Fluorescence Lifetime Measurements Research Articles

Efficient Intra‐Supramolecular Electron Transfer in Zinc Porphyrin‐Coumarin Dyads

AbstractWe report herein the electron transfer process of a novel supramolecular dyads composed of zinc tetraphenylporphyrin (ZnTPP) and zinc 5,15‐dinonyl‐10,20‐diphenylporphyrin (ZnDPP), as electron donors, and ethyl(4‐pyridyl) coumarin‐3‐carboxylate (EPCC), as an electron acceptor, through metal‐ligand coordination bond in dichloromethane. The optical absorption studies revealed the formation of the moderate stable supramolecular donor‐acceptor dyads. The fluorescence measurements showed a significant fluorescence quenching of the singlet‐excited state of the singlet‐excited states of ZnTPP and ZnDPP upon addition of different amounts of EPCC. Such quenching behavior could be attributed to the electron transfer from the singlet‐excited state of porphyrin to EPCC. The bimolecular quenching rates were determined to be 1.98×1012 and 7.59×1012 L mol−1 s−1 for ZnTPP‐EPCC and ZnDPP‐EPCC, respectively, respectively. The fluorescence lifetime measurements suggest fast and efficient intra‐supramolecular electron transfer from the singlet states of porphyrin derivatives to EPCC. Furthermore, the formation of the supramolecular dyads was confirmed by the Raman technique and computational studies. The finding that the examined zinc porphyrin ‐ coumarin supramolecular dyads absorb light in a wide range of UV‐visible spectrum, fast and efficient electron transfer render the examined supramolecular dyad as simple models for the reaction centers of the artificial photosynthetic systems.

Photoluminescence Study of Undoped and Eu-Doped Alkali-Niobate Aluminosilicate Glasses and Glass-Ceramics.

In this study, the photoluminescence (PL) behavior of two aluminosilicate glass series containing alkali-niobates ranging from 0.4 to 20 mol% was investigated. The glasses exhibit an intense visible emission centered at ~18,400 cm-1 for the peralkaline series and at higher energies (~19,300 cm-1) for the metaluminous glasses. However, the photoluminescence emission intensity varies significantly with the niobate content and the bulk chemistry. PL and fluorescence lifetime measurements indicate that the broad emission bands result from the overlap of different niobate populations, whose distribution changes with niobate content. The distinct PL behavior in the two glass series was related to the structural evolution of the niobate units upon niobium addition. An enhancement of the visible emission was observed for a higher fraction of distorted [NbO6] units. Eu-doping was carried out as a structural probe of the glass network, and also to determine if these glasses could be used as potential rare earth element (REE) activators. The crystal field strength around Eu ions is strongly dependent on the bulk chemistry and the niobate content. Furthermore, the peralkaline series showed energy transfer from the host [NbO6] to Eu3+, confirming the feasibility of exploring niobate glasses and glass-ceramics as lanthanide ion-activated luminescent materials. In addition, glass-ceramics (GCs) containing alkali-niobate phases with a perovskite-like structure were developed and studied to verify the optical performance of these materials. It was verified that the bulk chemistry influences crystallization behavior, and also the photoluminescence response. The transparent GC from the metaluminous series exhibits a quenching of the Eu3+ emission, whereas an enhanced emission intensity is observed for the peralkaline GC. The latter shows a strong excitation-dependent PL emission, suggesting energy transfer and migration of electronic excitation from one Eu population to another. Additionally, Eu3+ emissions arising from the D15 and D25 excited states were observed, highlighting the low phonon energy achievable in niobo-aluminosilicate hosts.

Customized carbon dots as a fluorescent sensor for detecting paraquat through enhanced excited state binding energy

A novel fluorescent sensor utilizing customized carbon dots (CDs) has been developed for the rapid and efficient detection of the herbicide paraquat. The 4,4′-diamino-2,2′-stilbenedisulfonic acid (DSD acid) functionalized CDs (DSD-CDs) were synthesized by a hydrothermal method using citric acid and L-cysteine as precursors, followed by amidation with DSD acid. The resultant DSD-CDs exhibited bright blue fluorescence upon UV excitation. The fluorescence of the functionalized carbon dots was effectively quenched by paraquat, following a static quenching mechanism as confirmed by fluorescence lifetime measurements. Interestingly, the mechanism study revealed that the excited-state of the DSD-CDs could interact effectively with paraquat, resulting in stronger fluorescence quenching compared to the ground-state. The sensor showed high sensitivity, selectivity, and stability, with a wide linear range of 0.01 ∼ 2 mg/L (R2 = 0.997) and a low detection limit of 0.003 mg/L. The developed fluorescent sensor demonstrated exceptional potential for paraquat detection in actual samples, encompassing blood, urine, soybean, and river water, with recovery rates exceeding 83 % and relative standard deviations (RSD) below 10 %. This underscores its practical utility in environmental protection and clinical testing applications.

Revealing the Improved Binding Interaction of Plant Alkaloid Harmaline with Human Hemoglobin in Molecular Crowding Condition.

Harmaline and harmine are two structurally similar β-carboline alkaloids with several therapeutic activities, such as anti-inflammatory, antioxidant, neuroprotective, nephroprotective, antidiabetic, and antitumor activities. It has been previously reported that the interaction between harmaline and hemoglobin (Hb) is weak in buffer media compared to harmine. Crowding agents induce a molecular crowding environment in the ex vivo condition, which is almost similar to the intracellular environment. In this present study, we have investigated the nature of the interactions of harmaline and harmine with Hb by increasing the percentage of the crowding agent in buffer solution. The results of the UV-vis and fluorescence spectroscopy analysis have showed that with an increasing proportion of crowding agents, the interaction between harmaline and Hb is steadily improving in comparison to harmine. It has been found that the binding constant of Hb-harmaline reaches 6.82 × 105 M-1 in the 40% polyethylene glycol 200-mediated crowding condition, indicating high affinity compared to very low interaction in buffer media. Steady-state fluorescence anisotropy along with fluorescence lifetime measurements further revealed that the rotational movement of harmaline is maximally restricted by Hb in high crowding environments. Stoichiometry results represent that Hb and harmaline interacts in a 1:1 ratio in different percentages of the crowding agent. The circular dichroism spectroscopic results predict stronger interaction of harmaline with Hb (secondary structure alterations) in a higher crowding environment. From the melting study, it was found that the reactions between Hb and harmaline in crowding environments are endothermic (ΔH > 0) and disordering (ΔS > 0) in nature, indicating that hydrogen bonding and van der Waals interactions are the main interacting forces between Hb and harmaline. Harmaline molecules are more reactive in molecular crowding conditions than in normal buffer condition. This study represents that the interaction between harmaline and Hb is stronger compared to the structurally similar harmine in a molecular crowding environment, which may enlighten the drug discovery process in cell-mimicking conditions.

Enhanced 2.8 μm emission of Ho,Pr:CaYAlO4 crystal

Ho,Pr:CaYAlO4 (Ho,Pr:CYA) crystal doped with 1 at.% Ho3+ and 0.1 at.% Pr3+ was successfully grown using the Czochralski method. Polarized absorption spectra, emission spectra, and fluorescence lifetime measurements were performed. The impact of Pr3+ co-doping on the ∼3 μm emission of Ho3+ ions was analyzed. The energy transfer efficiency from Ho3+:5I7 to Pr3+:3F2 energy level was calculated to be 60.66 %, indicating that Pr3+ effectively mitigated the self-termination effect in Ho,Pr:CYA crystals. The absorption cross-section at 645 nm was found to be 1.53 × 10−20 cm2 for σ polarization and 2.62 × 10−20 cm2 for π polarization. The emission cross-section at 2842 nm was calculated to be 0.86 × 10−20 cm2 for σ polarization and 1.33 × 10−20 cm2 for π polarization at 2908 nm, with a full width at half maximum (FWHM) of 139 nm and 88 nm, respectively. The fluorescence lifetimes of the 5I6 and 5I7 levels were measured to be 0.17 ms and 2.01 ms, respectively. These results collectively suggest that Ho,Pr:CYA crystals hold great potential as a candidate for 2.8 μm laser applications.

Highly sensitive detection of copper in aqueous media using a fluorescent probe developed from isophthaldehyde and (E)-1-(hydrazonomethyl) naphthlen-2-ol

A highly selective Schiff base PMB3 with AIEE activity was synthesized and characterized for detecting Cu2+ in aqueous media. The PMB3 aggregates exhibit a green fluorescence in the DMF-water mixed solvent, demonstrating a switch-off response specifically to Cu2+ ions over various other biologically significant metal ions. The quenching of fluorescence in PMB3 aggregates is likely attributed to the disassembly caused by the chelation of the imine-N atom and phenolic -O atom of PMB3 aggregates with Cu2+ ions. The molar ratio of the complex formed as per Job’s plot method was 1:1 between PMB3 and Cu2+. The fluorescence lifetime measurements confirmed the involvement of the dynamic quenching process in the reaction cycle. The analysis of the Stern-Volmer plot divulged a quenching constant of 3.75×1015 M−1. Remarkably, the limit of detection was determined to be 16.08×10−15 M (16.08fM), demonstrating a sensitivity far exceeding the permissible limit set by the World Health Organization.

Three coordination polymers based on 4,4′-bis(2-methylimidazol-1-yl)diphenyl ether: Synthesis, structure and selective fluorescent sensing properties

Three CPs [Zn2(PDA)2(BMIOPE)2·3H2O]n (1), [Co(Br-BDC)(BMIOPE)]n (2) and [Co(MIP)(BMIOPE)]n (3) were synthesized by solvothermal method based on dual-ligand strategy (H2PDA, Br-H2BDC, BMIOPE and H2MIP are 1,3-phenylenediacetic acid, 5-bromo-isophthalic acid, 4,4′-bis(2-methylimidazol-1-yl)diphenyl ether and 5-methylisophthalic acid, respectively). Complexes 1 and 3 exhibit twofold parallel interwoven sql nets. Complex 2 is 2D layer structure. The luminescence property investigations showed that complexes 1–3 could act as multi-responsive fluorescent sensors to detect UO22+, Cr2O72− and CrO42− and nitrofurantoin (NFT) through fluorescence turn-off process, presenting excellent sensitivity and selectivity. Finally, the possible fluorescent quenching mechanisms of complexes 1–3 toward the above pollutants are also further investigated by employing spectroscopic methods and quantum chemical calculations. The fluorescence lifetime measurements manifest the mechanism of fluorescence quenching is static quenching process.

Insights into the interaction and inhibitory action of palmatine on lysozyme fibrillogenesis: Spectroscopic and computational studies

Interaction under amyloidogenic condition between naturally occurring protoberberine alkaloid palmatine and hen egg white lysozyme was executed by adopting spectrofluorometric and theoretical molecular docking and dynamic simulation analysis. In spetrofluorometric method, different types of experiments were performed to explore the overall mode and mechanism of interaction. Intrinsic fluorescence quenching of lysozyme (Trp residues) by palmatine showed effective binding interaction and also yielded different binding parameters like binding constant, quenching constant and number of binding sites. Synchronous fluorescence quenching and 3D fluorescence map revealed that palmatine was able to change the microenvironment of the interacting site. Fluorescence life time measurements strongly suggested that this interaction was basically static in nature. Molecular docking result matched with fluorimetric experimental data. Efficient drug like interaction of palmatine with lysozyme at low pH and high salt concentration prompted us to analyze its antifibrillation potential. Different assays and microscopic techniques were employed for detailed analysis of lysozyme amyloidosis.Thioflavin T(ThT) assay, Congo Red (CR) assay, 8-anilino-1-naphthalenesulfonic acid (ANS) assay, Nile Red (NR) assay, anisotropy and intrinsic fluorescence measurements confirmed that palmatine successfully retarded and reduced lysozyme fibrillation. Dynamic light scattering (DLS) and atomic force microscopy (AFM) further reiterated the excellent antiamyloidogenic potency of palmatine.

Doping Ferrocene-Based Conjugated Microporous Polymers with 7,7,8,8-Tetracyanoquinodimethane for Efficient Photocatalytic CO2 Reduction.

The design and synthesis of organic photocatalysts remain a great challenge due to their strict structural constraints. However, this could be mitigated by achieving structural flexibility by constructing permanent porosity into the materials. Conjugated microporous polymers (CMPs) are an emerging class of porous materials with an amorphous, three-dimensional network structure, which makes it possible to integrate the elaborate functional groups to enhance photocatalytic performance. Here, we report the synthesis of a novel CMP, named TAPFc-TFPPy-CMP, constructed by 1,1'3,3'-tetra(4-aminophenyl)ferrocene (TAPFc) and 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) monomers. The integration of the p-type dopant 7,7,8,8-tetracyanoquinodimethane (TCNQ) into the TAPFc-TFPPy-CMP improved the light adsorption performance, leading to a decrease in the optical bandgap from 2.00 to 1.43 eV. The doped CMP (TCNQ@TAPFc-TFPPy-CMP) exhibited promising catalytic activity in photocatalytic CO2 reduction under visible light, yielding 546.8 μmol g-1 h-1 of CO with a selectivity of 96% and 5.2 μmol g-1 h-1 of CH4. This represented an 80% increase in the CO yield compared to the maternal TAPFc-TFPPy-CMP. The steady-state photoluminescence (PL) and fluorescence lifetime (FL) measurements reveal faster carrier separation and transport after the doping. This study provides guidance for the development of organic photocatalysts for the utilization of renewable energy.

Oxalohydrazide‐Based Chemosensor for Detection of Cu2+/Fe3+ Ions and Its Application in Live Cell Imaging

AbstractThe N1,N2‐diphenyloxalohydrazide OX(HA)2 chemosensor was synthesized and used as a colorimetric and fluorescent receptor to detect Cu2+ and Fe3+ ions in the presence of other metal ions. A range of physicochemical approaches were utilized to characterize the symmetrical oxalohydrazide‐based receptor, including FT‐IR, 1H and 13C NMR, TGA, and mass spectrometry. According to single crystal X‐ray diffraction investigation, OX(HA)2 crystallizes in monoclinic with space group C2/c. UV‐Vis and fluorescence spectroscopy were used to thoroughly explore OX(HA)2’s sensing capabilities towards diverse cations. Using measurements of fluorescence intensity, the binding constant for OX(HA)2 with Cu2+/Fe3+ ions was calculated to be 2.78×103 M−1 and 1.12×103 M−1 with the lower detection limit of 0.43 μM and 0.2 μM respectively. With a 1 : 1 binding mechanism validated by Job's plot, mass spectral analysis, FT‐IR spectra, and density functional theory, the dual‐sensing receptor exhibits remarkable selectivity and sensitivity towards Cu2+ and Fe3+ ions. The average fluorescence lifetimes of OX(HA)2, OX(HA)2+Cu2+, and OX(HA)2+Fe3+ were calculated to be 2.19 ns, 1.73 ns, and 1.26 ns, respectively. This fluorescence lifetime measurement results strongly support the complexation of Cu2+ and Fe3+. When Cu2+ and Fe3+ ions bind with OX(HA)2, they induce the ‘Turn‐Off’ signal. Then, fluorescence imaging of the OX(HA)2 receptor in MDA‐MB‐231 demonstrated that the receptor holds a lot of promise for usage in bioimaging and their IC50 value for cytotoxicity is 96.96 μg. Furthermore, fluorescence microscopy experiments demonstrate that OX(HA)2 can be utilized as a fluorescent probe for detecting Cu2+ and Fe3+ ions in living cells, making it potentially helpful as an anticancer medication.

Chloramphenicol-imprinted polychitosan bounded with carbon dots as fluorescent sensor, dispersive sorbent, and drug carrier.

Chitosan, an abundant natural polysaccharide, was conjugated with carbon dots (CDs) and self-polymerized with chloramphenicol (CAP) templates to synthesize CD-incorporated and molecularly CAP-imprinted polychitosan (CD-MIC). The CD-MIC was used for fluorescent sensing, dispersive sorption, and dosage release of CAP at different pH levels. The sphere of action mechanism, approved by emission and excitation fluorescence, UV-Vis absorption, and fluorescence lifetime measurements, regulated the fluorescence static quenching. By the Perrin model, the quenching extent was linearly correlated to CAP within 0.17 - 33.2μM (LOD = 37nM) at pH 7.0. With an imprinting factor of 3.1, the CD-MIC was more selective for CAP than CD, although it was less sensitive to CAP. The recoveries of 5.0μM CAP from milk matrix were 95% (RSD = 2.3%) for CD-MIC probes and 62% (RSD = 4.5%) for CD. The Langmuir and pseudo-second-order models preferably described the isothermal and kinetic sorptions of CAP into the imprinted cavities in CD-MICs, respectively. The Weber - Morris kinetic model showed three stages involved in intraparticle diffusion, which was pH-dependent and gradually arduous at the later stage, and showed external diffusion partly engaged in the diffusion mechanism. The 20 - 70% of CAP formulated in CAP-embedded CD-MICs were released in 8 - 48h. The release percentage was lower at pH 7.0 than at pH 5.0 and 9.0, but the equilibrium time was shorter. At pH 7.0, the release percentage reached 45% at 10min and slowly increased to 51% at 24h.

Fluorescence Lifetime Imaging of Human Retinal Pigment Epithelium in Pentosan Polysulfate Toxicity Using Adaptive Optics Scanning Light Ophthalmoscopy.

Fluorescence lifetime ophthalmoscopy (FLIO) is an emerging clinical modality that could provide biomarkers of retinal health beyond fluorescence intensity. Adaptive optics (AO) ophthalmoscopy provides the confocality to measure fluorescence lifetime (FL) primarily from the retinal pigment epithelium (RPE) whereas clinical FLIO has greater influence from fluorophores in the inner retina and lens. Adaptive optics fluorescence lifetime ophthalmoscopy (AOFLIO) measures of FL in vivo could provide insight into RPE health at different stages of disease. In this study, we assess changes in pentosan polysulfate sodium (PPS) toxicity, a recently described toxicity that has clinical findings similar to advanced age-related macular degeneration. AOFLIO was performed on three subjects with PPS toxicity (57-67years old) and six age-matched controls (50-64years old). FL was analyzed with a double exponential decay curve fit and with phasor analysis. Regions of interest (ROIs) were subcategorized based on retinal features on optical coherence tomography (OCT) and compared to age-matched controls. Twelve ROIs from PPS toxicity subjects met the threshold for analysis by curve fitting and 15 ROIs met the threshold for phasor analysis. Subjects with PPS toxicity had prolonged FL compared to age-matched controls. ROIs of RPE degeneration had the longest FLs, with individual pixels extending longer than 900 ps. Our study shows evidence that AOFLIO can provide meaningful information in outer retinal disease beyond what is obtainable from fluorescence intensity alone. More studies are needed to determine the prognostic value of AOFLIO.

Highly emissive pyrrolo[1,2-a]quinoxaline based narrow band fluorescent sensors for detection of nitroaromatics and their application in spot paper test

In the modern day, explosive detection is essential to public safety, and fluorescent small molecules have gained popularity for their quick and accurate detection. Herein, we present the design and synthesis of a series of pyrrolo[1,2-a]quinoxaline-based conjugated small organic fluorophores (PQ-Ph-OH, PQ-Ph-NMe, PQ-Ph-OMe, PQ-Ph-Me, and PQ-Ph-CN) as fluorescence-based sensors for explosive molecules. The sensor molecules were synthesized in good to excellent yields using a dehomologative functionalization strategy. They exhibited excellent photophysical characteristics, which was tunable based on the substituent on the phenyl linker at position 3. DFT studies showed that the pyrroloquinoxaline moiety could act as an on-demand electron donor or acceptor, depending on the phenyl substituent. The molecules also exhibited solid state emission due to twisted geometry around the CC single bond between the heterocyclic scaffold and the phenyl derivative. This resulted in low band intense emission for the synthesized molecules. In the presence of electron-deficient nitroaromatic explosives, all the fluorophores showed excellent fluorescence quenching. Detection limits in the range of 10−4 M were obtained for all the fluorophores. Stern-Volmer plots show high values of binding constants, indicating good interaction between the fluorophores and the explosive molecules. The mechanism of sensing was confirmed by UV-PL spectral overlap and fluorescence lifetime measurements, which suggest a static quenching based on the formation of a ground state complex. Owing to solid state emissions in some of the derivatives, the synthesized molecules were applied to paper strips for spot detection of explosive molecules.

Synthesis and Photophysical Characterization of a pH-Sensitive Quadracyclic Uridine (qU) Analogue.

Fluorescent base analogues (FBAs) have become useful tools for applications in biophysical chemistry, chemical biology, live-cell imaging, and RNA therapeutics. Herein, two synthetic routes towards a novel FBA of uracil named qU (quadracyclic uracil/uridine) are described. The qU nucleobase bears a tetracyclic fused ring system and is designed to allow for specific Watson-Crick base pairing with adenine. We find that qU absorbs light in the visible region of the spectrum and emits brightly with a quantum yield of 27 % and a dual-band character in a wide pH range. With evidence, among other things, from fluorescence lifetime measurements we suggest that this dual emission feature results from an excited-state proton transfer (ESPT) process. Furthermore, we find that both absorption and emission of qU are highly sensitive to pH. The high brightness in combination with excitation in the visible and pH responsiveness makes qU an interesting native-like nucleic acid label in spectroscopy and microscopy applications in, for example, the field of mRNA and antisense oligonucleotide (ASO) therapeutics.

Measuring conformational equilibria in allosteric proteins with time-resolved tmFRET

Proteins are the workhorses of biology, orchestrating a myriad of cellular functions through intricate conformational changes. Protein allostery, the phenomenon where binding of ligands or environmental changes induce conformational rearrangements in the protein, is fundamental to these processes. We have previously shown that transition metal Förster resonance energy transfer (tmFRET) can be used to interrogate the conformational rearrangements associated with protein allostery and have recently introduced novel FRET acceptors utilizing metal-bipyridyl derivatives to measure long (>20Å) intramolecular distances in proteins. Here, we combine our tmFRET system with fluorescence lifetime measurements to measure the distances, conformational heterogeneity, and energetics of maltose-binding protein, a model allosteric protein. Time-resolved tmFRET captures near-instantaneous snapshots of distance distributions, offering insights into protein dynamics. We show that time-resolved tmFRET can accurately determine distance distributions and conformational heterogeneity of proteins. Our results demonstrate the sensitivity of time-resolved tmFRET in detecting subtle conformational or energetic changes in protein conformations, which are crucial for understanding allostery. In addition, we extend the use of metal-bipyridyl compounds, showing that Cu(phen)2+ can serve as a spin label for pulse dipolar electron paramagnetic resonance (EPR) spectroscopy, a method that also reveals distance distributions and conformational heterogeneity. The EPR studies both establish Cu(phen)2+ as a useful spin label for pulse dipolar EPR and validate our time-resolved tmFRET measurements. Our approach offers a versatile tool for deciphering conformational landscapes and understanding the regulatory mechanisms governing biological processes.

Local Water Content in Polymer Gels Measured with Super-Resolved Fluorescence Lifetime Imaging.

Water molecules play an important role in the structure, function, and dynamics of (bio-) materials. A direct access to the number of water molecules in nanoscopic volumes can thus give new molecular insights into materials and allow for fine-tuning their properties in sophisticated applications. The determination of the local water content has become possible by the finding that H2 O quenches the fluorescence of red-emitting dyes. Since deuterated water, D2 O, does not induce significant fluorescence quenching, fluorescence lifetime measurements performed in different H2 O/D2 O-ratios yield the local water concentration. We combined this effect with the recently developed fluorescence lifetime single molecule localization microscopy imaging (FL-SMLM) in order to nanoscopically determine the local water content in microgels, i.e. soft hydrogel particles consisting of a cross-linked polymer swollen in water. The change in water content of thermo-responsive microgels when changing from their swollen state at room temperature to a collapsed state at elevated temperature could be analyzed. A clear decrease in water content was found that was, to our surprise, rather uniform throughout the entire microgel volume. Only a slightly higher water content around the dye was found in the periphery with respect to the center of the swollen microgels.

Lokaler Wassergehalt in Polymergelen bestimmt über superauflösende Fluoreszenzlebensdauer‐Bildgebung

AbstractWassermoleküle spielen eine wichtige Rolle für die Struktur, Funktion und Dynamik von (Bio‐) Materialien. Ein direkter Zugang zur Anzahl der Wassermoleküle in nanoskopischen Volumina kann daher neue molekulare Einblicke in Materialien geben und eine Feinabstimmung ihrer Eigenschaften in anspruchsvollen Anwendungen ermöglichen. Die Bestimmung des lokalen Wassergehalts wurde durch die Entdeckung möglich, dass H2O die Fluoreszenz von rot‐emittierenden Farbstoffen löscht. Da deuteriertes Wasser, D2O, keine signifikante Fluoreszenzlöschung hervorruft, lässt sich über Fluoreszenzlebensdauermessungen bei unterschiedlichen H2O/D2O‐Verhältnissen die lokale Wasserkonzentration bestimmen. Wir kombinierten diesen Effekt mit der vor Kurzem entwickelten Fluoreszenzlebensdauer‐Einzelmolekül‐Lokalisierungsmikroskopie (FL‐SMLM), um die lokale Wasserkonzentration in Mikrogelen, d. h. weichen Hydrogelpartikeln, die aus einem in Wasser gequollenen vernetzten Polymer bestehen, nanoskopisch zu bestimmen. Die Änderung des Wassergehalts von thermoresponsiven Mikrogelen beim Übergang von ihrem gequollenen Zustand bei Raumtemperatur zu einem kollabierten Zustand bei erhöhter Temperatur konnte analysiert werden. Es wurde eine deutliche Abnahme des Wassergehalts festgestellt, die zu unserer Überraschung über das gesamte Mikrogelvolumen recht gleichmäßig war. In der Peripherie der gequollenen Mikrogele war die Wasserkonzentration um den Farbstoff herum nur geringfügig größer als in deren Zentrum.

An amphiphilic dansyl based multianalyte sensor for the detection of Hg2+, PPi, and TNP: A three-in-one chemical sensor

A fluorescent dansyl-based amphiphilic probe, 5-(dimethylamino)-N-hexadecylnaphthalene-1-sulfonamide (DLC), was synthesized and characterized to detect multiple analytes at different sensing environments. In acetonitrile, DLC detects nitro explosives such as trinitrophenol (TNP) and 2,4-dinitrophenol (2,4-DNP) by an emission “on-off” response method, and the detection limits (LOD) were estimated to be as low as 4.3 µM and 17.4 µM, respectively. Amphiphilic long chains of the probe were embedded into lipid bilayers to form nanoscale vesicles DLC.Ves. Nanovesicular probe DLC.Ves was found to be highly selective for Hg2+ among other metal ions and for pyrophosphate (PPi) ions among various anions. DLC.Ves could detect Hg2+ with a turn “on–off” emission and PPi with ratiometric change in emission at 525 nm. It is proposed that DLC.Ves could detect Hg2+ via the Hg2+-induced aggregation quenching mechanism and PPi through the Hydrogen bonding. The LODs are estimated as 6.41 µM and 70.9 µM for Hg2+ and PPi, respectively. 1H NMR, SEM, and fluorescence lifetime measurements confirmed the binding mechanism. Thus, it is believed that the simple fluorescent probe DLC could be a prominent sensor to detect multiple analytes depending on the sensing medium.

Rhenium fac-Tricarbonyl Bisimine Chalcogenide Complexes: Synthesis, Photophysical Studies, and Confocal and Time-Resolved Cell Microscopy.

We describe the preparation, characterization, and imaging studies of rhenium carbonyl complexes with a pyta (4-(2-pyridyl)-1,2,3-triazole) or tapy (1-(2-pyridyl)-1,2,3-triazole)-based heteroaromatic N∧N ligand and thiolate or selenoate X ligand. The stability and photophysical properties of the selenolate complexes are compared with parent chloride complexes and previously described analogues with benzenethiolate ligands. Two complexes were imaged in A549 cells upon excitation at 405 nm. Colocalization studies suggest a lysosomal accumulation, while one parent chloride complex was described to localize at the Golgi apparatus. Preliminary fluorescence lifetime measurements and imaging demonstrate potential for application in time-resolved microscopy techniques due to the long and variable lifetimes observed in cellular environments, including an increase in lifetime between the solution and solid state many times larger than previously reported.

Facile synthesis of sulphur-doped carbon dots (S-CDs) using a hydrothermal method for the selective sensing of Cr6+ and Fe3+ ions: application to environmental water sample analysis.

In this work, we used a one-step hydrothermal method to synthesize blue-emission sulfur-doped carbon dots (S-CDs) using jaggery as a carbon precursor. The synthesized carbon quantum dots showed low toxicity, good water solubility, anti-interference properties, and stable fluorescence. When excited at 310 nm, the S-CDs produced bright emission with a quantum yield of 7.15% at 397 nm. The S-CDs exhibited selective and sensitive quenching responses with limits of detection (LODs) of 4.25 μg mL-1 and 3.15 μg mL-1 for variable concentrations of Cr6+ and Fe3+, respectively, accompanied by a consistent linear relationship between fluorescence intensity and these concentrations. Fluorescence lifetime measurements were used to investigate the fluorescence quenching mechanism, which supports the static type of quenching. Outstanding benefits of the developed S-CD based fluorescence probe include its low cost, excellent sensitivity and selectivity, and ease of use for the detection of Cr6+ and Fe3+ ions. The developed carbon dot based fluorescent probe was successfully used to detect Cr6+ and Fe3+ ions in real water samples with an excellent recovery ratio.