-based polymeric hydrogel

Integrating more than two properties into a single polymeric hydrogel to introduce the multi-functionality has been a challenge for the scientific community in recent times. In order to impart photo and temperature responsive characteristics added with adjustable mechanical properties into the polymeric hydrogel, herein we have added newly synthesized photo-responsive ionic liquid (IL) into the polymeric (κ-carrageenan) hydrogel. The IL used is having morpholine-based ester functionalized long chain cation and azobenzene based anion that exhibited trans to cis transformation when irradiated by light of 465 nm for 50 min and show surface-active properties with CMC of 6.83 mM. IL with such photo and temperature responsive properties when mixed with the hydrogel of κ-carrageenan in KCl solution gives the photo and thermo-responsive hybrid hydrogel. The three-dimensional network structure of hydrogel made up of the ellipsoidal aggregates with major and minor axis radius of 9.3 A0 and 1.6 A0, respectively is made up of a fibrous porous structure and gets disrupted through the light irradiation and initiated the gel to sol transition, studied through the SEM images, DLS data and rheological measurements. The (IL) based hydrogel gets disrupted after light irradiation as the anion of the IL starts transforming from trans to cis isomerization. Also, the thermo-reversible transition of hydrogel within room temperature to 54 °C is also shown by rheology. Kinetics of the trans to cis transformation, controlled strain and stress measurement and thermal stability of the hydrogel are assessed here. The studied photo and temperature responsive hydrogel could start a new range of smart materials.

Novel electrochemical sensing platform basing on di-functional stimuli-responsive imprinted polymers for simultaneous extraction and determination of metronidazole

A novel magnetic-controlled electrochemical sensor has been fabricated by combined photo-responsive surface molecular imprinted polymers (P-SMIPs) and electrochemical sensor. In particular, the P-SMIPs were obtained by living radical polymerization of photo-responsive functional monomer onto the magnetic Fe3O4 modified multi-walled carbon nanotubes nanocomposites. The magnetic glassy carbon electrode was introduced to make the anchoring and removal of P-SMIPs onto the magnetic-controlled glassy carbon electrode easy to manipulate. Driven by UV/vis light, the platform performs releasing and absorption of metronidazole basing on conformational variations of the photo-responsive monomer at the receptor sites part in the P-SMIPs. This process can be tested by the photo-responsive variations of metronidazole electrochemical signal. As the consequence, extracting of P-SMIPs sensor can be conveniently triggered by the controllable UV light intervention measure, leading to effectively improve in both analytes mass transfer rate to the receiving media and extraction efficiency. The experimental result indicated that the excellent recoveries of metronidazole were varied between 77.9% and 89.9% with RSDs ≤4.87% in the biological samples. Therefore, the P-SMIPs sensor shows satisfactory potential in reusable extractions that can be recycled several times with no significant loss of activity, and this utilization strategy can be extended to other analytes, achieving manifold applications of pharmaceutical and environmental.

Flexible Azo-Polyimide-Based Smart Surface with Photoregulatable Surface Micropatterns: Toward Rewritable Information Storage and Wrinkle-Free Device Fabrication

Stimulus-sensitive materials are of great fascination in surface and interface science owing to their dynamically tunable surface properties and/or morphologies. Herein, we have synthesized an azobenzene-containing polyimide (azo-PI) with enhanced chain flexibility for the fabrication of photosensitive surface patterns on a film/substrate wrinkle system or wrinkle-free devices. The phototriggered cis-trans isomerization kinetics of azobenzene groups in the novel azo-PI with various chain structures were systematically investigated. On the basis of the characteristics of stress relaxation that azobenzene reversible cis-trans isomerization induces in the wrinkled azo-PI film/substrate system, a variety of rewritable visual surface patterns with high resolution and a long legibility time (>30 days) could be easily constructed via visible-light irradiation, enabling the wrinkled azo-PI surfaces to be used as rewritable information storage media. Meanwhile, because of the visible-light irradiation strategy, these photoresponsive surfaces could find potential application in the fabrication of wrinkle-free flexible devices. This study not only sheds light on the influence of the azo-polymer chain structure on its photoresponsive behavior but also provides a versatile strategy for realizing tailor-made smart surface patterns on multilayer functional devices.

Erratum: "Photo-reconfigurable twisting structure in chiral liquid crystals triggered by photoresponsive surface" [J. Chem. Phys. 155, 061101 (2021)

Erratum: "Photo-reconfigurable twisting structure in chiral liquid crystals triggered by photoresponsive surface" [J. Chem. Phys. 155, 061101 (2021)

A comparative study of photoresponsive molecularly imprinted polymers with different shell thicknesses: Effects on 6-O-α-maltosyl-β-cyclodextrin separation.

Photoresponsive surface molecularly imprinted polymers (PSMIPs) with controlled nanoshell thicknesses were synthesized using different amounts of precursor materials to determine the effects of polymer shell layer thickness on the separation and purification of 6-O-alpha-maltosyl-beta-cyclodextrin (Mal-β-CD). The physicochemical properties and adsorption and desorption capacities of PSMIPs with different shell thicknesses were studied. Interestingly, the uniform thickness of the imprinted polymer shell layer could be adjusted from 10 to 60nm by varying the amount of polymerization precursors, and the average mesopore diameter of PSMIPs was not significantly affected by shell thickness. However, the removal efficiency and selective capacity of PSMIPs on Mal-β-CD were strongly correlated to their shell thickness. The adsorption behavior of PSMIPs on Mal-β-CD fitted well with the Langmuir adsorption model and pseudo-second-order kinetic model. Based on the obtained results, PSMIPs with a 30-nm imprinted layer were found to be an excellent adsorbent for Mal-β-CD separation, with an adsorption capacity of 18.12mg/g. They can therefore be used for industrial chromatographic separations of Mal-β-CD in the future. PRACTICAL APPLICATION: This article clearly demonstrated that the shell thickness of core-shell molecularly imprinted materials affected the degree and rate of cyclodextrin separation. Determining the optimal thickness is of great significance for the material in the separation and purification of cyclodextrin.

Photo-reconfigurable twisting structure in chiral liquid crystals triggered by photoresponsive surface.

Shape-transformable molecular additives with photoresponsivity, such as azobenzene or spiropyran, in matter are known to decrease the local order parameter and lead to drastic state variations under light irradiation. For example, a liquid crystalline state can be transformed to an isotropic liquid state by photo-exciting a tiny amount of azobenzene additives from trans- to cis-conformers. On the other hand, structural or shape transformation without changing the phase state is also intriguing since it offers an opportunity for manipulating specific structures. Here, we demonstrate an active control of the topology of chiral particle-like twisting structures, dubbed toron, by light. Interestingly, the individual twisting structure is fully reconfigurable between spherical and unique branched topological states. We reveal that the shape transformation is driven by the free-energy competition between the variation of surface anchoring strength and the elastic energy stored in the twisting structure. The mean-field simulation based on the Landau-de Gennes framework shows that the elastic anisotropy plays the dominant role in modifying the toron topology upon weak anchoring. The results offer a new path for understanding the process of topology-involved shape transformation and fabrication of novel functional materials.

Photoresponsive Surface Molecularly Imprinted Polymers for the Detection of Profenofos in Tomato and Mangosteen.

As a moderately toxic organophosphorus pesticide, profenofos (PFF) is widely used in agricultural practice, resulting in the accumulation of a high amount of PFF in agricultural products and the environment. This will inevitably damage our health. Therefore, it is important to establish a convenient and sensitive method for the detection of PFF. This paper reports a photoresponsive surface-imprinted polymer based on poly(styrene-co-methyl acrylic acid) (PS-co-PMAA@PSMIPs) for the detection of PFF by using carboxyl-capped polystyrene microspheres (PS-co-PMAA), PFF, 4-((4-(methacryloyloxy)phenyl)diazenyl) benzoic acid, and triethanolamine trimethacrylate as the substrate, template, functional monomer, and cross-linker, respectively. PS-co-PMAA@PSMIP shows good photoresponsive properties in DMSO/H2O (3:1, v/v). Its photoisomerization rate constant exhibits a good linear relationship with PFF concentration in the range of 0~15 μmol/L. PS-co-PMAA@PSMIP was applied for the determination of PFF in spiked tomato and mangosteen with good recoveries ranging in 94.4–102.4%.

Photo-Cleavable Peptide-Poly(Ethylene Glycol) Conjugate Surfaces for Light-Guided Control of Cell Adhesion.

Photo-responsive cell attachment surfaces can simplify patterning and recovery of cells in microdevices for medicinal and pharmaceutical research. We developed a photo-responsive surface for controlling the attachment and release of adherent cells on a substrate under light-guidance. The surface comprises a poly(ethylene glycol) (PEG)-based photocleavable material that can conjugate with cell-adhesive peptides. Surface-bound peptides were released by photocleavage in the light-exposed region, where the cell attachment was subsequently suppressed by the exposed PEG. Simultaneously, cells selectively adhered to the peptide surface at the unexposed microscale region. After culture, the adhered and spread cells were released by exposure to a light with nontoxic dose level. Thus, the present surface can easily create both cell-adhesive and non-cell-adhesive regions on the substrate by single irradiation of the light pattern, and the adhered cells were selectively released from the light-exposed region on the cell micropattern without damage. This study shows that the photo-responsive surface can serve as a facile platform for the remote-control of patterning and recovery of adherent cells in microdevices.

Reconfigurable Materials Based on Photocontrolled Metal–Ligand Coordination

Photoresponsive materials have attracted growing interest because of their potential applications in materials science, such as photoswitches, photopatterning, information storage, and so on. However, there are some challenges for photoresponsive materials for certain applications: 1) Only a few photoresponsive surfaces are transformed into multiple states after photoreactions to adapt to changing environmental conditions; 2) Photoresponsive materials may not function properly in cold environments, especially for gels. To address these problems, we have recently developed photoresponsive materials based on ruthenium (Ru) complexes. Such Ru complexes showed a photoinduced ligand substitution under visible light irradiation. Reconfigurable surfaces that can adapt to environmental changes and photoresponsive organohydrogels that function effectively at sub‐zero temperatures have been fabricated using photoresponsive Ru complexes. Herein, it is demonstrated that based on photocontrolled Ru–ligand coordination, reconfigurable surfaces can be modified for user‐defined functions via visible light irradiation and that photoresponsive gels can function even at –20 °C. As a perspective, Ru‐containing photoresponsive complexes could open up pathways for a variety of applications.

Photo-triggered large mass transport driven only by a photoresponsive surface skin layer

Since the discovery 25 years ago, many investigations have reported light-induced macroscopic mass migration of azobenzene-containing polymer films. Various mechanisms have been proposed to account for these motions. This study explores light-inert side chain liquid crystalline polymer (SCLCP) films with a photoresponsive polymer only at the free surface and reports the key effects of the topmost surface to generate surface relief gratings (SRGs) for SCLCP films. The top-coating with an azobenzene-containing SCLCP is achieved by the Langmuir–Schaefer (LS) method or surface segregation. A negligible amount of the photoresponsive skin layer can induce large SRGs upon patterned UV light irradiation. Conversely, the motion of the SRG-forming azobenzene SCLCP is impeded by the existence of a LS monolayer of the octadecyl side chain polymer on the top. These results are well understood by considering the Marangoni flow driven by the surface tension instability. This approach should pave the way toward in-situ inscription of the surface topography for light-inert materials and eliminate the strong light absorption of azobenzene, which is a drawback in optical device applications.

Photothermal Polymer Nanocomposites of Tungsten Bronze Nanorods with Enhanced Tensile Elongation at Low Filler Contents.

We present polymer nanocomposites of tungsten bronze nanorods (TBNRs) and ethylene propylene diene monomers (EPDM). The combination of these components allows the simultaneous enhancement in the mechanical and photothermal properties of the composites at low filler contents. The as-synthesized TBNRs had lengths and diameters of 14.0 ± 2.4 nm and 2.5 ± 0.5 nm, respectively, and were capped with oleylamine, which has a chemical structure similar to EPDM, making the TBNRs compatible with the bulk EPDM matrix. The TBNRs absorb a wide range of near-infrared light because of the sub-band transitions induced by alkali metal doping. Thus, the nanocomposites of TBNRs in EPDM showed enhanced photothermal properties owing to the light absorption and subsequent heat emission by the TBNRs. Noticeably, the nanocomposite with only 3 wt% TBNRs presented significantly enhanced tensile strain at break, in comparison with those of pristine EPDM, nanocomposites with 1 and 2 wt % TBNRs, and those with tungsten bronze nanoparticles, because of the alignment of the nanorods during tensile elongation. The photothermal and mechanical properties of these nanocomposites make them promising materials for various applications such as in fibers, foams, clothes with cold weather resistance, patches or mask-like films for efficient transdermal delivery upon heat generation, and photoresponsive surfaces for droplet transport by the thermocapillary effect in microfluidic devices and microengines.

An NIR-light-responsive surface molecularly imprinted polymer for photoregulated drug release in aqueous solution through porcine tissue.

The application of photoresponsive surface molecularly imprinted polymers based on azobenzene is limited by the UV light source required and their poor water solubility. Reducing the phototoxicity and solvent toxicity of the polymers therefore presents a challenge. In this work, an NIR-light-responsive surface molecularly imprinted polymer was fabricated by atom transfer radical polymerization using up-conversion nanoparticles as the core, a hydrophilic green-light-responsive azobenzene derivative as the functional monomer, and a drug as the template. The up-conversion nanoparticles core emitted green fluorescence in the range of 520-550 nm upon NIR irradiation (980 nm, 5 W cm-2), which was absorbed by the azobenzene containing molecularly imprinted polymers layer on the up-conversion nanoparticles surface. This caused the azobenzene chromophores to undergo trans→cis isomerization in phosphate buffered solution (pH = 7.4), thus resulting in NIR-light-induced drug release. The up-conversion fluorescence spectra were used to study the interaction mechanism between the azobenzene monomer and NIR light. Compared with structural analogues of the template (antifebrin and phenacetin), the NIR-light-responsive surface molecularly imprinted polymer showed excellent specificity of recognition for the template drug (paracetamol). The maximum adsorption capacity of the NIR-light-responsive surface molecularly imprinted polymer for loading of paracetamol was 16.80 μmol g-1. The NIR-light-responsive surface molecularly imprinted polymer was applied for NIR-light-induced paracetamol release in phosphate buffered solution (pH = 7.4) through porcine tissue. This work demonstrates the potential of drug delivery systems based on molecularly imprinted polymers for application in deep tissue delivery.

Photo-Irresponsive Molecule-Amplified Cell Release on Photoresponsive Nanostructured Surfaces.

Cell manipulation has raised extensive concern owing to its underlying applications in numerous biological situations such as cell-matrix interaction, tissue engineering, and cell-based diagnosis. Generally, light is considered as a superior candidate for manipulating cells (e.g., cell release) due to their high spatiotemporal precision and non-invasion. However, it remains a big challenge to release cells with high efficiency due to their potential limitation of the light-triggered wettability transition on photoresponsive surfaces. In this study, we report a photoresponsive spiropyran-coated nanostructured surface that enables highly efficient release of cancer cells, amplified by the introduction of a photo-irresponsive molecule. On one hand, structural recognition stems from topological interaction between nanofractal surfaces and the protrusions of cancer cells. On the other, molecular recognition can be amplified by a photo-irresponsive and hydrophilic molecule by reducing the steric hindrance of photoresponsive components and resisting nonspecific cell adhesion. Therefore, this study may afford a novel avenue for developing advanced smart materials for high-quality biological analysis and clinical diagnosis.

Doubly resonant sum frequency spectroscopy of mixed photochromic isomers on surfaces reveals conformation-specific vibronic effects.

Doubly resonant infrared-visible sum-frequency generation (DR-IVSFG) spectroscopy, encompassing coupled vibrational and electronic transitions, provides a powerful method to gain a deep understanding of nuclear motion in photoresponsive surface adsorbates and interfaces. Here, we use DR-IVSFG to elucidate the role of vibronic coupling in a surface-confined donor-acceptor substituted azobenzene. Our study reveals some unique features of DR-IVSFG that have not been previously reported. In particular, vibronic coupling resulted in prominent SFG signal enhancement of selective stretching modes that reveal electronic properties of coexisting photochromic isomers. Our analysis explores two concepts: (1) In partially isomerized azobenzene at the surface, coupling of the fundamental vibrations to the S0 → S1 transition is more prominent for the cis isomer due to symmetry breaking, whereas coupling to the S0 → S2 transition was dominant in the trans isomer. (2) A strong coupling between the fundamental vibrations and the valence π-electron density, promoted by the initial absorption of an infrared photon, may result in suppression of the intensity of the hot band vibronic transition. This may translate into a suppressed sum-frequency generation signal at sum frequency wavelengths resonant with the S0 → S2 transition of the trans isomer. The weaker coupling of the fundamental vibrations to the non-bonding electron density localized on the azo group can therefore produce detectable sum-frequency generation at the resonance wavelength of the weaker S0 → S1 transition in the cis form. These results are explained in the framework of a linear coupling model, involving both Franck-Condon and Herzberg-Teller coupling terms. Our theoretical analysis reveals the important role played by molecular conformation, orientation, and vibronic interference in DR-SFG spectroscopy.

Monodisperse hollow-shell structured molecularly imprinted polymers for photocontrolled extraction α-cyclodextrin from complex samples

In present study, monodisperse photoresponsive hollow-shell structured molecularly imprinted polymers (PHSMIPs) were fabricated based on surface imprinting technique and first proposed for selective recognition and adsorption of α-cyclodextrin (α-CD) from complex samples. The structure and the binding properties of PHSMIPs and photoresponsive surface molecularly imprinted polymers (PSMIPs) were compared. Results showed the average diameter of PHSMIPs were about 480 nm with an approximately 40 nm shell. PHSMIPs possessed BET surface areas of 273.4 m2/g, the pore volume of 0.333 cm3/g, and average pore diameters of 4.3 nm. PHSMIPs displayed higher binding capacity, better recognition ability, and faster mass transfer rate toward α-CD than PSMIPs. Furthermore, PHSMIPs was successfully used in the separation of α-CD in real reaction solution, indicating potential application for purification and selective extraction of α-CD from complex environment.

Photo-control of poly(N-[4-[(4-Nitrophenyl)azo]phenyl]acrylamide) brushes on graphene oxide coated silicon surface

Poly(N-[4-[(4-Nitrophenyl)azo]phenyl]acrylamide [poly(NPAPAA)] brushes were obtained via interface-mediated reversible addition–fragmentation chain transfer polymerization to design new photoresponsive surface on the graphene oxide coated silicon substrate. Switchable surface wettability was controlled successfully by these densely packed polymer brushes using light as the exterior stimulation. The relatively nonpolar trans azobenzene polymer brushes were converted to a polar cis form (with a larger dipole moment) utilizing light of the suitable wavelength. This conversion is reversible and can be switched back by employing visible light. Cis–trans photo-induced isomerization provided a reversible contact angle change (~ 9o) with UV and visible light for the poly(NPAPAA) brushes under successive irradiation cycles. This study may be promised to control cell culture surface without leaving any residual in terms of alternative medicine.

A photoresponsive molecularly imprinted polymer with rapid visible-light-induced photoswitching for 4-ethylphenol in red wine

The trans to cis isomerization of the azobenzene chromophore in most azobenzene-based photoresponsive molecularly imprinted polymers (MIPs) is initiated by UV irradiation. This limits the application of these materials in cases where UV light toxicity is an issue, such as in biological systems, food monitoring, and drug delivery. Herein we report a tetra-ortho-methyl substituted azobenzene, (4-[(4-methacryloyloxy)-2,6-dimethyl phenylazo]-3,5-dimethyl benzenesulfonic acid (MADPADSA). The photoswitching of MADPADSA could be induced by visible-light irradiation (550 nm for trans to cis and 475 nm for cis to trans) in 4-hydroxyethylpiperazineethanesulfonic acid (HEPES) buffer-ethanol (4:1, v/v) at pH 7.0, however, the photoisomerization was slow. With the use of MADPADSA as a functional monomer, NaYF4:Yb3+,Er3+ as a substrate, 4-ethylphenol (4-EP) as a template, a novel photoresponsive surface molecularly imprinted polymer NaYF4:Yb3+,Er3+@MIP was obtained. The NaYF4:Yb3+,Er3+@MIP displayed rapid visible-light-induced photoswitching. The NaYF4:Yb3+,Er3+ substrate could efficiently increase the trans to cis isomerization rate of the photoresponsive MIP on its surface, which was faster than that of the corresponding azobenzene monomer MADPADSA. Possible reasons for this effect were investigated by fluorescence spectroscopy. NaYF4:Yb3+,Er3+@MIP displayed good specificity toward 4-EP with a specific binding constant (Kd) of 3.67 × 10−6 mol L−1 and an apparent maximum adsorption capacity (Qmax) of 10.73 μmol g−1, respectively. NaYF4:Yb3+,Er3+@MIP was applied to determine the concentration of 4-EP in red wine with good efficiency and a limit of detection lower than the value that could cause an unpleasant off-flavor.

Reversible Photoisomerization of Monolayers of π‐Expanded Oligothiophene Macrocycles at Solid–Liquid Interfaces

AbstractSelf‐assembled monolayers of a π‐expanded oligothiophene macrocycle undergo photoisomerization between their Z,Z and E,E diastereomers at the interface between octanoic acid solutions and highly oriented pyrolytic graphite (HOPG). The switching process proceeds in situ at the solid–liquid interface and was followed by scanning tunneling microscopy (STM). Upon illumination with light at 365 nm (546 nm), a monolayer of Z,Z‐8mer (E,E‐8mer) photoisomerizes to the E,E‐8mer (Z,Z‐8mer) form with changes in 2D hexagonal packing. These findings provide insight towards the design of photoresponsive surfaces with desirable optoelectronic and structural (host–guest) properties.

Reversible Photoisomerization of Monolayers of π-Expanded Oligothiophene Macrocycles at Solid-Liquid Interfaces.

Self‐assembled monolayers of a π‐expanded oligothiophene macrocycle undergo photoisomerization between their Z,Z and E,E diastereomers at the interface between octanoic acid solutions and highly oriented pyrolytic graphite (HOPG). The switching process proceeds in situ at the solid–liquid interface and was followed by scanning tunneling microscopy (STM). Upon illumination with light at 365 nm (546 nm), a monolayer of Z,Z‐8mer (E,E‐8mer) photoisomerizes to the E,E‐8mer (Z,Z‐8mer) form with changes in 2D hexagonal packing. These findings provide insight towards the design of photoresponsive surfaces with desirable optoelectronic and structural (host–guest) properties.

Surface with Reversible Green-Light-Switched Wettability by Donor–Acceptor Stenhouse Adducts

In this report, we designed surfaces with reversible green-light-switched wettability via donor-acceptor Stenhouse adducts (DASAs). Photoresponsive micro/nanoparticles were prepared by coating the surfaces of silica micro/nanoparticles with polydopamine and then postmodifying with DASA molecules. Then, the particles were immobilized on a glass substrate surfaces either with double-sided adhesive tape or cross-linking poly(dimethylsiloxane). Silica micro/nanoparticles with various diameters (0.2, 2.5, and 85 μm) were used to fabricate the photoresponsive surface. Green light irradiation switches the hydrophobic linear DASA to a hydrophilic cyclic isomer, which further increases the wettability and contact angle hysteresis on the surface. On the other hand, heating (100 °C) induces the cyclic-to-linear isomerization of DASA molecules and switches the surface back to hydrophobic. The wettability of the DASA-modified surface is reversible under alternate green light irradiation and heating.