Spiropyran

Spiropyran (SP) and its derivatives are highly attractive owing to their distinctive merits in high contrast and fast response read-out systems. However, the realization of photoswitching properties of SP is hindered in the aggregate state, particularly in crystals owing to the dense packing of molecules leading to insufficient study of the relationship between the molecular structure/stacking mode and photoswitching behavior. Herein, we report three SP derivatives: different flexible chains (carboxyl group for SP-0 and ester group for SP-1) are attached to the indoline moiety, while the ester group is attached to the chromene moiety for SP-2...

The aim of this research is to synthesize a new sulfonic acid catalyst based on halloysite nanotubes (Hal-Py-SO3 H) and characterize it as a solid acid nanocatalyst by various analytical techniques such as Fourier-Transformed Infrared spectroscopy (FTIR), Thermal gravimetric Analysis (TGA), X-ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), Vibrating Energy-Dispersive X-ray analysis (EDX), Transmission electron microscopy (TEM) and X-ray atomic mapping. Furthermore, this new catalyst was evaluated in synthesizing spiropyran derivatives via multicomponent reactions (MCRs) and Xanthen derivatives under environmentally sustainable conditions...

Fast and programmable transport of droplets on a substrate is desirable in microfluidic, thermal, biomedical, and energy devices. Photoresponsive surfactants are promising candidates to manipulate droplet motion due to their ability to modify interfacial tension and generate "photo-Marangoni" flow under light stimuli. Previous works have demonstrated photo-Marangoni droplet migration in liquid media; however, migration on other substrates, including solid and liquid-infused surfaces (LIS), remains an outstanding challenge...

Over the past few decades, there has been significant interest in smart drug delivery systems capable of carrying multiple drugs efficiently, particularly for treating genetic diseases such as cancer. Despite the development of various drug delivery systems, a safe and effective method for delivering both anticancer drugs and therapeutic genes for cancer therapy remains elusive. In this study, we describe the synthesis of a photoswitchable smart polymeric vehicle comprising a photoswitchable spiropyran moiety and an amino-acid-based cationic monomer-based block copolymer using reversible addition-fragmentation chain transfer (RAFT) polymerization...

Organic multi-stimulus-responsive materials are widely used in anti-counterfeiting and information encryption due to their unique response characteristics and designability. However, progress in obtaining multi-stimulus-responsive smart materials has been very slow. Herein, a spiropyran derivative is constructed, which shows photochromic, thermochromic and mechanical photochromic properties, and has reversible absorption/luminescence adjustment ability. By introducing non-covalent interactions such as van der Waals force and hydrogen bond, this new molecule is more sensitive to external stimuli and exhibits better photochromic, mechanochromic and thermochromic properties with rapid speed and high contrast...

The development of photoresponsive systems with non-invasive orthogonal control by distinct wavelengths of light is still in its infancy. In particular, the design of photochemically triggered-orthogonal systems integrated into solid materials that enable multiple dynamic control over their properties remains a longstanding challenge. Here we report the orthogonal and reversible control of two types of photoswitches in an integrated solid porous framework, that is, visible-light responsive o-fluoroazobenzene and nitro-spiropyran motifs...

Density functional theory (DFT) is the workhorse of computational quantum chemistry. One of its main limitations is that choosing the right functional is a non-trivial task left for human experts. The choice is particularly hard for excited state calculations when using its time-dependent formulation (TD-DFT). This is due to the approximations of the method, but also because the photophysical properties of a molecule are defined by a manifold of states that all need to be properly described. This includes not only the relative energy of the states, but also capturing the correct character, order, and intensity of the transitions...

Peptides work as both functional molecules to modulate various biological phenomena and self-assembling artificial materials. The introduction of photoresponsive units to peptides allows the spatiotemporal remote control of their structure and function upon light irradiation. This article overviews the photoresponsive peptide design, interaction with biomolecules, and applications in self-assembling materials over the last 30 years. Peptides modified with photochromic (photoisomerizable) molecules, such as azobenzene and spiropyran, reversibly photo-controlled the binding to biomolecules and nanostructure formation through self-assembly...

The stability of merocyanine forms formed under UV irradiation of a solution of a spiropyran salt, in which an organic part acts as a cation and a compact bromide ion as an anion, their photophysical properties, and the formation mechanism are studied in this work using time-dependent density functional theory. Theoretical calculations show that TTC and CTT are the most stable open forms (the difference in stability energies is 10.5 and 12.0 kcal mol-1 relative to the formation energy of spiropyran, respectively)...

A novel probe C1 combining benzothiazole with a spiropyran section was developed for the specific detection of human serum albumin (HSA). The molecular docking suggested that the sulphonic acid group modification allowed C1 to form specific hydrogen bonds with lysine (Lys137) at fatty acid site 1 (FA1) of HSA, thus enabling fluorescence differentiation between HSA and BSA.

With the progress of forgery and decryption, the traditional encryption technology is apparent not enough, which strongly requires the development of advanced multidimensional encryption strategies and technologies. Photo-stimuli responsive fluorescent materials are promising as candidate materials for advanced information encryption. Here, we have reported new photo-stimuli responsive materials by encapsulating photochromic molecules spiropyrans (SPs) into naphthalimide-functionalized silica aerogels. By introducing different modification groups (dimethylamino) into 1,8-naphthalimide, we obtained two kinds of silica aerogels that emit blue and green colors...

Multiresponsive materials with reversible and durable characteristics are indispensable because of their promising applications in environmental change detections. To fabricate multiresponsive materials in mass production, however, complex reactions and impractical situations are often involved. Herein, a dual responsive (light and pH) spiropyran-based smart sensor fabricated by a simple layer-by-layer (LbL) assembly process from upcycled thermoplastic polyester elastomer (TPEE) materials derived from recycled polyethylene terephthalate (r-PET) is proposed...

Advanced functional polymeric materials based on spiropyrans (SPs) feature multi-stimuli responsive characteristics, such as a change in color with exposure to light (photochromism) or acids (halochromism). The inclusion of stimuli-responsive molecules in general - and SPs in particular - as main-chain repeating units is a scarcely explored macromolecular architecture compared to side chain responsive polymers. Herein, we establish the effects of substitution patterns on SPs within a homopolymer main-chain synthesized via head-to-tail Acyclic Diene METathesis (ADMET) polymerization...

Polymer particles capable of dynamic shape changes in response to light have received substantial attention in the development of intelligent multifunctional materials. In this study, we develop a light-responsive block copolymer (BCP) particle system that exhibits fast and reversible shape and color transitions. The key molecular design is the integration of spiropyran photoacid (SPPA) molecules into the BCP particle system, which enables fast and dynamic transformations of polystyrene- b -poly(4-vinylpyridine) (PS- b -P4VP) particles in response to light...

This research presents the successful development and optimization of a spiropyran-assisted cellulose aerogel (CNF-SP) aerogel with UV-induced switchable wettability, and the evaluation of its performance as an effective sorbent for oil spill cleanup. The aerogel initially exhibited strong hydrophobicity (124°) and showed UV-induced switchable wettability due to the photo-response structure of spiropyran. Upon UV irradiation, the hydrophobicity of the aerogel could be switched to hydrophilicity (31°), while visible light irradiation could restore its hydrophobicity...

Environmentally adaptive hydrogels that are capable of reconfiguration in response to external stimuli have shown great potential toward bioinspired actuation and soft robotics. Previous efforts have focused mainly on either the sophisticated design of heterogeneously structured hydrogels or the complex manipulation of external stimuli, and achieving self-regulated reversal shape deformation in homogenous hydrogels under a constant stimulus has been challenging. Here, we report the molecular design of structurally homogenous hydrogels containing simultaneously two spiropyrans that exhibit self-regulated transient deformation reversal when subjected to constant illumination...

Photoisomerizable peptides are promising drug candidates in photopharmacology. While azobenzene- and diarylethene-containing photoisomerizable peptides have already demonstrated their potential in this regard, reports on the use of spiropyrans to photoregulate bioactive peptides are still scarce. This work focuses on the design and synthesis of a spiropyran-derived amino acid, (S)-2-amino-3-(6´-methoxy-1´,3´,3´-trimethylspiro-[2H-1-benzopyran-2,2´-indolin-6-yl])propanoic acid, which is suitable for the preparation of photoisomerizable peptides...

Here we introduce an octupolar design paradigm to develop a new family of visible light organic photoswitches, namely multi-branched octupolar Stenhouse Adducts (MOPSAs) featuring a C3-symmetrical A3-(D-core) architecture, which exploits multi-dimensional geometric and electronic effects of MOPSAs to enable robust ultrafast reversible photoswitching in bulk polymers. The optimal MOPSA in polyurethane films accomplishes nearly 100 % discoloration in 6 s under visible light with ~ 100 % thermal-recovery in 17...

The spiropyran mechanophore (SP) is employed as a reporter of molecular tension in a wide range of polymer matrices, but the influence of surrounding environment on the force-coupled kinetics of its ring opening has not been quantified. Here, we report single-molecule force spectroscopy studies of SP ring opening in five solvents that span normalized Reichardt solvent polarity factors ( E T N ) of 0.1-0.59. Individual multimechanophore polymers were activated under increasing tension at constant 300 nm s-1 displacement in an atomic force microscope...

Photoswitching of photoluminescence has sparked tremendous research interests for super-resolution imaging, high-security-level anti-counterfeiting, and other high-tech applications. However, the excitation of photoluminescence is usually ready to trigger the photoswitching process, making the photoluminescence readout unreliable. Herein, we report a new photoswitch by the marriage of spiropyran with platinum(II) coordination complex. Viable photoluminescence can be achieved upon excitation by 480 nm visible light while the photoswitching can be easily triggered by 365 nm UV light...