Photoinduced Electron Transfer Process Research Articles

Post-synthetic modified luminescent metal-organic framework for the detection of berberine hydrochloride in a traditional Chinese herb.

In this work, a novel fluorescence sensor UiO-66-PSM based on post-synthetic modified metal-organic frameworks was prepared for the detection of berberine hydrochloride (BBH) in the traditional Chinese herb Coptis. UiO-66-PSM was synthesized by a simple Schiff base reaction with UiO-66-NH2 and phthalaldehyde (PAD). The luminescence quenching can be attributed to the photo-induced electron transfer process from the ligand of UiO-66-PSM to BBH. The UiO-66-PSM sensor exhibited fast response time, low detection limit, and high selectivity to BBH. Moreover, the UiO-66-PSM sensor was successfully applied to the quantitative detection of BBH in the traditional Chinese herb Coptis, and the detection results obtained from the as-fabricated fluorescence sensing assay were consistent with those of high-performance liquid chromatography (HPLC), indicating that this work has potential applicability for the detection of BBH in traditional Chinese herbs.

Novel spectrofluorometric approach for assessing vilazodone by blocking photoinduced electron transfer: analytical performance, and greenness-blueness evaluation.

In this paper, vilazodone (VLD), a serotonin modulator prescribed for major depressive disorder, was investigated using a rapid, highly sensitive, and eco-friendly spectrofluorometric approach. The native fluorescence of VLD, originating from its indole moiety, exhibited an emission peak at 486 nm upon excitation at 241 nm. However, the presence of a piperazinyl nitrogen atom in the VLD structure, acting as an electron donor, significantly diminished the fluorescence intensity through photoinduced electron transfer (PET) to the indole ring. However, by protonating this nitrogen atom using 0.02 M Teorell-Stenhagen buffer (pH 3.5), inhibition of the PET process effectively blocked electron transfer, restoring the fluorescent properties of the drug. Further, an enhancement in the fluorescence was achieved by employing methanol as the solvent, resulting in a 1.5-fold increase. The combined use of PET blockage and methanol enabled the detection of VLD at levels as low as 0.78 ng mL-1. Calibration analysis demonstrated linearity within the range 5-400 ng mL-1, exhibiting a correlation coefficient of 0.9998 and a limit of quantification of 2.37 ng mL-1. The method obeyed the requirements of International Council on Harmonization (ICH). The proposed approach was applied for the accurate measurement of VLD in pharmaceutical tablets, content uniformity testing based on USP requirements, and determining VLD concentration in spiked human plasma. Moreover, the environmental impact, in addition to practical effectiveness, of the proposed approach was evaluated using different metrics.

Saltwater-Induced Rapid Gelation of Photoredox-Responsive Mucomimetic Hydrogels.

Shear-thinning hydrogels represent an important class of injectable soft materials that are often used in a wide range of biomedical applications. Creation of new shear-thinning materials often requires that factors such as viscosity, injection rate/force, and needle gauge be evaluated to achieve efficient delivery, while simultaneously protecting potentially sensitive cargo. Here, a new approach to establishing shear-thinning hydrogels is reported where a host-guest cross-linked network initially remains soluble in deionized water but is kinetically trapped as a viscous hydrogel once exposed to saltwater. The shear-thinning properties of the hydrogel is then "switched on" in response to heating or exposure to visible light. These hydrogels consist of polynorbornene-based bottlebrush copolymers with porphyrin- and oligoviologen-containing side chains that are cross-linked through the reversible formation of β-cyclodextrin-adamantane inclusion complexes. The resultant viscous hydrogels display broad adhesive properties across polar and nonpolar substrates, mimicking that of natural mucous and thus making it easier to distribute onto a wide range of surfaces. Additional control over the hydrogel's mechanical properties (storage/loss moduli) and performance (adhesion) is achieved post-injection using a low-energy (blue light) photoinduced electron-transfer process. This work envisions these injectable copolymers and multimodal hydrogels can serve as versatile next-generation biomaterials capable of light-based mechanical manipulation post-injection.

Γ-Graphyne: A Promising Electron Acceptor for Organic Photovoltaics

The most significant discovery of recent years is graphene, which consists of a single layer of sp2-hybrid carbon atoms arranged in a two-dimensional (2D) honeycomb lattice nanostructure.Graphynes – a two-dimensional materials similar to graphene, but composed of sp-hybridized carbons periodically integrated into a sp2-hybridized carbon network. Structure of graphynes were first theoretically proposed in 1987 by Baughman et al.[1] More than 20 years later, in 2010, Li et al. developed the first successful methodology for creating γ-graphdiyne films [2]. Despite the significant attention from the scientific community, only recently Hu et al. reported the synthesis of γ -graphyne with unified long-range crystalline structure [3].We demonstrate that γ -graphyne is an efficient electron acceptor due to its low LUMO and its ability to delocalize an excess charge. Moreover, in contrast to other 2D sheets like graphene its electronic properties are not sensitive to vacancy defects. Investigation of photoinduced electron transfer processes in complexes of γ -graphyne with typical electron-accepting and electron-donating partners shows that the lowest excited states with donors are charge separated states formed by the electron transfer from partner to γ -graphyne. This electron transfer is thermodynamically favorable and occurs on nano-to-picosecond time scale. In contrast, electron transfer from γ -graphyne to strong electron acceptors such as fullerenes or arylenediimides is unlikely [4].

Electrostatic loading and photoredox-accelerated release of antibiotics from oligoviologen-crosslinked hydrogels using red light

Hydrogel drug delivery is the subject of an ever-expanding industry where delivery occurs by numerous methods, many of them passive in nature. On-command, stimuli-driven release, particularly using light to initiate spatiotemporal, controlled release of cargo is a more attractive approach than passive release methods. Here, we report a novel method for electrostatically loading negatively charged dye and antibiotic cargo in biocompatible, oligoviologen-crosslinked hydrogels equipped with an integrated Aza-boron-dipyrromethene (Aza-BODIPY) photocatalyst. Following loading, the release of the electrostatically bound cargos can be accelerated upon irradiation with red light (660 nm) through a photoinduced electron transfer (PET) process that reduced the oligoviologen subunits. A free radical polymerization method was used to fabricate the hydrogels with a hydroxyethyl acrylate backbone, co-crosslinked by a viologen hexamer (6V-St•12Cl) and Aza-BODIPY derivative. Irradiation of the Aza-BODIPY photocatalyst led to a reduction of the viologen subunits to their monoradical cation oxidation state via PET. The photocatalyst was regenerated in situ in a triethanolamine (TEOA) solution, which served as a sacrificial reductant. Negatively charged dye (i.e., methyl orange, MO) was electrostatically loaded into the hydrogel through counteranion metathesis, followed by irradiation with red light to release the dye as the subunits of the viologen crosslinker lost positive charges (i.e., V2+ to V●+). Controlled release of the dye was tracked by UV/Vis absorption spectroscopy, yielding up to 74 % of cargo released in 75 h. Negatively charged antibiotic cargo (i.e., nalidixic acid) was then electrostatically loaded into and released from hydrogels by the same method. Controlled release of the drug was tracked by agar diffusion and liquid broth microdilution antibacterial susceptibility assays, where bacterial growth inhibition was recorded, confirming the same release trends observed for the dye cargo.

Ratiometric Fluorescent Detection of Chromium(III) Based on One-Dimensional Imine-Linked Covalent Organic Framework.

Chromium (Cr3+) as a highly toxic pollutant has aroused much attention due to its wide industrial applications. Covalent organic frameworks (COFs) have been considered as one of the most promising metal ion sensors due to their open pore channels and abundant adsorption sites. Herein, a novel luminescent one-dimensional COF (Py-An COF) was constructed by the condensation of 5'-(anthracen-9-yl)-[1,1':3',1″-terphenyl]-4,4″-dicarbaldehyde (An-2CHO) and 1,3,6,8-tetrakis(p-aminophenyl) pyrene (PyTTA). The resulting COF showed high crystallinity, comparative high surface area, and good thermal stability, which can be utilized for Cr3+ fluorescent sensors with high sensitivity and selectivity. Furthermore, the coordination between Schiff-base N atoms and Cr3+ inhibits the photoinduced electron transfer (PET) process, resulting in the enhanced fluorescence intensity of chromophores (436 nm) and decreased the fluorescence intensity of Py-An COF (512 nm) simultaneously, which eventually realizes a highly efficient ratiometric fluorescent sensor for trace Cr3+. Compared with other porous fluorescent materials, Py-An COF possesses a lower detection limit, higher sensitivity, and better selectivity. This work provides strategic guidance for the design of COFs as ratiometric fluorescence sensors.

Engineered protein-iron and/or gold-protein-iron nanocomposites in aqueous solutions upon UVA light: Photo-induced electron transfer possibilities and limitations

Occurrence/suppression of photo-induced electron transfer (PI-ET) process in solutions of nanocomposites represents a very hot topic in several photo-related research domains. In this work, this phenomenon is investigated in aqueous solutions using iron-containing mono-/bi-metallic nanocomposites that have been engineered through protein-templated syntheses, with the aim to potentially create new biocompatible imaging contrast agents for medical diagnostics. Two types of iron-containing nanocomposites, mono-metallic (protein-Fe) and bi-metallic (Au-protein-Fe), have been synthesized and characterized with the aid of several experimental techniques, such as high-resolution transmission electron microscopy (HR-TEM), steady-state fluorescence, electron paramagnetic resonance (EPR) and light-induced EPR (LEPR). Theoretical model of the N-terminal region of the bovine serum albumin protein interacting with Fe cations and simulations of the EPR spectral features upon UVA light irradiation complemented the material’s analysis. Two iron forms within the mono-/bi-metallic nanocomposites have been detected experimentally: (i)complexed iron cations (giving EPR signal at g = 4.29) and (ii)superparamagnetic iron oxide nanoparticles (SPIONs; expressing EPR resonances at g// = 2.21 and g⊥ = 2.09). Upon UVA-light irradiation (325 nm), PI-ET between the two iron forms have been observed in the protein-Fe nanocomposite; however, this electronic communication is suppressed in the Au-protein-Fe system. The presence of luminescent Au nanoclusters and dissimilar sizes of SPIONs in bi-metallic nanocomposites (around 5 nm vs. approx. 2 nm in the monometallic protein-Fe system) represent the two possible reasons underneath suppression of the PI-ET process in the former. Moreover, OH radicals were detected in aqueous solutions in both iron-containing nanocomposites (Fe and Au/Fe systems) when irradiated at 325 nm for 5 min at r.t. The reported evidence of PI-ET in iron-containing nanocomposite aqueous solutions can thus have a large impact on their potential medical and/or environmental applications.

A sensitive “turn-on” Schiff-base fluorescent probe for the selective detection of Fe3+ and bio-imaging

A novel Schiff-base fluorescent probe, 4-(N-(2- hydroxyl-1-naphthalymethylimino)-ethylamino) −7-nitro-1,2,3-benzoxadiazole (HENB) was synthesized and utilized for spectral sensing of Fe3+ ions at neutral pH. The binding of Fe3+ to HENB in C2H5OH-HEPES buffer (1:1 v/ v, 25 mM, pH 7.2) resulted in a pronounced emission enhancement at 530 nm, which is possibly due to the inhibition of photo-induced electron transfer (PET) process as well as the chelation enhanced fluorescence (CHEF) effect. HENB shows good selectivity and sensitivity toward Fe3+ with the detection limit as low as 4.51 nM. Test strips made of HENB was used for rapid “naked-eye” detection of Fe3+ ions in aqueous medium. Moreover, HENB was successfully applied in fluorescence imaging of exogenous and endogenous Fe3+ in live Hela cells as well as zebrafish. Importantly, HENB is capable of effectively monitoring the variations of Fe3+ in living cells during ferroptosis process.

Unraveling the dual sensing mechanism of hydrogen peroxide probe: Photoinduced electron transfer and unusual local excited state intramolecular proton transfer

An understanding of hydrogen peroxide's (H2O2) sensing process is crucial for the development of effective fluorescent probes. In this investigation, we unraveled the sensing mechanism of the H2O2 fluorescent probe (BBD) derived from phthalimide-borate. The fluorescence of probe BBD is quenching and our findings establish this phenomenon can be attributed to a nonclassical photoinduced electron transfer (PET) process, wherein a crossing of energy curves between the local excited and charge transfer states is observed. The reaction between BBD and H2O2 causes the phenylboronic acid ester to oxidize and release a hydroxyl group, which turns off the PET process and causes the product HMD to enhance the fluorescence significantly. In addition, the results show that the generated HMD-N likewise undergoes fluorescence quenching, and the fluorescence band seen in the experiment originates from the HMD-T created by the unusual local excited state intramolecular proton transfer (ESIPT) process. In conclusion, our theoretical findings provide a comprehensive explanation for the fluorescence characteristics exhibited by BBD and HMD with an unusual local ESIPT combined PET process.

Spectroscopic and theoretical study of novel copper(II) complexes based on phenothiazine ligands: UV–Visible absorption and photoinduced electron transfer

This study presents three novel copper (II) complexes based on phenothiazine ligands that were synthesized and revealed their structures by spectral and analytical measurements. The synthesized complexes offered potential opportunities to explore their UV–visible absorption properties and photoinduced electron transfer with triethylamine. We performed density functional theory (DFT) calculations for Cu(II) (HL1)2 compounds and studied their frontier molecular orbitals in different environments. The calculations were done by using PBE1PBE functional and 6-31G(d)/Lanl2dz basis sets. We applied the LANL2DZ basis set for Cu. The treatment of all the other atoms was done by a 6-31G(d) basis set. For the calculation of the electronic structure, the basis set 6–31 + G(d)/Lanl2dz and SMD solvation model with MeCN and DMF were employed. We computed the frequencies to confirm the stability of the structures. Theoretical calculations can help explain the experimental findings, provide insights into the electronic transitions responsible for UV–visible absorption, and elucidate the photoinduced electron transfer processes involved.

Eosin Y-Based Metal-Organic Framework Synergistic with Cobalt(II) Complex for Hydrogen Evolution through Photoinduced Intermolecular Electron Transfer.

Photocatalytic hydrogen evolution reaction (HER) is a promising approach for producing clean energy and has the potential to play an important role in the transition toward a more sustainable and environmentally friendly energy system. Optimizing the photoinduced electron transfer (PET) process and increasing visible-light utilization play a central role in photocatalysis. Herein, we built a novel Eosin Y-based metal-organic framework (Zn-EYTP) by synergizing a cobalt(II) complex for boosting the H2 evolution efficiency through photoinduced intermolecular electron transfer. Under optimized conditions, the maximum H2 evolution efficiency for Zn-EYTP was determined to be a turnover number (TON) value of 11,100 under green LED irradiation. And the synthesized Zn-EYTP photocatalysts could be easily recycled to restore the initial photocatalytic activity even after 3 cycles. Detailed studies reveal that the significantly enhanced HER activity in Zn-EYTP could be ascribed to the effective separation of photogenerated charges and the synergistic intermolecular interaction between Zn-EYTP and [Co(bpy)3]Cl2. The present work enables a deeper understanding of the importance of the PET process for enhanced HER photocatalytic activities, which will provide a viable strategy for the development of highly efficient photocatalysts.

Ortho-Vanillin-based fluorescent sensor with ESIPT characteristics for selective detection of Al(III) in aqueous solutions and its application for plant and live-cell imaging

A new acylhydrazone fluorescent sensor (VN62) with excited intramolecular proton transfer (ESIPT) characteristics has been designed and synthesized through condensation of o-vanillin with 6‑hydroxy-2-naphthoic hydrazide for selective detection of Al3+ in aqueous medium. The structure of the VN62 sensor was characterized by various techniques such as 1H and 13C NMR and mass spectrometry, and also confirmed by single crystal X-ray diffraction. The VN62 sensor showed a remarkable fluorescence enhancement response to Al3+ over a broad pH range in a nearly 100 % aqueous solution without interference by most of tested metal ions and anions. Through fluorescence titration and a Job's plot experiment, the binding stoichiometry of VN62 with Al3+ was found to be 1:1. The limit of detection of VN62 toward Al3+ was determined as 39.6 nM and the binding constant was 2.66 × 104 M−1. Comprehensive analyses by HR-MS, 1H NMR and density functional theory calculations illustrated that the VN62 sensor coordinated with Al3+, forming a stable trigonal bipyramid structure complex, which blocked the ESIPT and photoinduced electron transfer processes and simultaneously promoted an intramolecular charge transfer process, thereby leading to strong cyan fluorescence. Moreover, VN62-loaded test strips were successfully applied for rapid and visual detection of Al3+. Furthermore, the VN62 sensor was used to visualize Al3+in plants and live cells. The results indicated that the VN62 sensor has great potential for detecting Al3+in biological systems.

A colorimetric and NIR fluorescent probe for ultrafast detecting bisulfite and organic amines and its applications in food, imaging, and monitoring fish freshness

Herein, for the first time, we have successfully constructed a novel near-infrared (NIR) emission fluorescent probe Dpyt for ultrafast detecting (within 5 s) bisulfate and organic amines based on a 1,2-dihydrocyclopenta[b]chromene-barbiturate conjugation system. Upon addition of bisulfate or organic amines, Dpyt displayed a distinct color change from blue to colorless or from purple to blue, respectively, suggesting that the Dpyt can be used to detect two analytes by the naked eye. Based on quantum chemistry calculations, the fluorescence quenching of Dpyt after the addition of HSO3− is caused by the photoinduced electron transfer (PET) process of the adduct Dpyt-HSO3−. The fluorescence enhancement of Dpyt caused by most organic amines is due to the enhanced intramolecular charge transfer (ICT) process of deprotonated Dpyt. Notably, Dpyt can be applied for detecting HSO3− in actual food samples such as red wine and sugar, as well as for imaging of HSO3− and representative propylamine in living cells. And more importantly, indicator labels constructed by filter paper loaded with Dpyt can visually monitor the freshness of salmon in real-time by daylight and fluorescence dual-mode. The comparison with national standard method of China manifests that indicator labels are a valid tool to assess the freshness of seafood.

In Silico DFT (Density Functional Theory) Study of Chemosensor Selectivity of 3-Oxo-3H-Benzo[f]chromen-2-Carboxylic Acid (ABKK) on Sodium Metal Ion Using FMO (Frontier Molecular Orbital) Analysis

The chemosensor selectivity of 3-oxo-3H-benzo[f]chromen-2-carboxylic acid (ABKK) toward Na+ metal ionhas been successfully studied in silico using FMO (Frontier Molecular Orbital) analysis method. The geometry of the ABKK structure was optimized by the DFT (Density Functional Theory) method with a function/basis set: M06/6-31G (d, p). Afterward, the electronic properties of the ABKK structure before and after binding to sodium ion were analyzed and compared with the ABKK+other metal ion structures representing valence charges 1-3 and within the constraints of the basis set used. The results of geometry optimization showed that 1ABKK+Na+ has a more positive frequency/minima than 2ABKK+Na+ with interaction energies of 145 and 200.5 kcal/mol, respectively. Ignoring the role of solvents, FMO analysis revealed that the bandgap energy of fluorophore and receptor interactions (∆E LUMO Fl-Rs 1ABKK+Na+) and (∆E HOMO Fl-Rs 2ABKK+Na+) were 0.631 and 0.336 eV, correspondingly. In addition, the bandgap energy of fluorophore/∆E Fl 1ABKK+Na+ and 2ABKK+Na+ were calculated at 4.347 and 4.362 eV. Comparing those two types of bandgap energies with the bandgap belonging to ABKK+other metal ions, the excitation, and PET (Photoinduced Electron Transfer) processes were estimated to be relatively favorable experienced by 2ABKK+Na+. Finally, the selectivity of ABKK toward sodium metal ions from the computational calculations was relatively in agreement with the laboratory experimental results.

Application of surface nitrogen-doped graphene quantum dots in the sensing of ferric ions and glutathione: Spectroscopic investigations and DFT calculations

Developing a sensing platform that can quickly and accurately measure glutathione (GSH) is crucial for the early detection of various human diseases. GQDs have shown great potential in many technological and biological applications. This study focused on synthesizing nitrogen-doped GQDs (NGQDs) with stable blue fluorescence using a simple and easy hydrothermal method in one step. The bamboo fiber was used as the green source for this synthesis. The NGQDs had a tiny particle size of 4.7 nm and emitted light at 405 nm when excited. They displayed a remarkable quantum yield of 40.36 % and were effectively used as fluorescent probe to specifically detect Fe3+. The energy transfer mechanism led to the NGQDs' fluorescence being deactivated by Fe3+ ions (turn- “off”). However, with the addition of GSH to the system, the fluorescence intensity of NGQDs was reactivated (turn- “on”). Thus, a fluorescence turn “off–on” system was developed for the sensitive detection of Fe3+ and GSH. Using density functional theory (DFT), it was theoretically calculated that the surface of the fabricated NGQDs possess lone pairs of electrons on oxygens and doped nitrogen causing a photo-induced electron transfer (PET) process to occur. This PET process was suppressed previously owing to complex formation between oxygen atoms of modeled structure and ferric ions. The sensing platform displayed a sensitive response to Fe3+ in the 1–1000 μM range with LOD of 34 nM and GSH in the range of 1–50 μM, with a detection limit of 45 nM. Furthermore, the NGQDs exhibited high selectivity towards Fe3+ and GSH over other electrolytes and biomolecules. Additionally, the probe exhibited non-cytotoxicity and was practically applicable for the detection of GSH in HeLa cells.

Isomeric fluorescence sensors for wide range detection of ionizing radiations

In order to achieve a wider range of ionizing radiations detection, novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer (PET) effect. Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized, and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry (HRMS), nuclear magnetic resonance hydrogen and carbon spectroscopy (1H and 13C NMR). The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration. The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process. Despite the similarities in chemical structures, the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine. In the direct irradiation experiments of ionizing radiation, the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4, respectively. Furthermore, density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 eV and 1.13 eV, respectively. A wider energy range has a stronger driving force on electrons, which is conducive to fluorescence quenching. Both femtosecond transient absorption spectroscopy (fs-TAS) and transient fluorescence spectroscopy (TFS) tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant. Although both isomers can significantly reduce LOD during PET process, PDI-B with aromatic amine has a wider detection range of 0.118–240 Gy due to its larger emission enhancement, which is a leap of three orders of magnitude. It breaks through the detection range of gamma radiation reported in existing studies, and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.

(Eu-MOF)-derived Smart luminescent sensing for Ultrasensitive on-site detection of MiR-892b

MicroRNAs (miRNAs) are important biomacromolecules used as biomarkers for the diagnosis of several diseases. However, current detection strategies are limited by expensive equipment and complicated procedures. Here, we develop a portable, sensitive, and stable (Eu-MOF)-based sensing platform to detect miRNA via smartphone. The Eu-MOF absorbs the carboxyfluorescein (FAM)-tagged probe DNA (pDNA) to generate hybrid pDNA@Eu-MOF, which can efficiently quench the fluorescence of FAM through a photoinduced electron transfer (PET) process. When integrated with a smartphone, the nonemissive pDNA@ Eu-MOF hybrid could be utilized as a portable and sensitive platform to sense miRNA (miR-892b) with a detection limit of 0.32 pM, which could be even distinguished by the naked eye. Moreover, this system demonstrates high selectivity for identifying miRNA family members with single-base mismatches. Furthermore, the expression levels of miRNA in cancer cell samples could be analyzed accurately. Therefore, the proposed method offers a promising guideline for the design of MOF-based sensing strategies and expands their potential applications for diagnostic purposes.

Design of smart polymeric sensor based on poly(N-isopropylacrylamide) and anthrapyrazolone derived fluorescent crosslinker for the detection of nitroaromatics in aqueous medium

Explosive detection in aqueous medium using fluorometric titrations is of paramount importance for security and safety, as it offers a susceptible and rapid method to identify potential threats in water sources or aqueous environments, ensuring the protection of critical infrastructure and public safety. Previously, we have investigated fluorescence-based explosive detection via π-electron-rich anthrapyrazolone-derived fluorophore moiety (dye) as an effective sensor in an organic medium. However, the dye's solubility in water makes it difficult to identify nitroaromatics (NACs) in aqueous media. In the current study, thermoresponsive crosslinked polymer (TCP) with dye [DHBBI(MA)2] added as a crosslinker between the polymer chains is synthesised by straightforward and easy free radical polymerization. The emission intensity of TCP is significantly reduced with interaction with NACs like TNP, ATNP, DNP, and PNP, primarily through static quenching attributed to a photoinduced electron transfer (PET) process. TNP exhibited the most efficient quenching, with a Ksv value of 10.7 × 102 M−1 for TCP and 6.189 × 102 M−1 for DHBBI(MA)2. The limit of detection (LOD) was 0.12 nM for TCP and 0.135 nM for DHBBI(MA)2. TCP proved to be approximately 1.72 and 1.12 times more efficient in TNP detection than DHBBI(MA)2 in terms of Ksv value and LOD. At higher temperatures beyond the LCST of the polymer, TCP exhibits additional fluorescence quenching, making it effective for NAC detection. This switch in fluorescence quenching near the cloud point temperature (TCP) of PNIPAM in aqueous media indicates TCP's potential for real-world applications, including rapid detection and identification of nitroaromatics and environmental monitoring in soil and water.

Dopamine-Coated Carbon Nanodots: A Supramolecular Approach to Polydopamine Composite.

The development of biocompatible composites constituted by polydopamine and fluorescent carbon dots represents a promising way of exploiting the extraordinary adhesive properties of polydopamine for multi-purpose technologies. Here, a supramolecular complex is realized by the assembly of dopamine on the carbon dots surface, and the optical and structural properties are investigated by means of different spectroscopic techniques, from time-resolved fluorescence to Raman and NMR spectroscopies. The results suggest that the catechol unit of dopamine plays the main role in the formation of the supramolecular complex, in which carbon nanodot fluorescence emission is quenched by a photoinduced electron transfer process. The interaction with the nanodots' basic surface sites promotes the oxidation of dopamine and drives to its oligomerization/polymerization on the nanodot surface.

A buffering fluorogenic probe for real-time lysosomal pH monitoring

Real-time monitoring of lysosomal pH is critical for understanding lysosome-related biological processes and diseases, but few lysosome probes can achieve this response effectively. Therefore, it is essential to develop pH-sensitive probes with better performance. In this study, we designed and synthesized a lysosome-targeting “buffering fluorogenic probe” (Lyso-BFP) by introducing a salicylamide group to naphthalimide for buffering strategy and a hydroxyethyl piperazine unit to target lysosome as well as specific pH response. Lyso-BFP demonstrated excellent photostability, pH specificity, and responsiveness to lysosomal acidification in living cells, thanks to its well-suit pKa. Density functional theory calculation revealed that Lyso-BFP’s excellent pH sensing performance resulted from the inhibition of the photo-induced electron transfer (PET) process from hydroxyethyl piperazine to the naphthalimide moiety after the piperazine ring’s protonation at low pH. Remarkably, Lyso-BFP allowed for wash-free imaging and long-term real-time monitoring of lysosome pH changes based on its off-on fluorescence behavior and buffer strategy. With its superior pH selectivity and real-time pH monitoring capability, Lyso-BFP holds great potential in the diagnosis of lysosome-related disease, and the design concept of this fluorogenic probe provides a new perspective for real-time tracking of cell organelles.