Large Shift Research Articles

Improving the Cellular Internalization of Zr(IV) Nanocages by Tuning Hydrophilicity and Lipophilicity.

Nanoscale molecular materials have emerged as a new class of compounds at the nanometer scale with well-defined chemical structures, remarkable uniformity and high reproducibility. Among these materials, zirconium-based metal-organic cages (MOCs) have attracted significant attention due to their exceptional stability and applications in catalysis, recognition and separation and so on. However, their poor water solubility impedes their biomedical applications. In this study, decorating the ligand with Ru(II) complexes can not only improve the water solubility but also endow bright red fluorescence with large Stokes shift (180 nm). Notably, butyl-modification of the cyclopentadiene rings can significantly enhance the cell uptake (100 folds) of nanocages via actin- and dynamin-mediated endocytosis. The unique advantages and easy modifiability of these nanocages make them highly promising candidates for diverse biological applications.

Multicomponent Diversity-Oriented Access to Boronic-Acid-Derived Pyrrolide Salicyl-Hydrazone Fluorophores with Strong Solid-State Emission.

Fluorescent molecular platforms are highly sought after for their applications in biology and optoelectronics but face challenges with solid-state emission quenching. To address this, bulky substituents or aggregation-induced emission luminogens to restrict intramolecular motion are used to enhance the brightness. Here, we have successfully engineered a novel class of boron complexed pyrrolide salicyl-hydrazone fluorophores named BPSHY. These dyes were synthesized through a diversity-oriented condensation of pyrrole and salicylaldehyde derivatives combined with various aromatic boronic acids. The resulting 3D structures, owing to bulky boron axially substituted aryl groups, impart excellent solubility in a variety of solvents. Significantly, the BPSHY dyes exhibit strong absorption in the visible region and remarkably large Stokes shifts. Crucially, they demonstrate intense emission in aqueous solutions due to aggregation-induced emission effects. In solid-states, these dyes achieve high quantum yields, reaching up to 58%. Further expanding their utility, we developed two new BPSHY probes: one incorporating morpholine and another containing triphenylphosphine salt. Both of them are found to specifically label subcellular organelles such as lysosomes and mitochondria within live cells. Notably, these probes demonstrate exceptional staining efficacy and two-photon fluorescence feature. This highlights the considerable promise of BPSHY fluorophores for monitoring and visualizing the dynamic transformations of organelles.

A Fluorescent Probe with Large Stokes Shift Based on Benzothiadiazole Scaffolds for Selective Detection of Hg2+ in Lysosomes and Its Application in Biological Imaging.

Mercury is highly toxic, and appropriate amounts of the mercury-selenium complex can protect plasma. However, when excessive mercury (II) ions (Hg2+) are exposed to human skin or ingested directly, it can lead to irreversible accumulation in the body. Therefore, detecting the presence of Hg2+ in cells is important. A novel fluorescent probe BTD-Hg-Lyso was designed and constructed based on the intramolecular charge transfer mechanism. Thiotaldehyde could specifically recognize Hg2+ so that the probe could produce a fluorescence enhancement effect. In addition, the fluorescent probe BTD-Hg-Lyso exhibited the advantages of large Stokes shift (210 nm) and good selectivity. More importantly, the probe BTD-Hg-Lyso could be used for the determination of Hg2+ in cellular lysosomes. BTD-Hg-Lyso was able to image Hg2+ in HeLa cells, zebrafish, and tobacco seedlings (rhizome and stem) successfully.

Synthesis of Boron–Imidazole Complexes and Studies on their Multi‐Stimuli‐Responsive Fluorescence Properties

AbstractOrganoboron complexes represented by BODIPY are one of the candidates for fluorescent skeletons exhibiting good fluorescence properties in the solution. However, because most BODIPY have high planar skeletons and small Stokes shifts, their fluorescence is quenched in the solid state. Therefore, numerous approaches were challenged to prepare the solid state fluorescent BODIPYs. On the other hand, an alternative approach to developing solid state fluorophores involves imidazole‐boron complexes. Herein, imidazole‐based boron complexes featuring the imidazo[1,2‐c][1,3,2]diazaborole skeleton were synthesized. This skeleton comprised two fused five‐membered rings and could introduce substituent at the 2‐, 3‐, 5‐, and 6‐positions. The boron complexes with aryl groups at the 3,5,6‐positions exhibited fluorescence in both the solution and solid states. These compounds exhibited Stokes shifts exceeding 120 nm, effectively suppressing self‐absorption. DFT calculations suggested that the large Stokes shift could be attributed to the planarization of π‐conjugation upon excitation. In the solid state, the complexes displayed mechanofluorochromism, with the altered fluorescence color being recovered upon annealing at 150 °C. Compounds with two or three methoxy groups underwent a phase transition to a glass state, resulting in long‐wavelength fluorescence. Furthermore, they demonstrated mechanochromism, thermochromism, and thermofluorochromism in the solid state, indicating their potential as scaffolds for multifunctional fluorophores.

Molecular Design and Synthetic Approaches for the Realization of Multichannel Radiative Decay Pathways in Gold(III) Complexes and Their Applications in Organic Light-Emitting Devices.

A unique class of tridentate diaryltriazine ligand-containing gold(III) complexes with thermally activated delayed fluorescence (TADF) and/or thermally stimulated delayed phosphorescence (TSDP) properties has been designed and synthesized. With a simple structural modification on the coordination of carbazole moiety in the monodentate ligand, a large spectral shift of ∼160 nm (ca. 4900 cm-1) spanning from sky blue to red emissions has been demonstrated in solid-state thin films. Three-state or four-state models have been employed in fitting the emission lifetimes of the gold(III) complexes at various temperatures. The findings clearly indicate the presence of three emitting states, S1, T1, and T1', suggesting the coexistence of TADF, phosphorescence, and TSDP. Notably, a minor structural change in the donor moiety between phenylcarbazolyl and diphenylaminoaryl has been demonstrated to turn on/off the TSDP, resulting in TADF-TSDP-phosphorescence or TADF-phosphorescence emitters. The TADF and/or TSDP properties have also been supported by temperature-dependent ultrafast transient absorption studies, with the direct observation of reverse intersystem crossing (RISC) and reverse internal conversion (RIC) and the determination of the activation parameters and excited state dynamics. Solution-processed and vacuum-deposited organic light-emitting devices (OLEDs) have been prepared, in which sky blue emitting devices based on 5 exhibit an operational lifetime LT70 ∼ 5 times longer than the previously reported sky blue emitting analogue that shows only TSDP property. These results have provided valuable insights into the manipulation of the excited states via rational molecular design toward the realization of gold(III)-based TSDP and/or TADF materials with multiple radiative decay pathways that show enhanced radiative decay rate constants (kr) for practical OLED applications.

Selective Inhibition of hsp90 Paralogs: Uncovering the Role of Helix 1 in Grp94-Selective Ligand Binding.

Grp94 is the endoplasmic reticulum paralog of the hsp90 family of chaperones, which have been targeted for therapeutic intervention via their highly conserved ATP binding sites. The design of paralog-selective inhibitors relies on understanding the protein structural elements that drive higher affinity in selective inhibitors. Here, we determined the structures of Grp94 and Hsp90 in complex with the Grp94-selective inhibitor PU-H36, and of Grp94 with the non-selective inhibitor PU-H71. In Grp94, PU-H36 derives its higher affinity by utilizing Site 2, a Grp94-specific side pocket adjoining the ATP binding cavity, but in Hsp90 PU-H36 occupies Site 1, a side pocket that is accessible in all paralogs with which it makes lower affinity interactions. The structure of Grp94 in complex with PU-H71 shows only Site 1 binding. While changes in the conformation of helices 4 and 5 in the N-terminal domain occur when ligands bind to Site 1 of both Hsp90 and Grp94, large conformational shifts that also involve helix 1 are associated with the engagement of the Site 2 pocket in Grp94 only. Site 2 in Hsp90 is blocked and its helix 1 conformation is insensitive to ligand binding. To understand the role of helix 1 in ligand selectivity, we tested the binding of PU-H36 and other Grp94-selective ligands to chimeric Grp94/Hsp90 constructs. These studies show that helix 1 is the major determinant of selectivity for Site 2 targeted ligands and also influences the rate of ATPase activity in Hsp90 paralogs.

Characterisation of proteomic alterations in worker bees in response to amitraz treatment during summer to winter transition in Apis mellifera colonies

The application of treatments to reduce/control the number of Varroa destructor mites within Apis mellifera colonies is a common apicultural practice. The effectiveness of the treatments in reducing Varroa mites from colonies has been extensively studied, however, the effects of these treatments on the bees within the colonies are poorly characterised. This work utilised label-free quantitative proteomic analysis to investigate how the presence of the anti-Varroa treatment amitraz, affected worker bees. Samples of A. mellifera were isolated from colonies one week before amitraz treatment (T0) and 1, 3, 6 and 8 weeks post-treatment application. The trial was conducted during the transition period from short-lived summer workers to long-lived winter workers. The results highlight two large proteomic shifts; a decrease in the abundance of cuticular proteins and an increase in ribosomal protein abundance in Weeks 3, 6, and 8. The changes in the protein abundance in Week 8 may not be a response to amitraz exposure alone but may also be attributed to a potential change in the population of short-lived to long-lived winter bees. The work provides insight into the effect of amitraz on the honey bee proteome during the transition period from summer to winter colony and how it may contribute to inducing a stress response in individual bees.

Rationally Designed G-Quadruplex Selective "Turn-On" NIR Fluorescent Probe with Large Stokes Shift for Nucleic Acid Research-Based Applications.

Guanine-rich DNA/RNA sequences can form Hoogsteen bonds to adopt noncanonical secondary structures called G-quadruplexes, and these have been associated with diverse cellular processes. There has been considerable research interest in the design of G4-interacting ligands for cellular probing of the G4 structure and understanding its associated biological function. Most of the fluorescent G4 ligands either do not have significant selectivity over other nucleic acid structures, have high Stokes shift, or are not in the near-infrared (NIR) region, which limits its cellular visualization. The current work involves the rational design and synthesis of NIR fluorescent probes comprising a (Z)-1-methyl-2-((3-methylbenzo[d]thiazol-2(3H)-ylidene)methyl)quinolin-1-ium scaffold. Among the designed molecules, 4a exhibited far-red fluorescence (λmax = 680 nm) with large Stokes shift (∼182 nm) upon selective binding to human telomeric G-quadruplexes. The dye 4a does not disturb the conformation and stability of G-quadruplexes, thereby making it suitable for nucleic acid research based applications. Interestingly, 4a showed remarkable selectivity over single- and double-stranded structures in contrast to a commercially available quadruplex binding probe, Thiazole orange (TO). The molecular docking studies indicate that 4a binds at the groove region of the telomeric DNA G-quadruplex through π-π stacking interactions with the quinoline and amine-substituted phenyl ring and with the phosphate backbone through anion-π interactions with the benzothiazole ring. The designed molecule 4a has interesting photophysical properties, cell permeability, and biocompatibility with minimal cytotoxicity. Fluorescence imaging studies in live HeLa cells showed that probe 4a binds to the transient population of the DNA G-quadruplex in the nucleus and RNA quadruplexes in the cytoplasm. In brief, G-quadruplex NIR fluorescent probe 4a with a higher signal/noise ratio has significant potential for cellular imaging studies and thus opens avenues to decipher the biological pathways for better understanding of G-quadruplex biology.

A Novel Near-Infrared Tricyanofuran-Based Fluorophore Probe for Polarity Detection and LD Imaging.

In this paper, LD-TCF, a targeting probe for lipid droplets (LDs) with a near-infrared emission wavelength and large Stokes shift, was fabricated for polarity detection by assembling a donor-π-acceptor (D-π-A) molecule with typical twisted intramolecular charge transfer (TICT) characteristics. Surprisingly, the fluorescence emission wavelength of the newly constructed probe LD-TCF was stretched to 703 nm, and the Stokes shift was amplified to 126 nm. Furthermore, LD-TCF could specifically answer the change in polarity efficiently and did not experience interference from other biologically active materials. Importantly, LD-TCF exhibited the ability to target lipid droplets, providing valuable insights for the early diagnosis and tracking of pathophysiological processes underlying LD polarity.

Cavity dark mode mediated by atom array without atomic scattering loss

We realize a ring cavity strongly interacting with an atom array with configurable spatial structures. By preparing the atom array with a maximized structure factor, we observe the emergence of a cavity dark mode, where the standing-wave nodes are dynamically locked to the positions of the atoms. The dark mode is decoupled from the atoms, protecting the system from dissipation through atomic scattering, but still mediates strong coupling and enables efficient conversion between two optical modes. Moreover, we impart an arbitrary large phase shift on the converted optical fields by translating the atom array. This strongly interacting ring cavity system with single-atom addressability opens ways to quantum optical engineering and the generation of photonic quantum states based on the geometrical structure of atom arrays. Published by the American Physical Society 2024

One N-glycan regulates natural killer cell antibody-dependent cell-mediated cytotoxicity and modulates Fc γ receptor IIIa/CD16a structure.

Both endogenous antibodies and a subset of antibody therapeutics engage Fc gamma receptor (FcγR)IIIa/CD16a to stimulate a protective immune response. Increasing the FcγRIIIa/IgG1 interaction improves the immune response and thus represents a strategy to improve therapeutic efficacy. FcγRIIIa is a heavily glycosylated receptor and glycan composition affects antibody-binding affinity. Though our laboratory previously demonstrated that natural killer (NK) cell N-glycan composition affected the potency of one key protective mechanism, antibody-dependent cell-mediated cytotoxicity (ADCC), it was unclear if this effect was due to FcγRIIIa glycosylation. Furthermore, the structural mechanism linking glycan composition to affinity and cellular activation remained undescribed. To define the role of individual amino acid and N-glycan residues, we measured affinity using multiple FcγRIIIa glycoforms. We observed stepwise affinity increases with each glycan truncation step, with the most severely truncated glycoform displaying the highest affinity. Removing the N162 glycan demonstrated its predominant role in regulating antibody-binding affinity, in contrast to four other FcγRIIIa N-glycans. We next evaluated the impact of the N162 glycan on NK cell ADCC. NK cells expressing the FcγRIIIa V158 allotype exhibited increased ADCC following kifunensine treatment to limit N-glycan processing. Notably, an increase was not observed with cells expressing the FcγRIIIa V158 S164A variant that lacks N162 glycosylation, indicating that the N162 glycan is required for increased NK cell ADCC. To gain structural insight into the mechanisms of N162 regulation, we applied a novel protein isotope labeling approach in combination with solution NMR spectroscopy. FG loop residues proximal to the N162 glycosylation site showed large chemical shift perturbations following glycan truncation. These data support a model for the regulation of FcγRIIIa affinity and NK cell ADCC whereby composition of the N162 glycan stabilizes the FG loop and thus the antibody-binding site.

One N-glycan regulates natural killer cell antibody-dependent cell-mediated cytotoxicity and modulates Fc γ receptor IIIa/CD16a structure

Both endogenous antibodies and a subset of antibody therapeutics engage Fc gamma receptor (FcγR)IIIa/CD16a to stimulate a protective immune response. Increasing the FcγRIIIa/IgG1 interaction improves the immune response and thus represents a strategy to improve therapeutic efficacy. FcγRIIIa is a heavily glycosylated receptor and glycan composition affects antibody-binding affinity. Though our laboratory previously demonstrated that natural killer (NK) cell N-glycan composition affected the potency of one key protective mechanism, antibody-dependent cell-mediated cytotoxicity (ADCC), it was unclear if this effect was due to FcγRIIIa glycosylation. Furthermore, the structural mechanism linking glycan composition to affinity and cellular activation remained undescribed. To define the role of individual amino acid and N-glycan residues, we measured affinity using multiple FcγRIIIa glycoforms. We observed stepwise affinity increases with each glycan truncation step, with the most severely truncated glycoform displaying the highest affinity. Removing the N162 glycan demonstrated its predominant role in regulating antibody-binding affinity, in contrast to four other FcγRIIIa N-glycans. We next evaluated the impact of the N162 glycan on NK cell ADCC. NK cells expressing the FcγRIIIa V158 allotype exhibited increased ADCC following kifunensine treatment to limit N-glycan processing. Notably, an increase was not observed with cells expressing the FcγRIIIa V158 S164A variant that lacks N162 glycosylation, indicating that the N162 glycan is required for increased NK cell ADCC. To gain structural insight into the mechanisms of N162 regulation, we applied a novel protein isotope labeling approach in combination with solution NMR spectroscopy. FG loop residues proximal to the N162 glycosylation site showed large chemical shift perturbations following glycan truncation. These data support a model for the regulation of FcγRIIIa affinity and NK cell ADCC whereby composition of the N162 glycan stabilizes the FG loop and thus the antibody-binding site.

A mitochondria-targeted nitric oxide probe with large Stokes shift for real-time imaging and evaluation of inflammatory bowel disease in situ

BackgroundInflammatory bowel disease (IBD) is a prevalent inflammatory disorder, and the abnormal expression of nitric oxide (NO) produced by biocatalysis of iNOS enzyme in mitochondria is directly associated with the occurrence and progression of IBD. Activatable fluorescent probes offer promising tools for early diagnosis of IBD, however, inadequate biodistribution and limited targeting properties of these probes in vivo severely impede accurate diagnosis of IBD and real-time evaluation of inflammatory levels in situ. Therefore, it is necessary to designed a highly efficient fluorescent probe towards NO to overcome inadequate biodistribution and achieve accurate diagnosis and evaluation of IBD in situ. ResultsWe designed a highly efficient mitochondria-targeted “turn-on” NIR fluorescent probe Cy-OMe which has excellent targeting properties and imaging ability. The response mechanism is probe Cy-OMe rapidly undergoes N-nitrosation reaction resulting in turn-on NIR fluorescence signal when exposed to NO. Cy-OMe exhibits high sensitivity and specificity in detecting NO content in vitro, owing to its large Stokes shift. Furthermore, the probe Cy-OMe not only efficiently targets mitochondria but also enables precise assessment of fluctuations in endogenous NO concertation across various cell types. Importantly, by virtue of large Stokes shift and excellent mitochondrial targeting ability, Cy-OMe has the capability to specifically evaluate dynamic fluctuations of NO in lipopolysaccharide (LPS)‐stimulated IBD mouse models in situ and Cy-OMe was achieved high-contrast imaging and precision diagnosis of intestinal inflammation diseases. SignificanceCy-OMe can accurately assess fluctuations in NO levels and show high signal fidelity in the diseased intestine region, which has prospects in the non-invasive diagnosis of intestinal inflammation in vivo. At the same time, it is expected to serve as a potential diagnose platform for investigating the physiological processes underlying NO-related inflammatory diseases and promoting understanding of the pathological functions of NO across diverse inflammatory diseases.

Europium-Infused Polystyrene Nanoparticles for Enhanced Bacterial Labeling in Microscopic Imaging

Luminescence microscopic imaging has become an indispensable tool in diagnostics and therapeutics. Lanthanide luminescent complexes (LLCs) have proven to be invaluable in this endeavor due to certain attractive characteristics such as long decay times, large Richardson shifts and narrow emission bands. However, the insolubility of these complexes and the negative effects of the aqueous environment on their photophysical properties still restrict their biological applications. By embedding luminescent Eu3+ complexes into polystyrene nanoparticles (NPs), these complexes can not only maintain their photophysical properties, but even enhance them. This leads to exceptionally high quantum yields (> 90 %) and decay times ( >800 μs). In addition, the surfaces of the NPs described here are covered with primary amine groups, which may be exploited for various interesting bioconjugation chemistries. In the present application, they were modified with N-hydroxysuccinimide (NHS) esters and then coupled either electrostatically or covalently to both, Gram-positive and Gram-negative bacteria, labeling them for luminescence microscopic imaging. This, to the best of our knowledge, is the first report of polymer NPs infused with LLCs for bacteria labeling.

High Quantum Yields and Biomedical Fluorescent Imaging Applications of Photosensitized Trivalent Lanthanide Ion-Based Nanoparticles.

In recent years, significant advances in enhancing the quantum yield (QY) of trivalent lanthanide (Ln3+) ion-based nanoparticles have been achieved through photosensitization, using host matrices or capping organic ligands as photosensitizers to absorb incoming photons and transfer energy to the Ln3+ ions. The Ln3+ ion-based nanoparticles possess several excellent fluorescent properties, such as nearly constant transition energies, atomic-like sharp transitions, long emission lifetimes, large Stokes shifts, high photostability, and resistance to photobleaching; these properties make them more promising candidates as next-generation fluorescence probes in the visible region, compared with other traditional materials such as organic dyes and quantum dots. However, their QYs are generally low and thus need to be improved to facilitate and extend their applications. Considerable efforts have been made to improve the QYs of Ln3+ ion-based nanoparticles through photosensitization. These efforts include the doping of Ln3+ ions into host matrices or capping the nanoparticles with organic ligands. Among the Ln3+ ion-based nanoparticles investigated in previous studies, this review focuses on those containing Eu3+, Tb3+, and Dy3+ ions with red, green, and yellow emission colors, respectively. The emission intensities of Eu3+ and Tb3+ ions are stronger than those of other Ln3+ ions; therefore, the majority of the reported studies focused on Eu3+ and Tb3+ ion-based nanoparticles. This review discusses the principles of photosensitization, several examples of photosensitized Ln3+ ion-based nanoparticles, and in vitro and in vivo biomedical fluorescent imaging (FI) applications. This information provides valuable insight into the development of Ln3+ ion-based nanoparticles with high QYs through photosensitization, with future potential applications in biomedical FI.

An Ultrahigh Affinity DNA Aptamer for Quinine and Its Intrinsic Fluorescence Based Label-free Detection.

Measuring quinine is critical for the detection of its overdose, understanding its pharmacological and toxicological effects, and monitoring its pollution. While a previously reported aptamer named MN4 can bind quinine, it was not selected for it, leading to compromised binding affinity and specificity. In this work, a new quinine aptamer was isolated using the library immobilization capture-SELEX technique. The Q1 aptamer has a Kd value of 10 nM determined by an isothermal titration calorimetry experiment and 45 nM in a fluorescence binding assay. A 3.5 nM quinine limit of detection was obtained based on the aptamer binding-induced quenching of the intrinsic fluorescence of quinine. A large blue shift in fluorescence was observed for quinine upon binding to Q1, whereas binding to MN4 led to a very small red shift, indicating different ways of quinine binding by these two aptamers. Q1 did not bind cocaine based on NMR spectroscopy and fluorescence assays also indicated excellent selectivity against other tested molecules. This work has supplied a high affinity aptamer for quinine that can be useful for its detection and fundamental aptamer binding studies. It also highlights the advantages of using capture-SELEX to isolate aptamers for small molecules.

A Cascade Activation Probe with Double-Enhanced Near-Infrared Imaging for Monitoring Peroxynitrite Fluctuations in Vivo.

Monitoring peroxynitrite (ONOO-) fluctuations is particularly important for assessing pathological progression and oxidative damage due to their crucial role in maintaining the redox balance of organisms. However, due to the lack of efficient tools for differentially monitoring ONOO- fluctuations at different concentration ranges in vivo, the precise detection of endogenous ONOO- fluctuations under pathological conditions in living systems remains challenging. Herein, we rationally designed a double-enhanced emission cascade activatable near-infrared (NIR) fluorescent probe (B-TCF) for the measurement of ONOO-, which consists of a borate ester response group and a malononitrile hemicyanine fluorophore. Especially, after sequential oxidative hydrolysis of the borate ester group and xanthene skeleton, B-TCF exhibited a sequentially double-enhanced NIR emission response at 776 and 625 nm for different ONOO- concentration ranges. Moreover, B-TCF revealed excellent and promising performance for ONOO- in terms of high selectivity, sensitivity, and reaction rate (k = 28.2 M-1 s-1). Motivated by the two-step emission signal enhancement and large wavelength shift in the NIR region, B-TCF enabled discriminative imaging of ONOO- with the low and high concentrations in living cells. Importantly, B-TCF was successfully applied for assessing the pathological progression of isoniazid and acetaminophen-induced liver damage in vivo by detecting the endogenous different ONOO- levels. Overall, this study not only demonstrates the first double-enhanced emission cascade activatable NIR fluorescent probe for measuring the dynamic variation of ONOO- in related diseases but also shows great potential as an effective molecular tool for evaluating the various stages of drug-induced liver damage.

Fluorescence Entrenched Probe for Onsite Detection of Amoxicillin Residue in Bovine Milk.

A novel fluorescent probe (E)-3-(4-hydroxyphenyl)-2-((pyrene-1-ylmethylene) amino)propanoic acid (PyT) was developed for the 'turn-on' detection of amoxicillin(AM), residues. The PyT molecule was developed by a simple condensation reaction between a biologically important tyrosine amino acid and pyrene carboxaldehyde. The small fluorophore molecule has spectacular photoluminescence properties such as large stock shift, high photostability, selectivity and sensitivity toward the analytes. The PyT upon dispersion in the liquid phase becomes highly luminescent possessing the restricted intramolecular rotation (RIR) and excited stated intramolecular proton transfer (ESIPT) properties which are the major criteria for aggregation induced emission enhancement (AIEE) mechanism prevailing the aggregation caused quenching (ACQ). PyT molecule shows a binding constant of 3.285 × 104 L mol-1for amoxicillin (AM). The limit of detection(LOD) values are found to be 1.67µM. Consuming bovine milk with antibiotic residues exceeding the maximum residue limit (MRL) can lead to food toxicity and life threatening diseases in humans. The milk sample with AM antibiotic residue in presence of PyT probe shows a distinct blue colour which infers the selectivity and sensitivity of the probe towards the analyte. The fluorescence probe adheres with merits like on site and visual examination by naked eye without aid of any instruments.

The Role of Spacers as a Probe in Variation of Photoluminescence Properties of Mono- and Bi-Nuclear Boron Compounds.

A series of N,O donor-based mono- and binuclear four-coordinated boron complexes were synthesized. Depending on the substitution and spacer, these complexes exhibit intense blue, green and yellow emission in solution states. Notably, the fluorescence quantum yields (ΦF) and fluorescence decay (lifetime, τ) of mononuclear boron complexes (2 a-2 e) were higher than the binuclear boron complexes (2 f-2 k). The lowest lifetime and quantum yield in binuclear boron complexes were due to intramolecular rotation induced non radiative processes. The disulphide spacer-based boron complexes 2 i-2 k showed aggregation-caused quenching in the THF/H2O mixture whereas no other complexes were ACQ responsive. These complexes show large Stokes shift, one of them i. e. 2 e has the highest Stokes shift of 130 nm. Further, the electrochemical study suggests the presence of two redox incidences. Theoretical studies show close corroboration between the TD-DFT computed and experimentally measured absorption maxima as well as DFT (GIAO) calculated and experimentally measured 11B NMR values. This complements the appropriate selection of the theoretical methods to shed light on the electronic transitions in the mono- and binuclear BF2 complexes.

Double-Shell Encapsulation of Lead-Free Tin Halide Perovskite for Self-Powered Smart Windows.

Luminescent solar concentrators (LSC) have the potential application in building integrated photovoltaic (BIPV). 0D tin-based perovskites are a promising embedding phosphor in LSC due to the large Stokes shift and high photoluminescence quantum yield. But the instability and uncontrollable crystal growth are severe limiting their successful utilization in device fabrication. To tackle these issues, double-shell encapsulated configurations are presented, soft ligands of hypophosphorous acid and hard-shell of hollow mesoporous silica are simultaneously suppressing the oxidation of Sn2+ and restricting crystal growth within nano-matrix. The stable phosphor is subsequently embedded into LSC for harvesting solar energy and the resulting output power efficiently drives the combined electrochromic glass under natural light. These fabricated devices also offer the self-adaptable switch on/off functionality to regulate light absorption with variable solar irradiation intensity in real time. This approach is anticipated to open new avenues for utilizing lead-free perovskite nanomaterials in self-powered smart windows for BIPV.