Fluorescence Spectroscopic Studies Research Articles

2,6-Bis(5-(tert-butyl)-1H-pyrazol-3-yl)pyridine: Effects of the Peripheral Aliphatic Side Chain on the Coordination of Actinides(III) and Lanthanides(III).

To improve our understanding of the interaction mechanism in trivalent lanthanide and actinide complexes, studies with structurally different hard and soft donor ligands are of great interest. For that reason, the coordination chemistry of An(III) and Ln(III) with 2,6-bis(5-(tert-butyl)-1H-pyrazol-3-yl)pyridine (C4-BPP) has been explored. Time-resolved laser fluorescence spectroscopy (TRLFS) studies have revealed the formation of [Cm(C4-BPP)n]3+ (n = 1-3) (log β1' = 7.2 ± 0.4, log β2' = 10.1 ± 0.5, and log β3' = 11.8 ± 0.6) and [Eu(C4-BPP)m]3+ (m = 1-2) (log β1' = 4.9 ± 0.2 and log β2' = 8.0 ± 0.4). The absence of the [Eu(C4-BPP)3]3+ complex shows a more favorable complexation of Cm(III) over that of Eu(III). Additionally, complementary NMR measurements have been conducted to examine the M(III)-N bond in Ln(III) and Am(III) C4-BPP complexes. 15N NMR data have revealed notable differences in the chemical shifts of the coordinating nitrogen atoms between the Am(III) and Ln(III) complexes. In the Am(III) complex, the coordinating nitrogen atoms have shown a shift by 260 ppm, indicating a higher fraction of covalent bonding in the Am(III)-N bond compared with the Ln(III)-N bond. This observation aligns excellently with the differences in the stability constants obtained from TRLFS studies.

A mechanistic insight into the structure, conformational dynamics, affinity profile and energetics of Metanil yellow- serum protein complex

Metanil yellow (MYL) is a toxic azo dye extensively used in food preparations and in textile industry as major colorant. It affects important biological processes leading to development of toxicity in different organ systems. Toxicological profile assessment has also revealed its potential for multi-organ toxicity. This work investigates the affinity, energetics, and structural dynamics of MYL binding with Human serum albumin (HSA) in Thyroxine binding site using multi-spectroscopic techniques and molecular simulations. Fluorescence spectroscopic studies of MYL-HSA complex at different temperatures revealed that MYL binds with HSA with stronger affinity (∼27 kJ/mole). The overall binding showed significant static quenching and was entropy driven. Circular dichroism studies showed that the secondary structure of HSA remained predominantly alpha helix. To accommodate within the Tr5 region of HSA, MYL underwent minor alterations in its conformation and position facilitated by the subtle expansion of the binding site (∼2 Å). The role of water in providing stability to the complex via water bridges and hydrogen bonds has also been investigated. Quantum Mechanics studies further revealed that the minor strain observed in the pyramidalamino nitrogen assisted MYL in the complexation.

Encapsulation of three different types of polyphenols in casein using a customized pH-driven method: Preparation and characterization

Phenolic compounds represent natural compounds endowed with diverse biological functionalities. However, their inherent limitations, characterized by poor water solubility and low oral bioavailability, limit their broader applications. Encapsulation delivery systems are emerging as a remedy, able to ameliorate these limitations by enhancing the stability and solubility of phenolic compounds. In this study, a novel, customized pH-driven approach was developed by determining the optimal deprotonation and protonation points of three different types of polyphenols: ferulic acid, resveratrol, and rhein. The polyphenols were successfully encapsulated in a casein carrier. The solubility, stability, LogD, and LogS curves of the three polyphenols at different pH values were analyzed to identify the optimal deprotonation points for ferulic acid (pH 9), resveratrol (pH 11), and rhein (pH 10). Based on these findings, three different nanoparticles were prepared. The encapsulation efficiencies of the three phenolic compounds were 95.86%, 94.62%, and 94.18%, respectively, and the casein nanoparticles remained stable at room temperature for seven days. FTIR spectroscopy, fluorescence spectroscopy, and molecular docking study substantiated the encapsulation of phenolic compounds within the hydrophobic core of casein-based complexes, facilitated by hydrogen bonding interactions and hydrophobic interactions. Furthermore, the analysis of antioxidant activity elucidated that casein nanoparticles heightened both the water solubility and antioxidant efficacy of the phenolic compounds. This customized encapsulation technique, by establishing a transitional pH value, resolves the challenges of chemical instability and facile degradation of polyphenols under alkaline conditions in the application process of pH-driven methods. It presents novel insights for the application of polyphenols in the domains of food and biomedical fields.

Synthesis, Binding and Docking Studies of Indole‐1,3,4‐Thiadiazole Derivatives As Potent Α‐Amylase and Lox Inhibitors

AbstractSeries of indole‐1,3,4‐thiadiazole compounds (IT 1–7) were synthesized and characterized by FT‐IR, 1H NMR, 13C NMR and ESI‐MS spectral data. Further, the compounds (IT 1–7) were screened for antidiabetic, antioxidant and anti‐inflammatory activities. Most of these compounds exhibited moderate to good antidiabetic, antioxidant and anti‐inflammatory activities against α‐amylase enzyme, ABTS and lipoxygenase enzyme, respectively. Among these, IT‐1 displayed the better activity compared to that of standard drugs. The mechanism of binding of IT‐1, IT‐5 and IT‐6 with a transporter protein, human serum albumin was investigated by fluorescence spectroscopic and circular dichroism studies. These compounds quenched the intrinsic fluorescence intensity of HSA and moderate binding was evident from the values of binding constants which are in the order of 105 M−1. The molecular docking studies of the compounds were performed against human pancreatic alpha‐amylase in complex with montbretin A (PDB ID: 4W93). The studied compounds interacted with amino acid residues (ASP197, GLU240 and TYR151) which were similar to that of the reference drug, acarbose. The ADME properties of designed compounds were studied using SwissADME software. All the compounds obeyed Lipinski's rule of five. All the compounds showed low or non‐toxicity towards different toxicity classes as analyzed using ProTox‐II online tool.

Fluorescence Imaging Using Deep-Red Indocyanine Blue, a Complementary Partner for Near-Infrared Indocyanine Green.

Indocyanine Blue (ICB) is the deep-red pentamethine analogue of the widely used clinical near-infrared heptamethine cyanine dye Indocyanine Green (ICG). The two fluorophores have the same number of functional groups and molecular charge and vary only by a single vinylene unit in the polymethine chain, which produces a predictable difference in spectral and physicochemical properties. We find that the two dyes can be employed as a complementary pair in diverse types of fundamental and applied fluorescence imaging experiments. A fundamental fluorescence spectroscopy study used ICB and ICG to test a recently proposed Förster Resonance Energy Transfer (FRET) mechanism for enhanced fluorescence brightness in heavy water (D2O). The results support two important corollaries of the proposal: (a) the strategy of using heavy water to increase the brightness of fluorescent dyes for microscopy or imaging is most effective when the dye emission band is above 650 nm, and (b) the magnitude of the heavy water florescence enhancement effect for near-infrared ICG is substantially diminished when the ICG surface is dehydrated due to binding by albumin protein. Two applied fluorescence imaging studies demonstrated how deep-red ICB can be combined with a near-infrared fluorophore for paired agent imaging in the same living subject. One study used dual-channel mouse imaging to visualize increased blood flow in a model of inflamed tissue, and a second mouse tumor imaging study simultaneously visualized the vasculature and cancerous tissue in separate fluorescence channels. The results suggest that ICB and ICG can be incorporated within multicolor fluorescence imaging methods for perfusion imaging and hemodynamic characterization of a wide range of diseases.

Inhibition of Human Colorectal Cancer by a Natural Product 7-Acetylhorminone and Interactions with BSA/HSA: Multispectral Analysis and In Silico and In Vitro Studies.

We have semi-synthesized a natural product 7-acetylhorminone from crude extract of Premna obtusifolia (Indian headache tree), which is active against colorectal cancer after probation through computational screening methods as it passed through the set parameters of pharmacokinetics (most important nonblood-brain barrier permeant) and drug likeliness (e.g., Lipinski's, Ghose's, Veber's rule) which most other phytoconstituents failed to pass combined with docking with EGFR protein which is highly upregulated in the colorectal carcinoma cell. The structure of 7-acetylhorminone was confirmed by single crystal X-ray diffraction studies and 1H NMR, 13C NMR, and COSY studies. To validate the theoretical studies, first, in vitro experiments were carried out against human colorectal carcinoma cell lines (HCT116) which revealed the potent cytotoxic efficacy of 7-acetylhorminone and verified preliminary investigation. Second, the drugability of 7-acetylhorminone interaction with serum albumin proteins (HSA and BSA) is evaluated both theoretically and experimentally via steady-state fluorescence spectroscopic studies, circular dichroism, isothermal titration calorimetry, and molecular docking. In summary, this study reveals the applicability of 7-acetylhorminone as a potent drug candidate or as a combinatorial drug against colorectal cancer.

Unveiling large charge transfer character of PSII in an iron-deficient cyanobacterial membrane: A Stark fluorescence spectroscopy study.

In this work, we applied Stark fluorescence spectroscopy to an iron-stressed cyanobacterial membrane to reveal key insights about the electronic structures and excited state dynamics of the two important pigment-protein complexes, IsiA and PSII, both of which prevail simultaneously within the membrane during iron deficiency and whose fluorescence spectra are highly overlapped and hence often hardly resolved by conventional fluorescence spectroscopy. Thanks to the ability of Stark fluorescence spectroscopy, the fluorescence signatures of the two complexes could be plausibly recognized and disentangled. The systematic analysis of the SF spectra, carried out by employing standard Liptay formalism with a realistic spectral deconvolution protocol, revealed that the IsiA in an intact membrane retains almost identical excited state electronic structures and dynamics as compared to the isolated IsiA we reported in our earlier study. Moreover, the analysis uncovered that the excited state of the PSII subunit of the intact membrane possesses a significantly large CT character. The observed notably large magnitude of the excited state CT character may signify the supplementary role of PSII in regulative energy dissipation during iron deficiency.

Effects of Chrysin and Chrysin-7-sulfate on Ochratoxin A-Albumin Interactions and on the Plasma and Kidney Levels of the Mycotoxin in Rats.

The nephrotoxic mycotoxin ochratoxin A (OTA) is a common food contaminant. OTA binds to the Sudlow's Site I region of serum albumin with very high affinity, resulting in its slow elimination. The displacement of OTA from albumin may be beneficial due to the faster excretion of the mycotoxin, while it may also lead to the increased tissue uptake of OTA. Furthermore, it is challenging to displace the mycotoxin from albumin even with high-affinity Site I ligands. In this study, we tested the impacts of Site I and Heme site ligands on OTA-albumin interactions by applying fluorescence spectroscopic, ultracentrifugation, and modeling studies. Chrysin-7-sulfate (C7S) strongly displaced OTA from both human and rat albumins; therefore, the impacts of C7S (single intravenous administration) and the parent flavonoid chrysin (repeated peroral treatment) were examined on the plasma and kidney levels of OTA in rats. Chrysin barely influenced the concentrations of mycotoxin in plasma and kidneys. In the first few hours, C7S significantly decreased the plasma levels of OTA compared to the control animals; while after 24 h, only minor differences were noticed. Our study highlights the superior displacing ability of C7S vs OTA regarding human and rat albumins.

Mechanism for formation of porcine blood hydrogels used as additives in the mortar of traditional Chinese architectural painting

Ancient Chinese architecture drawing is a unique form of ancient Chinese art. Porcine blood hydrogels are distinctive ingredients used to prepare the composite material of the substrate layer for architecture drawing. This investigation was focused on the mechanism for porcine blood hydrogel formation. Based on the traditional Chinese recipe for the preparation of porcine blood-lime mortar, samples with different ratios of porcine blood and lime water were prepared, and the molecular-scale interactions between the lime water and proteins in the porcine blood were examined with FTIR spectroscopy, Raman spectroscopy, XRD, XPS, fluorescence spectroscopy, contact angle and rheology studies. The mechanical properties and morphological features of the samples were detected with a rheometer, universal material testing machine and SEM. The results indicated that an appropriate amount of lime water was required for gelation of the porcine blood. With the appropriate alkalinity, sufficient carboxyl groups on the fibrin chains were deprotonated, and coordination with Ca2+ ions formed enough cross-links for support networks within the structure of the porcine blood hydrogel. Complexation of deprotonated carboxyl groups on the fibrin chains with Ca2+ ions led to the formation of a hydrophobic surface due alterations of the fibrin conformation and increased the adhesive properties of the hydrogel. With the hydrogel used as an ingredient in the preparation of a substrate layer composite, it is suggested that the hydrophobic surface of the hydrogel facilitated mixing with hydrophobic tung oil during preparation of the composite material, and strong adhesion of the hydrogel increased the mechanical strength and crack resistance of the substrate layer.

Inhibition of fluorescent advanced glycation end-products by ferulic acid and chlorogenic acid: A fluorescence spectroscopy and molecular docking study

The effects of ferulic acid (FA) and chlorogenic acid (CGA) on fluorescent advanced glycation end-products (fAGEs) were investigated through the Maillard reaction. Model systems were incubated with different concentrations (0, 10, 20, 40, 80, and 160 μg/mL) of FA or CGA at 55 °C for 12 h, and fluorescence intensity of advanced glycation end-products (AGEs) was measured. After adding 160 μg/mL FA and CGA, the fluorescence intensity of AGEs was suppressed by 15.988% ± 0.556% and 16.544% ± 0.275%, respectively (P < 0.05). Compared with control group, free amino groups levels were the highest in model systems containing 160 μg/mL FA (0.096 ± 0.011 mg l-leucine equivalent/mL) and CGA (0.130 ± 0.000 mg l-leucine equivalent/mL) (P < 0.05). Carbonyls content decreased in a dose-dependent fashion with increasing concentrations of FA and CGA (P < 0.05). Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) results demonstrated that FA and CGA could impede the generation of bovine serum albumin (BSA)-glucose cross-linking substances. Spectroscopy results indicated that the binding constant of BSA-CGA was higher than that of BSA-FA. Meanwhile, molecular docking results suggested that the binding affinity of CGA to BSA was greater than to FA. These results suggested that CGA had a stronger inhibitory effect on the fluorescence intensity of AGEs. Therefore, FA and CGA may be potent natural antioxidants in mitigating the accumulation of AGEs during food thermal processing.

Characterization of the Binding Properties of Ten Aptamers Using the Intrinsic Fluorescence of Oxytetracycline.

Tetracyclines are a class of commonly used four-ringed antibiotics. A series of DNA aptamers were recently obtained using the capture-SELEX (systematic evolution of ligands by exponential enrichment) method to bind to oxytetracycline, and one of the aptamers can bind to a few other tetracycline antibiotics as well. Upon binding to the aptamers, the intrinsic fluorescence of tetracycline antibiotics can be enhanced. At least 10 different DNA aptamers were isolated from the previous selection experiment. In this work, a systematic characterization of these ten aptamers was performed. Each of these aptamers shows a different degree of fluorescence enhancement ranging from around 1-fold to over 20-fold. Fluorescence enhancement was boosted in the presence of Mg2+ . Isothermal titration calorimetry (ITC) studies were done and showed a great variety in dissociation constant (Kd ) from 62 nM to 1.6 μM. Steady-state fluorescence spectroscopy and fluorescence lifetime studies showed a correlation between fluorescence lifetime and degree of fluorescence enhancement. A few aptamers showed slow binding kinetics, although no correlation was found between the kinetics of fluorescence change and degree of fluorescence enhancement. This is the first study of ten different aptamers for the same target, providing fundamental insights into aptamer binding and bioanalytical applications.

Host-Guest Mechanism via Induced Fit Fullerene Complexation in Porphin Receptor to Probe Salivary Alpha-Amylase in Dental Caries for Clinical Applications.

Salivary α-amylase is the most abundant protein of human saliva that potentially binds to streptococcus and other bacteria via specific surface-exposed α-amylase-binding proteins and plays a significant role in caries development. The detection of α-amylase in saliva can be used as a bioindicator of caries development. Herein, a facile strategy has been applied, tailoring the photochemical properties of 5,10,15,20-tetrakis(4-hydroxyphenyl)-21H,23H-porphine (TPPOH) and the fullerene C60 complex. The fluorescence emission of TPPOH is quenched by starch-coated fullerene C60 via charge-transfer effects, as determined by UV absorption and fluorescence spectroscopic studies. The starch-coated C60 has been thoroughly characterized via Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), optical microscopy, thermal gravimetric analysis (TGA), static water contact angle measurements, and zeta potential measurements. The analytical response of the assay showed a linear fluorescent response in α-amylase concentrations ranging from 0.001-0.1 Units/mL, with an LOD of 0.001 Units/mL. The applicability of the method was tested using artificial saliva with quantitative recoveries in the range 95-100%. The practicability of the procedure was verified by inspecting saliva samples of real clinical samples covering all age groups. We believe that the proposed method can serve as an alternative analytical method for caries detection and risk assessment that would also minimize the cost of professional preventive measures and treatments.

Exploring Brilliant Blue FCF Assembly with Beta Cyclodextrin, Characterizations and Applications in Biological Systems Using Physicochemical and Computational Methods

AbstractThis research delvedinto the BrilliantBlue FCF (BB) dye encapsulation within the nano hydrophobic cavity of β‐cyclodextrin (β‐CD) utilizing various spectroscopic and physicochemical techniques. Job's plot using UV‐visible and Fluorescence spectroscopy, surface tension, and conductance study confirmed 1 : 1 stoichiometry of theinclusion complex (BBIC).1H NMR and FT‐IR studies demonstrated the possible binding mode of BB into the β‐CD cavity, which wasin good agreement withthe DFT study. The degree of affinity of β‐CD for BB in the ground state and excited state were estimatedfromUV‐visible andFluorescence spectroscopy(binding constant=8113.9451 M−1and10199.563 M−1), andthe negative free binding energyshowedthe encapsulation process to bethermodynamically feasible. PXRD analysis and SEM image studies revealed the formation of the BBIC. After complexation with β‐CD, the photostability of BB was found to be enhanced. The interaction study of BB and BBIC with CT‐DNA revealed the sustained release of BB from the complex. Furthermore, neither BBICnor free BB exhibited a significant cytotoxic effect on the normal cell line HEK‐293. However, BBIC complex (IC50=6.15 μM) showed significant in vitrocytotoxic activity compared to pure BB (IC50=8.90 μM) towards cancer cell line A549.

Identification of natural xanthine oxidase inhibitors: Virtual screening, anti-xanthine oxidase activity, and interaction mechanism

Xanthine oxidase (XO) is a crucial target for hyperuricemia treatment(s). Naturally occurred XO inhibitors with minimal toxicity and high efficacy have attracted researchers' attention. With the goal of quickly identifying natural XO inhibitors, an integrated computational screening strategy was constructed by molecular docking and calculating the free energy of binding. Twenty-seven hits were achieved from a database containing 19,377 natural molecules. This includes fourteen known XO inhibitors and four firstly-reported inhibitors (isolicoflavonol, 5,7-dihydroxycoumarin, parvifolol D and clauszoline M, IC50 < 40 μM). Iolicoflavonol (hit 8, IC50 = 8.45 ± 0.68 μM) and 5,7-dihydroxycoumarin (hit 25, IC50 = 10.91 ± 0.71 μM) displayed the great potency as mixed-type inhibitors. Docking study and molecular dynamics simulation revealed that both hits could interact with XO's primarily active site residues ARG880, MOS1328, and ASN768 of XO. Fluorescence spectroscopy studies showed that hit 8 bound to the active cavity region of XO, causing changes in XO's conformation and hydrophobicity. Hits 8 and 25 exhibit favorable Absorption, Distribution, Metabolism, and Excretion (ADME) properties. Additionally, no cytotoxicity against human liver cells was observed at their median inhibition concentrations against XO. Therefore, the present study offers isolicoflavonol and 5,7-dihydroxycoumarin with the potential to be disease-modifying agents for hyperuricemia.

Bioactive porphyrin magnesium (II) complex. Synthesis, molecular structure and spectroscopic characterization. Biological activity and molecular docking studies

We have synthesized and characterized porphyrin structures by UV–visible, IR and fluorescence spectroscopy studies and single crystal XRD analysis; H2(TPP) (I) (meso-tetraphenylporphyrin), [Mg(TPP)(DMF)] (II); (DMF: dimethylformamide) and [Mg(TPP)(H2O)]0.2(4-CNpy) (III); (4-CNpy: 4-Cyanopyridine). The crystal packing of the porphyrin structures is stabilized by intermolecular hydrogen bonds and by intermolecular CH⋯Cg π interactions where Cg is the centroid of the phenyl and pyrrole rings. UV–Vis spectroscopic data confirmed the creation of Mg-meso-porphyrin complexes by the red-shifted Soret bands for our derivatives compared to the free-base porphyrin. The optical gap energy values of (I), (II) and (III) are 1.92, 2.07 and 2.00 eV. Gram-positive and Gram-negative bacteria were tested against free porphyrin (I), metallated porphyrin (II) and complex (III). The results show that the magnesium porphyrin derivative is highly effective compared to H2TPP free-base porphyrins and metallated porphyrin [Mg(TPP)] and has higher inhibition character against the tested bacteria. The molecular docking of the complex (III), in the active sites of bacterial proteins was carried out to detect the degree of antibacterial activity of recognition.

Thermodynamics of the Eu(III)-Mg-SO4-H2O and Eu(III)-Na-SO4-H2O systems. Part II: spectroscopy experiments, complexation and Pitzer/SIT models.

A time-resolved laser fluorescence spectroscopy (TRLFS) study was carried out to investigate the Eu(III)-SO4 complexation at room temperature over a wide range of Na2SO4 concentrations (0-2 mol kg-1). Spectroscopic observations confirm the step-wise formation of the aqueous complexes Eu(SO4)+, Eu(SO4)2- and Eu(SO4)33- over the investigated Na2SO4 concentrations. Combining TRLFS data obtained in this study and solubility data reported in Part I of this work for the Eu2(SO4)3-Na2SO4-H2O and Eu2(SO4)3-MgSO4-H2O systems, thermodynamic and activity models were derived based on the SIT and Pitzer formalisms. A combination of the geochemical calculation codes PhreeqC (SIT), PhreeSCALE (Pitzer) and the parameter estimation code PEST was used to determine the solubility products of Eu2(SO4)3·8H2O(cr) and Na2Eu2(SO4)4·2H2O(cr), stability constants of the Eu(III)-SO4 complexes (β0i), and the specific binary and ternary interaction parameters (εij, β(0)ij, β(1)ij, Cϕij, θik, Ψijk) for both activity models. The thermodynamic constants determined in this work are discussed with reference to values available in the literature.

Dendrimer Induced Bilayer Disintegration of Hybrid Vesicles.

Physicochemical investigations on the inclusion of anionic polyamidoaminesuccinamic acid dendrimer, generation 5 (PAMAM-SA, G5) with positively charged hybrid vesicles (HCV), prepared using soylecithin, ion pair amphiphile (IPA), cholesterol and dihexadecyldimethylammonium bromide, were investigated by dynamic light scattering, transmission electron/atomic force microscopy (TEM/AFM), differential scanning calorimetry, fluorescence spectroscopy and surface pressure-time isotherm studies. Adsorption of dendrimer onto vesicle surface and subsequent bilayer disruption strongly depends on the bilayer composition and dendrimer concentration. Change in the zeta potential value with increasing dendrimer concentration suggests the dendrimer-vesicle interaction to be electrostatic in nature. AFM studies also confirm the adsorption of dendrimer as well as hole formation in the bilayer. Impact of the inclusion of dendrimer into the bilayer were further investigated through differential scanning calorimetry by monitoring the chain melting temperature and enthalpy of the chain melting processes. Dendrimer at low concentration does not alter bilayer integrity, while hole formations are noted at higher dendrimer concentration. Fluorescence anisotropy studies confirm the adsorption and subsequent bilayer disruption due to dendrimer inclusion. Dendrimer induced vesicle disintegration kinetics conclusively illustrate the transformation of cationic bilayer to monolayer and thereby exposing the role of IPA. In vitro cytotoxicity studies on PAMAM-SA, G5 and HCVs mixtures against human breast cancer cell line suggest that dendrimer-liposome aggregates (dendriosomes) exhibit substantial anticancer activities with insignificant side effects. It is expected that the dendriosomes may have application to host and deliver anticancer drug in the field of targeted drug delivery.

Comparison of In Vivo Study of Co-Polarized and Cross-Polarized Fluorescence Spectroscopy to Co-Minus Cross-Polarized Fluorescence Spectroscopy to Diagnose Precancerous Cervical Lesions by Handheld Probe

Comparison of In Vivo Study of Co-Polarized and Cross-Polarized Fluorescence Spectroscopy to Co-Minus Cross-Polarized Fluorescence Spectroscopy to Diagnose Precancerous Cervical Lesions by Handheld Probe

Rotaxane-Functionalized Dyes for Charge-Rectification in p-Type Photoelectrochemical Devices.

A supramolecular photovoltaic strategy is applied to enhance power conversion efficiencies (PCE) of photoelectrochemical devices by suppressing electron-hole recombination after photoinduced electron transfer (PET). Here, the author exploit supramolecular localization of the redox mediator-in close proximity to the dye-through a rotaxane topology, reducing electron-hole recombination in p-type dye-sensitized solar cells (p-DSSCs). Dye PRotaxane features 1,5-dioxynaphthalene recognition sites (DNP-arms) with a mechanically-interlocked macrocyclic redox mediator naphthalene diimide macrocycle (3-NDI-ring), stoppering synthetically via click chemistry. The control molecule PStopper has stoppered DNP-arms, preventing rotaxane formation with the 3-NDI-ring. Transient absorption and time-resolved fluorescence spectroscopy studies show ultrafast (211 ± 7 fs and 2.92 ± 0.05ps) PET from the dye-moiety of PRotaxane to its mechanically interlocked 3-NDI-ring-acceptor, slowing down the electron-hole recombination on NiO surfaces compared to the analogue . p-DSSCs employing PRotaxane (PCE = 0.07%) demonstrate a 30% PCE increase compared to PStopper (PCE = 0.05%) devices, combining enhancements in both open-circuit voltages (VOC = 0.43 vs 0.36V) and short-circuit photocurrent density (JSC = -0.39vs -0.34mA cm-2 ). Electrochemical impedance spectroscopy shows that PRotaxane devices exhibit hole lifetimes (τh ) approaching 1 s, a 16-fold improvement compared to traditional I- /I3 - -based systems (τh = 50ms), demonstrating the benefits obtained upon nanoengineering of interfacial dye-regeneration at the photocathode.

A comparative study of fluorescence and Raman spectroscopy for discrimination of virgin olive oil categories: Chemometric approaches and evaluation against other techniques

Spectroscopic techniques are presented as a reliable and economical alternative for the discrimination of olive oil quality categories. In this work, fluorescence and Raman spectroscopic techniques have been compared by evaluating different characteristics focused on sample preparation and analysis time, as well as classification percentages by chemometric models (PLS-DA) to classify olive oils into three categories: extra virgin (EVOO), virgin (VOO), and lampante (LOO). A statistical evaluation of the quality of the chemometric models was performed by comparing the parameters of sensitivity in terms of the true positive rate (%TPR), specificity (or true negative rate %TNR), and classification error in calibration, cross-validation and prediction. Fluorescence spectroscopy was the screening technique with the best overall accuracy in the ternary models for prediction (78.60%), with higher results than those obtained by Raman (66.03%), the latter being below the average error in the tasting panels. Regarding the classification obtained in binary models (EVOO/Non-EVOO and LOO/Non-LOO), fluorescence spectroscopy continued to present better results than Raman, with classifications of 92.5% and 88.5 % for both models, respectively (Raman obtained percentages of 70.7% and 66.6%). A comparison of the results obtained with confirmation techniques (headspace-gas chromatography-ion mobility spectrometry, HS-GC-IMS) and other spectroscopic techniques (NIR and MIR) studied in previous research was carried out, where it was observed that fluorescence spectroscopy obtained the closest classification percentage to the HS-GC-IMS technique (86.4%) in ternary models. On the other hand, the NIR technique obtained the highest classification percentage in binary models, with 92.6% for EVOO/Non-EVOO and 88.9% for LOO/Non-LOO compared to the value obtained using GC-IMS (95.4 and 86.4 %). Evaluating the rest of the parameters of interest for the olive industry, IR (both NIR and MIR) was the most interesting technique because it is a cheap, simple sensor with fast chemometric treatments and is environmentally-friendly. The results of this comparative study can be used to provide solutions and alternatives for applying new analytical strategies to support the work of tasting panels.