Changes In Emission Spectra Research Articles

Near-Infrared Ratiometric Hemicyanine Fluorescent Probes for Monitoring Mitochondrial pH Dynamics in Live Cells during Oxidative Stress and Hypoxia.

Novel near-infrared ratiometric molecules (probes A and B) produced by linking formyl-functionalized xanthene and methoxybenzene moieties, respectively, onto a xanthene-hemicyanine framework are detailed. Probe A exhibited a primary absorption peak at 780 nm and a shoulder peak at 730 nm and exhibited fluorescence at 740 nm↓ (signifies a downward shift in intensity upon acidification) in a pH 9.3 buffer and 780 nm↑ at pH 2.8 under excitation at 700 nm. Probe B featured absorptions at 618 and 668 nm at pH 3.2 and at 717 nm at pH 8.6, and fluorescence at 693 nm↑ at pH 3.2 and at 739 nm↓ at pH 8.6, in mostly the red to near-IR region. The ratiometric changes in the intensity of the fluorescent absorptions were reversed between A and B upon acidification as indicated by the arrows. Theoretical calculations confirmed that there were slight changes in conformation between probes and the protonated molecules, suggesting that the changes in emission spectra were due mostly to conjugation effects. Calculations at the APFD/6-311+g(d,p) level with a solvent described by the polarizable continuum model resulted in pK a values for A at 6.33 and B at 6.41, in good agreement with the experimentally determined value of 6.97 and an average of 6.40, respectively. The versatilities of the probes were demonstrated in various experimental contexts, including the effective detection of mitochondrial pH fluctuations. Live cell experiments involving exposure to different pH buffers in the presence of H+ ionophores, monitoring mitophagy processes during cell starvation, studying hypoxia induced by CoCl2 treatment, and investigating responses to various oxidative stresses are detailed. Our findings highlight the potential of attaching xanthene and methoxybenzaldehyde groups onto xanthene-hemicyanine structures as versatile tools for monitoring pH changes in a variety of cellular environments and processes.

Influence of N2 admixture on mode transition of discharge in N2–Ar helicon plasma

Effects of N2 admixture on multiple wave modes and transitions were investigated in N2–Ar helicon plasma under fixed input power and magnetic field. The structures of helicon waves were measured by a B-dot probe to verify the different eigenmodes. The experimental results show that the plasma morphology, emission spectrum, and spatial profile change significantly during mode transitions with the N2–Ar ratio. The calculated results from the pressure balance model indicate that the densities of species N2, N+, Ar, and Ar+ will change largely during mode transition around some specific N2 percentages, which will help to improve the application of N2–Ar helicon plasma in material processing greatly.

A ratiometric fluorescent probe for cysteine and glutathione differentiation and its application for cysteine detection in foods

Cysteine (Cys) and glutathione (GSH) are crucial biothiols implicated in cellular redox balance, necessitating accurate detection methods. Herein, we developed a novel fluorescent probe based on the fluorescent dye pyronin (PYR), capable of monitoring both Cys-and GSH using ratiometric fluorescence signals. The probe, named PYR-CG, where "C" stands for Cys-and "G" stands for GSH, demonstrates selective detection capabilities for Cys-and GSH. UV absorption and fluorescence emission spectra changes revealed distinct shifts upon interaction with Cys-and GSH. Theoretical and experimental studies validated PYR-CG's responsiveness to Cys-and GSH, elucidating its mechanism as a ratiometric probe. Notably, PYR-CG exhibited rapid response kinetics for Cys-and GSH, with low detection limits of 88 nM and 164 nM, respectively. Importantly, PYR-CG demonstrated exceptional selectivity for Cys-and GSH over interfering analytes. Screening of molecules with similar structures to Cys-further affirmed PYR-CG's specificity, particularly towards N-terminal Cys-in peptides. Furthermore, recovery experiments underscored PYR-CG's reliability for quantitative Cys-detection in complex food samples. Our findings highlight the innovative design and practical applicability of PYR-CG, offering a valuable tool for sensitive and selective detection of Cys-in diverse biological and food samples.

P‐198: Ideal Design of Platinum (II) Complex with Bulky Blocking Group for Narrow Emission and High Efficiency in Blue Organic Light‐Emitting Diodes

Platinum phosphorescent materials are emerging as promising candidates for efficient blue organic light‐emitting diodes. Especially, tetradentate ligands with a 5/6/6 configuration have the advantage of having twisted structure to minimize intermolecular interactions. However, the reported platinum complexes in the 5/6/6 configuration still exhibit relatively broad luminescence spectra and low efficiency at high doping concentration due to insufficient intermolecular interaction suppression. It is necessary to introduce the appropriate blocking group at the proper position on the ligand to ensure that intermolecular interactions are inhibited. In this work, we propose an ideal design introducing blocking group for platinum (II) complexes with small changes in efficiency and emission spectra at high doping concentration. The bulky blocking group, 2,6‐diisopropylphenyl, introduced at the 3‐position of the carbazole is distorted vertically due to steric hindrance, so the energy is still retained. However, the photophysical and device properties were improved by suppression of intermolecular interaction. As a result, Pt‐dipCz showed high efficiency of 25.0% with narrow full width at half maximum (FWHM) of 22 nm at 5 wt.% doping concentration. When doping concentration increased to 20 wt.%, high efficiency and narrow FWHM were maintained with small changes of only 4.8% reduction and 2 nm increase, respectively. These values indicate that 2,6‐diisopropylphenyl group introduced at carbazole is efficient for suppression of intermolecular interaction.

Pt-S Bond-Enabled Temperature-Dependent Phosphorescence in S-Heteroaryl Tetradentate Pt(S^C^N^O) Complexes.

This study presents the rare examples of S-heteroaryl tetradentate Pt(S^C^N^O) luminescent complexes (PtSZ and PtSZtBu) containing a Pt-S bond. The presence of the Pt-S bond allows the novel Pt(S^C^N^O) complexes to exhibit temperature-dependent phosphorescent emission behavior. The PtSZtBu exhibits dual-emission phenomena and biexponential transient decay spectra above 250 K, indicating the presence of two minimal excited states in the potential energy surface (PES) of the T1 state. Through complementary experimental and computational studies, we have identified changes in orbital composition between Pt(dxy)-S(px) and Pt(dyz)-S(pz) in excited states with increasing temperature. This results in two energy minima, enabling the excited states to decay selectively and radiatively at different temperatures. Consequently, this leads to remarkable steady-state and transient emission spectra changes. Our work not only provides valuable insights for the development of novel Pt-S bond-based tetradentate Pt(II) complexes but also enhances our understanding of the distinctive properties governed by the Pt-S bond.

Spectroscopic behavior of bufotenine and bufotenine N-oxide: Solvent and pH effects and interaction with biomembrane models

Bufotenine is a fluorescent analog of Dimethyltryptamine (DMT) that has been widely studied due to its psychedelic properties and biological activity. However, little is known about its spectroscopic properties in different media. Thus, we present in this work, for the first time, the spectroscopic behavior of bufotenine and bufotenine N-oxide by means of their fluorescence properties. Both molecules exhibit changes in optical absorption and emission spectra with variations in pH of the medium and in different solvents. Assays in the presence of biomembranes models, like micelles and liposomes, were also performed. In surfactants titration experiments, the spectral shift observed in fluorescence shows the interaction of both molecules with pre-micellar structures and with micelles. Steady state anisotropy measurements show that both bufotenine and bufotenine N-oxide, in the studied concentration range, interact with liposomes without causing changes in the fluidity of the lipid bilayer. These results can be useful in studies that aim at searching for new compounds, inspired by bufotenine and bufotenine N-oxide, with relevant pharmacological activities and also in studies that use these molecules as markers of psychiatric disorders.

Unveiling structural and energetic characterization of the emissive RNA alphabet anchored in the methylthieno[3,4-d]pyrimidine heterocycle core.

This study presents a comprehensive theoretical exploration of the fluorescent non-natural emissive nucleobases- mthA, mthG, mthC, and mthU derived from the methylthieno[3,4-d]pyrimidine heterocycle. Our calculations, aligning with experimental findings, reveal that these non-natural bases exert minimal influence on the geometry of classical Watson-Crick base pairs within an RNA duplex, maintaining H-bonding akin to natural bases. In terms of energy, the impact of the modified bases, but for mthG, is also found to be little significant. We delved into an in-depth analysis of the photophysical properties of these non-natural bases. This investigation unveiled a correlation between their absorption/emission peaks and the substantial impact of the modification on the energy levels of the highest unoccupied molecular orbitals (HOMO) and the lowest unoccupied molecular orbital (LUMO). Notably, this alteration in energy levels resulted in a significant reduction of the HOMO-LUMO gap, from approximately 5.4-5.5 eV in the natural bases, to roughly 3.9-4.7 eV in the modified bases. This shift led to a consequential change in absorption and emission spectra towards longer wavelengths, elucidating their bathochromic shift.

Effect of Chloride, Sulfate, and Ferrate Salts on Electronic Energy Levels of Anthracene Proving it a Potential Candidate as an ON and ON-OFF UV-Vis Sensor.

Anthracene molecule possesses remarkable optical activity and till today this molecule is of special interest of scientists. Present study is focused on the study of effects of Chloride, Sulfate, Nitrate and Ferrate salts on absorption and emission spectra of targeted fluorophore in carbontetrachloride, chloroform, dichloromethane and methanol. Prominent solvatochromic effects shows dependence of HOMO-LUMO orbitals on solvent polarity. Anthracene molecules exhibits changes in absorption and emission spectra, and show both ON and ON-OFF behavior on addition of said ions. Based on experimental results it was concluded that fluorophore molecule could be used more effectively as UV-Visible (UV-V) sensors in comparison to the emission sensor.

3-Aryl-5-aminobiphenyl Substituted [1,2,4]triazolo[4,3-c]quinazolines: Synthesis and Photophysical Properties.

Amino-[1,1']-biphenyl-containing 3-aryl-[1,2,4]triazolo[4,3-c]quinazoline derivatives with fluorescent properties have been designed and synthesized. The type of annelation of the triazole ring to the pyrimidine one has been unambiguously confirmed by means of an X-ray diffraction (XRD) method; the molecules are non-planar, and the aryl substituents form the pincer-like conformation. The UV/Vis and photoluminescent properties of target compounds were investigated in two solvents of different polarities and in a solid state. The samples emit a broad range of wavelengths and display fluorescent quantum yields of up to 94% in toluene solutions. 5-(4'-Diphenylamino-[1,1']-biphenyl-4-yl)-3-(4-(trifluoromethyl)phenyl)-[1,2,4]triazolo[4,3-c]quinazoline exhibits the strongest emission in toluene and a solid state. Additionally, the solvatochromic properties were studied for the substituted [1,2,4]triazolo[4,3-c]quinazolines. Moreover, the changes in absorption and emission spectra have been demonstrated upon the addition of water to MeCN solutions, which confirms aggregate formation, and some samples were found to exhibit aggregation-induced emission enhancement. Further, the ability of triazoloquinazolines to detect trifluoroacetic acid has been analyzed; the presence of TFA induces changes in both absorption and emission spectra, and acidochromic behavvior was observed for some triazoloquinazoline compounds. Finally, electronic-structure calculations with the use of quantum-chemistry methods were performed for synthesized compounds.

Citizen scientists report global rapid reductions in the visibility of stars from 2011 to 2022.

The artificial glow of the night sky is a form of light pollution; its global change over time is not well known. Developments in lighting technology complicate any measurement because of changes in lighting practice and emission spectra. We investigated the change in global sky brightness from 2011 to 2022 using 51,351 citizen scientist observations of naked-eye stellar visibility. The number of visible stars decreased by an amount that can be explained by an increase in sky brightness of 7 to 10% per year in the human visible band. This increase is faster than emissions changes indicated by satellite observations. We ascribe this difference to spectral changes in light emission and to the average angle of light emissions.

The choice of spectrum of LED irradiators affect the life of lighting systems in horticulture

The article presents the results of experimental studies of LED degradation in greenhouse irradiators for horticulture. It was found that in the process of operation of the irradiators the emission spectrum changes. This is caused by different decrease rate of photosynthetic photon flux of different colored LEDs. For a longer service life it is recommended to use greenhouse irradiators with a large proportion of red LEDs.

Selective Recognition and Reversible “Turn-Off” Fluorescence Sensing of Acetate (CH3COO−) Anion at Ppb Level Using a Simple Quinizarin Fluorescent Dye

A simple and cost-effective optical sensing system based on quinizarin fluorescent dye (QZ) for the selective and reversible sensing of CH3COO− anions is reported. The anion binding affinity of QZ towards different anions was monitored using electronic absorption and fluorescence emission titration studies in DMSO. The UV-visible absorption spectrum of QZ showed a decrease in the intensity of the characteristic absorption peaks at λ = 280, 323, and 475 nm, while a new peak appeared at λ = 586 nm after the addition of CH3COO− anions. Similarly, the initial strong emission intensity of QZ was attenuated following titration with CH3COO− anions. Notably, similar titration using other anions, such as F−, Cl−, I−, NO3−, NO2−, and H2PO4-, caused no observable changes in both absorption and emission spectra. The selective sensing of CH3COO− anions was also reflected by a sharp visual color change from bright green to faint green under room light. Further, the binding was found to be reversible, and this makes QZ a potential optical and colorimetric sensor for selective, reversible, and ppb-level detection of CH3COO− anions in a DMSO medium.

Structural, DFT calculations and photophysical and photochemical characteristics of 1-((E)-2-phenylethenyl)-2-(4-(2-((E)-2-phenylethenyl) phenoxy) butoxy) benzene (PPPBB)

X-ray single crystal structure and spectroscopic and photophysical parameters of the titled compound were studied. The titled compound shows thermal stability prior to melting at 126.17 °C with Δ H value of 109.991 J g−1. Photophysical parameters include singlet electronic absorption, molar absorption coefficient, oscillator strength, and dipole moment of electronic transition, fluorescence spectra, excited state lifetime, and fluorescence quantum yield for 1-((E)-2-phenylethenyl)-2-(4-(2-((E)-2-phenylethenyl) phenoxy) butoxy) (PPPBB) in different solvents. PPPBB displays a little change in maximum absorption and emission spectra with solvent polarity, indicating a slight change in dipole moment of dye molecules upon excitation. The dipole moments' (Δ μ) difference between the excited and ground states was obtained from the Lippert–Mataga method. Ground and electronic excited states' geometric optimization was performed using density functional theory (DFT) and time-dependent density functional theory (time dependent-DFT), complemented with spectral findings. A good agreement between theoretical data and experimental observations was found. The net photochemical quantum yield (φc) of PPPBB dye was calculated in various solvents.

A highly photostable and versatile two-photon fluorescent probe for the detection of a wide range of intracellular nitric oxide concentrations in macrophages and endothelial cells.

Nitric oxide (NO) is involved in many biological processes affecting the cardiovascular, nervous and immune systems. Intracellular NO can be monitored using fluorescent probes in combination with fluorescence imaging techniques. Most of the currently available NO fluorescent molecular probes are excited via one-photon excitation using UV or Vis light, which results in poor penetration and high photodamage to living tissues. Here, we report a two-photon fluorescent molecular probe, DANPY-NO, able to detect NO in live cells. The probe consists of an o-phenylenediamine linked to a naphthalimide core; and operates via photoinduced electron transfer. DANPY-NO exhibits good sensitivity (LOD of 77.8nM) and high selectivity towards NO, and is stable over a broad range of pHs. The probe targeted acidic organelles within macrophages and endothelial cells, and demonstrated enhanced photostability over a commercially available NO probe. DANPY-NO was used to selectively detect endogenous NO in RAW264.7ϒ NO- macrophages, THP-1 human leukemic cells, primary mouse (bone marrow-derived) macrophages and endothelial cells. The probe was also able to detect exogenous NO in endothelial cells and distinguish between increasing concentrations of NO. The NO detection was evidenced using confocal laser scanning and two-photon microscopies, and flow cytometry. Further evidence was obtained by recording the changes in the intracellular fluorescence emission spectrum of the probe. Importantly, the probe displayed negligible toxicity to the analysed biological samples. The excellent sensitivity, selectivity, stability and versatility of DANPY-NO confirm its potential for in vitro and in vivo imaging of NO.

Uniaxial Strain Engineering via Core Position Control in CdSe/CdS Core/Shell Nanorods and Their Optical Response.

Anisotropic strain engineering has emerged as a powerful strategy for enhancing the optoelectronic performance of semiconductor nanocrystals. Here, we show that CdSe/CdS dot-in-rod structures offer a platform for fine-tuning the optical response of CdSe quantum dots through anisotropic strain. By controlling the spatial position of the CdSe core within a growing CdS nanorod shell, varying degrees of uniaxial strain can be introduced. Placing CdSe cores at the end of the CdS nanorod induces strong asymmetric compression along the c-axis of the wurtzite CdSe core, dramatically altering its absorption and emission characteristics, whereas CdSe cores located near the middle of the nanorod experience a comparatively weak uniaxial strain field. The change in absorption and emission spectra and dynamics for highly strained end-position CdSe/CdS nanorods is explained by (1) relative shifting of the valence band light hole and heavy hole levels and (2) introduction of a strong piezoelectric potential, which spatially separates the electron and hole wave functions. The ability to tune the degree of uniaxial strain through core position control in a nanorod structure creates opportunities for precisely modulating the electronic properties of CdSe nanocrystals while simultaneously taking advantage of dielectric and optical anisotropies intrinsic to 1D nanostructures.

Functional flexibility of cyanobacterial light harvesting phycobilisomes enable acclimation to the complex light regime of mixing marine water columns.

The light environment in a mixing water column is arguably the most erratic condition under which photosynthesis functions. Shifts in light intensity, by an order of magnitude, can occur over the time scale of hours. In marine Synechococcus, light is harvested by massive, membrane attached, phycobilisome chromophore-protein complexes (PBS). We examined the ability of a phycobilisome-containing marine Synechococcus strain (WH8102) to acclimate to illumination perturbations on this scale. Although changes in pigment composition occurred gradually over the course of days, we did observe significant and reversible changes in the pigment's fluorescence emission spectra on a time scale of hours. Upon transition to ten-fold higher intensities, we observed a decrease in the energy transferred to Photosystem II. At the same time, the spectral composition of PBS fluorescence emission shifted. Unlike fluorescence quenching mechanisms, this phenomenon resulted in increased fluorescence intensities. These data suggest a mechanism by which marine Synechococcus WH8102 detaches hexamers from the phycobilisome structure. The fluorescence yield of these uncoupled hexamers is high. The detachment process does not require protein synthesis as opposed to reattachment. Hence, the most likely process would be the degradation and resynthesis of labile PBS linker proteins. Experiments with additional species yielded similar results, suggesting that this novel mechanism might be broadly used among PBS-containing organisms.

New stilbene-biscarbothioamide based colorimetric chemosensor and turn on fluorescent probe for recognition of Hg2+ cation

A new symmetrical biscarbothioamide based stilbene 2,2′-(4,4′-(ethene-1,2-diyl)bis(benzoyl))bis(N-phenylhydrazine-1-carbothioamide) (TUS) as turn on fluorescent probe and colorimetric chemosensor for detection of mercury cation was synthesized and characterized by NMR spectra, Mass spectra, IR spectra, and elemental analyses. The selectivity towards various metal cations was investigated at pH 5, TUS exhibited good colorimetric selectivity to Hg2+ ion that could be directly observed by naked-eye color change from colorless to faint yellow with short response time. Moreover, the stoichiometric ratio and the interaction of TUS fluorescent probe with Hg2+ was determined to be 1:2 complex formation, which confirmed by Job's plot, mass spectra and 1H NMR titration. The detection limit of TUS towards Hg2+ was calculated to be 0.15 µM. The effect of the pH change in absorption and emission spectra with the absence and presence of Hg2+ cations were studied. The TUS was used for bio-imaging of HepG-2 cells and intracellular detection of Hg2+ by confocal microscope.

Scrutinzing the interaction of bovine serum albumin and human hemoglobin with isatin-triazole functionalized rhodamine through spectroscopic and In-silico approaches

• Spectral methods have been used to investigate the interaction of R1 with HHb and BSA. • Thermodynamic parameters suggested exothermic spontaneous binding processes involving hydrogen bonding and van der Waal interaction. • Molecular docking and molecular dynamics have been utilized to discuss the principle binding sites of proteins for R1 . • R1 proposes preferentially binding to the hydrophobic cavity in site III of proteins. A Rhodamine-based fluorescent probe R1 has been successfully utilized to detect BSA and HHb proteins via non-covalent bonding. The protein binding nature with R1 has been unravelled by the characteristic changes in absorption, emission and circular dichroism spectra that indicated their noticeable interaction. The experimental results have also shown the moderate strength between proteins and R1 from the quenching of proteins through the static quenching mechanism. The hyperchromism in the absorption band of proteins with R1 has given vital information and binding affinity values have been calculated from Stern-Volmer plots. The calculated values of the thermodynamic parameters revealed a spontaneous binding processes occurring primarily via hydrogen bonding and van der Waal interactions. Furthermore, in-silico approaches have been utilized to make a comparison and conclusion with spectroscopic results. The outcome of these studies could be useful to examine the drug-protein binding for further exploitation.

Naked‐eye colorimetric and optical assay of heavy metals based on nano‐architectured prototype of organically functionalized mesoporous titania grafted with 4‐chloro‐2‐(4′‐methyl‐benzothiazol‐2′‐ylazo)‐phenol

Heavy metals are extremely toxic, causing harm to aquatic and human life. Thus, this study focused on developing simple, colorimetric, and low‐cost optical sensors for detection of metal ions with high selectivity and sensitivity. Here, a novel benzothiazole azo‐dye, namely, 4‐chloro‐2‐(4′‐methyl‐benzothiazol‐2′‐ylazo)‐phenol (CMBTAP) was synthesized and characterized by Fourier transform infrared spectroscopy (FT‐IR), 1H‐nuclear magnetic resonance (NMR), 13C‐NMR, and mass spectroscopic techniques. This azo‐dye has been anchored into the amino‐functionalized mesoporous TiO2 which synthesized using pluornic123 and cetyltrimethylammonium bromide as templates to yield CMBTAP‐M‐TiO2 (1) and CMBTAP‐M‐TiO2 (2), respectively. The designed nanosensors were characterized by FT‐IR, transmission electron microscopy, nitrogen adsorption–desorption isotherms, X‐ray diffraction, and thermogravimetric analyses. The colorimetric and optical sensing behavior of CMBTAP and its nanosensor analogs toward different metal ions like Ba2+, Fe3+, Co2+, Ni2+, Cu2+, Cd2+, Hg2+, and Al3+ were explored using naked‐eye observations, steady‐state absorption, and emission techniques. Significant changes in colors, the absorption and emission spectra were observed. The action of these nanosensors is reversible where on adding ethylenediaminetetraacetic acid to the formed complexes, the original absorption and emission spectra of the free sensors are restored, demonstrating that the chelation process is reversible. For CMBTAP and the nanosensors, the binding constants of the complexes formed with the used metal ions, and limit of detection (LOD) were calculated. In comparison with CMBTAP, the results revealed that the nanosensors exhibited a stronger binding affinity, selectivity, sensitivity, and lower LODs for the studied metal ions, implying that the sensing efficiency of CMBTAP is improved after loading onto the nanostructured TiO2. Thus, we have successfully converted the hazardous azo dye into an environmentally safe optical sensor for detection of toxic metal ions in wastewater with high sensitivity.

Further Develop 1,3,4-Thiadiazole Based Probe to Effectively Detect 2,4,6-Trinitrophenol with the Help of DFT Calculations.

Four fluorimetric probes had been developed to rapidly detect 2,4,6-trinitrophenol (TNP). They were designed and synthesized on the basis of 1,3,4-thiadiazole framework combining calculation with experiment. Among them, SK-1 displayed strong blue emission with fluorescence quantum yield as high as 63.6% in solution. Further evaluation demonstrated that SK-1 displays good selectivity and high sensitivity for rapid and visual detection of TNP. It brought significant changes in both colour and fluorescence emission spectrum. The detection limit was as low as 38nM. Quenching mechanism was confirmed as photo-induced electron transfer (PET) by nuclear magnetic titration and DFT calculations. What's more, application in real water samples and solid phase paper tests illustrated the practical significance of detection of TNP in both vapor and solution.