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13 pages, 4035 KiB  
Communication
Use of Laccase Enzymes as Bio-Receptors for the Organic Dye Methylene Blue in a Surface Plasmon Resonance Biosensor
by Araceli Sánchez-Álvarez, Gabriela Elizabeth Quintanilla-Villanueva, Osvaldo Rodríguez-Quiroz, Melissa Marlene Rodríguez-Delgado, Juan Francisco Villarreal-Chiu, Analía Sicardi-Segade and Donato Luna-Moreno
Sensors 2024, 24(24), 8008; https://doi.org/10.3390/s24248008 (registering DOI) - 15 Dec 2024
Viewed by 108
Abstract
Methylene blue is a cationic organic dye commonly found in wastewater, groundwater, and surface water due to industrial discharge into the environment. This emerging pollutant is notably persistent and can pose risks to both human health and the environment. In this study, we [...] Read more.
Methylene blue is a cationic organic dye commonly found in wastewater, groundwater, and surface water due to industrial discharge into the environment. This emerging pollutant is notably persistent and can pose risks to both human health and the environment. In this study, we developed a Surface Plasmon Resonance Biosensor employing a BK7 prism coated with 3 nm chromium and 50 nm of gold in the Kretschmann configuration, specifically for the detection of methylene blue. For the first time, laccases immobilized on a gold surface were utilized as bio-receptors for this organic dye. The enzyme was immobilized using carbodiimide bonds with EDC/NHS crosslinkers, allowing for the analysis of samples with minimal preparation. The method demonstrated validation with a limit of detection (LOD) of 4.61 mg L−1 and a limit of quantification (LOQ) of 15.37 mg L−1, a working range of 0–100 mg L−1, and an R2 value of 0.9614 during real-time analysis. A rainwater sample spiked with methylene blue yielded a recovery rate of 122.46 ± 4.41%. The biosensor maintained a stable signal over 17 cycles and remained effective for 30 days at room temperature. Full article
(This article belongs to the Section Biosensors)
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Figure 1
<p>Chemical structure of methylene blue.</p>
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<p>Possible recognition process and first step of degradation of methylene blue by laccases.</p>
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<p>Immobilization process of laccases on the thin chromium–gold film chip. In the step 1, alkanethiols are added to the thin gold surface. In step 2, the EDC is added, forming an unstable intermediate. In step 3, the NHS is added, creating a sulfo-NHS ester. In step 4, NHS is replaced by the laccase through an amide bond.</p>
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<p>Assembly of the prism and the chip on the SPR equipment: (<b>a</b>) assembly of the prism, the chip with a thin gold film with the immobilized laccases, the prism and other components. (<b>b</b>) Set up of the prism, sample cell, chip with immobilized laccases and the other on the SPR equipment.</p>
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<p>Reflectance spectra obtained by angular sweep.</p>
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<p>Immobilization process of laccass from <span class="html-italic">Rhus vernicifera</span> in real-time by SPR.</p>
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<p>FTIR analysis of different stages of laccase immobilization.</p>
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<p>(<b>a</b>) SPR analysis of stocks with different concentrations of methylene blue. (<b>b</b>) Calibration curve and equation of a straight line.</p>
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<p>Comparison of the intensity of reflectance of solutions of methylene blue at day 1 and day 30.</p>
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17 pages, 10169 KiB  
Article
Controlling the Morphology of Poly(ethylene glycol)-b-poly(lactide) Self-Assemblies in Solution: Interplay of Homopolymer Additives and Kinetic Traps
by Pei Qi Lim, Srirangam Ramanujam Vaibavi, Atul N. Parikh, Subbu Venkatraman and Bertrand Czarny
Nanomaterials 2024, 14(24), 2015; https://doi.org/10.3390/nano14242015 (registering DOI) - 14 Dec 2024
Viewed by 279
Abstract
This study investigates the effects of homopolymer additives and kinetic traps on the self-assembly of poly(ethylene glycol)-b-poly(lactide) (PEG-PLA) block copolymer (BCP) nanostructures in aqueous environments. By using non-adsorbing PEG homopolymers to kinetically trap PEG-PLA nanostructures, we demonstrate that varying the concentration and molecular [...] Read more.
This study investigates the effects of homopolymer additives and kinetic traps on the self-assembly of poly(ethylene glycol)-b-poly(lactide) (PEG-PLA) block copolymer (BCP) nanostructures in aqueous environments. By using non-adsorbing PEG homopolymers to kinetically trap PEG-PLA nanostructures, we demonstrate that varying the concentration and molecular weight of the added PEG induces a reversible micelle-to-vesicle transition. This transition is primarily driven by changes in the molecular geometry of the PEG-PLA BCPs due to excluded volume screening effects. Additionally, the reversible vesicle-to-micelle transition upon PEG’s removal shows time and temperature dependency, highlighting the influence of the system’s kinetic nature. Intermediate structures observed during the transition support a mechanism based on shifts in the molecular geometry of PEG-PLA. As a proof of concept, we show that PEG-PLA vesicles can act as thermoresponsive delivery systems, retaining dye at low temperatures (4 °C) and releasing it upon heating (37 °C). Overall, this work presents a novel approach to controlling BCP nanostructures’ morphology, with implications for drug delivery and material science applications. Full article
(This article belongs to the Section Biology and Medicines)
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Figure 1
<p>Transmission electron microscopy (TEM) images of PEG-PLA structures formed in deionized water with varying PEG molecular weights and concentrations (<b>A</b>) PEG2k dissolved in deionized water at concentrations of (i) 0.5% <span class="html-italic">w</span>/<span class="html-italic">w</span>, (ii) 0.7% <span class="html-italic">w</span>/<span class="html-italic">w</span>, and (iii) 1.0% <span class="html-italic">w</span>/<span class="html-italic">w</span>. (<b>B</b>) PEG6k dissolved in deionized water at concentrations of (i) 0.1% <span class="html-italic">w</span>/<span class="html-italic">w</span>, (ii) 0.3% <span class="html-italic">w</span>/<span class="html-italic">w</span>, and (iii) 0.5% <span class="html-italic">w</span>/<span class="html-italic">w</span>. (<b>C</b>) PEG10k dissolved in deionized water at concentrations of (i) 0.1% <span class="html-italic">w</span>/<span class="html-italic">w</span>, (ii) 0.3% <span class="html-italic">w</span>/<span class="html-italic">w</span>, and (iii) 0.5% <span class="html-italic">w</span>/<span class="html-italic">w</span>. Scale bars are indicated on individual panels.</p>
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<p>TEM images of PEG-PLA vesicles after incubation at 4 °C, 37 °C, and 60 °C for 1 h and 24 h, depicting the resulting structural changes under each condition.</p>
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<p>In situ monitoring of the samples’ turbidity upon incubation at various temperatures (30 °C, 40 °C and 50 °C) for 30 mins. (<b>a</b>) Photos showing the turbidity of PEG-PLA samples before and after the incubation process. (<b>b</b>) Plot of normalized absorbance at 600 nm (to track changes in turbidity) against time for each of the different samples.</p>
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<p>TEM images depicting the shape transition of PEG-PLA vesicles incubated at 37 °C over a 6 h period. The images show key intermediate stages of the transition, including porated vesicles at 15 min, a “jellyfish” structure at 30 min with an open bilayer and elongated edges, and irregular clumps with extended protrusions observed after 3 h. These intermediates illustrate the progressive transformation of vesicles into micelles, capturing the dynamic structural changes during the vesicle-to-micelle conversion.</p>
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<p>(<b>a</b>) Diagram illustrating the morphological transitions of PEG-PLA structures at varying PEG concentrations and molecular weights (MW), as determined by transmission electron microscopy (TEM). The blue regions on the bars indicate samples in which micelles (spherical or cylindrical) were observed, while the red regions highlight samples with vesicle formation. The transition zone, where both micelles and vesicles coexist, is represented between the blue and red areas. The dotted line marks the estimated boundary of this transition across different PEG concentrations and molecular weights. (<b>b</b>) DSC analysis of PEG-PLA structures formed in deionized water.</p>
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<p>Diagram illustrating the proposed mechanism for shape transition driven by the screening of the excluded volume effect. The schematic shows changes in PEG chain size and BCP geometry with increasing PEG concentrations. Red represents the hydrophobic PLA block, blue represents the hydrophilic PEG block, and green represents the added free PEG homopolymers.</p>
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<p>Schematic representation of the proposed pathway for the transition of PEG-PLA vesicles into micelles. The illustration details the sequential structural changes that occur during the transition process. The hydrophilic PEG block is represented by blue, while the hydrophobic PLA block of the BCPs is depicted in red. The pathway begins with pore formation in the vesicles, leading to a curved, open lamella structure. This structure evolves into a “jellyfish” configuration, characterized by an expanded pore and frayed edges that extend into elongated protrusions. As the process continues, these protrusions elongate further, and the bilayer structure recedes, ultimately resulting in the complete dissociation of the bilayer and stabilization of the micellar structures. This schematic highlights the relationship between the packing geometry of the BCPs and the observed morphological transitions.</p>
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<p>Effect of different homopolymer additives (PEG10k, Dextran10k, and PVP10k) at various concentrations on PEG-PLA nanostructures. (<b>a</b>) TEM images of PEG-PLA structures formed with each homopolymer at increasing concentrations, with red arrows indicating large aggregates. Note that due to the limited TEM field of view, larger aggregates may not be fully captured in a single image. Scale bar: 200 nm (<b>b</b>) DLS measurements comparing the Z-average size (Z-Avg) and polydispersity index (PDI) of PEG-PLA structures. Note: The symbol “^” denotes samples flagged by the DLS software as too polydisperse, suggesting that measurements may be unreliable. (<b>c</b>) Schematic illustrating the potential influence of different homopolymer additives on the self-assembly of PEG-PLA block copolymers, resulting in distinct final nanostructures.</p>
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<p>Results of the release experiment for PEG-PLA vesicles incubated at different temperatures. (<b>a</b>) DLS analysis of the Z-average (Z-Avg) and polydispersity index (PDI) for samples before and after a 72 h release experiment. Statistically significant differences (<span class="html-italic">p</span> ≤ 0.05) are indicated by *, and datasets without statistically significant differences (<span class="html-italic">p</span> &gt; 0.05) are marked with #. (<b>b</b>) Release profile of NaFluo dye from PEG-PLA vesicles, with the initial release rate calculated from data collected during the first 3 h.</p>
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21 pages, 4985 KiB  
Article
DSSCs Sensitized with Phenothiazine Derivatives Containing 1H-Tetrazole-5-acrylic Acid as an Anchoring Unit
by Muhammad Faisal Amin, Paweł Gnida, Jan Grzegorz Małecki, Sonia Kotowicz and Ewa Schab-Balcerzak
Materials 2024, 17(24), 6116; https://doi.org/10.3390/ma17246116 (registering DOI) - 14 Dec 2024
Viewed by 204
Abstract
Phenothiazine-based photosensitizers bear the intrinsic potential to substitute various expensive organometallic dyes owing to the strong electron-donating nature of the former. If coupled with a strong acceptor unit and the length of N-alkyl chain is appropriately chosen, they can easily produce high efficiency [...] Read more.
Phenothiazine-based photosensitizers bear the intrinsic potential to substitute various expensive organometallic dyes owing to the strong electron-donating nature of the former. If coupled with a strong acceptor unit and the length of N-alkyl chain is appropriately chosen, they can easily produce high efficiency levels in dye-sensitized solar cells. Here, three novel D-A dyes containing 1H-tetrazole-5-acrylic acid as an acceptor were synthesized by varying the N-alkyl chain length at its phenothiazine core and were exploited in dye-sensitized solar cells. Differential scanning calorimetry showed that the synthesized phenothiazine derivatives exhibited behavior characteristic of molecular glasses, with glass transition and melting temperatures in the range of 42–91 and 165–198 °C, respectively. Based on cyclic and differential pulse voltammetry measurements, it was evident that their lowest unoccupied molecular orbital (LUMO) (−3.01–−3.14 eV) and highest occupied molecular orbital (HOMO) (−5.28–−5.33 eV) values were fitted to the TiO2 conduction band and the redox energy of I/I3 in electrolyte, respectively. The experimental results were supported by density functional theory, which was also utilized for estimation of the adsorption energy of the dyes on the TiO2 and its size. Finally, the compounds were tested in dye-sensitized solar cells, which were characterized based on current–voltage measurements. Additionally, for the compound giving the best photovoltaic response, the efficiency of the DSSCs was optimized by a photoanode modification involving the use of cosensitization and coadsorption approaches and the introduction of a blocking layer. Subsequently, two types of tandem dye-sensitized solar cells were constructed, which resulted in an increase in photovoltaic efficiency to 6.37%, as compared to DSSCs before modifications, with a power conversion value of 2.50%. Full article
(This article belongs to the Special Issue Advances in Solar Cell Materials and Structures—Second Edition)
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Figure 1
<p><sup>1</sup>H NMR spectra of (<b>a</b>) <b>PETA</b>, (<b>b</b>) <b>PBTA</b>, and (<b>c</b>) <b>POTA</b>.</p>
Full article ">Figure 1 Cont.
<p><sup>1</sup>H NMR spectra of (<b>a</b>) <b>PETA</b>, (<b>b</b>) <b>PBTA</b>, and (<b>c</b>) <b>POTA</b>.</p>
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<p>(<b>a</b>) DSC thermogram of <b>PETA</b>. (<b>b</b>) Thermal investigation data of compounds starting from phenothiazine.</p>
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<p>The voltammograms of the (<b>a</b>) reduction and oxidation process measured in the cyclic voltammetry method and (<b>b</b>) voltammograms of the oxidation process measured in the differential pulse voltammetry method (GC, 0.1 mol/dm<sup>3</sup> Bu<sub>4</sub>NPF<sub>6</sub> in DMF, 100 mV/s; the dashed lines mean reduction, and the solid lines mean oxidation).</p>
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<p>Molecular electrostatic potential surfaces on the molecules of the dyes (scale range −7.03 × 10<sup>−2</sup> (red) to 7.03 × 10<sup>−2</sup> (blue) neural and −0.19 a.u. (red) to 0.19 a.u (blue) anionic form).</p>
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<p>Adsorption of the dyes on Ti<sub>30</sub>O<sub>66</sub>H<sub>12</sub> cluster calculated in acetonitrile solutions (values calculated in the gas phase are given in brackets).</p>
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<p>Adsorption of the dyes on Ti<sub>30</sub>O<sub>66</sub>H<sub>12</sub> cluster calculated in acetonitrile solutions (values calculated in the gas phase are given in brackets).</p>
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<p>UV–Vis absorption spectra of the dyes (<b>a</b>) in solution form (c = 2 × 10<sup>−5</sup> mol dm<sup>−3</sup>), (<b>b</b>) adsorbed on TiO<sub>2</sub> surface, and (<b>c</b>) PL spectra of the dyes in solution form.</p>
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<p>Block diagram of ongoing research on DSSCs.</p>
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<p>(<b>a</b>) J–V curves for DSSCs sensitized with PTZ dyes and N719 with and without BL. (<b>b</b>) Schematic energy level diagram of dyes under vacuum in terms of eV.</p>
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<p>J–V characteristics of tandem DSSCs with (<b>a</b>) FTO/BL/TiO<sub>2</sub>@<b>POTA</b> photoanode in top cell, (<b>b</b>) FTO/BL/TiO<sub>2</sub>@<b>POTA</b> photoanode in bottom cell.</p>
Full article ">Scheme 1
<p>Scheme of the designed dyes synthesis. (<b>i</b>) Acetone, TBAI, reflux 24 h. (<b>ii</b>) DMF, POCl<sub>3</sub>, 1,2-dichloroethane, reflux 24 h. (<b>iii</b>) Diethylamine, 1H-tetrazole-5-acetic acid, CH<sub>3</sub>CN, reflux 24 h.</p>
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22 pages, 8100 KiB  
Article
Optically Controlled Drug Delivery Through Microscale Brain–Machine Interfaces Using Integrated Upconverting Nanoparticles
by Levente Víg, Anita Zátonyi, Bence Csernyus, Ágoston C. Horváth, Márton Bojtár, Péter Kele, Miklós Madarász, Balázs Rózsa, Péter Fürjes, Petra Hermann, Orsolya Hakkel, László Péter and Zoltán Fekete
Sensors 2024, 24(24), 7987; https://doi.org/10.3390/s24247987 (registering DOI) - 14 Dec 2024
Viewed by 231
Abstract
The aim of this work is to incorporate lanthanide-cored upconversion nanoparticles (UCNP) into the surface of microengineered biomedical implants to create a spatially controlled and optically releasable model drug delivery device in an integrated fashion. Our approach enables silicone-based microelectrocorticography (ECoG) implants holding [...] Read more.
The aim of this work is to incorporate lanthanide-cored upconversion nanoparticles (UCNP) into the surface of microengineered biomedical implants to create a spatially controlled and optically releasable model drug delivery device in an integrated fashion. Our approach enables silicone-based microelectrocorticography (ECoG) implants holding platinum/iridium recording sites to serve as a stable host of UCNPs. Nanoparticles excitable in the near-infrared (lower energy) regime and emitting visible (higher energy) light are utilized in a study. With the upconverted higher energy photons, we demonstrate the induction of photochemical (cleaving) reactions that enable the local release of specific dyes as a model system near the implant. The modified ECoG electrodes can be implanted in brain tissue to act as an uncaging system that releases small amounts of substance while simultaneously measuring the evoked neural response upon light activation. In this paper, several technological challenges like the surface modification of UCNPs, the immobilization of particles on the implantable platform, and measuring the stability of integrated UCNPs in in vitro and in vivo conditions are addressed in detail. Besides the chemical, mechanical, and optical characterization of the ready-to-use devices, the effect of nanoparticles on the original electrophysiological function is also evaluated. The results confirm that silicone-based brain–machine interfaces can be efficiently complemented with UCNPs to facilitate local model drug release. Full article
(This article belongs to the Special Issue Sensing Technologies in Neuroscience and Brain Research)
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<p>Schematic representation of the surface modification steps.</p>
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<p>Uncaging (photocleavage) mechanism after NIR light exposure of the UCNPs.</p>
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<p>The molecular structure of TetPPG-Rhod, the click and the uncaging process [<a href="#B44-sensors-24-07987" class="html-bibr">44</a>]. NMR spectrum of the dye system can be found in the <a href="#app1-sensors-24-07987" class="html-app">Supporting Information</a> of the cited article.</p>
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<p>Contact angle of the modified silicone (PDMS) model substrate. (<b>a</b>) Bare substrate, (<b>b</b>) plasma treated substrate, (<b>c</b>) NPTES-treated substrate, (<b>d</b>) BCN-NHS-modified substrate (scalebars indicate 1 mm).</p>
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<p>FTIR spectra recorded after each modification step of a PDMS disk. (<b>a</b>) Bare substrate, (<b>b</b>) plasma-treated substrate, (<b>c</b>) NPTES-treated substrate.</p>
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<p>SEM images of the UCNP-ECoG system. (<b>a</b>) The whole probe surface with numbered recording sites, (<b>b</b>) a closer look at recording site 9 at larger magnification, (<b>c</b>) UCNP coverage on the substrate surface near site 4, (<b>d</b>) particles detected with Matlab, near site 4 (white scalebars show 1 mm, 50 µm and 2 µm, respectively).</p>
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<p>EIS measurements of the ECoG systems, represented on Bode plots. (<b>a</b>) Resistance (magnitude) of the unmodified and UCNP-modified ECoGs, (<b>b</b>) reactance (phase angle) of the unmodified and UCNP-modified ECoGs.</p>
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<p>Fluorescence spectroscopy measurements of the ECoG systems. (<b>a</b>) RFI (relative fluorescent intensity) changes due to the IR laser irradiation, (<b>b</b>) Observing the effect of natural light vs. IR laser light on the system.</p>
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<p>Averages of the image histograms of 2P images taken on sample regions of unmodified PDMS discs and a fully modified UCNP-ECoG device with different light intensities. The histograms of UCNP devices (orange, 1.72 mW; red, 8.6 mW) show increased fluorescence on these images, suggesting successful uncaging.</p>
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<p>Sample in vivo electrophysiological recording with a UCNP-modified ECoG device from a ketamine–xylazine anesthetized mouse, showing characteristic oscillations evoked by the anesthesia. The 8 traces are simultaneous recordings from the 8 channels of the device. The signal is low pass filtered to below 150 Hz. 50 Hz line-frequency noise was band-stop filtered.</p>
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21 pages, 2721 KiB  
Article
Exploring Imaging Applications of a Red-Emitting π-Acceptor (π-A) Pyrene-Benzothiazolium Dye
by Chathura S. Abeywickrama, Enya Huang, Wenhui Yan, Michael A. Vrionides, Paaramitha Warushavithana, Kristen A. Johnson, Robert V. Stahelin, Yi Pang, Tomoyasu Mani and Kaveesha J. Wijesinghe
Biosensors 2024, 14(12), 612; https://doi.org/10.3390/bios14120612 - 13 Dec 2024
Viewed by 279
Abstract
Bright biocompatible fluorescent imaging dyes with red to near-infrared (NIR) emissions are ideal candidates for fluorescence microscopy applications. Pyrene–benzothiazolium hemicyanine dyes are a new class of lysosome-specific probes reported on recently. In this work, we conduct a detailed implementation study for a pyrene–benzothiazolium [...] Read more.
Bright biocompatible fluorescent imaging dyes with red to near-infrared (NIR) emissions are ideal candidates for fluorescence microscopy applications. Pyrene–benzothiazolium hemicyanine dyes are a new class of lysosome-specific probes reported on recently. In this work, we conduct a detailed implementation study for a pyrene–benzothiazolium derivative, BTP, to explore its potential imaging applications in fluorescence microscopy. The optical properties of BTP are studied in intracellular environments through advanced fluorescence microscopy techniques, with BTP exhibiting a noticeable shift toward blue (λem ≈ 590 nm) emissions in cellular lysosomes. The averaged photon arrival time (AAT)-based studies exhibit two different emissive populations of photons, indicating the probe’s dynamic equilibrium between two distinctively different lysosomal microenvironments. Here, BTP is successfully utilized for time-lapse fluorescence microscopy imaging in real-time as a ‘wash-free’ imaging dye with no observed background interference. BTP exhibits an excellent ability to highlight microorganisms (i.e., bacteria) such as Bacillus megaterium through fluorescence microscopy. BTP is found to be a promising candidate for two-photon fluorescence microscopy imaging. The two-photon excitability of BTP in COS-7 cells is studied, with the probe exhibiting an excitation maximum at λTP ≈ 905 nm. Full article
(This article belongs to the Special Issue Advanced Fluorescence Biosensors)
12 pages, 3700 KiB  
Article
Improvement of Dye-Sensitized Solar Cell Performance via Addition of Azopyridine Derivative in Polymer Gel Electrolytes
by Muhammad Faisal Amin, Paweł Gnida, Jolanta Konieczkowska, Magdalena Szubka and Ewa Schab-Balcerzak
Materials 2024, 17(24), 6107; https://doi.org/10.3390/ma17246107 - 13 Dec 2024
Viewed by 208
Abstract
In this study, a polymer gel electrolyte based on polyacrylonitrile was synthesized with varying polymer-to-liquid-electrolyte ratios. DSSCs incorporating a 1:3 ratio showed optimum PV parameters. Choosing this proportion, the effect of incorporating the photoresponsive AZO dye into this polymer electrolyte was studied. When [...] Read more.
In this study, a polymer gel electrolyte based on polyacrylonitrile was synthesized with varying polymer-to-liquid-electrolyte ratios. DSSCs incorporating a 1:3 ratio showed optimum PV parameters. Choosing this proportion, the effect of incorporating the photoresponsive AZO dye into this polymer electrolyte was studied. When irradiated with a UV light of 365 nm, the AZO dye underwent photoisomerization, which allowed the gel electrolyte to absorb heat from the UV irradiation and increase its ionic conductivity. It was found that by the addition of azopyridine into the polymer electrolyte, there was an improvement in the photovoltaic parameters of cells. By increasing the dye content from 1% to 10% by weight in the electrolyte, an 11% growth in short current density was observed, resulting in about a 10% rise in cell efficiency. Full article
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<p>Chemical structure of the dyes used in this study.</p>
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<p>Synthesis scheme of AZO dye.</p>
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<p>Schematic representation of PGE synthesis without AZO dye.</p>
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<p>Schematic representation of dye-sensitized solar cell fabrication process.</p>
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<p>SEM pictures of the (<b>a</b>) azopyridine-derived polymer matrix morphology during electrolyte preparation and (<b>b</b>) photoanode.</p>
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<p>J–V curves of dye-sensitized solar cells incorporating PGEs of varying redox concentrations.</p>
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<p>UV-vis spectra of AZO dye in different solvents (c = 10<sup>−5</sup> mol/L).</p>
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<p>Current density–voltage characteristics of the prepared DSSCs.</p>
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45 pages, 16580 KiB  
Review
Bisindole Compounds—Synthesis and Medicinal Properties
by Maria Marinescu
Antibiotics 2024, 13(12), 1212; https://doi.org/10.3390/antibiotics13121212 - 13 Dec 2024
Viewed by 680
Abstract
The indole nucleus stands out as a pharmacophore, among other aromatic heterocyclic compounds with remarkable therapeutic properties, such as benzimidazole, pyridine, quinoline, benzothiazole, and others. Moreover, a series of recent studies refer to strategies for the synthesis of bisindole derivatives, with various medicinal [...] Read more.
The indole nucleus stands out as a pharmacophore, among other aromatic heterocyclic compounds with remarkable therapeutic properties, such as benzimidazole, pyridine, quinoline, benzothiazole, and others. Moreover, a series of recent studies refer to strategies for the synthesis of bisindole derivatives, with various medicinal properties, such as antimicrobial, antiviral, anticancer, anti-Alzheimer, anti-inflammatory, antioxidant, antidiabetic, etc. Also, a series of natural bisindole compounds are mentioned in the literature for their various biological properties and as a starting point in the synthesis of other related bisindoles. Drawing from these data, we have proposed in this review to provide an overview of the synthesis techniques and medicinal qualities of the bisindolic compounds that have been mentioned in recent literature from 2010 to 2024 as well as their numerous uses in the chemistry of materials, nanomaterials, dyes, polymers, and corrosion inhibitors. Full article
(This article belongs to the Section Novel Antimicrobial Agents)
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Graphical abstract

Graphical abstract
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<p>Material applications of indole and bisindole compounds with medicinal properties reported in the literature [<a href="#B24-antibiotics-13-01212" class="html-bibr">24</a>,<a href="#B25-antibiotics-13-01212" class="html-bibr">25</a>,<a href="#B26-antibiotics-13-01212" class="html-bibr">26</a>,<a href="#B27-antibiotics-13-01212" class="html-bibr">27</a>,<a href="#B28-antibiotics-13-01212" class="html-bibr">28</a>,<a href="#B29-antibiotics-13-01212" class="html-bibr">29</a>,<a href="#B30-antibiotics-13-01212" class="html-bibr">30</a>,<a href="#B31-antibiotics-13-01212" class="html-bibr">31</a>,<a href="#B32-antibiotics-13-01212" class="html-bibr">32</a>,<a href="#B33-antibiotics-13-01212" class="html-bibr">33</a>,<a href="#B34-antibiotics-13-01212" class="html-bibr">34</a>,<a href="#B35-antibiotics-13-01212" class="html-bibr">35</a>,<a href="#B36-antibiotics-13-01212" class="html-bibr">36</a>,<a href="#B37-antibiotics-13-01212" class="html-bibr">37</a>,<a href="#B38-antibiotics-13-01212" class="html-bibr">38</a>].</p>
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<p>Natural bisindolic compounds with various therapeutic properties.</p>
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<p>Medicinal properties of bisindolic compounds.</p>
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<p>The structures of <span class="html-italic">bis</span>(indolyl)methanes <b>62</b>–<b>67</b> with antimicrobial properties.</p>
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<p>The structures of <span class="html-italic">bis</span>(indolyl)methanes <b>68</b>–<b>70</b> with antimicrobial properties.</p>
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<p>The structures of bisindoles <b>76</b>–<b>84</b> with antimicrobial properties.</p>
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<p>The structures of bisindoles <b>86</b>–<b>87</b> with antimicrobial properties.</p>
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<p>The structures of bisindole compounds <b>94</b>–<b>98</b> with antimicrobial properties.</p>
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<p>Binding mode of compound <b>100e</b> and active site residue in isoform 1 of Bcl-2. Adapted from [<a href="#B149-antibiotics-13-01212" class="html-bibr">149</a>].</p>
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<p>The structures of bisindole compounds <b>102</b>–<b>105</b> with antitubercular properties.</p>
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<p>The structures of bisindole compounds <b>106</b>–<b>111</b> with antimalarial properties.</p>
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<p>The structures of bisindole compounds <b>112</b>–1<b>38</b> with antileishmanial properties.</p>
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<p>(<b>a</b>) Binding mode of the most active compounds in pteridine reductase active site. (<b>b</b>) Binding mode of compound <b>119</b> (green color) in comparison with pentamidine (blue color). Adapted from [<a href="#B161-antibiotics-13-01212" class="html-bibr">161</a>].</p>
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<p>Bisindoles with antiviral properties.</p>
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<p>Docked pose of <b>142</b> in the hydrophobic pocket of gp41 (PDB 2xra), allowing movement of side chains of Gln 575 and Trp 571. A salt bridge from one carbonyl oxygen on the ligand to Lys574-εNH<sub>2</sub> is shown as an orange dotted line, and a hydrogen bond is predicted from the second carbonyl oxygen to the lysine eNH<sub>2</sub>. Adapted from [<a href="#B167-antibiotics-13-01212" class="html-bibr">167</a>].</p>
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<p>Bisindoles with anticancer properties.</p>
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<p>Possible binding mode of the most potent compounds and target proteins. Binding modes of the cocrystallized ligand Ibrutinib (orange), compound <b>152</b> (green), and <b>153</b> (magenta) against the anticancer target EGFR (PDB ID: 5YU9). Adapted from [<a href="#B178-antibiotics-13-01212" class="html-bibr">178</a>].</p>
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<p>Dock pose of indole derivatives <b>154</b> and <b>155</b> with Bcr-Abl and GSK-3β proteins. Adapted from [<a href="#B179-antibiotics-13-01212" class="html-bibr">179</a>].</p>
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<p>Bisindoles <b>157</b>–<b>162</b> with anticancer properties.</p>
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<p>Molecular orbital energy-generated 2D interaction plot of bisindoles (<b>a</b>) <b>161</b>; (<b>b</b>) <b>162</b>. Adapted from [<a href="#B160-antibiotics-13-01212" class="html-bibr">160</a>].</p>
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<p>Bisindoles <b>168</b>–<b>179</b> as MARK4 inhibitors.</p>
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<p>Bisindoles <b>182</b>–<b>193</b> with anti-inflammatory properties.</p>
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<p>Bisindoles <b>194</b>–<b>197</b> with anti-inflammatory activity.</p>
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<p>Bisindoles <b>200</b>–<b>197</b> with anti-Alzheimer properties.</p>
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<p>(<b>a</b>) A 2D interaction diagram of compound <b>205</b> within the binding site of MAO-A (PDB ID = 2Z5X); (<b>b</b>) 2D interaction diagram of compound <b>205</b> within the binding site of MAO-B (PDB ID = 2V5Z). Adapted from [<a href="#B195-antibiotics-13-01212" class="html-bibr">195</a>].</p>
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<p>Bisindole <b>209</b> with antioxidant properties.</p>
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<p>Bisindoles <b>212</b>–<b>219</b> with antidiabetic properties.</p>
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<p>Bisindoles <b>221a</b> and <b>221b</b> as carbonic anhydrase II inhibitors.</p>
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<p>Synthesis of bis(indolyl)methanes <b>3</b> using different catalysts.</p>
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<p>Synthesis of bis(indolyl)methanes <b>6</b> by LiO<span class="html-italic">t</span>-Bu-promoted alkylation of indoles <b>4</b>.</p>
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<p>Synthesis of bis(indolyl)methane phosphonates <b>9</b> using In(OTf)<sub>3</sub> as catalyst.</p>
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<p>Synthesis of 3,3-bis(indol-3-yl)propanoates <b>12</b> FeCl<sub>3</sub>/AgOTf as catalyst.</p>
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<p>Synthesis of bis(indolyl)methanes <b>14</b> from indole <b>1</b> and ketones [<a href="#B107-antibiotics-13-01212" class="html-bibr">107</a>,<a href="#B108-antibiotics-13-01212" class="html-bibr">108</a>,<a href="#B109-antibiotics-13-01212" class="html-bibr">109</a>].</p>
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<p>Synthesis of bis(indolyl)methanes <b>16</b> from indole <b>1</b> and electron-deficient alkenes <b>15</b>.</p>
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<p>Synthesis of bis(indolyl)methanes <b>19</b> using a domino reaction.</p>
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<p>Synthesis of <span class="html-italic">homo</span>-bisindolylmethanes <b>22</b> using RMgX <b>21</b> as reactant.</p>
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<p>Synthesis of <span class="html-italic">homo</span>-bis(indolyl)methanes <b>25</b> using RLi <b>24</b> as reactant.</p>
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<p>Synthesis of <span class="html-italic">homo</span>-bis(indolylmethanes) <b>28</b> using alkynyl lithium reagents <b>27</b> as reactants.</p>
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<p>Synthesis of bis(indolyl) oximes <b>31</b> via hetero-Diels-Alder reaction.</p>
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<p>Synthesis of bis(indolyl) hydrazones <b>34</b> via hetero-Diels-Alder reaction.</p>
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<p>Synthesis of bisindoles <b>37</b> using a multicomponent reaction.</p>
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<p>Synthesis of 3,3-bis(1<span class="html-italic">H</span>-indol-3-yl)indolin-2-ones <b>40</b>.</p>
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<p>Synthesis of isatin bisindoles <b>43</b>.</p>
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<p>Synthesis of acenaphthene bisindoles <b>46</b>.</p>
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<p>Synthesis of acenaphthene bisindoles <b>48</b>.</p>
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<p>Synthesis of acenaphthene bisindoles <b>51</b>.</p>
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<p>Synthesis of amide bisindoles <b>54</b>, <b>55</b>, and <b>57</b>.</p>
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<p>Synthesis of O,O′-dimethyl scalaridine A <b>62</b>.</p>
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<p>Synthesis of bisindoles <b>74</b> and <b>75</b>.</p>
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<p>Synthesis of antimicrobial bisindoles <b>93</b>.</p>
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<p>Synthesis of antileishmanial bisindoles <b>112</b>–<b>138</b>.</p>
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<p>Synthesis of antileishmanial seleno-bisindole <b>139</b>.</p>
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<p>Synthesis of anti-HIV-1 bisindoles <b>140a</b>–<b>140m</b>.</p>
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<p>Synthesis of anticancer bisindoles <b>148</b> and <b>149</b>.</p>
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<p>Synthesis of anticancer bisindoles <b>154</b>–<b>156</b>.</p>
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<p>Synthesis of anticancer bisindoles <b>180</b>–<b>181</b>.</p>
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<p>Synthesis of anti-Alzheimer bisindole <b>204</b>.</p>
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<p>Synthesis of antioxidant bisindole <b>210</b>.</p>
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<p>Synthesis of antidiabetic bisindole <b>211</b>.</p>
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<p>Synthesis of antidiabetic bisindole <b>213</b>.</p>
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<p>Synthesis of analgesic bisindoles <b>220a</b> and <b>220b</b>.</p>
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15 pages, 3605 KiB  
Article
Restoring Multidrug-Resistant Escherichia coli Sensitivity to Ampicillin in Combination with (−)-Epigallocatechin Gallate
by Anong Kiddee, Atchariya Yosboonruang, Achiraya Siriphap, Grissana Pook-In, Chittakun Suwancharoen, Acharaporn Duangjai, Ratsada Praphasawat, Masami Suganuma and Anchalee Rawangkan
Antibiotics 2024, 13(12), 1211; https://doi.org/10.3390/antibiotics13121211 - 13 Dec 2024
Viewed by 501
Abstract
Multidrug-resistant (MDR) bacteria, especially Escherichia coli, are a major contributor to healthcare-associated infections globally, posing significant treatment challenges. This study explores the efficacy of (−)-epigallocatechin gallate (EGCG), a natural constituent of green tea, in combination with ampicillin (AMP) to restore the effectiveness [...] Read more.
Multidrug-resistant (MDR) bacteria, especially Escherichia coli, are a major contributor to healthcare-associated infections globally, posing significant treatment challenges. This study explores the efficacy of (−)-epigallocatechin gallate (EGCG), a natural constituent of green tea, in combination with ampicillin (AMP) to restore the effectiveness of AMP against 40 isolated MDR E. coli strains. Antimicrobial activity assays were conducted to determine the minimum inhibitory concentrations (MIC) of EGCG using the standard microdilution technique. Checkerboard assays were employed to assess the potential synergistic effects of EGCG combined with AMP. The pharmacodynamic effects of the combination were evaluated through time-kill assays. Outer membrane disruption was analyzed by measuring DNA and protein leakage and with assessments using N-phenyl-1-naphthylamine (NPN) and rhodamine 123 (Rh123) fluorescence dyes. Biofilm eradication studies involved biofilm formation assays and preformed biofilm biomass and viability assays. Scanning electron microscopy (SEM) was used to examine changes in cellular morphology. The results indicated that EGCG demonstrated activity against all isolates, with MICs ranging from 0.5 to 2 mg/mL, while AMP exhibited MIC values between 1.25 and 50 mg/mL. Importantly, the EGCG-AMP combination showed enhanced efficacy compared to either treatment alone, as indicated by a fractional inhibitory concentration index between 0.009 and 0.018. The most pronounced synergy was observed in 13 drug-resistant strains, where the MIC for EGCG dropped to 8 µg/mL (from 1 mg/mL alone) and that for AMP to 50 µg/mL (from 50 mg/mL alone), achieving a 125-fold and 1000-fold reduction, respectively. Time-kill assays revealed that the bactericidal effect of the EGCG-AMP combination occurred within 2 h. The mechanism of EGCG action includes the disruption of membrane permeability and biofilm eradication in a dose-dependent manner. SEM confirmed that the combination treatment consistently outperformed the individual treatments. This study underscores the potential of restoring AMP efficacy in combination with EGCG as a promising strategy for treating MDR E. coli infections. Full article
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Figure 1
<p>Effect of EGCG-AMP combination on MDR <span class="html-italic">E. coli</span> E48 strain. Time-kill kinetics for EGCG, ampicillin (AMP), and their combination were analyzed. Bacterial samples were taken at 1, 2, 4, 8, 16, and 24 h to measure viable cell counts. Dashed bars indicate the bactericidal threshold.</p>
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<p>Effect of EGCG-AMP combination on membrane permeability. The <span class="html-italic">E. coli</span> E48 strain was exposed to EGCG alone (at 1×, 2×, and 4× MIC), AMP alone, or the EGCG-AMP combination for 1 h at 37 °C. DNA (<b>a</b>) and protein (<b>b</b>) levels were measured. The relative fluorescence intensity (RFI) of NPN (<b>c</b>) and Rh123 (<b>d</b>) was also assessed. Triton X-100 (0.1%) served as the positive control (TX). Significant differences compared to untreated controls are indicated by asterisks (*** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Effect of EGCG-AMP combination on biofilm formation. The <span class="html-italic">E. coli</span> E48 strain was exposed to EGCG alone (at 1×, 2×, and 4× MIC), AMP alone, or the EGCG-AMP combination for biofilm formation assays, as well as assays measuring preformed biofilm biomass and viability. Biofilm formation (<b>a</b>) and preformed biofilm (<b>b</b>) were evaluated using crystal violet staining. The viability of preformed biofilm (<b>c</b>) was assessed via the MTT assay. Significant differences compared to untreated controls are indicated by asterisks (* <span class="html-italic">p</span> &lt; 0.05, *** <span class="html-italic">p</span> &lt; 0.001).</p>
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<p>Effect of EGCG-AMP combination on bacterial cell morphology. The <span class="html-italic">E. coli</span> E48 strain was exposed for 4 h at 37 °C to either EGCG or AMP alone, and to their combination. Scanning electron microscopy (SEM) images at a magnification of 25,000× illustrate (<b>a</b>) the control; (<b>b</b>) EGCG at a concentration of 1 mg/mL; (<b>c</b>) AMP at a concentration of 50 mg/mL; and (<b>d</b>) treatment with the EGCG-AMP combination (EGCG 0.008 mg/mL + AMP 0.05 mg/mL).</p>
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13 pages, 8828 KiB  
Article
Multispectral Imaging and OCT-Guided Precision Treatment of Rhinophyma with CO2 and Dye Lasers: A Comprehensive Diagnostic and Therapeutic Approach
by Simone Amato, Steven Paul Nisticò, Alessandro Clementi, Giorgio Stabile, Fortunato Cassalia, Annunziata Dattola, Giuseppe Rizzuto and Giovanni Cannarozzo
Cosmetics 2024, 11(6), 221; https://doi.org/10.3390/cosmetics11060221 - 13 Dec 2024
Viewed by 322
Abstract
Background/Objectives: Rhinophyma, an advanced form of rosacea, is characterized by significant nasal tissue enlargement and deformation, leading to aesthetic and psychosocial challenges. Traditional treatments are often invasive with variable outcomes, emphasizing the need for improved therapeutic approaches. This study evaluates the efficacy of [...] Read more.
Background/Objectives: Rhinophyma, an advanced form of rosacea, is characterized by significant nasal tissue enlargement and deformation, leading to aesthetic and psychosocial challenges. Traditional treatments are often invasive with variable outcomes, emphasizing the need for improved therapeutic approaches. This study evaluates the efficacy of a dual-laser therapy (CO2 and dye lasers) in treating rhinophyma. An innovative diagnostic algorithm using multispectral imaging guided treatment decisions, while Optical Coherence Tomography (OCT) was utilized to analyze post-treatment vascular and collagen changes. Methods: A prospective study was conducted involving 20 patients with rhinophyma. Multispectral imaging was used to guide the tailored application of CO2 laser, dye laser, or both, depending on the predominant vascular or glandular components in the nasal tissue. Post-treatment analysis employed OCT to assess changes in vascular and collagen density, providing insights into the tissue modifications induced by laser therapy. Results: The treatment significantly reduced vascular density from 35,526.75 to 26,577.55 at 300 microns and from 46,916.25 to 35,509.25 at 500 microns. Collagen density decreased from 81.35 to 66.34. All reductions were statistically significant, with highly significant p-values. These findings highlight the dual-laser therapy’s effectiveness in addressing the pathological features of rhinophyma. Conclusions: Dual-laser therapy guided by multispectral imaging provides a targeted and effective treatment for rhinophyma, addressing its vascular and glandular components. The use of OCT enhances understanding of laser-induced tissue changes and confirms significant reductions in vascular and collagen density. This approach represents a significant advancement in the management of rhinophyma, offering improved precision and therapeutic outcomes. Full article
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Figure 1
<p>Vertical image captured at the depth of 46 mm displays the pre-treatment condition with evident vascularization, particularly a uniform red vascular blotch in the middle third of the nose’s dorsum. The green line indicates the depth of the skin being analyzed, while the blue symbols mark the area of focus.</p>
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<p>Vertical image captured at the depth of 46 mm. It shows the disappearance of the vascular feature in the post-treatment phase, underscoring the effectiveness of the combined CO<sub>2</sub> and dye laser therapy in reducing vascular abnormalities and improving the skin texture and structure in rhinophyma. The green line indicates the depth of the skin being analyzed, while the blue symbols mark the area of focus.</p>
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<p>Pixel density measurement on horizontal D-OCT 6 × 6 mm image. In this example of pixel density measurement on horizontal D-OCT 6 × 6 mm images, we used the ‘ImageJ’ software, a tool for image processing and analysis in Java, available for free in its 2014 version from the USA. This approach allows for the counting of pixels after reducing ‘background noise’ through a color saturation threshold set at 190 points. Pixel counting is performed by the software using the ‘measure analysis’ command, with outcomes displayed in a results box, which is highlighted here with a red square. Importantly, this image was acquired at a depth of 300 microns, allowing for the clear visualization of vascular structures.</p>
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<p>D-OCT imaging at a depth of 300 microns. (<b>a</b>) pre laser treatment; (<b>b</b>) post laser treatment.</p>
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<p>D-OCT imaging at a depth of 500 microns. (<b>a</b>) before laser treatment; (<b>b</b>) post laser treatment.</p>
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<p>D-OCT imaging at a depth of 500 microns. Pixel density measurement on horizontal D-OCT 6 × 6 mm image pre- (<b>a</b>) and post- (<b>b</b>) dye laser treatment. The figure demonstrates the reduction of vascular patterns following the application of dye laser treatment.</p>
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<p>Collagen density pre-treatment. Density value: 52.301688. The area within the white rectangle is the one analyzed.</p>
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<p>(<b>a</b>) Vascular rhinophyma at baseline; (<b>b</b>) typical post-PDL purpura after dye laser; (<b>c</b>) rhinophyma after CO<sub>2</sub> laser.</p>
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<p>(<b>a</b>) Vascular rhinophyma before treatment; (<b>b</b>) rhinophyma after laser therapy.</p>
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<p>Multispectral analysis: (<b>a</b>) vascular rhinophyma at baseline; (<b>b</b>) rhinophyma after dye laser and CO<sub>2</sub> laser.</p>
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28 pages, 12272 KiB  
Article
New Derivatives of Chalcones, Chromenes, and Stilbenoids, Complexed with Methyl-β-Cyclodextrin with Antioxidant Properties and Antibacterial Synergism with Antibiotics
by Igor D. Zlotnikov, Sergey S. Krylov, Natalya G. Belogurova, Alexander N. Blinnikov, Victor E. Kalugin and Elena V. Kudryashova
Biophysica 2024, 4(4), 667-694; https://doi.org/10.3390/biophysica4040044 - 13 Dec 2024
Viewed by 226
Abstract
Cyclodextrins (CDs) are natural cyclic oligosaccharides with the ability to form inclusion complexes with various organic substances. In this paper, we investigate the potential of CD complex formation to enhance the antibacterial activity and antioxidant properties of poorly soluble bioactive agents, such as [...] Read more.
Cyclodextrins (CDs) are natural cyclic oligosaccharides with the ability to form inclusion complexes with various organic substances. In this paper, we investigate the potential of CD complex formation to enhance the antibacterial activity and antioxidant properties of poorly soluble bioactive agents, such as chalcones, chromenes, stilbenoids and xanthylium derivatives, serving as potential adjuvants, in comparison with standard antiseptics. The interaction of these bioactive agents with the hydrophobic pocket of methyl-β-cyclodextrin (MCD) was confirmed using spectroscopic methods such as UV-vis, FTIR, 1H and 13C NMR, mass-spectrometry. CD-based delivery system allows for combining multiple active agents, improving solubility, antibacterial efficacy by enhancing penetration into target bacterial cells (E. coli selectivity demonstrated via confocal microscopy). Novel compounds of chalcones and stilbenoids derivatives additionally enhance efficacy by inhibiting bacterial efflux pumps, increasing membrane permeability, and inhibiting bacterial enzymes, and showed a synergy when used in combination with metronidazole. The intricate relationship between the structural characteristics and functional properties of chalcones and stilbenoids in terms of their antibacterial and antioxidative capabilities is revealed. The substituents within aromatic rings significantly influence this activity, where position of electron-donating methoxy groups playing a crucial role. Among chalcones, stilbenoids, ana xanthyliums, the compounds caring a benzodioxol ring, analogous to natural bioactive compounds like apiol, dillapiol, and myristicin, emerge as prominent antibacterial activity. To explore the possibility to create theranostic formulations, we used fluorescent markers to visualize target cells, antiseptics to provide antibacterial activity, and bioactive agents as chalcones acting as adjuvants. Additionally, new antioxidant compounds were found such as Xanthylium derivative (R351) and chromene derivative: 1-methyl-3-(2-amino-3-cyano-7-methoxychromene-4-yl)-pyridinium methanesulfate: the pronounced antioxidant properties of these substances are observed comparable to quercetin in the efficiency. Rhodamine 6G, gentian violet, and Congo Red exhibit good antioxidant properties, although their activity is an order of magnitude lower than that of quercetin. However, they have remarkable potential due to their multifaceted nature, including the ability to visualize target cells. The most effective theranostic formulation is the combination of the antibiotic (metronidazole) + dye/fluorophore (methylene blue/rhodamine 6G) for visualization of target cells + adjuvant (chalcones or xanthylium derivatives) for antiinflammation effect. This synergistic combination, results in a promising theranostic formulation for treating bacterial infections, with enhanced efficiency, selectivity and minimizing side effects. Full article
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Figure 1
<p>UV/vis absorption spectra of the investigated dyes and chalcones in free form in a buffer solution and complexed with methyl-cyclodextrin (MCD): (<b>a</b>) Congo Red 8 µM; (<b>b</b>) Methylene blue 15 µM; (<b>c</b>) Malachite green 10 µM; (<b>d</b>) R351-ClO<sub>4</sub><sup>−</sup> 2.5 µM; (<b>e</b>) sample 9–50 µM; (<b>f</b>) Brilliant green 35 µM, toluidine blue 5 µM, gentian violet 3 µM, sudan III 7 µM. PBS (0.01M, pH 7.4). DMSO could be added to enhance the solubility of free samples. T = 37 °C.</p>
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<p>UV/vis absorption spectra of the investigated dyes and chalcones in free form in a buffer solution and complexed with methyl-cyclodextrin (MCD): (<b>a</b>) Congo Red 8 µM; (<b>b</b>) Methylene blue 15 µM; (<b>c</b>) Malachite green 10 µM; (<b>d</b>) R351-ClO<sub>4</sub><sup>−</sup> 2.5 µM; (<b>e</b>) sample 9–50 µM; (<b>f</b>) Brilliant green 35 µM, toluidine blue 5 µM, gentian violet 3 µM, sudan III 7 µM. PBS (0.01M, pH 7.4). DMSO could be added to enhance the solubility of free samples. T = 37 °C.</p>
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<p>FTIR spectra of the investigated «drug candidates» in free form in a buffer solution and complexed with methyl-cyclodextrin (MCD): (<b>a</b>) chalcone (9), (<b>b</b>) 1-methyl-3-(2-amino-3-cyano-7-methoxychromene-4-yl)-pyridinium methanesulfate (17). PBS (0.01M, pH 7.4). T = 37 °C.</p>
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<p><sup>1</sup>H NMR spectra of the «drug candidate» sample 9: (<b>a</b>) in free form in d<sub>6</sub>-DMSO; (<b>b</b>) complexed with methyl-cyclodextrin (MCD) (1:5 mol/mol) in D<sub>2</sub>O with predicted peak correlations. T = 25 °C. (<b>c</b>) The proposed structure of the chalcone 9—MCD complex obtained during computer modeling. Carbon atoms are indicated in green (MCD) and blue (the guest molecule, compound <b>9</b>); oxygen atoms are indicated in red. hydrogen—white, sulfur—yellow, nitrogen—blue. The purple sphere is Na<sup>+</sup>. The simulation was performed using the PyMOL program. (<b>d</b>) Schematic cyclodextrin torus representation.</p>
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<p><sup>1</sup>H NMR spectra of the «drug candidate» sample 9: (<b>a</b>) in free form in d<sub>6</sub>-DMSO; (<b>b</b>) complexed with methyl-cyclodextrin (MCD) (1:5 mol/mol) in D<sub>2</sub>O with predicted peak correlations. T = 25 °C. (<b>c</b>) The proposed structure of the chalcone 9—MCD complex obtained during computer modeling. Carbon atoms are indicated in green (MCD) and blue (the guest molecule, compound <b>9</b>); oxygen atoms are indicated in red. hydrogen—white, sulfur—yellow, nitrogen—blue. The purple sphere is Na<sup>+</sup>. The simulation was performed using the PyMOL program. (<b>d</b>) Schematic cyclodextrin torus representation.</p>
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<p>ABTS antioxidant test of the “drug candidates” complexed with methyl-cyclodextrin (MCD) (1:5 mol/mol): (<b>a</b>) Dyes and fluorophores; (<b>b</b>) Chalcone and stilbene derivatives. PBS (0.01M, pH 7.4). T = 37 °C.</p>
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<p>ABTS antioxidant test of the “drug candidates” complexed with methyl-cyclodextrin (MCD) (1:5 mol/mol): (<b>a</b>) Dyes and fluorophores; (<b>b</b>) Chalcone and stilbene derivatives. PBS (0.01M, pH 7.4). T = 37 °C.</p>
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<p>The structures of the drug candidates in the relationships with antioxidant and antibacterial properties. The circles highlight significant fragments of molecules.</p>
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<p>Confocal laser scanning microscopy images of (<b>a</b>,<b>b</b>) <span class="html-italic">E. coli</span> cells and (<b>c</b>,<b>d</b>) <span class="html-italic">Lactobacilli</span> cells, stained with R6G (10 µg/mL) in free form or complexed with MCD (100 µg/mL). λexci, max = 488 nm, λemi = 530–580 nm. The scale bar is 20 µm.</p>
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<p>Synthesis scheme of compound <b>17</b>.</p>
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<p>Synthesis scheme of Xanthylium derivatives R351 salts compounds.</p>
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<p>Synthesis scheme of the chalcone and stilbenoid derivatives.</p>
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11 pages, 5810 KiB  
Article
Reading Dye-Based Colorimetric Inks: Achieving Color Consistency Using Color QR Codes
by Ismael Benito-Altamirano, Laura Engel, Ferran Crugeira, Miriam Marchena, Jürgen Wöllenstein, Joan Daniel Prades and Cristian Fàbrega
Chemosensors 2024, 12(12), 260; https://doi.org/10.3390/chemosensors12120260 - 13 Dec 2024
Viewed by 254
Abstract
Color consistency when reading colorimetric sensors is a key factor for this technology. Here, we demonstrate how the usage of machine-readable patterns, like QR codes, can be used to solve the problem. We present our approach of using back-compatible color QR codes as [...] Read more.
Color consistency when reading colorimetric sensors is a key factor for this technology. Here, we demonstrate how the usage of machine-readable patterns, like QR codes, can be used to solve the problem. We present our approach of using back-compatible color QR codes as colorimetric sensors, which are common QR codes that also embed a set of hundreds of color references as well as colorimetric indicators. The method allows locating the colorimetric sensor within the captured scene and to perform automated color correction to ensure color consistency regardless of the hardware used. To demonstrate it, a CO2-sensitive colorimetric indicator was printed on top of a paper-based substrate using screen printing. This indicator was formulated for Modified Atmosphere Packaging (MAP) applications. To verify the method, the sensors were exposed to several environmental conditions (both in gas composition and light conditions). And, images were captured with an 8M pixel digital camera sensor, similar to those used in smartphones. Our results show that the sensors have a relative error of 9% when exposed with a CO2 concentration of 20%. This is a good result for low-cost disposable sensors that are not intended for permanent use. However, as soon as light conditions change (2500–6500 K), this error increases up to ϵ20 = 440% (rel. error at 20% CO2 concentration) rendering the sensors unusable. Within this work, we demonstrate that our color QR codes can reduce the relative error to ϵ20 = 14%. Furthermore, we show that the most common color correction, white balance, is not sufficient to address the color consistency issue, resulting in a relative error of ϵ20 = 90%. Full article
(This article belongs to the Special Issue Novel Gas Sensing Approaches: From Fabrication to Application)
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<p>A Back-compatible Color QR Code [<a href="#B18-chemosensors-12-00260" class="html-bibr">18</a>] for the evaluation of colorimetric indicators. This QR code is read by commercial scanners and should display the URL: <a href="http://c-s.is/#38RmtGVV6RQSf" target="_blank">c-s.is/#38RmtGVV6RQSf</a> (accessed on 12 December 2024). It includes up to 125 reference colors, and the colorimetric dye is printed above the lower finder pattern, represented here as seven purple modules.</p>
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<p>The structure of the color QR code from <a href="#chemosensors-12-00260-f001" class="html-fig">Figure 1</a>: (<b>a</b>,<b>b</b>) Possible sensor inks placements. (<b>a</b>) Big sensor outside the QR code. (<b>b</b>) Smaller factor forms (<math display="inline"><semantics> <mrow> <mn>3</mn> <mo>×</mo> <mn>2</mn> </mrow> </semantics></math>, <math display="inline"><semantics> <mrow> <mn>1</mn> <mo>×</mo> <mn>1</mn> </mrow> </semantics></math>, …) within the QR code. (<b>c</b>) Color references and how they are spread over the QR code area. (<b>d</b>) Whole sensor layout of the gas-sensitive color QR code.</p>
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<p>The sensor changes from purple to yellow when exposed to <math display="inline"><semantics> <mrow> <mi>C</mi> <msub> <mi>O</mi> <mn>2</mn> </msub> </mrow> </semantics></math>.</p>
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<p>A mass-flow controller station, a capture station, and a user-access computer. The mass-flow controller station supplies a chamber in which the gas sensors are placed with modified atmospheres. The capture station takes time-lapse images of the sensor through an optical window of the chamber under controlled light settings. Finally, the user computer presents a web page interface to operate the system.</p>
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<p>A printed sensor featuring a color QR code and two different colorimetric indicators (<math display="inline"><semantics> <mrow> <mi>C</mi> <msub> <mi>O</mi> <mn>2</mn> </msub> </mrow> </semantics></math> indicator above, <math display="inline"><semantics> <mrow> <mi>N</mi> <msub> <mi>H</mi> <mn>3</mn> </msub> </mrow> </semantics></math> below, which was not used in this experiment) inside the sensor chamber. The image shows the sensor before exposure to the target gas under three different light conditions: 2500 K (<b>left</b>), 4500 K (<b>middle</b>) and 6500 K (<b>right</b>).</p>
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<p>Response of the green channel under nine different light conditions (2500 K to 6500 K) with all pulses overlapped in the same time frame and after correction of the measured values using a color correction method. Each target gas concentration (20%, 30%, 35%, 40%, 50%) was exposed three times under the respective light condition, resulting in a total of 27 pulses for every gas concentration.</p>
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<p><b>Up</b>: Fitting the responses to a model without performing any color correction (NONE), which is the worst-case scenario, with different color in the data points indicating different illumination conditions and different transparency indicating different repetition sample. <b>Down</b>: Fitting the responses to a model for the ground-truth responses (PERF), which is the best-case scenario, where all color corrections recover the D65 color of the sensor perfectly.</p>
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13 pages, 4650 KiB  
Article
A Phthalimide-Functionalized Heptamethine Cyanine Dye for Tumor-Targeted Photothermal Therapy
by Yoonbin Park, Juhui Yang and Hoon Hyun
Cancers 2024, 16(24), 4155; https://doi.org/10.3390/cancers16244155 - 13 Dec 2024
Viewed by 275
Abstract
Background: A phthalimide-functionalized heptamethine cyanine dye, named Ph790H, is used for targeted photothermal cancer therapy in vivo. We highlight that the chemical structure of Ph790H is newly designed and synthesized for the first time in this study. Objectives: By possessing a rigid chloro-cyclohexenyl [...] Read more.
Background: A phthalimide-functionalized heptamethine cyanine dye, named Ph790H, is used for targeted photothermal cancer therapy in vivo. We highlight that the chemical structure of Ph790H is newly designed and synthesized for the first time in this study. Objectives: By possessing a rigid chloro-cyclohexenyl ring in the heptamethine cyanine backbone, the bifunctional near-infrared (NIR) fluorescent dye Ph790H can be preferentially accumulated in tumor without the need for additional targeting ligands, which is defined as the “structure-inherent tumor targeting” concept. Methods: The phototherapeutic effect of Ph790H is evaluated in HT-29 human colorectal cancer xenografts to be used as a cancer-targeting photothermal agent. Results: The results reveal that the Ph790H shows enhanced tumor accumulation in HT-29 xenografts 48 h post-injection with a high tumor-to-background ratio. After determination of the optimal timing for photothermal therapy (PTT), the HT-29 tumor-possessing nude mice pretreated with Ph790H are subsequently irradiated with an 808 nm NIR laser for 5 min. The tumor-targeted PTT treatment can efficiently inhibit the tumor development compared with that of control groups. Moreover, no tumor regrowth or Ph790H-induced mortality occurs after the treatment of Ph790H and laser irradiation during a period of monitoring. Conclusions: Therefore, this work demonstrates that the bifunctional phototheranostic agent Ph790H can be utilized for targeted cancer imaging and fluorescence-guided phototherapy simultaneously. Full article
(This article belongs to the Special Issue Novel Therapeutic Approaches for Cancer Treatment)
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<p>(<b>a</b>) Synthetic process and (<b>b</b>) mass data of Ph790H. (<b>c</b>) Physicochemical and optical properties of ICG [<a href="#B24-cancers-16-04155" class="html-bibr">24</a>] and Ph790H.</p>
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<p>(<b>a</b>) Absorbance and fluorescence of Ph790H measured in serum. (<b>b</b>) Cytotoxicity analysis of Ph790H using NIH/3T3, NCI-H460, MDA-MB-231, MCF-7, and HT-29 cells. (<b>c</b>) Cell binding of Ph790H in HT-29 cells. Scale bars = 100 μM.</p>
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<p>(<b>a</b>) Thermal images of PBS and Ph790H (100 μM) solutions before and after laser irradiation for 1 min. (<b>b</b>) Temperature changes in PBS and Ph790H (20, 50, and 100 μM) solutions were monitored for 120 s under laser irradiation. (<b>c</b>) Heating and cooling curve of Ph790H (50 μM) under laser irradiation. (<b>d</b>) Three on/off cycles of the Ph790H (50 μM) solution.</p>
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<p>Fluorescence images of HT-29 cells treated with or without PTT treatment. Calcein-AM (green color) and propidium iodide (red color) were used to stain the HT-29 cells after each treatment. Scale bars = 100 μm.</p>
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<p>(<b>a</b>) In vivo NIR fluorescence imaging of HT-29 xenografts after injection of Ph790H. Arrowheads indicate the tumor area. Scale bars = 1 cm. (<b>b</b>) Fluorescence intensity and (<b>c</b>) tumor-to-background ratio at the tumor area for 72 h. (<b>d</b>) Thermal images and (<b>e</b>) temperature changes in each mouse group at the tumor area. Data are expressed as mean ± S.D. (<span class="html-italic">n</span> = 3). ** <span class="html-italic">p</span> &lt; 0.01.</p>
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<p>(<b>a</b>) Photographs of changes in tumor volume in HT-29 xenografts for 11 days. Arrowheads indicate the tumor area. Scale bars = 1 cm. (<b>b</b>) Tumor volumes, (<b>c</b>) a photograph of tumors collected from each mouse group at day 11, and (<b>d</b>) body weights were measured for 11 days. Data are expressed as mean ± S.D. (<span class="html-italic">n</span> = 3). ** <span class="html-italic">p</span> &lt; 0.01; *** <span class="html-italic">p</span> &lt; 0.001. (<b>e</b>) H&amp;E staining of tumor sections collected from each mouse group (<span class="html-italic">n</span> = 3). Scale bars = 50 μm.</p>
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13 pages, 3939 KiB  
Article
CuO-TiO2–Saponite Ternary Nanocomposite for Efficient Removal of Bromocresol Green Dye
by Pollyana Trigueiro, Willams A. Albuquerque, Aimée G. Jerônimo, Monica Sá Rodrigues, Emanoel L. Tavares França and Ramón Raudel Peña-Garcia
Minerals 2024, 14(12), 1268; https://doi.org/10.3390/min14121268 - 13 Dec 2024
Viewed by 400
Abstract
This study presents the synthesis of a CuO-TiO2–saponite ternary nanocomposite via a hydrothermal method, designed to efficiently remove bromocresol green dye. Characterization techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy, confirmed significant interactions between metal oxide nanoparticles [...] Read more.
This study presents the synthesis of a CuO-TiO2–saponite ternary nanocomposite via a hydrothermal method, designed to efficiently remove bromocresol green dye. Characterization techniques, including X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy, confirmed significant interactions between metal oxide nanoparticles and the clay mineral matrix. Diffuse reflectance and photoluminescence analyses revealed a narrow band gap and surface defects, such as oxygen vacancies, enhancing the material’s photocatalytic properties. Under UV irradiation, the nanocomposite achieved 83% discoloration of bromocresol green dye within 150 min. The inhibitor studies identified hydroxyl and superoxide radicals as key species in the degradation mechanism. This work underscores the potential of clay-mineral-based nanocomposites, where clay minerals function both as structural support and as enhancers of the semiconductor’s photocatalytic activity. Full article
(This article belongs to the Section Clays and Engineered Mineral Materials)
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<p>XRD pattern: (<b>a</b>) raw saponite and (<b>b</b>) CuO-TiO<sub>2</sub>–saponite nanocomposite obtained by hydrothermal synthesis.</p>
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<p>FTIR spectrum: (<b>a</b>) raw saponite and (<b>b</b>) CuO-TiO<sub>2</sub>–saponite nanocomposite obtained by hydrothermal synthesis.</p>
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<p>SEM images: (<b>a</b>) raw saponite and (<b>b</b>) CuO-TiO<sub>2</sub>–saponite nanocomposite.</p>
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<p>UV–Vis DRS spectrum and the optical band gap for the CuO-TiO<sub>2</sub>–saponite nanocomposite. The insert represents the band gap calculation using Tauc’s relation.</p>
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<p>Photoluminescence spectrum of the CuO-TiO<sub>2</sub>–saponite nanocomposite.</p>
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<p>(<b>a</b>) Absorbance spectra and (<b>b</b>) degradation ratio of the bromocresol green dye using the CuO-TiO<sub>2</sub>–saponite nanocomposite</p>
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<p>Scavengers’ tests of the bromocresol green dye photocatalytic removal using the CuO-TiO<sub>2</sub>–saponite nanocomposite under UV irradiation for 150 min.</p>
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<p>Reuse tests of CuO-TiO<sub>2</sub>–saponite for bromocresol green dye decolorization under UV irradiation for 150 min.</p>
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<p>Representation of bromocresol green dye decolorization mechanism over CuO-TiO<sub>2</sub>–saponite nanocomposite under UV irradiation.</p>
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12 pages, 3194 KiB  
Case Report
Imaging-Based Molecular Interaction Between Src and Lamin A/C Mechanosensitive Proteins in the Nucleus of Laminopathic Cells
by Stefania Petrini, Giulia Bagnato, Michela Piccione, Valentina D’Oria, Valentina Apollonio, Marco Cappa, Claudia Castiglioni, Filippo Maria Santorelli, Teresa Rizza, Rosalba Carrozzo, Enrico Silvio Bertini and Barbara Peruzzi
Int. J. Mol. Sci. 2024, 25(24), 13365; https://doi.org/10.3390/ijms252413365 - 13 Dec 2024
Viewed by 243
Abstract
Laminopathies represent a wide range of genetic disorders caused by mutations in gene-encoding proteins of the nuclear lamina. Altered nuclear mechanics have been associated with laminopathies, given the key role of nuclear lamins as mechanosensitive proteins involved in the mechanotransduction process. To shed [...] Read more.
Laminopathies represent a wide range of genetic disorders caused by mutations in gene-encoding proteins of the nuclear lamina. Altered nuclear mechanics have been associated with laminopathies, given the key role of nuclear lamins as mechanosensitive proteins involved in the mechanotransduction process. To shed light on the nuclear partners cooperating with altered lamins, we focused on Src tyrosine kinase, known to phosphorylate proteins of the nuclear lamina. Here, we demonstrated a tight relationship between lamin A/C and Src in skin fibroblasts from two laminopathic patients, assessed by advanced imaging-based microscopy techniques. With confocal laser scanning and Stimulated Emission Depletion (STED) microscopy, a statistically significant higher co-distribution between the two proteins was observed in patients’ fibroblasts. Furthermore, the time-domain fluorescence lifetime imaging microscopy, combined with Förster resonance energy transfer detection, demonstrated a decreased lifetime value of Src (as donor fluorophore) in the presence of lamin A/C (as acceptor dye) in double-stained fibroblast nuclei in both healthy cells and patients’ cells, thereby indicating a molecular interaction that resulted significantly higher in laminopathic cells. All these results demonstrate a molecular interaction between Src and lamin A/C in healthy fibroblasts and their aberrant interaction in laminopathic nuclei, thus creating the possibilities of new diagnostic and therapeutic approaches for patients. Full article
(This article belongs to the Special Issue Protein Signal Transduction in the Nucleus)
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<p>Confocal microscopy imaging of Src (in green) and lamin A/C (in red) in control and laminopathic fibroblasts. (<b>A</b>) Src immunofluorescence showed a punctate and diffuse distribution in the nuclear and cytoplasmic compartments, with a higher concentration in the nuclei, both in healthy cells and patients’ cells. Orange pixels showed the overlay of Src and Lamin A/C fluorescence in doubled-stained cells. Colocalization masks of double-stained cells (white pixels) showed the Src-lamin A/C co-distribution both at the nuclear envelope (arrows and arrowheads) and in the nucleoplasm. (<b>B</b>) Intensity line profiles of Src (green) and lamin A/C (red) across the focal central plane, as indicated by the white dotted line of representative nuclei in the overlay images. Scale bars: 10 μm for all images except insets (5 μm). (<b>C</b>) Src mean fluorescence intensity decreased in patients’ nuclei, significantly in Pt 1, compared to controls (* <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>STED nanoscopy of Src and lamin A/C in nuclei from healthy and laminopathic fibroblasts. (<b>A</b>) In the healthy control nuclei, Src labeling (green) was thickened at the nuclear periphery, with a diffuse and dotted distribution in the nuclear matrix, whereas some anomalous aggregates were observed (arrows) in patients’ nuclei. Alterations in the structural organization of the lamin A/C (red) meshworks have been seen in several nuclei of the fibroblasts of patient 1 and patient 2 (arrowheads). Colocalization masks (yellow) showed the co-distribution of Src and lamin A/C at the nuclear rim in all samples and a higher concentration in the nucleoplasm of patients’ cells (high magnification of insets). Bars: 5 µm and 2 µm. (<b>B</b>) Mean values of the overlap coefficient quantified in STED images of double-stained fibroblast nuclei. (** <span class="html-italic">p</span> &lt; 0.01; * <span class="html-italic">p</span> &lt; 0.05).</p>
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<p>FLIM and FLIM-FRET microscopy of Src and lamin A/C in healthy and laminopathic fibroblast nuclei. (<b>A</b>) Fluorescence lifetime imaging of Src-AF488 donor in the absence (τ<sub>D</sub>, left panel) or in the presence (τ<sub>DA</sub>, right panel) of a lamin A/C-AF594 acceptor. Different τ values were visualized via color code lifetime scale bar (from 2.0 to 3.5 ns of range). (<b>B</b>) Src-AF488 mean lifetime values in the absence of the acceptor (τ<sub>D</sub>) showed a significant increase in laminopathic nuclei compared to controls (**** <span class="html-italic">p</span> &lt; 0.0001 in Pt 1; ** <span class="html-italic">p</span> &lt; 0.01 in Pt 2). (<b>C</b>) The statistical analysis of the Src-AF488 mean τ<sub>D</sub> values in the two specific ROIs revealed significant lifetime changes between controls and patients’ nuclei, both in the lamina and in the nuclear matrix regions (**** <span class="html-italic">p</span> &lt; 0.0001; * <span class="html-italic">p</span> &lt; 0.05). (<b>D</b>) Src-AF488 donor lifetime in the presence of the acceptor molecule (τ<sub>DA</sub>, amplitude weighted lifetime) was significantly decreased in all samples, with a greater extent in patients’ fibroblasts (**** <span class="html-italic">p</span> &lt; 0.0001). (<b>E</b>–<b>G</b>) Quantified FRET efficiency values (mean ± sem) of the Src-AF488 and lamin A/C-AF 594 pair obtained in all selected ROIs (<b>E</b>), at the nuclear rim (<b>F</b>) and in the nucleoplasm (<b>G</b>) in controls (gray dots), in Pt 1 (red dots) and Pt 2 (green dots) nuclei (**** <span class="html-italic">p</span> &lt; 0.0001; ** <span class="html-italic">p</span> &lt; 0.01; * <span class="html-italic">p</span> &lt; 0.05).</p>
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22 pages, 6321 KiB  
Review
A Review of Innovative Cucurbituril-Based Photocatalysts for Dye Degradation
by Mosab Kaseem
Catalysts 2024, 14(12), 917; https://doi.org/10.3390/catal14120917 (registering DOI) - 12 Dec 2024
Viewed by 643
Abstract
This review explores the advancements in photocatalysis facilitated by cucurbiturils (CBs), specifically focusing on CB[5], CB[6], CB[7], and CB[8]. Cucurbiturils have gained prominence due to their exceptional ability to enhance photocatalytic reactions through mechanisms such as improved charge separation, high adsorption capacities, and [...] Read more.
This review explores the advancements in photocatalysis facilitated by cucurbiturils (CBs), specifically focusing on CB[5], CB[6], CB[7], and CB[8]. Cucurbiturils have gained prominence due to their exceptional ability to enhance photocatalytic reactions through mechanisms such as improved charge separation, high adsorption capacities, and the generation of reactive oxygen species. The review summarizes recent research on the use of CBs in various photocatalytic applications, including dye degradation, pollutant removal, and wastewater treatment. Studies highlight CB[5]’s utility in dye removal and the creation of efficient nanocomposites for improved degradation rates. CB[6] is noted for its high adsorption capacities and photocatalytic efficiency in both adsorption and degradation processes. CB[7] shows promise in adsorbing and degrading toxic dyes and enhancing fluorescence in biomedical applications, while CB[8] leads to significant improvements in photocatalytic activity and stability. The review also discusses the synthesis, properties, and functionalization of cucurbiturils to maximize their photocatalytic potential. Future research directions include the optimization of cucurbituril-based composites, the exploration of new application areas, and scaling up their use for practical environmental and industrial applications. This comprehensive review provides insights into the current capabilities of cucurbituril-based photocatalysts and identifies key areas for future development in sustainable photocatalytic technologies. Full article
(This article belongs to the Special Issue Green Chemistry and Catalysis)
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<p>(<b>a</b>) Acid-catalyzed synthesis of cucurbituril (CB[n]) homologues through the condensation of glycoluril (1) and formaldehyde. (<b>b</b>) Various representations of the CB[7] structure, highlighting its chemical framework, three-dimensional geometry, and dimensional parameters [<a href="#B34-catalysts-14-00917" class="html-bibr">34</a>].</p>
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<p>Chemical structures of cucurbiturils with double cavities and their schematic representations [<a href="#B17-catalysts-14-00917" class="html-bibr">17</a>].</p>
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<p>(<b>a</b>) the 3D view of the complex resulted from the hybridization (W<sub>6</sub>O<sub>19</sub>)<sup>2−</sup> and (Me<sub>10</sub>CB[5]). (<b>b</b>) Decolorization rates of RhB solutions with different materials [<a href="#B67-catalysts-14-00917" class="html-bibr">67</a>].</p>
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<p>(<b>a</b>) SEM image of pure CdS nanoparticles showing large aggregates. (<b>b</b>) SEM image of CdS/CB[5] composite with smaller, dispersed particles due to CB[5]. (<b>c</b>) Photocatalytic degradation of Methylene Blue (MB) with different CdS/CB[5] proportions under visible light, showing enhanced degradation with more CB[5]. (<b>d</b>) Comparison of MB degradation between pure CdS and CdS/CB[5], demonstrating the higher efficiency of the CdS/CB[5] composite [<a href="#B69-catalysts-14-00917" class="html-bibr">69</a>].</p>
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<p>(<b>a</b>) Structural assembly of the CB[6]-POM composite, illustrating the hydrogen bonding interactions between the {Ni-CB[6]}n chain and the POM chain. (<b>b</b>) Decolorization rates of methyl orange (MO) under different reaction conditions; MO/photocatalyst/H<sub>2</sub>O<sub>2</sub>, MO/photocatalyst, and MO/H<sub>2</sub>O<sub>2</sub>. (<b>c</b>) Proposed dual-pathway mechanism for the photodegradation of MO involving superoxide radicals (O<sub>2</sub><sup>•−</sup>) and hydroxyl radicals (<sup>•</sup>OH) [<a href="#B74-catalysts-14-00917" class="html-bibr">74</a>].</p>
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<p>Regeneration and real-water performance of CB/MMCNT adsorbent: (<b>a</b>–<b>c</b>) adsorption capacity retention after seven cycles for MB, MG, and GV; (<b>d</b>) removal efficiency in real water samples, showing over 92% effectiveness [<a href="#B78-catalysts-14-00917" class="html-bibr">78</a>].</p>
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<p>Optimized structures of the 2CB[7]@TfT complex, showing stabilization with and without magnesium cations. Magnesium cations act as “lids”, enhancing the complex’s stability and fluorescence performance [<a href="#B83-catalysts-14-00917" class="html-bibr">83</a>].</p>
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<p>Formation of 2D Polypseudorotaxanes with Cucurbit[8]uril (CB[8]). CB[8] binds to naphthol-modified porphyrin (TPP-Np) and viologen derivatives (DMV) through charge-transfer interactions, forming a stable, single-layer 2D network [<a href="#B92-catalysts-14-00917" class="html-bibr">92</a>].</p>
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