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Keywords = xanthene dyes

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16 pages, 3439 KB  
Article
Mesoporous Confinement of Fluorescent Dyes in Ultra-Transparent Silica Aerogel Films via Tailored Sol–Gel Kinetics
by Zhizhong Qin, Yuntao Li, Guifeng Wang, Fengyu Li, Pengchao Song, Xihao Sun, Yong Jiang, Jialu Lu and Wei Wei
Gels 2026, 12(8), 676; https://doi.org/10.3390/gels12080676 - 30 Jul 2026
Viewed by 312
Abstract
Silica aerogel films are highly promising matrices for advanced optical applications, yet balancing ultra-high transmittance with structural stability during functionalization remains a critical challenge. Directly incorporating organic dyes often leads to aggregation and severe photodegradation, necessitating a robust host–guest encapsulation strategy. Herein, we [...] Read more.
Silica aerogel films are highly promising matrices for advanced optical applications, yet balancing ultra-high transmittance with structural stability during functionalization remains a critical challenge. Directly incorporating organic dyes often leads to aggregation and severe photodegradation, necessitating a robust host–guest encapsulation strategy. Herein, we report the fabrication of ultra-transparent, fluorescent silica aerogel films via precisely tailored acid/base two-step sol–gel kinetics and dip-coating. The optimized pure silica matrix achieves a peak visible transmittance of 97.4% and sub-nanometer surface smoothness (RMS = 276.7 pm). By utilizing this pristine network, Rhodamine 6G (Rh6G) and Rhodamine B (RhB) dyes were effectively confined within the amorphous mesoporous pores. Notably, RhB exhibited superior matrix integration, indicated by an H4 hysteresis loop transition and a significantly reduced pore volume (0.019 cm3/g). This mesoporous confinement successfully suppressed dye quenching, prolonging the fluorescence lifetimes to 5.22 ns and 5.36 ns for Rh6G and RhB, respectively. Crucially, we elucidate that the electrostatic and hydrogen-bonding interactions between the silica pore walls and the dye’s xanthene rings elevate the excited-state energy, inducing a distinct matrix-driven emission blue shift. This work provides a scalable pathway for high-performance optical coatings and offers deep insights into host–guest interfacial coupling in gel networks. Full article
(This article belongs to the Special Issue Aerogels: Promising Materials for Environmental Applications)
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21 pages, 3073 KB  
Article
Fenton Catalytic Degradation of Rhodamine B by Zero-Valent Iron/Alumina Catalyst
by Kexin Ge, Shuaiqi Chen, Boning Jiang, Xuhui Wang, Xiangyu Xu and Jiaqing Song
Molecules 2026, 31(13), 2270; https://doi.org/10.3390/molecules31132270 - 29 Jun 2026
Viewed by 336
Abstract
Rhodamine B (RhB) is a typical xanthene-based cationic dye. Its widespread application has brought serious safety and environmental risks. Heterogeneous Fenton systems based on zero-valent iron (Fe0) are promising for RhB degradation. However, bare Fe0 suffers from severe agglomeration and [...] Read more.
Rhodamine B (RhB) is a typical xanthene-based cationic dye. Its widespread application has brought serious safety and environmental risks. Heterogeneous Fenton systems based on zero-valent iron (Fe0) are promising for RhB degradation. However, bare Fe0 suffers from severe agglomeration and surface passivation. In this study, alumina with a large pore volume and high specific surface area was employed as a support to enhance Fe0 dispersion and stability. The catalyst was prepared via a glucose-assisted carbothermal reduction method, and the formation of Fe0 was confirmed by X-ray diffraction and electron microscopy analyses. Under optimal conditions (pH = 3.58, catalyst dosage = 0.8 g·L−1, H2O2 = 10 mM), 10 mg·L−1 RhB was completely degraded within 25 min, with a pseudo-first-order rate constant of 0.432 min−1. This exhibits a faster degradation rate and efficiency advantage. Radical quenching experiments indicated that hydroxyl radicals (•OH) were the dominant reactive species, while singlet oxygen (1O2) also contributed to the degradation process. Two primary degradation pathways, including N-deethylation and hydroxylation, were identified. The catalyst showed moderate reusability with slight deactivation after repeated cycles. This study demonstrates that tailoring the pore structure of alumina supports is an effective strategy to enhance Fe0 dispersion, mass transfer, and catalytic performance in heterogeneous Fenton systems. Full article
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67 pages, 3784 KB  
Review
Light-Activated Antimicrobial Agents and Biomaterials for Bacterial and Fungal Infections
by Rostyslav Marunych, Dorota Bartusik-Aebisher, Barbara Smolak, Klaudia Dynarowicz and David Aebisher
Micro 2026, 6(2), 45; https://doi.org/10.3390/micro6020045 - 17 Jun 2026
Viewed by 768
Abstract
Photodynamic therapy (PDT) represents a promising non-antibiotic strategy for addressing bacterial and fungal infections, particularly in the context of increasing antimicrobial resistance and biofilm-associated disease. PDT is based on the light-induced activation of photosensitizers, leading to the generation of reactive oxygen species (ROS), [...] Read more.
Photodynamic therapy (PDT) represents a promising non-antibiotic strategy for addressing bacterial and fungal infections, particularly in the context of increasing antimicrobial resistance and biofilm-associated disease. PDT is based on the light-induced activation of photosensitizers, leading to the generation of reactive oxygen species (ROS), including singlet oxygen (1O2), which induce oxidative damage to multiple microbial targets. Unlike conventional antimicrobial drugs that often act through specific molecular pathways, antimicrobial PDT produces simultaneous damage to membranes, proteins, nucleic acids, and extracellular biofilm components, thereby reducing the probability of resistance development. This review critically analyzes the cellular, biochemical, and biophysical determinants that govern PDT selectivity toward bacterial and fungal cells in comparison with mammalian host tissues. Particular attention is given to photosensitizer localization, membrane interactions, photobleaching, oxygen dependence, light penetration, and the balance between Type I and Type II photochemical mechanisms. The review provides a comparative overview of major molecular photosensitizer classes, including phenothiazines, porphyrins, chlorins, phthalocyanines, xanthene dyes, natural polyphenols, endogenous compounds, and advanced targeted photosensitizers. In addition, this review distinguishes molecular photosensitizers from nanotechnology-based platforms and delivery systems. Nanoparticles, polymeric carriers, hydrogels, and light-activated coatings are discussed not only as photosensitizer delivery tools, but also as systems that modulate aggregation, improve localization, enhance biofilm penetration, and enable surface-confined ROS generation. ROS are capable of causing phototoxic effects wherever they are located. Unless selectively accumulated by target organisms, there can be systemic phototoxicity. Overall, PDT should be regarded as a modular antimicrobial platform in which photosensitizer chemistry, formulation, light delivery, oxygen availability, and infection biology must be co-optimized. Although further studies are required to address clinical translation, regulatory complexity, material safety, and standardized treatment protocols, PDT offers a scientifically robust and clinically relevant approach that may complement conventional antibacterial and antifungal therapies, especially in localized, biofilm-associated, and device-related infections. Full article
(This article belongs to the Section Microscale Biology and Medicines)
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17 pages, 6198 KB  
Article
Substituent Effects on the Photophysical Properties of Neutral and Anionic Seminaphthofluorones: A Computational Study
by Stefania-Renata Stepanov and Vasile Chiș
Photochem 2026, 6(2), 16; https://doi.org/10.3390/photochem6020016 - 9 Apr 2026
Viewed by 490
Abstract
Seminaphtofluorones (SNAFRs) are a family of benzannulated xanthene dyes that exhibit strong fluorescence in both neutral and anionic states and can reach emission wavelengths in the deep-red to near-infrared region. Their optical response is highly sensitive to regioisomerism and functionalization, making them attractive [...] Read more.
Seminaphtofluorones (SNAFRs) are a family of benzannulated xanthene dyes that exhibit strong fluorescence in both neutral and anionic states and can reach emission wavelengths in the deep-red to near-infrared region. Their optical response is highly sensitive to regioisomerism and functionalization, making them attractive candidates for systematic structure–property investigations. Here, we computed the photophysical properties of six SNAFR regioisomers for both neutral and anionic species and correlate the calculated results with available experimental data. From the six dyes, we further chose two of them, SNAFR4 and SNAFR6, to further investigate how phenyl-ring functionalization modulates SNAFR properties by introducing methyl (–CH3) and carboxyl (–COOH) substituents at the ortho (o), meta (m), and para (p) positions. The calculations indicate that substitution induces measurable changes in geometries, as well as in excitation and emission energies, with particularly pronounced effects for the anionic derivatives. Overall, these results provide a computational framework for the rational tuning of SNAFRs’ optical properties and the design of derivatives with tailored optical characteristics for fluorescence imaging and applications in photodynamic therapy. Full article
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18 pages, 1587 KB  
Review
Fluorescent Dyes in Hydrological Tracing: Application Methods, Ecotoxicological Effects, and Safe Application Levels
by Carlos J. A. Campos, Louis A. Tremblay, Olivier Champeau and Gregory Goblick
J. Xenobiotics 2026, 16(2), 45; https://doi.org/10.3390/jox16020045 - 3 Mar 2026
Cited by 2 | Viewed by 2480
Abstract
Fluorescent dyes are commonly used as tracers in hydrological investigations to quantify transport pathways, residence times, mixing behavior, and connectivity in surface water, groundwater, and coastal systems. Despite their long history of application, the ecological implications of deliberate dye releases are not well [...] Read more.
Fluorescent dyes are commonly used as tracers in hydrological investigations to quantify transport pathways, residence times, mixing behavior, and connectivity in surface water, groundwater, and coastal systems. Despite their long history of application, the ecological implications of deliberate dye releases are not well understood. This review synthesizes current knowledge on the physico-chemical characteristics, environmental behavior, and ecotoxicological effects of major dye classes, with emphasis on rhodamines, fluorescein derivatives, and sulfonated xanthene dyes commonly used in water tracing studies. Toxicity data for algae, cyanobacteria, invertebrates, and fish show large inter-specific variability. Some dyes, particularly rhodamine B and eosin Y, show acute or sub-lethal effects at concentrations detected during poorly controlled applications. By contrast, dyes with high polarity and extensive sulfonation (e.g., rhodamine WT, sulforhodamine B, pyranine, and fluorescein) show consistently low toxicity and minimal bioaccumulation potential. Environmental fate processes, including photolysis, sorption, and transformation into potentially more reactive products, influence exposure dynamics, especially in clear, shallow, or slow-moving systems. This review also evaluates regulatory frameworks and operational guidance for safe use, identifies gaps in toxicological and fate data, and proposes recommendations for minimizing environmental impact through dye selection, mass optimization, injection design, and monitoring. The findings support the continued use of fluorescent dyes but highlight the need for more systematic assessment of transformation products, chronic and sub-lethal responses, and cumulative exposure in sensitive environments. Full article
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25 pages, 5169 KB  
Article
Natural Sunlight Driven Photocatalytic Degradation of Methylene Blue and Rhodamine B over Nanocrystalline Zn2SnO4/SnO2
by Maria Vesna Nikolic, Zorka Z. Vasiljevic, Milena Dimitrijevic, Nadezda Radmilovic, Jelena Vujancevic, Marija Tanovic and Nenad B. Tadic
Nanomaterials 2025, 15(14), 1138; https://doi.org/10.3390/nano15141138 - 21 Jul 2025
Cited by 16 | Viewed by 3753
Abstract
The natural sunlight driven photocatalytic degradation of organic pollutants is a sustainable solution for water purification. The use of heterojunction nanocomposites in this process shows promise for improved photodegradation efficiency. In this work, nanocrystalline Zn2SnO4/SnO2 obtained by the [...] Read more.
The natural sunlight driven photocatalytic degradation of organic pollutants is a sustainable solution for water purification. The use of heterojunction nanocomposites in this process shows promise for improved photodegradation efficiency. In this work, nanocrystalline Zn2SnO4/SnO2 obtained by the solid-state synthesis method was tested as a heterojunction photocatalyst material for the degradation of methylene blue (MB) and Rhodamine B (RhB) dyes as single and multicomponent systems in natural sunlight. Characterization of the structure and morphology of the synthesized nanocomposite using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDS), and photoluminescence (PL) spectroscopy confirmed the formation of Zn2SnO4/SnO2 and heterojunctions between Zn2SnO4 and the SnO2 nanoparticles. A photodegradation efficiency of 99.1% was achieved in 120 min with 50 mg of the photocatalyst for the degradation of MB and 70.6% for the degradation of RhB under the same conditions. In the multicomponent system, the degradation efficiency of 97.9% for MB and 53.2% for RhB was obtained with only 15 mg of the photocatalyst. The degradation of MB occurred through N-demethylation and the formation of azure intermediates and degradation of RhB occurred through sequential deethylation and fragmentation of the xanthene ring, both in single and multicomponent systems. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Water Remediation (2nd Edition))
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18 pages, 671 KB  
Review
Evaluating the Efficacy of Rose Bengal as a Photosensitizer in Antimicrobial Photodynamic Therapy Against Candida albicans: A Systematic Review
by Jakub Fiegler-Rudol, Barbara Lipka, Katarzyna Kapłon, Magdalena Moś, Dariusz Skaba, Aleksandra Kawczyk-Krupka and Rafał Wiench
Int. J. Mol. Sci. 2025, 26(11), 5034; https://doi.org/10.3390/ijms26115034 - 23 May 2025
Cited by 12 | Viewed by 2926
Abstract
Candida albicans is a significant pathogen in various fungal infections, including oral candidiasis and denture stomatitis. As antifungal resistance rises globally, there is an urgent need for alternative treatment strategies. Antimicrobial photodynamic therapy (aPDT), utilizing a photosensitizer and light to produce reactive oxygen [...] Read more.
Candida albicans is a significant pathogen in various fungal infections, including oral candidiasis and denture stomatitis. As antifungal resistance rises globally, there is an urgent need for alternative treatment strategies. Antimicrobial photodynamic therapy (aPDT), utilizing a photosensitizer and light to produce reactive oxygen species (ROS), has emerged as a promising approach. Rose Bengal (RB), a xanthene dye, exhibits a high singlet oxygen quantum yield, making it a candidate for aPDT. However, its efficacy in C. albicans treatment has been inconsistent, particularly against biofilm-associated infections, which are more resistant to conventional therapies. This systematic review evaluates the efficacy of Rose Bengal-mediated aPDT in combating C. albicans infections by synthesizing data from studies conducted over the past decade. We focus on the effectiveness of RB across different experimental conditions, including planktonic and biofilm forms of C. albicans. The review also explores the synergy between RB and other agents, such as potassium iodide, and compares the outcomes of RB-mediated aPDT to other photosensitizers and conventional antifungal treatments. Despite its potential, RB-aPDT shows variable effectiveness due to differences in experimental protocols, such as the photosensitizer concentration, incubation times, and light parameters. The review identifies the key limitations, such as RB’s poor biofilm penetration and high dark toxicity at elevated concentrations, which hinder its clinical applicability. The combination of RB with potassium iodide enhances its antifungal efficacy, suggesting that further optimization could improve its clinical potential. Overall, while Rose Bengal-mediated aPDT holds promise as a novel antifungal treatment, further research is needed to standardize protocols, enhance delivery systems, and validate its efficacy in vivo and clinical settings. Full article
(This article belongs to the Special Issue Photodynamic Therapy and Photodetection, 2nd Edition)
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14 pages, 1733 KB  
Article
Facile Synthesis of Pyridyl Rosamines as Potential Photosensitizers
by Éva Bakos, Henrietta Ágoston, Rebeka Ignácz, Attila Hunyadi, Miklós Poór, János Erostyák, Zoltán Kele, Csilla Özvegy-Laczka and Erzsébet Mernyák
Int. J. Mol. Sci. 2025, 26(4), 1482; https://doi.org/10.3390/ijms26041482 - 10 Feb 2025
Cited by 3 | Viewed by 2016
Abstract
Rosamines represent one of the most promising groups of xanthene dyes. Their excellent photophysical properties allow their widespread application. Their use as photosensitizers in photodynamic therapy has recently gained considerable attention. Here, we report the facile, effective, microwave-assisted synthesis of rosamine dyes. Pyridylbenzaldehyde [...] Read more.
Rosamines represent one of the most promising groups of xanthene dyes. Their excellent photophysical properties allow their widespread application. Their use as photosensitizers in photodynamic therapy has recently gained considerable attention. Here, we report the facile, effective, microwave-assisted synthesis of rosamine dyes. Pyridylbenzaldehyde derivatives were reacted with 1,3-dialkylaminophenols or 8-hydroxyjulolidine in toluene without any additive. The resulting pyridyl rosamines were investigated for their cytotoxic effect against the A431 human epidermoid carcinoma cell line to estimate their potential as photosensitizers. The compounds displayed light-induced toxicity in the submicromolar or occasionally in the low nanomolar range. One of the julolidine-based derivatives exhibited a phototoxic index above 100, indicating an increase in light-induced cytotoxic efficacy of two orders of magnitude compared to its negligible dark toxicity. This compound is a particularly promising candidate for the development of novel pyridyl-rosamine-based photosensitizers for photodynamic therapy of skin cancer. Full article
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20 pages, 4190 KB  
Article
Arthrocolin B Impairs Adipogenesis via Delaying Cell Cycle Progression During the Mitotic Clonal Expansion Period
by Guang Cao, Xuemei Liao, Shuang Zhao, Mengwen Li, Zhengyuan Xie, Jinglan Yang, Yanze Li, Zihao Zhu, Xiaoru Jin, Rui Huang, Ziyin Guo, Xuemei Niu and Xu Ji
Int. J. Mol. Sci. 2025, 26(4), 1474; https://doi.org/10.3390/ijms26041474 - 10 Feb 2025
Cited by 1 | Viewed by 2147
Abstract
Obesity and its related diseases severely threaten people’s health, causing persistently high morbidity and mortality worldwide. The abnormal proliferation and hypertrophy of adipocytes mediate the expansion of adipose tissue, which is the main cause of obesity-related diseases. Inhibition of cell proliferation during the [...] Read more.
Obesity and its related diseases severely threaten people’s health, causing persistently high morbidity and mortality worldwide. The abnormal proliferation and hypertrophy of adipocytes mediate the expansion of adipose tissue, which is the main cause of obesity-related diseases. Inhibition of cell proliferation during the mitotic clonal expansion (MCE) period of adipogenesis may be a promising strategy for preventing and treating obesity. Arthrocolins are a series of fluorescent dye-like complex xanthenes from engineered Escherichia coli, with potential anti-tumor and antifungal activities. However, the role and underlying mechanisms of these compounds in adipocyte differentiation remain unclear. In this study, we discovered that arthrocolin B, a member of the arthrocolin family, significantly impeded adipogenesis by preventing the accumulation of lipid droplets and triglycerides, as well as by downregulating the expression of key factors involved in adipogenesis, such as SREBP1, C/EBPβ, C/EBPδ, C/EBPα, PPARγ, and FABP4. Moreover, we revealed that this inhibition might be a consequence of cell cycle arrest during the MCE of adipocyte differentiation, most likely by modulating the p53, AKT, and ERK pathways, upregulating the expression of p21 and p27, and repressing the expression of CDK1, CDK4, Cyclin A2, Cyclin D1, and p-Rb. Additionally, arthrocolin B could promote the expression of CPT1A during adipocyte differentiation, implying its potential role in fatty acid oxidation. Overall, our research concludes that arthrocolin B has the ability to suppress the early stages of adipocyte differentiation mainly by modulating the signaling proteins involved in cell cycle progression. This work broadens our understanding of the function and mechanisms of arthrocolins in regulation of adipogenesis and might provide a potential lead compound for treating the obesity. Full article
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14 pages, 7557 KB  
Article
Hats Off to Modeling! Profiling Early Synthetic Dyes on Historic Woolen Samples with ATR-FTIR Spectroscopy and Multivariate Curve Resolution–Alternating Least Square Algorithm
by Tiziana Forleo, Lorena Carla Giannossa, Anna De Juan Capdevila, Giovanni Lagioia and Annarosa Mangone
Molecules 2024, 29(19), 4651; https://doi.org/10.3390/molecules29194651 - 30 Sep 2024
Viewed by 1697
Abstract
This research focuses on analyzing wool samples dyed with synthetic dyes from the early 20th century. A methodology to identify and distinguish wool fibers dyed with azo, triphenylmethane, and xanthene dyes, which are no longer in use, using the ATR-FTIR spectra, is presented. [...] Read more.
This research focuses on analyzing wool samples dyed with synthetic dyes from the early 20th century. A methodology to identify and distinguish wool fibers dyed with azo, triphenylmethane, and xanthene dyes, which are no longer in use, using the ATR-FTIR spectra, is presented. Firstly, the dataset was subjected to PCA, which revealed the similarities and differences among the samples, illustrating a distribution pattern based on dye classes. MCR-ALS was employed to extract the spectral profiles of the dyed fibers, thereby enhancing the efficacy of the analytical techniques and extracting the comprehensive information from a single instrument. The combination of ATR-FTIR spectroscopy with chemometric methods, such as PCA and MCR-ALS, has proven to be an effective strategy for identifying and differentiating wool fibers dyed with early azo, triphenylmethane, and xanthene dyes. This approach has demonstrated particular effectiveness in enabling rapid analysis without requiring sampling or pretreatment. Moreover, the analysis is supported by thorough bibliographic research on these no longer used colorants. In order to maximize the potential of non-destructive spectroscopic techniques, such as ATR-FTIR, the approach used has proven to be crucial. This study underscores how chemometric techniques expand the capabilities of spectroscopy, extracting extensive information from a single instrument and aligning with the goals of cultural heritage analysis. Full article
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17 pages, 775 KB  
Review
Intralesional and Infusional Updates for Metastatic Melanoma
by Michelle M. Dugan, Adrienne B. Shannon, Danielle K. DePalo, Matthew C. Perez and Jonathan S. Zager
Cancers 2024, 16(11), 1957; https://doi.org/10.3390/cancers16111957 - 22 May 2024
Cited by 12 | Viewed by 4957
Abstract
Locoregionally advanced and metastatic melanoma represent a challenging clinical problem, but in the era of immune checkpoint blockade and intralesional and infusional therapies, more options are available for use. Isolated limb infusion (ILI) was first introduced in the 1990s for the management of [...] Read more.
Locoregionally advanced and metastatic melanoma represent a challenging clinical problem, but in the era of immune checkpoint blockade and intralesional and infusional therapies, more options are available for use. Isolated limb infusion (ILI) was first introduced in the 1990s for the management of advanced melanoma, followed by the utilization of isolated extremity perfusion (ILP). Following this, intralesional oncolytic viruses, xanthene dyes, and cytokines were introduced for the management of in-transit metastases as well as unresectable, advanced melanoma. In 2015, the Food and Drug Administration (FDA) approved the first oncolytic intralesional therapy, talimogene laherparepvec (T-VEC), for the treatment of advanced melanoma. Additionally, immune checkpoint inhibition has demonstrated efficacy in the management of advanced melanomas, and this improvement in outcomes has been extrapolated to aid in the management of in-transit metastatic disease. Finally, percutaneous hepatic perfusion (PHP), also approved by the FDA, has been reported to have a significant impact on the treatment of hepatic disease in uveal melanoma. While some of these treatments have less utility due to inferior outcomes as well as higher toxicity profiles, there are selective patient profiles for which these therapies carry a role. This review highlights intralesional and infusional therapies for the management of metastatic melanoma. Full article
(This article belongs to the Special Issue Contemporary Surgical Management of Melanoma)
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18 pages, 3230 KB  
Article
3′-Nitro- and 3′-Aminofluoresceins: Appearance of Previously Missing Dyes
by Sergey V. Shekhovtsov, Iryna V. Omelchenko, Svitlana V. Shishkina, Andrey O. Doroshenko, Kateryna O. Vus, Hanna S. Vlasenko and Nikolay O. Mchedlov-Petrossyan
Colorants 2023, 2(3), 500-517; https://doi.org/10.3390/colorants2030024 - 30 Jul 2023
Cited by 4 | Viewed by 3181
Abstract
Contrary to the 4′- and 5′-nitro- and aminofluoresceins, the corresponding 3′-derivatives are practically unexplored. In this paper, we describe the synthesis and spectral properties of 3′-nitrofluorescein and 3′-aminofluorescein, as well as their methyl esters. Among other methods, X-ray analysis, 13C NMR spectroscopy, [...] Read more.
Contrary to the 4′- and 5′-nitro- and aminofluoresceins, the corresponding 3′-derivatives are practically unexplored. In this paper, we describe the synthesis and spectral properties of 3′-nitrofluorescein and 3′-aminofluorescein, as well as their methyl esters. Among other methods, X-ray analysis, 13C NMR spectroscopy, and ESI mass spectrometry made it possible to establish the molecular structure of the target compounds as well as intermediates and by-products. Some unexpected products, though in small amounts, were revealed within the course of study. Whereas the fluorescence of the double-charged R2− ion of 3′-nitrofluorescein in both aqueous and organic solvents is weak, the R2− anion of 3′-aminofluorescein in a non-hydrogen bonding donor solvent, but not in water, exhibits intensive fluorescence, analogous to the case of 4′- and 5′-aminofluoresceins. Interestingly, the λmax values in water of the R2− ions bearing an NO2 group in the 3′- and 6′-positions are 7 to 10 nm higher than those of the 4′- and 5′-nitro derivatives. The difference was also observed in dimethyl sulfoxide. This correlates with the angles between the xanthene and phthalic planes of the dyes. The dye 3′-aminofluorescein could be used as a fluorescent indicator sensitive to hydrogen bonding ability of the solvent. It could also serve as a platform for synthesizing fluorescent molecular probes for biochemical research, analogous to the very popular application of 4′- and 5′-amino derivatives. Full article
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13 pages, 5977 KB  
Article
Functioning of a Fluorescein pH-Probe in Aqueous Media: Impact of Temperature and Viscosity
by Darya P. Surzhikova, Lev A. Sukovatyi, Elena V. Nemtseva, Elena N. Esimbekova and Evgenia A. Slyusareva
Micromachines 2023, 14(7), 1442; https://doi.org/10.3390/mi14071442 - 18 Jul 2023
Cited by 13 | Viewed by 5362
Abstract
In this work, we considered the influence of viscogenic agents (glycerol, sucrose) as well as the temperature on the fluorescent characteristics of fluorescein at pH 6.5 in order to describe the acid-base status of local environment in terms of a spectrally detectable dianion-anion [...] Read more.
In this work, we considered the influence of viscogenic agents (glycerol, sucrose) as well as the temperature on the fluorescent characteristics of fluorescein at pH 6.5 in order to describe the acid-base status of local environment in terms of a spectrally detectable dianion-anion equilibrium. The protolytic equilibrium of fluorescein was found to depend on the solvent viscosity in a complex way. Whereas in the presence of sucrose the ratiometric signal of fluorescein (I488/I435) remains rather unchanged, the addition of glycerol (up to 40% w/w) results in the increase of the signal (up to 19%), that can be attributed to the different mechanisms of cosolvents effects on dye molecules in the ground state. Molecular dynamics of the dye in the presence of glycerol and sucrose revealed that the cosolvents preferentially interact with fluorescein monoanion and dianion, displacing water molecules from the local environment which in turn reduces the average number of the hydrogen bonds between xanthene ring of the dye and water molecules. The ratiometric signal demonstrates linear growth with the temperature in the range of 10–80 °C regardless of the presence of viscogenic agents. A linear correlation between the temperature sensitivity of the ratiometric signal and the change in the molar enthalpy of the proton dissociation reaction in buffer and viscous media was determined. Full article
(This article belongs to the Special Issue Biosensors for Biomedical and Environmental Applications)
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14 pages, 1596 KB  
Article
Investigating the Effects of Donors and Alkyne Spacer on the Properties of Donor-Acceptor-Donor Xanthene-Based Dyes
by Ishanka N. Rajapaksha, Jing Wang, Jerzy Leszczynski and Colleen N. Scott
Molecules 2023, 28(13), 4929; https://doi.org/10.3390/molecules28134929 - 22 Jun 2023
Cited by 6 | Viewed by 3387
Abstract
NIR dyes have become popular for many applications, including biosensing and imaging. For this reason, the molecular switch mechanism of the xanthene dyes makes them useful for in vivo detection and imaging of bioanalytes. Our group has been designing NIR xanthene-based dyes by [...] Read more.
NIR dyes have become popular for many applications, including biosensing and imaging. For this reason, the molecular switch mechanism of the xanthene dyes makes them useful for in vivo detection and imaging of bioanalytes. Our group has been designing NIR xanthene-based dyes by the donor-acceptor-donor approach; however, the equilibrium between their opened and closed forms varies depending on the donors and spacer. We synthesized donor-acceptor-donor NIR xanthene-based dyes with an alkyne spacer via the Sonogashira coupling reaction to investigate the effects of the alkyne spacer and the donors on the maximum absorption wavelength and the molecular switching (ring opening) process of the dyes. We evaluated the strength and nature of the donors and the presence and absence of the alkyne spacer on the properties of the dyes. It was shown that the alkyne spacer extended the conjugation of the dyes, leading to absorption wavelengths of longer values compared with the dyes without the alkyne group. In addition, strong charge transfer donors shifted the absorption wavelength towards the NIR region, while donors with strong π-donation resulted in xanthene dyes with a smaller equilibrium constant. DFT/TDDFT calculations corroborated the experimental data in most of the cases. Dye 2 containing the N,N-dimethylaniline group gave contrary results and is being further investigated. Full article
(This article belongs to the Special Issue Dye Chemistry—In Memory of Prof. Michael R. Detty)
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15 pages, 3175 KB  
Article
Covalent Grafting of Eosin Y to the Giant Keplerate {Mo132} through an Organosilicon Linker in Homogeneous Regime
by Andrey Denikaev, Grigory Kim, Evgeny Greshnyakov, Nikolai Moskalenko and Kirill Grzhegorzhevskii
Inorganics 2023, 11(6), 239; https://doi.org/10.3390/inorganics11060239 - 30 May 2023
Cited by 4 | Viewed by 2779
Abstract
The template effect of giant polyoxometalates (POM) shows promising results towards the supramolecular design of hybrid materials suitable for photocatalytic reactions. Here, we demonstrate a novel synthetic approach for covalently grafting the xanthene dye eosin Y (EY) to the nanoscale Keplerate POM {Mo [...] Read more.
The template effect of giant polyoxometalates (POM) shows promising results towards the supramolecular design of hybrid materials suitable for photocatalytic reactions. Here, we demonstrate a novel synthetic approach for covalently grafting the xanthene dye eosin Y (EY) to the nanoscale Keplerate POM {Mo132} via an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS) in a homogeneous regime. Using a phase transfer agent, tetrabutylammonium bromide, we solubilize the Keplerate POM modified with six {Si(CH2)3NH2} groups, {Mo132}@Si6, in a series of organic solvents—acetonitrile, acetone, tetrahydrofuran, and dichloromethane—to perform post-functionalization by using an NHS-ester of EY. Both IR and Raman spectroscopy affirm the preservation of the POM’s structure and showcase an amide bond formation between POM and EY in the obtained conjugate {Mo132}@Si6@EY@TBA. Grafting’s success is observed through significant downfield shifting of EY’s aromatic protons’ signals on the 1H NMR spectrum as compared to the spectra of EY and EY-NHS. The current synthetic approach enables us to exercise precise control of the stoichiometry in the POM-dye conjugates—1:1 for the POM-EY system—as confirmed by elemental analysis. Comprehensive photophysical analysis of {Mo132}@Si6@EY@TBA by means of UV-Vis and steady-state and time-resolved fluorescence measurements points to an existing strong interaction between molecular orbitals of EY and {Mo132}, leading to a photoinduced electron transfer, partial fluorescence quenching, and elongation of the excited state’s lifetime. These findings demonstrate that using APTMS as an organosilicon linker in tandem with the Keplerate POM as a nanoscale template can be readily applied as a routine synthetic procedure for grafting various organic dyes or other organic molecules bearing a carboxylic group in their structure to the giant POM surface in a variety of aprotic organic solvents. Full article
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