Changes In Fluorescence Spectra Research Articles

Solvatochromism, electric dipole moments, optical properties and electronic structure of biphenylcarbonitrile liquid crystals

The UV–Vis. absorbance and fluorescence spectra of 4HC (4′-heptyl-4-biphenyl carbonitrile) and 4OB (4′-Octyl-4-biphenylcarbonitrile) liquid crystals were measured in 23 solvents with different polarities. As dependent on changing of solvents, while the change in absorbance spectrum of liquid crystals have less, change in fluorescence spectrum have more. Molecular interactions were quantitavely investigated by using Linear solvation energy relationships. Optical forbidden energy gap has been determined with using Tauc plot. The refractive index has been calculated with semi-empirical methods. The relationships between refractive index and Eg has been commented in n-hexane, acetic acid, water and 1,4-dioxane. The electric dipole moment has been calculated by using the Bilot-Kawski, Lippert-Mataga, Bakshiev, Kawski-Chamma-Viallet and Reichardt methods. Solvatochromic shifts showed to having large dipole moments of 4OB and 4HC LCs. Their molecular orbital energies, electric dipole moments, MEP, SAS, and reactivity properties of 4HC and 4OB LCs has been found by quantum chemical calculations. It was observed that the dipole moment of 4HC was higher than 4OB.

Low-moisture extruded mung bean protein isolate and wheat gluten: Structure, techno-functional characteristics and establishment of rehydration kinetics of the products

Low-moisture extruded products provide excellent shelf-life and stability, making the exploration of new formulations with various proteins highly valuable. This study prepared and compared products with different ratios of mung bean protein isolate (MPI) to wheat gluten (WG) (10:0, 9:1, 8:2, 7:3, 6:4, and 5:5). Results showed significant improvements (P < 0.05) in L∗-value and product quality with increasing WG ratios, peaking at an MPI/WG ratio of 7:3. Increased WG also enhanced protein cross-linking aggregation, as evidenced by changes in particle size, secondary structure, and fluorescence spectra. However, excessive WG (MPI/WG = 6:4) adversely affected product structure and techno-functional characteristics. Rehydration kinetics were best described by the Peleg model, with rehydrated products showing decreased hardness (291.25 N) and chewiness (227.45 N), but increased tensile resistance (P < 0.05). Eleven quadratic polynomial equations were developed to predict color and techno-functional characteristics based on WG percentage (0–50%). The findings provide a theoretical basis for expanding the application of MPI in new low-moisture extruded products.

Effects and avoidance of photoconversion-induced artifacts in confocal and STED microscopy

Fluorescence microscopy is limited by photoconversion due to continuous illumination, which results in not only photobleaching but also conversion of fluorescent molecules into species of different spectral properties through photoblueing. Here, we determined different fluorescence parameters of photoconverted products for various fluorophores under standard confocal and stimulated emission depletion (STED) microscopy conditions. We observed changes in both fluorescence spectra and lifetimes that can cause artifacts in quantitative measurements, which can be avoided by using exchangeable dyes.

Selective and Effective Sensing of Cyanide Ion with no Interference in Water by Phenothiazine-indolium Fused Optical Sensor.

The sensor with electron donor phenothiazine-2-carbaldehyde and electron acceptor indolium carboxylic acid, is developed with an intramolecular charge transfer transition between them. The synthesized molecule senses cyanide ion in water. The cyanide ion reacts with the molecule via nucleophilic addition in the indolium ring with a noticeable purple to colorless change in the solution observed. Also with the cyanide ion interaction, the sensor exhibits change in UV-visible absorption and fluorescence spectra. While the other ion does not show spectral and visual changes when interacts with the sensor molecule. Also the interference study reveals that the molecule is highly selective towards cyanide ion. Different source of water samples confirms the CN- ion sensing efficiency of the molecule. 1:1 interaction between the molecule PTI and cyanide ion is confirmed from the results of Jobs plot, 1H NMR and HRMS. Paper strips were prepared and this can act as a simple tool to sense cyanide ion in various water samples.

Self-indicating polymers: a pathway to intelligent materials.

Self-indicating polymers have emerged as a promising class of smart materials that possess the unique ability to undergo detectable variations in their physical or chemical properties in response to various stimuli. This article presents an overview of the most important mechanisms through which these materials exhibit self-indication, including aggregation, phase transition, covalent and non-covalent bond cleavage, isomerization, charge transfer, and energy transfer. Aggregation is a prevalent mechanism observed in self-indicating polymers, where changes in the degree of molecular organization result in variations in optical or electrical properties. Phase transition-induced self-indication relies on the transformation between different phases, such as liquid-to-solid or crystalline-to-amorphous transitions, leading to observable changes in color or conductivity. Covalent bond cleavage-based self-indicating polymers undergo controlled degradation or fragmentation upon exposure to specific triggers, resulting in noticeable variations in their structural or mechanical properties. Isomerization is another crucial mechanism exploited in self-indicating polymers, where the reversible transformation between the different isomeric forms induces detectable changes in fluorescence or absorption spectra. Charge transfer-based self-indicating polymers rely on the modulation of electron or hole transfer within the polymer backbone, manifesting as changes in electrical conductivity or redox properties. Energy transfer is an essential mechanism utilized by certain self-indicating polymers, where energy transfer between chromophores or fluorophores leads to variations in the emission characteristics. Furthermore, this review article highlights the diverse range of applications for self-indicating polymers. These materials find particular use in sensing and monitoring applications, where their responsive nature enables them to act as sensors for specific analytes, environmental parameters, or mechanical stress. Self-indicating polymers have also been used in the development of smart materials, including stimuli-responsive coatings, drug delivery systems, food sensors, wearable devices, and molecular switches. The unique combination of tunable properties and responsiveness makes self-indicating polymers highly promising for future advancements in the fields of biotechnology, materials science, and electronics.

Ultrafast spectroscopy of the hydrophilic carotenoid crocin at various pH.

This study delves into the pH-dependent effects on the excited-state behavior of crocin, a hydrophilic carotenoid with diverse functions in biological systems. Steady-state spectroscopy demonstrates notable changes in absorption and fluorescence spectra, characterized by a pH-dependent blue shift and altered resolution of vibrational bands. Transient absorption spectra further elucidate these effects, highlighting a significant blue shift in the S1-Sn peak with increasing pH. Detailed kinetic analysis shows the pH-dependent dynamics of crocin's excited states. At pH 11, a shortening of effective conjugation is observed, resulting in a prolonged S1/ICT lifetime. Conversely, at pH 9, our data suggest a more complex scenario, suggesting the presence of two distinct crocin species with different relaxation patterns. This implies structural alterations within the crocin molecule, potentially linked to the deprotonation of hydroxyl groups in crocin and/or saponification at high pH.

An ultrafast and highly sensitive fluorescent probe for the detection of HSO3− and its application in food samples and SO2 gas

SO2 is one of the main components of air pollution gas, its derivatives HSO3− and SO32− were considerable used as food additive because of their antiseptic and bacteriostatic effects. Excessive intake of HSO3− is harmful to human health, so it is extremely important to detect the content of HSO3− in food sample by effective method. In this work, a small molecular fluorescence probe TPE-O based on tetraphenylethene fluorophore was designed and synthesized. The probe showed ultrafast (< 3 s) and obvious colorimetric response to HSO3− with high selectivity and sensitivity (LOD = 210 nM). The possible Michael-type addition of HSO3− on the activated C = C bond blocked the π-conjugated system, thus lead to changes in fluorescence and absorption spectra. Probe TPE-O not only can detect the content of HSO3− in sugar and wine, but also can be loaded on agarose hydrogel to detect SO2 gas. Therefore, this work provided a powerful tool for the detection of HSO3− in food samples and SO2 gas.

Photochemical reactivity of water-soluble dissolved organic matter from microplastics and microfibers

Plastics in aquatic environments are a source of dissolved organic matter (DOM). However, its production pathways and environmental fate remain poorly understood. This study investigated the yields, characterization, and photochemical reactivities of water-soluble DOM from seven pristine microplastics (MPs) and three microfibers (MFs). We found yields of plastic-derived DOM per unit mass of MPs or MFs, including chromophoric DOM (CDOM) and dissolved organic carbon (DOC), were significantly influenced by polymer chemical structures. Notably, MFs exhibited consistently higher DOM yields compared to MPs. In addition, plastics containing aromatic rings, such as PETE and PS, were found to generate higher CDOM yields, although PVC also showed elevated CDOM yields. The plastic-derived DOM had a diverse molecular size-range, spanning from 60 nm (polyester-DOM) to 937 nm (LDPE-DOM), while Zeta potentials, which were predominantly negatively charged, varied from −42.5 mV (nylon-DOM) to +4.6 mV (LMW-PVC-DOM). Degradation rate constants for CDOM (0.001–0.022 h−1) were generally higher than DOC (0.0009–0.020 h−1), with a shorter half-life for PETE- and PS-derived DOM. The reactivity and degradation kinetics of plastic-derived DOM were notably manifested in changes of fluorescence spectra (excitation-emission matrixes) during photochemical weathering, showing the influence of polymeric composition/structures. This baseline study provides an improved understanding of the characterization and environmental fate of microfiber- and plastic-derived DOM in aquatic environments.

A new hydrazone linkage-based covalent organic framework for ratiometric fluorescent probe detection of hypochlorite

A new hydrazone-linked covalent organic framework (TFTH-COF) was synthesized and characterized. TFTH-COF has porous crystalline framework structure with high thermal stability. TFTH-COF exhibited highly selective fluorescence blue-shift response towards hypochlorite (ClO−) in ethanol and accompanied by the obvious color change under both day light and UV light. TFTH-COF has the ratiometric fluorescence sensing ability for hypochlorite with high sensitivity. The ratiometric fluorescence intensity of TFTH-COF presented a linear change against hypochlorite concentration with a low detection limit of 0.417 μM. The results of XPS, FT-IR and fluorescence lifetime indicated the formation of hydrogen bond between the O and N atoms of hydroxyl and amine of TFTH-COF with hypochlorite. The DFT calculation further confirmed the formation of hydrogen bond and resulted in the change of fluorescence spectra. Its practical application ability was confirmed by good recovery rate of TFTH-COF in the quantitative detection of hypochlorite in 84 disinfectants and water samples. Moreover, TFTH-COF can also identify hypochlorite through fluorescent test strips by the naked eye. This work sheds light on the fabrication of COFs as ratiometric fluorescence probes for easily-operable, instantaneous and accurate detection and identification of different analytes.

HOMO- AND HETERONUCLEAR Yb(III) AND Lu(III) COMPLEXES WITH CALIX[4]ARENE MODIFIED WITH PORPHYRIN SUBSTITUENTS.

In this work we describe the approaches for the synthesis of lanthanide-containing homo- and heteronuclear complexes using 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-bis[(N-meso-­(p-aminophenyl)-meso-triphenylporphyrincarbonyl)methoxy]-calix[4]arene (1). Such spatially preorganizedcalix[4]arene macrocycle facilitates lanthanide cation coordination, impacting the structure and analytical signal of porphyrin substituents. The study employs two synthesis stra­tegies resulting in mononuclear and homobinuclear complexes, influenced by steric effects and changes in hydrogen bonding. The complexes exhibit changes in fluorescence spectra due to intramolecular dimerization and hydrogen bonding during complex formation. Mononuclear complexes (Ln-1) are synthesized under mild conditions, while homobinuclear complexes (Ln2-1) require high-boiling solvents and specific reaction conditions, detailed synthesis procedures are described. The structural changes during complex formation were analyzed with the use of NMR analysis. The absorption spectra of lanthanide complexes demonstrate shifts in maxima, reflecting coordination changes, with notable variations between mononuclear and homobinuclear complexes. Additionally, heteronuclear compounds with copper(II), zinc(II), and palladium(II) exhibit distinctive absorption patterns, emphasizing the role of d-metal ions. Luminescence stu­dies reveal the sensitization of 4f-luminescence by both calix[4]arene and porphyrin fragments. The use of deuterated solvents enhances 4f-luminescence intensity, highlighting solvent effects. Furthermore, 4f-luminescence characteristics were investigated in both solid and solution states for heterometallic compounds, emphasizing differences between copper-containing and zinc/palladium-containing complexes. The results offer valuable insights into the design, synthesis, and spectral properties of these complexes, showcasing their potential applications in various fields, and the findings contribute to the understanding of lanthanide-porphyrin systems and their coordination behavior.

Arthrospira cell residue valorization: A study on protein hydrolysate production by limited enzymatic hydrolysis

Arthrospira cell residue (ACR) is a byproduct of the spirulina industry that can be valorized into protein hydrolysates. In this study, we used alkaline protease to hydrolyze ACR and evaluated the effects of hydrolysis time on the properties and functionalities of the hydrolysates. We measured the degree of hydrolysis (DH), particle size, fluorescence, UV‒visible absorption, surface hydrophobicity, emulsification, solubility, and antioxidant activity of the hydrolysates. The DH reached a maximum of 10.2% ± 0.6% after 240 min. Hydrolysis also altered the structure and conformation of the ACR protein, as shown by changes in fluorescence, UV-visible absorption, and FTIR spectra. Hydrolysis enhanced the solubility, surface hydrophobicity, and emulsifying activity of the hydrolysates but not the emulsion stability. The hydrolysates also exhibited higher antioxidant activity than ACR. These results indicate that enzymatic hydrolysis can convert ACR into valuable protein hydrolysates.

Tracking transformation behavior of soluble to insoluble components in liquid egg yolk under heat treatment and the intervention effect of xylitol

The heat sensitivity of egg yolk limits its application, and xylitol can improve its thermal stability. The soluble and insoluble components of egg yolk and egg yolk containing xylitol treated at different temperatures were explored from the aspects of thermal instability behavior characterization and structure property. Magnetic resonance imaging and low field nuclear magnetic resonance showed that increased temperature induced liberation and transfer of hydrogen protons. Meanwhile, the apparent viscosity of soluble components increased, while that of insoluble components decreased. Microstructure showed that heat treatment induced aggregation and lipid transfer. SDS-PAGE showed that heat treatment induced aggregation and transformation of γ-livetin and apo-LDL. The change in crystal structure, Raman spectroscopy, and 3D fluorescence spectra showed that heat treatment resulted in the unfolding of yolk proteins, especially plasma proteins. Xylitol could alleviate transformation of components by stabilizing protein structure, alleviating the damage in protein integrity and elevation in aggregation size.

Naphthalimide-based probe as an in situ indicator of photochemical reaction for self-reporting imidazole ring formation

Fluorescent probes were promising ultrasensitive candidates in the sensing area. Herein, a fluorescent indicator bearing an active photochemical reactive site based on naphthalimide was designed and synthesized. Under UV irradiation, the photocyclization reaction to form imidazole occurred through the intramolecular addition reaction between α-amine and imine. This photochemical reaction was dynamically monitored in real time by significant fluorescence and UV spectrum changes. The reaction mechanism was further verified by NMR, MS, IR and free radical quenching reaction. The photocyclization reactions of analogous substrates based on this mechanism were also monitored by self-reporting spectrum changes.

Imidazole-based optical sensors as a platform for bisulfite sensing and BSA/HSA interaction study. An experimental and theoretical investigation

The fluorescent lapachones were obtained from lapachol, a natural product extracted from the heartwood of Tabebuia sp. (Tecoma). The extracted lapachol was oxidized and cyclized to obtain the compounds β-lapachone and nor-β-lapachone, and treatment with terephthalaldehyde led to the final products with ∼ 60% yield. The photophysical studies showed absorption maxima in the violet region (∼400 nm) and fluorescence emission maxima depending on the solvent, ranging from 430 to 575 nm with a relatively large positive solvatochromism, confirmed by the Lippert-Mataga plot. Theoretical calculations corroborate the experimental observations regarding the ICT mechanism. The imidazoles showed a selective response to bisulfite ion (HSO3−) over other common anions, displaying a large change in both fluorescence and absorption spectra immediately after the addition of bisulfite, proving their potential application in tracing the bisulfite in future biological systems. The binding capacity of the imidazoles with human or bovine serum albumin (HSA and BSA, respectively) is spontaneous, weak (102–103 M−1 range), and subdomains IIA (Site I) and IB (Site III) are the main binding regions for the imidazoles depending on the nature of the metabolite or drug previously complexed with the albumin structure. Overall, both albumins have the same capacity to interact with the imidazoles under study.

Oxidation of Cathepsin D by Hydroxy Radical: Its Effect on Enzyme Structure and Activity against Myofibrillar Proteins Extracted from Coregonus peled.

In this study, cathepsin D was oxidized in vitro with different concentrations of H2O2, and the activity, structure, and extent of myofibrillar protein degradation by oxidized cathepsin D were evaluated. The sulfhydryl content of cathepsin D decreased to 9.20% after oxidation, while the carbonyl content increased to 100.06%. The β-sheet in the secondary structure altered due to oxidation as well. The changes in the intrinsic fluorescence and UV absorption spectra indicated that oxidation could cause swelling and aggregation of cathepsin D molecules. The structure of cathepsin D could change its activity, and the activity was highest under 1 mM H2O2. Cathepsin D could degrade myofibrillar proteins in different treatment groups, and the degree of degradation is various. Therefore, this study could provide a scientific basis for the mechanism of interaction among hydroxyl radical oxidation, cathepsin D, and MP degradation.

Year-Round Testing of Coastal Waters of the Gulf of Gdańsk in the Baltic Sea for Detecting Oil in a Seawater Column Using the Fluorescence Method

Progressive climate changes and the increase in the occurrence of extreme weather phenomena indicate the need to take action to mitigate the negative effects of climate change. One of the main factors affecting climate change is the state of waters that transport heat. Oil pollution present in the water contributes to the absorption of radiation and physico-chemical changes in the sea, which has an impact on the marine ecosystem. This indicates the need to develop methods for effective oil spill detection. This study aimed to improve the methods of early detection of threats related to oil spills in the marine environment, especially when the source of oil may be invisible in the depths of the sea. Therefore, the method based on the fluorometric index is proposed, and its effectiveness for oil detection in seawater is studied. The study has answered the question of how biological activity during a whole year influences the effectiveness of oil detection by the proposed fluorometric index method. Therefore, for the calculation of the fluorometric index, the changes in the seawater fluorescence spectrum in the ultraviolet range were determined, which occurred under the influence of diffusion of some oil components in the sea. The principle of detection of oil contaminants based on the excitation-emission fluorescence spectrum is described. For the measurements, natural seawater samples used in the laboratory were exposed to a mixture of crude oil and oils commonly found in navigation. The effectiveness of oil substance detection using the fluorometric index in the biologically productive and unproductive seasons was analyzed for seawater in the vicinity of Gdynia and Gdansk ports in Poland in northern Europe. The results of excitation-emission spectra and fluorometric index indicate that the changes in the biological activity during the year do not affect the detectability of oil present in seawater for the considered oil-to-water ratio. Summarize the sensitivity analysis of the method indicates the possibility of detection of oil contamination regardless of the season. The obtained results pave the way for the construction of an underwater device to detect oil in the vicinity of such a detector.

Designing of efficient two-armed colorimetric and fluorescent indole appended organosilicon sensors for the detection of Al(III) ions: Implication as paper-based sensor

Metal ions have significant roles in diagnosis, industry, human health, and the environment. To design and develop new lucid molecular receptors for the selective detection of metal ions is important for environmental and medical applications. In the present work, two-armed indole appended Schiff bases conjoined with 1,2,3-Triazole bis-organosilane and bis-organosilatrane skelton sensors for naked eye colorimetric and fluorescent detection sensors for Al(III) are developed. The introduction of Al(III) in sensor 4 and 5 show red shift in UV–visible spectra, changes in fluorescence spectra and immediate color change from colorless to dark yellow. Furthermore, the pH and time response studies were explored for both sensors 4 & 5. The sensors 4 and 5 exhibited significantly low detection limit (LOD) in nano-molar range 1.41 × 10−9 M and 0.17 × 10−9 M respectively from emission titration. The LOD form absorption titration was found to be 0.6 × 10−7 M for sensor 4 and 0.22 × 10−7 M for sensor 5. In addition, the sensing model is developed as paper based sensor for its practical applicability. The theoretical calculations were performed on Gaussian 03 program by relaxing the structures using Density functional theory.

Performance of resin adsorption and ozonation pretreatment in mitigating organic fouling of reverse osmosis membrane

Effective pretreatment of reverse osmosis (RO) influent is of great importance for reducing membrane fouling risks during coking wastewater desalination. In this study, the combined resin adsorption and ozonation pretreatment was investigated on alleviating RO membrane organic fouling. The performance of combined process was compared with only resin adsorption or ozonation, which was evaluated in terms of changes in chemical oxygen demand (COD), ultraviolet-visible index, and three-dimensional excitation-emission matrix fluorescence spectra. RO membrane fouling tests were conducted to examine the effects of pretreatment on flux decline and filtration resistance. The surface morphology and functional groups of membrane before and after fouling was characterized by scanning electron microscopy and infrared spectroscopy. The correlation between major organic matter in the wastewater and normalized RO membrane flux was established via multiple linear regression equations. The results showed that ozonation was more effective in removing COD and fluorescent organics than resin adsorption. Moreover, the combined bifunctional resin adsorption/ozonation unit showed the best performance, with COD and UV254 removal rates of 49.4 % and 88.0 %, respectively. The fluorescence intensity of each component decreased significantly. Meanwhile, the polysaccharide and protein components of the RO membrane fouling layer were effectively reduced by 67.2 % and 80.8 %, respectively. Most importantly, the combined pretreatment substantially reduced the decline in membrane flux and filtration resistance. Meanwhile, the fulvic acid-like organics in the wastewater showed high correlations with normalized membrane flux. The regression equation was beneficial for RO membrane fouling evaluation.

Inhibitory Potential of α-Amylase, α-Glucosidase, and Pancreatic Lipase by a Formulation of Five Plant Extracts: TOTUM-63.

Controlling post-prandial hyperglycemia and hyperlipidemia, particularly by regulating the activity of digestive enzymes, allows managing type 2 diabetes and obesity. The aim of this study was to assess the effects of TOTUM-63, a formulation of five plant extracts (Olea europaea L., Cynara scolymus L., Chrysanthellum indicum subsp. afroamericanum B.L.Turner, Vaccinium myrtillus L., and Piper nigrum L.), on enzymes involved in carbohydrate and lipid absorption. First, in vitro inhibition assays were performed by targeting three enzymes: α-glucosidase, α-amylase, and lipase. Then, kinetic studies and binding affinity determinations by fluorescence spectrum changes and microscale thermophoresis were performed. The in vitro assays showed that TOTUM-63 inhibited all three digestive enzymes, particularly α-glucosidase (IC50 of 13.1 µg/mL). Mechanistic studies on α-glucosidase inhibition by TOTUM-63 and molecular interaction experiments indicated a mixed (full) inhibition mechanism, and higher affinity for α-glucosidase than acarbose, the reference α-glucosidase inhibitor. Lastly, in vivo data using leptin receptor-deficient (db/db) mice, a model of obesity and type 2 diabetes, indicated that TOTUM-63 might prevent the increase in fasting glycemia and glycated hemoglobin (HbA1c) levels over time, compared with the untreated group. These results show that TOTUM-63 is a promising new approach for type 2 diabetes management via α-glucosidase inhibition.

A cyanine carbazole oxime fluorescent probe selectively detects hypochlorite in Hi5 cells and C. elegans

Quantitative detection and visualization of hypochlorous acid (HClO) in biological samples has emerged as a hot topic in biochemical research because of the important role of this biomolecule in live organisms. In this contribution, a novel hemicyanine-based fluorescence probe, CVDI (1-ethyl-2-((E)-2-(9-ethyl-6-((E)-(hydroxyimino)methyl)-9H-carbazol-3-yl)vinyl)-3,3-dimethyl-3H-indol-1-ium), was designed and synthesized for HClO detection in aqueous solutions and in biological systems. In the presence of HClO, significant changes in absorption and fluorescence spectra were observed and the fluorescence response has increased by a factor of nine, which allow for the quantitative detection of HClO in PBS buffer. CVDI has excellent fluorescence properties: fast response time (20 s) and remarkable stability at wide pH range (7.0–10.0). The detection limit for HClO was determined to be 1.304 μM. Imaging of exogenous HClO in live Hi5 cells and C. elegans was then successfully performed using CVDI. We anticipate that CVDI could be employed for the diagnosis of pathological inflammation in clinic in near future.