Ring-opened Form Research Articles

Electronic Influences on the Dynamic Range of Photoswitchable Dithienylethene-Thiourea Organocatalysts.

Thiourea-based organocatalysts bearing a photoswitchable dithienylethene (DTE) core and a wide range of substituents were prepared and extensively tested for their ability to accelerate the Michael reaction between acetylacetone and trans-β-nitrostyrene. There is a strong correlation between the Hammett parameter of the modulating groups and catalytic activity following UV irradiation. Electron-withdrawing groups afford the largest reactivity difference between the catalysts in their ring-open form and their ring-closed isomer, with evidence for electronic coupling between the two halves in both oDTE and cDTE.

Photo-Induced Fluorochromism of a Star-Shaped Photochromic Dye with 2,4-Dimethylthiazole Attaching to Triangle Terthiophene.

A photochrmic triangle terthiophene dye with 2,4-dimethylthiazole attached was synthesized and shows regular photochromic properties when irradiated with UV/Vis light alternately. It was found that the attaching of 2,4-dimethylthiazole has a significant effect on both the photochromism and fluorescence of triangle terthiophene. During the photocyclizatioin prcess, not only the color but also the fluorescence of the dye in THF can be toggled between ring-open and ring-closed forms of the dye. Additionally, the absolute quantum yields (AQY) of ring-open and ring-closed forms of the dye (0.32/0.58) were greatly larger than the literature report. Along with the 254nm light irradiation, the fluorescence color changed from deep blue (428nm) to sky blue (486nm) in THF. A fluorochromism cycle could be established based on the UV/visible light irradiation cycle, which provides a strategy for the design of new type fluorescent diarylethene derivatives for biological application.

Smart One-for-All Agent with Adaptive Functions for Improving Photoacoustic /Fluorescence Imaging-Guided Photodynamic Immunotherapy.

Multifunctional phototheranostics that integrate several diagnostic and therapeutic strategies into one platform hold great promise for precision medicine. However, it is really difficult for one molecule to possess multimodality optical imaging and therapy properties that all functions are in the optimized mode because the absorbed photoenergy is fixed. Herein, a smart one-for-all nanoagent that the photophysical energy transformation processes can be facilely tuned by external light stimuli is developed for precise multifunctional image-guided therapy. A dithienylethene-based molecule is designed and synthesized because it has two light-switchable forms. In the ring-closed form, most of the absorbed energy dissipates via nonradiative thermal deactivation for photoacoustic (PA) imaging. In the ring-open form, the molecule possesses obvious aggregation-induced emission features with excellent fluorescence and photodynamic therapy properties. In vivo experiments demonstrate that preoperative PA and fluorescence imaging help to delineate tumors in a high-contrast manner, and intraoperative fluorescence imaging is able to sensitively detect tiny residual tumors. Furthermore, the nanoagent can induce immunogenic cell death to elicit antitumor immunity and significantly suppress solid tumors. This work develops a smart one-for-all agent that the photophysical energy transformation and related phototheranostic properties can be optimized by light-driven structure switch, which is promising for multifunctional biomedical applications.

Coumarin Xanthene Combined Probe for the Multi-Color Detection of Metal Ions and Electrospun Fibers Developed for Real-Time Monitoring.

A coumarin-rhodamine (RhBC)-fused colorimetric/fluorescent probe was designed and synthesized. The probe is effective in Cu2+/Hg2+ ion sensing. With the added Cu2+ to RhBC in water: N, N-dimethyl formamide (8:2, v/v), the cyclic form of RhBC, is converted into the open ring form and shows a clear color change from yellow to red. In the presence of additional participating cations, this moiety shows effectiveness for Cu2+ and Hg2+ ions. The RhBC's detection limit by the UV-visible spectral method was 8.81 × 10-6M for Cu2+ ions and 2.26 × 10-5M for Hg2+ ions. The detection limit in the fluorescence titration spectra was 2.02 × 10-7M for Cu2+ ions and 6.11 × 10-8M for Hg2+ ions. A 1:1 stoichiometric ratio was validated between the probe and copper/mercury ions by the method of the job plot. Moreover, RhBC-combined polyurethane electrospun nanofibers were synthesized. These nanofibers could detect Cu2+ in real samples with no complications, with an instinctive color difference from yellow to red and a weak orange color for mercury ions.

A Rhodamine Based Fluorometric and Colorimetric Probe for Detection of pH in Aqueous Medium

Present study involves a rhodamine based fluorescent probe, which is reported to exhibit high fluorescence and colorimetric response in the pH range 2.0-5.5, where 55-fold fluorescence intensity change was identified with the lowering of pH of the medium. The working principle of the probe is based on its reversible structural inter-conversion between spirocyclic ring-close (non-fluorescent) and spirocyclic ringopen (fluorescent) forms of rhodamine base along with a reversible color change between colourless and pink with change in the pH medium. The closed spirocyclic form (AX) of the probe converts gradually into the spirocyclic open-ring (HAX) with increasing acidity of the medium and which in turn results in the strong orange fluorescence emission along with visible colorimetric responses. The calculated pKa ~ 4.0 for such conversion indicates that the probe can be useful to detect the pH of the aqueous medium in the range 3.0-5.0. The probe displays high sensitivity, good photostability, and reversible pH dependence. Detailed analysis of the pH sensing capability of the probe were performed by means of UV-vis spectroscopy, steady state and time resolved fluorescence techniques and DFT/TD-DFT based theoretical calculations.

Spirocyclic rhodamine B benzoisothiazole derivative: a multi-stimuli fluorescent switch manifesting ethanol-responsiveness, photo responsiveness, and acidochromism.

Multi-stimuli fluorescent switching materials have been extensively employed in chemistry, biochemistry, physics, and materials science. Although rhodamine-based spirolactams have been specifically considered for metal ion sensing by photoluminescence, only some of them manifest photochromic behavior, and further development of rhodamine B (RHB)-based photochromic materials is required. RHB and its cyclic amides are advantageous in various sensing applications owing to their colorimetric responses to external stimulation. Hence, the current work reports a novel multifunctional active molecular material (3',6'-bis(diethylamino))-2-(5-nitrobenzo[c]isothiazol-3-yl)spiro[isoindoline-1,9'-xanthen]-3-one (RHBIT) by linking rhodamine B with 3-amino,5-nitro[2,1]benzoisothiazole (ANB) in a facile synthetic pathway; that perceives both emission color change and switching between off-on states. RHBIT shows acidochromism, photochromism, and pH sensitivity accompanied by unique ethanol responsiveness, with potential applications in anti-counterfeiting and drug delivery. Notably, RHBIT is highly acid sensitive and reverts to the ring-closed form on treatment with triethylamine (base), visible with the naked eye amidst colorless-pink-colorless transformations. On short UV irradiation, RHBIT provides a two-fold rise in the lifetime for the ring-open form in CHCl3 and DCM compared to the spirolactam (closed form). DFT and TDDFT studies provide electronic characterization for the absorption spectra of the open and closed forms. Using the photoresponsive feature of RHBIT, an information protection application has been enacted via a rewritable platform.

Comprehensive Characterization of an "Off/On" Rhodol-Based Lysosomal Tracker for Orthogonal Cellular Analysis by Confocal Imaging.

Two florescent xanthene-cyanamide lysosomal trackers emitting strongly at ∼525 nm were prepared from fluorescein and rhodol methyl esters in microwave-assisted reactions. Both forms named "off" (nonfluorescent lactam) and "on" (strongly fluorescent ring-opened amide) have been comprehensively characterized out by using a combination of NMR spectroscopy, X-ray analysis, fluorimetry and confocal microscopy. Known rhodamines bearing electron-withdrawing groups (EWGs) exhibit an equilibrium between non-fluorescent (off) and fluorescent (on) depending on the dielectric constant of the medium. Here, cyanamide was introduced as EWG amine into the fluorescein and rhodol framework. Unlike rhodamine-type dyes, the ring-opened forms of fluorescein- and rhodol-cyanamides are stable in protic solvents under circumneutral and basic pH conditions. The osteoblastic cell line MC3T3-E1 from C57BL/6 mouse calvaria was used for confocal imaging where the different organelles and nuclei were distinguished by using an orthogonal combination of fluorescent dyes.

Structure Identification for Force-Induced Reaction Using Single-Molecule Conductance Measurement

Structure Identification for Force-Induced Reaction Using Single-Molecule Conductance Measurement

Optically Switchable NIR Photoluminescence of PbS Semiconducting Nanocrystals using Diarylethene Photoswitches.

Precisely modulated photoluminescence (PL) with external control is highly demanded in material and biological sciences. However, it is challenging to switch the PL on and off in the NIR region with a high modulation contrast. Here, we demonstrate that reversible on and off switching of the PL in the NIR region can be achieved in a bicomponent system comprised of PbS semiconducting nanocrystals (NCs) and diarylethene (DAE) photoswitches. Photoisomerization of DAE to the ring-closed form upon UV light irradiation causes substantial quenching of the NIR PL of PbS NCs due to efficient triplet energy transfer. The NIR PL fully recovers to an on state upon reversing the photoisomerization of DAE to the ring-open form with green light irradiation. Importantly, fully reversible switching occurs without obvious fatigue, and the high PL on/off ratio (>100) outperforms all previously reported assemblies of NCs and photoswitches.

The SOS response-associated peptidase (SRAP) domain of YedK catalyzes ring opening of abasic sites and reversal of its DNA–protein cross-link

Apurinic/apyrimidinic (AP, or abasic) sites in DNA are one of the most common forms of DNA damage. AP sites are reactive and form cross-links to both proteins and DNA, are prone to strand breakage, and inhibit DNA replication and transcription. The replication-associated AP site repair protein HMCES protects cells from strand breaks, inhibits mutagenic translesion synthesis, and participates in repair of interstrand DNA cross-links derived from AP sites by forming a stable thiazolidine DNA–protein cross-link (DPC) to AP sites in single-stranded DNA (ssDNA). Despite the importance of HMCES to genome maintenance and the evolutionary conservation of its catalytic SRAP (SOS Response Associated Peptidase) domain, the enzymatic mechanisms of DPC formation and resolution are unknown. Using the bacterial homolog YedK, we show that the SRAP domain catalyzes conversion of the AP site to its reactive, ring-opened aldehyde form, and we provide structural evidence for the Schiff base intermediate that forms prior to the more stable thiazolidine. We also report two new activities, whereby SRAP reacts with polyunsaturated aldehydes at DNA 3′-ends generated by bifunctional DNA glycosylases and catalyzes direct reversal of the DPC to regenerate the AP site, the latter of which we observe in both YedK and HMCES-SRAP proteins. Taken together, this work provides insights into possible mechanisms by which HMCES DPCs are resolved in cells.

Towards in vivo photomediated delivery of anticancer peptides: Insights from pharmacokinetic and -dynamic data.

An in vivo study of a photoswitchable cytotoxic peptide LMB040 has been undertaken on a chemically induced hepatocellular carcinoma model in immunocompetent rats. We analysed the pharmacokinetic profile of the less toxic photoform ("ring-closed" dithienylethene) of the compound in tumors, plasma, and healthy liver. Accordingly, the peptide can reach a tumor concentration sufficiently high to exert a cytotoxic effect upon photoconversion into the more active ("ring-open") photoform. Tissue morphology, histology, redox state of the liver, and hepatic biochemical parameters in blood serum were analysed upon treatment with (i) the less active photoform, (ii) the in vivo light-activated alternative photoform, and (iii) compared with a reference chemotherapeutic 5-fluorouracil. We found that application of the less toxic form followed by a delayed in vivo photoconversion into the more toxic ring-open form of LMB040 led to a higher overall survival of the animals, and signs of enhanced immune response were observed compared to the untreated animals.

Synthesis and Optical Characterization of a Rhodamine B Spirolactam Dimer

Amide derivatives of xanthene dyes such as rhodamine B are useful in a variety of sensing applications due to their colorimetric responses to stimuli such as acidity changes and UV light. The optical properties of these molecules can be influenced by intermolecular associations into dimeric structures, but the exact impact can be hard to predict. We have designed a covalently linked intramolecular dimer of the dye rhodamine B utilizing p-phenylenediamine to link the two dyes via amide bonds. The doubly closed spirolactam version of this dimer, RSL2, is isolated as a colorless solid. Under acidic conditions or UV exposure, RSL2 solutions develop a pink color that is expected for the ring-opened form of the molecule. However, nuclear magnetic resonance (NMR) and single-crystal diffraction data show that the equilibrium still prefers the closed dimer state. Interestingly, the emission profile of RSL2 shows solvatochromic blue fluorescence. Control studies of model compounds with similar structural motifs do not display similar blue fluorescence, indicating that this optical behavior is unique to the dimeric form. This behavior may lend itself to applications of such xanthene dimers to more sophisticated sensors beyond those with traditional binary on/off fluorescence profiles.

Single Fluorescent Probe for Zero-Crosstalk Discrimination of Lipid Droplets and the Endoplasmic Reticulum Based on Reversible Cyclization Reaction.

The interactions between different organelles are ubiquitous and crucial for life activities. Thus, development of a single fluorescent probe enabling the simultaneous two-color visualization of two organelles is of great significance for the study of organelle interplay. Herein, using the reversible ring-opening/closing reactions of rhodamine dyes, we have fabricated a robust fluorescent probe to distinguish lipid droplets (LDs) and the endoplasmic reticulum (ER) in dual-emission channels with negligible crosstalk. The probe 6'-(diethylamino)-4'-((7-(diethylamino)-2-oxo-2H-chromen-3-yl)methylene)-1',2',3',4'-tetrahydro-3H-spiro[isobenzofuran-1,9'-xanthen]-3-one, which was sensitive to the changes in the water content in the organism, displayed strong green fluorescence in the hydrophobic LDs from its ring-closed form, while it existed in a ring-opened form in the ER to illuminate a strong near-infrared emission. Importantly, the spectral difference was up to 320 nm, and thus the crosstalk between two channels was negligible. With the unique probe, the lipid accumulation in cells treated with different concentrations of oleic acid, cholesterol, and stearic acid has been successfully observed. The changes of LDs and the ER in living cells stimulated by temperature changes and hypoxia stimulation have also been revealed. Meanwhile, the different sizes and distribution of LDs and the ER in various tissues were also studied using the robust probe. This work provides a new approach to the design of dual-emissive probes and contributes to a significant molecular tool to promote the study of organelle interactions.

A novel class of xanthene dyes with chemically linked UV absorber molecule and their photophysical properties

In this paper, we prepared a new class of chemically linked UV absorber XU2 &XU3, and their photophysical, chemical properties and substrate durability were investigated. Spectroscopic behavior at various solvent and pH levels for this dye solution has been evaluated. Successfully designed an open ring form of xanthene moiety, linked a UV absorber to it, and made XU2 &XU3 that have shown good absorbance and emission band maxima at all solvents and pH mediums. Further, the found UV–Vis absorbance band maxima (λmax), PL emission maxima (λem), molar extinction coefficient (εmax) and Stokes shifts (ΔνST) when compared to commercially available dye 1. The synthesised XU2 &XU3 have shown brilliant results from exposed UV light at irradiation processing time, due to the light energy passes through the molecule by keto-enol tautomerisation between phenolic hydrogen and carbonyl carbon like a six-member ring. So it can be acted as radioless behaviour in the visible region, and it can relax the energy without any assistance. Hence, the UV absorber has protected the compound like a UV Resistance.

Switchable photochromic transparent wood as smart packaging materials

Transparent wood (TW) has been developed to combine the optical and functional aspects of wood. Many efforts have been dedicated to adding quantum dots, nanoparticles, or dyes to TW to provide additional functionalities, such as luminescent, electrochromic, thermochromic, and photo-switchable TW. However, the UV shielding performance and its new application of transparent wood are needed to explore. Herein, we report a photochromic transparent wood (PTW) by incorporating poly(methyl methacrylate) and UV/visible light switchable molecules into the delignified wood template. The focus is to investigate the relationship of process-structure-property of the PTW. The dispersion of photochromic molecules in PTW is shown by using energy-dispersive X-ray spectroscopy. The transmittance and the color of the PTW are switchable under UV and visible light excitation due to a change from the closed-ring to the open-ring form. Moreover, the PTW was found to possess, UV shielding performance, favorable thermal and mechanical properties, as well as excellent dimensional stability. We also demonstrate the potential smart packaging application of the UV-blocking PTW. We envision this PTW could be utilized for anti-counterfeit materials, intelligent sensors, and smart indicators.

Reflectance and photophysical properties of rhodamine 6G/2-(4-methyl-2-oxo-2H-chromen-7-yloxy) acetic acid as cold hybrid colorant

Rhodamine 6G (Rh6G) is modified by ethylenediamine to obtain rhodamine with amine functional groups (Rh6G-NH2). Rh6G-NH2 as an initial core is used to bond coumarin derivatives. Synthesized fluorescent colorants are specified using Fourier transform infrared spectroscopy (FT-IR), proton and carbon nuclear magnetic resonance (1H NMR and 13C NMR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-SEM) to analyze the structure of the fluorescent pigments. Fluorescence microscopy, fluorescence spectrophotometer, and UV–visible–NIR reflectance spectra are used to demonstrate the optical properties. UV–Vis–NIR reflectance spectra showed that synthesized colorants were transparent in NIR region. Also, photophysical properties of 2-(4-methyl-2-oxo-2H-chromen-7-yloxy) acetic acid (MOHCYAA), Rh6G-NH2, and hybrid 2-(4-methyl-2-oxo-2H-chromen-7-yloxy) acetic acid/rhodamine 6G (HMR) were investigated. Type of solvent had a strong effect on quantum yield. Rh6G-NH2 (ϕs = 0.66) and HMR (ϕs = 0.72) displayed the maximum quantum yield in ethanol due to good interaction with ethanol and the formation of ring-opened amide form of rhodamine group. Finally, Rh6G-NH2 and HMR displayed the maximum quantum yield in ethanol due to good interaction of structure with ethanol and the formation of ring-opened amide form of rhodamine group in compound.

A Rhodol-based Fluorescent Probe with a Pair of Hydrophilic and Rotatable Wings for Sensitively Monitoring Intracellular Polarity.

Cell polarity, as a vital intracellular microenvironment characteristic, has immense effects on numerous pathological and biological processes. Therefore, the tracking of polarity variations is highly essential to explore the role and mechanism of the polarity in pathophysiological processes. Herein, we designed and synthesized a novel rhodol-based fluorescent probe (RDS) sensitive to polarity by introducing a bis(2-hydroxyethylthio)methyl group, like a pair of hydrophilic and rotatable wings, into the rhodol skeleton. This unique design makes RDS adopt the colorless and non-fluorescent spirocyclic form in a low-polarity medium while the colored and fluorescent ring-open form is present in a high-polarity system, resulting in a positive-correlation response of fluorescence intension to polarity. Importantly, RDS was successfully applied to monitor the polarity changes in living cells including cancer cells, healthy cells and senescent healthy cells, visualizing that the polarity of cancer cells is lower than that of healthy cells in which the more senescent ones have higher polarity.

Photochromic Dithienylethene Monolayer-Modified Gold Nanoparticles as a Tunable Floating Gate in the Fabrication of Nonvolatile Organic Memory.

Nonvolatile memory (NVM) devices were fabricated by implanting a self-assembled monolayer (SAM) of functional dithienylethene (DTE) derivative on the gold nanoparticle (Au-NP) surface in a pentacene-based organic transistor. The Au-NPs and DTE served as a charge-trapping medium and tunneling barrier layer, respectively. The transfer characteristic of the NVM device showed a narrow hysteresis window and wide memory window, indicating that the DTE-SAM served as a variable barrier layer to regulate the trapping and detrapping of external free charges at the Au-NPs. The energy gap introduced by the DTE-SAM is modulated through photoisomerization between a ring-open form and a ring-closed form by absorbing UV or visible light. For a memory device, the ring-closed DTE allows more free charge injection into the trapping sites, and the ring-open one better retains the trapped charges. A longer anchoring alkanethiol chain at the DTE moiety can further extend the device's retention time. For the NVM operation, programming with the ring-closed DTE and then switching the DTE structure to the ring-open form for erasing can facilitate the charge trapping and charge retention with the same molecule compared to operating all in the ring-open form or all in the ring-closed form of DTE. The structural characterization and electronic characteristics of these devices are discussed in detail.

Tunable Symmetry-Breaking-Induced Dual Functions in Stable and Photoswitched Single-Molecule Junctions.

The aim of molecular electronics is to miniaturize active electronic devices and ultimately construct single-molecule nanocircuits using molecules with diverse structures featuring various functions, which is extremely challenging. Here, we realize a gate-controlled rectifying function (the on/off ratio reaches ∼60) and a high-performance field effect (maximum on/off ratio >100) simultaneously in an initially symmetric single-molecule photoswitch comprising a dinuclear ruthenium-diarylethene (Ru-DAE) complex sandwiched covalently between graphene electrodes. Both experimental and theoretical results consistently demonstrate that the initially degenerated frontier molecular orbitals localized at each Ru fragment in the open-ring Ru-DAE molecule can be tuned separately and shift asymmetrically under gate electric fields. This symmetric orbital shifting (AOS) lifts the degeneracy and breaks the molecular symmetry, which is not only essential to achieve a diode-like behavior with tunable rectification ratio and controlled polarity, but also enhances the field-effect on/off ratio at the rectification direction. In addition, this gate-controlled symmetry-breaking effect can be switched on/off by isomerizing the DAE unit between its open-ring and closed-ring forms with light stimulus. This new scheme offers a general and efficient strategy to build high-performance multifunctional molecular nanocircuits.

Visible-Light-Mediated Strategies for the Preparation of Oxime Ethers Derived from O-H Insertions of Oximes into Aryldiazoacetates.

Two visible-light-mediated O-H insertion protocols involving oximes and aryldiazoacetates leading to different products depending on the solvent employed are reported. In DCM, direct O-H insertion takes place. In THF, there is the additional incorporation of the ring-opened form of this solvent into the structure of the product. These metal-free protocols are mild and tolerant to air and moisture. The preparation of an acaricide has been developed as an example of synthetic application.