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1.
Photochem Photobiol ; 2024 Jul 02.
Artículo en Inglés | MEDLINE | ID: mdl-38953399

RESUMEN

Aiming at the application to photodynamic therapy, natural bacteriochlorophyll-a was converted to chemically stable free-base derivatives possessing different kinds of hydrophilic C17-propionate residues. These semi-synthetic bacteriochlorins were found to have self-assembling ability in an aqueous environment and formed stable J-type aggregates in a cell culture medium containing 0.2% DMSO. The electronic absorption spectra of all the sensitizers showed Qy absorption maxima at 754 nm in DMSO as their monomeric states, while a drastic shift of the red-most bands to ca. 880 nm was observed in the aqueous medium. The circular dichroism spectra in the medium showed much intense signals compared to those measured in DMSO, supporting the formation of well-ordered supramolecular structures. By introducing hydrophilic side chains, the bacteriochlorin sensitizers could be dispersed in the aqueous medium as their J-aggregates without the use of any surfactants. Cellular uptake efficiencies as well as photodynamic activities were evaluated using human cervical adenocarcinoma HeLa cells. Among the 11 photosensitizers investigated, the best result was obtained for a charged derivative possessing trimethylammonium terminal (17-CH2CH2COOCH2CH2N+(CH3)3I-) and photocytotoxicity of EC50 = 0.09 µM was achieved by far-red light illumination of 35 J/cm2 from an LED panel (730 nm).

2.
Nanomaterials (Basel) ; 14(13)2024 Jun 27.
Artículo en Inglés | MEDLINE | ID: mdl-38998711

RESUMEN

We present the design, synthesis, and evaluation of novel metal-free photosensitizers based on D-π-A structures featuring tri-arylamine as an electron donor, cyanoacrylic acid as an anchoring group, and substituted derivative π-bridges including 9,9-dimethyl-9H-fluorene, benzo[b]thiophene, or naphtho [1,2-b:4,3-b']dithiophene. The aim of the current research is to unravel the relationship between chemical structure and photovoltaic performance in solar cell applications by investigating the properties of these organic sensitizers. The newly developed photosensitizers displayed variations in HOMO-LUMO energy gaps and photovoltaic performances due to their distinct π-bridge structures and exhibited diverse spectral responses ranging from 343 to 490 nm. The t-shaped and short linear photosensitizers demonstrated interesting behaviors in dye-sensitized solar cells, such as the effect of the molecular size in electron recombination. The study showed that a t-shaped photosensitizer with a bulky structure reduced electron recombination, while short linear photosensitizers with a smaller molecular size resulted in a higher open-circuit voltage value and enhanced photovoltaic performance. Impedance analysis further supported the findings, highlighting the influence of dye loading and I3- ion surface passivation on the overall performance of solar cells. The molecular design methodology proposed in this study enables promising photovoltaic performance in solar cells, addressing the demand for highly efficient, metal-free organic photosensitizers.

3.
Int J Mol Sci ; 25(13)2024 Jun 29.
Artículo en Inglés | MEDLINE | ID: mdl-39000317

RESUMEN

Chemotherapy is among the main classical approaches to the treatment of oncologic diseases. Its efficiency has been comprehensively proven by clinical examinations; however, the low selectivity of chemotherapeutic agents limits the possibilities of this method, making it necessary to search for new approaches to the therapy of oncologic diseases. Photodynamic therapy is the least invasive method and a very efficient alternative for the treatment of malignant tumors; however, its efficiency depends on the depth of light penetration into the tissue and on the degree of oxygenation of the treatment zone. In this work, a hitherto unknown conjugate of a natural bacteriochlorin derivative and doxorubicin was obtained. In vitro and in vivo studies showed a more pronounced activity of the conjugate against MCF-7 and 4T1 cells and its higher tumorotropicity in animal tumor-bearing animals compared to free anthracycline antibiotic. The suggested conjugate implements the advantages of photodynamic therapy and chemotherapy and has great potential in cancer treatment.


Asunto(s)
Doxorrubicina , Fotoquimioterapia , Porfirinas , Doxorrubicina/farmacología , Doxorrubicina/química , Doxorrubicina/uso terapéutico , Fotoquimioterapia/métodos , Animales , Humanos , Ratones , Porfirinas/química , Porfirinas/farmacología , Porfirinas/uso terapéutico , Femenino , Células MCF-7 , Fármacos Fotosensibilizantes/química , Fármacos Fotosensibilizantes/uso terapéutico , Fármacos Fotosensibilizantes/farmacología , Línea Celular Tumoral , Ratones Endogámicos BALB C , Antibióticos Antineoplásicos/química , Antibióticos Antineoplásicos/farmacología , Antibióticos Antineoplásicos/uso terapéutico , Ensayos Antitumor por Modelo de Xenoinjerto , Antineoplásicos/química , Antineoplásicos/farmacología , Antineoplásicos/uso terapéutico
4.
Cells ; 13(13)2024 Jun 22.
Artículo en Inglés | MEDLINE | ID: mdl-38994936

RESUMEN

Although our skin is not the primary visual organ in humans, it acts as a light sensor, playing a significant role in maintaining our health and overall well-being. Thanks to the presence of a complex and sophisticated optotransduction system, the skin interacts with the visible part of the electromagnetic spectrum and with ultraviolet (UV) radiation. Following a brief overview describing the main photosensitive molecules that detect specific electromagnetic radiation and their associated cell pathways, we analyze their impact on physiological functions such as melanogenesis, immune response, circadian rhythms, and mood regulation. In this paper, we focus on 6-formylindolo[3,2-b]carbazole (FICZ), a photo oxidation derivative of the essential amino acid tryptophan (Trp). This molecule is the best endogenous agonist of the Aryl hydrocarbon Receptor (AhR), an evolutionarily conserved transcription factor, traditionally recognized as a signal transducer of both exogenous and endogenous chemical signals. Increasing evidence indicates that AhR is also involved in light sensing within the skin, primarily due to its ligand FICZ, which acts as both a chromophore and a photosensitizer. The biochemical reactions triggered by their interaction impact diverse functions and convey crucial data to our body, thus adding a piece to the complex puzzle of pathways that allow us to decode and elaborate environmental stimuli.


Asunto(s)
Carbazoles , Receptores de Hidrocarburo de Aril , Piel , Humanos , Receptores de Hidrocarburo de Aril/metabolismo , Piel/metabolismo , Carbazoles/farmacología , Luz , Animales , Visión Ocular/fisiología , Transducción de Señal
5.
J Photochem Photobiol B ; 258: 112979, 2024 Jul 11.
Artículo en Inglés | MEDLINE | ID: mdl-39003970

RESUMEN

Bioluminescence resonance energy transfer photodynamic therapy, which uses light generated by bioluminescent proteins to activate photosensitizers and produce reactive oxygen species without the need for external irradiation, has shown promising results in cancer models. However, the characterization of delivery systems that can incorporate the components of this therapy for preferential delivery to the tumor remains necessary. In this work, we have characterized parvovirus B19-like particles (B19V-VLPs) as a platform for a photosensitizer and a bioluminescent protein. By chemical and biorthogonal conjugation, we conjugated rose Bengal photosensitizer and firefly luciferase to B19V-VLPs and a protein for added specificity. The results showed that B19V-VLPs can withstand decoration with all three components without affecting its structure or stability. The conjugated luciferase showed activity and was able to activate rose Bengal to produce singlet oxygen without the need for external light. The photodynamic reaction generated by the functionalized VLPs-B19 can decrease the viability of tumor cells in vitro and affect tumor growth and metastasis in the 4 T1 model. Treatment with functionalized VLPs-B19 also increased the percentage of CD4 and CD8 cell populations in the spleen and in inguinal lymph nodes compared to vehicle-treated mice. Our results support B19V-VLPs as a delivery platform for bioluminescent photodynamic therapy components to solid tumors.

6.
Int J Mol Sci ; 25(13)2024 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-39000219

RESUMEN

Chlorin e6 is a well-known photosensitizer used in photodynamic diagnosis and therapy. A method for identifying and purifying a novel process-related impurity during the synthesis of chlorin e6 has been developed. Its structure was elucidated using NMR and HRMS. This new impurity is formed from chlorophyll b rather than chlorophyll a, which is the source of chlorin e6. The intermediates formed during chlorin e6 synthesis were monitored using HPLC-mass spectrometry. This new impurity was identified as rhodin g7 71-ethyl ester, the structure of which remains unknown to date. The cytotoxic effects of this novel compound in both dark and light conditions were studied against five cancer cell lines (HT29, MIA-PaCa-2, PANC-1, AsPC-1, and B16F10) and a normal cell line (RAW264.7) and compared to those of chlorin e6. Upon irradiation using a laser at 0.5 J/cm2, rhodin g7 71-ethyl ester demonstrated higher cytotoxicity (2-fold) compared to chlorin e6 in the majority of the cancer cell lines. Furthermore, this new compound exhibited higher dark cytotoxicity compared to chlorin e6. Studies on singlet oxygen generation, the accumulation in highly vascular liver tissue, and the production of reactive oxygen species in MIA-PaCa-2 cancer cells via rhodin g7 71-ethyl ester correspond to its higher cytotoxicity as a newly developed photosensitizer. Therefore, rhodin g7 71-ethyl ester could be employed as an alternative or complementary agent to chlorin e6 in the photodynamic therapy for treating cancer cells.


Asunto(s)
Clorofilidas , Fármacos Fotosensibilizantes , Porfirinas , Porfirinas/química , Porfirinas/farmacología , Humanos , Animales , Ratones , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/química , Línea Celular Tumoral , Células RAW 264.7 , Especies Reactivas de Oxígeno/metabolismo , Supervivencia Celular/efectos de los fármacos , Fotoquimioterapia/métodos , Oxígeno Singlete/metabolismo , Antineoplásicos/farmacología , Antineoplásicos/química
7.
BMC Complement Med Ther ; 24(1): 270, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-39010043

RESUMEN

BACKGROUND: Medicinal plant-mediated combinational therapies have gained importance globally due to minimal side effects and enhanced treatment outcomes compared to single-drug modalities. We aimed to analyze the cytotoxic potential of each conventional treatment i.e., photodynamic therapy (PDT), chemotherapy (doxorubicin hydrochloride; Dox-HCl) with or without various concentrations of medicinal plant extracts (PE) on soft tissue cancer Rhabdomyosarcoma (RD) cell line. METHODS: The Rhabdomyosarcoma (RD) cell line was cultured and treated with Photosensitizer (Photosense (AlPc4)), Chemo (Dox-HCl), and their combinations with different concentrations of each plant extract i.e., Thuja occidentalis, Moringa oleifera, Solanum surattense. For the source of illumination, a Diode laser (λ = 630 nm ± 1 nm, Pmax = 1.5 mW) was used. Photosensitizer uptake time (∼ 45 min) was optimized through spectrophotometric measurements (absorption spectroscopy). Drug response of each treatment arm was assessed post 24 h of administration using 3-(4, 5-dimethyl-2-thiazolyl)-2, 5- 5-diphenyl-2 H- tetrazolium bromide (MTT) assay. RESULTS: PE-mediated Chemo-Photodynamic therapy (PDT) exhibited synergistic effects (CI < 1). Moreover, Rhabdomyosarcoma culture pretreated with various plant extracts for 24 h exhibited significant inhibition of cell viability however most effective outcomes were shown by low and high doses of Moringa oleifera compared to other plant extracts. Post low doses treated culture with all plant extracts followed by PDT came up with more effectiveness when compared to all di-therapy treatments. CONCLUSION: The general outcome of this work shows that the ethanolic plant extracts (higher doses) promote the death of cancerous cells in a dose-dependent way and combining Dox-HCl and photo-mediated photodynamic therapy can yield better therapeutic outcomes.


Asunto(s)
Doxorrubicina , Fotoquimioterapia , Fármacos Fotosensibilizantes , Extractos Vegetales , Plantas Medicinales , Rabdomiosarcoma , Fotoquimioterapia/métodos , Humanos , Doxorrubicina/farmacología , Rabdomiosarcoma/tratamiento farmacológico , Extractos Vegetales/farmacología , Línea Celular Tumoral , Fármacos Fotosensibilizantes/farmacología , Plantas Medicinales/química , Solanum/química , Supervivencia Celular/efectos de los fármacos , Moringa oleifera/química
8.
Photochem Photobiol ; 2024 Jun 02.
Artículo en Inglés | MEDLINE | ID: mdl-38824412

RESUMEN

Photochemical generation of singlet oxygen (1O2) often relies on homogenous systems; however, a dissolved photosensitizer (PS) may be unsuitable for some applications because it is difficult to recover, expensive to replenish, and hazardous to the environment. Isolation of the PS onto a solid support can overcome these limitations, but implementation faces other challenges, including agglomeration of the solid PS, physical quenching of 1O2 by the support, photooxidation of the PS, and hypoxic environments. Here, we explore a superhydrophobic polydimethylsiloxane (SH-PDMS) support coated with the photosensitizer 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin (TFPP). This approach seeks to address the challenges of a heterogeneous system by using a support that exhibits low 1O2 physical quenching rates, a fluorinated PS that is chemically resistant to photooxidation, and a superhydrophobic surface that entraps a layer of air, thus preventing hypoxia. Absorbance and fluorescence spectroscopy reveal the monomeric arrangement of TFPP on SH-PDMS surfaces, a surprising but favorable characteristic for a solid-phase PS on 1O2 yields. We also investigated the effect of incident wavelength on 1O2 yields for TFPP in aqueous solution and immobilized on SH-PDMS and found overall yields to be dependent on the absorption coefficient, while the yield per absorbed photon exhibited wavelength independence, in accordance with Kasha-Vavilov's rule.

9.
Bioorg Med Chem ; 109: 117810, 2024 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-38906069

RESUMEN

The antimicrobial activity of new acid-functionalized porphyrins, with or without ultra-high irradiance, was investigated. Antibacterial efficacy was evaluated against Staphylococcus aureus (methicillin-resistant or methicillin-sensitive strains) and antifungal efficacy was evaluated against the yeast Candida albicans and the filamentous fungi Aspergillus fumigatus. Overall, the porphyrins tested are more effective against S. aureus. The best results were obtained with zinc diacid porphyrins 4 and 5 after only 3 min of ultra-high irradiation (500 mW/cm2, 405 nm), demonstrating that acid-functionalized porphyrins are promising as novel antimicrobial drugs for surface disinfection.


Asunto(s)
Antifúngicos , Aspergillus fumigatus , Candida albicans , Pruebas de Sensibilidad Microbiana , Porfirinas , Porfirinas/farmacología , Porfirinas/química , Porfirinas/síntesis química , Aspergillus fumigatus/efectos de los fármacos , Candida albicans/efectos de los fármacos , Antifúngicos/farmacología , Antifúngicos/síntesis química , Antifúngicos/química , Antibacterianos/farmacología , Antibacterianos/química , Antibacterianos/síntesis química , Bacterias Grampositivas/efectos de los fármacos , Staphylococcus aureus/efectos de los fármacos , Relación Estructura-Actividad , Estructura Molecular , Relación Dosis-Respuesta a Droga , Hongos/efectos de los fármacos
10.
Int J Mol Sci ; 25(12)2024 Jun 11.
Artículo en Inglés | MEDLINE | ID: mdl-38928126

RESUMEN

Photodynamic Therapy (PDT) is recognized for its exceptional effectiveness as a promising cancer treatment method. However, it is noted that overexposure to the dosage and sunlight in traditional PDT can result in damage to healthy tissues, due to the low tumor selectivity of currently available photosensitizers (PSs). To address this challenge, we introduce herein a new strategy where the small molecule-targeted agent, erlotinib, is integrated into a boron dipyrromethene (BODIPY)-based PS to form conjugate 6 to enhance the precision of PDT. This conjugate demonstrates optical absorption, fluorescence emission, and singlet oxygen generation efficiency comparable to the reference compound 7, which lacks erlotinib. In vitro studies reveal that, after internalization, conjugate 6 predominantly accumulates in the lysosomes of HepG2 cells, exhibiting significant photocytotoxicity with an IC50 value of 3.01 µM. A distinct preference for HepG2 cells over HELF cells is observed with conjugate 6 but not with compound 7. In vivo experiments further confirm that conjugate 6 has a specific affinity for tumor tissues, and the combination treatment of conjugate 6 with laser illumination can effectively eradicate H22 tumors in mice with outstanding biosafety. This study presents a novel and potential PS for achieving precise PDT against cancer.


Asunto(s)
Clorhidrato de Erlotinib , Neoplasias Hepáticas , Fotoquimioterapia , Fármacos Fotosensibilizantes , Porfobilinógeno , Humanos , Fotoquimioterapia/métodos , Animales , Ratones , Porfobilinógeno/análogos & derivados , Porfobilinógeno/química , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/química , Células Hep G2 , Neoplasias Hepáticas/tratamiento farmacológico , Neoplasias Hepáticas/patología , Clorhidrato de Erlotinib/farmacología , Clorhidrato de Erlotinib/química , Compuestos de Boro/química , Compuestos de Boro/farmacología
11.
Nano Lett ; 2024 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-38857313

RESUMEN

The quantum yield of reactive oxygen species is of central importance for the development of organic photosensitizers and photodynamic therapy (PDT). A common molecular design approach for optimizing organic photosensitizers involves the incorporation of heavy atoms into their backbones. However, this raises concerns regarding heightened dark cytotoxicity and a shortened triplet-state lifetime. Herein, we demonstrate a heavy-atom-free (HAF) photosensitizer design strategy founded on the singlet fission (SF) mechanism for cancer PDT. Through the "single-atom surgery" approach to deleting oxygen atoms in pyrazino[2,3-g]quinoxaline skeleton photosensitizers, photosensitizers PhPQ and TriPhPQ are produced with Huckel's aromaticity and Baird's aromaticity in the ground state and triplet state, respectively, enabling the generation of two triplet excitons through SF. The SF process endows photosensitizer PhPQ with an ultrahigh triplet-state quantum yield (186%) and an outstanding 1O2 quantum yield (177%). Notably, HAF photosensitizers PhPQ and TriPhPQ enhanced PDT efficacy and potentiated αPD-L1 immune check blockade therapy in vivo, which show their promise for translational oncology treatment.

12.
F1000Res ; 13: 152, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38854440

RESUMEN

Background: Managing recalcitrant oral lichen planus (OLP) can be challenging. Laser therapy has been suggested as an alternative to corticosteroids for treatment. Photodynamic therapy (PDT) is a non-invasive technique that enables the removal of lesions without surgery. Photobiomodulation therapy (PBMT) can promote healing and recovery of the lesions. Case presentation: The objective was to treat unresponsive bilateral OLP of the whole buccal mucosae with a combination of PDT and PBMT. Results: A 43-year-old Thai male presented with the severe painful reticular type of OLP of bilateral buccal mucosae involving upper and lower vestibular areas. The lesions were not remitted with either prednisolone systemic steroids or fluocinolone topical corticosteroids. After undergoing ten sessions of PDT with 10% 5-Aminolevulinic acid (5-ALA) in the form of thermoplastic gel and a 635 nm diode laser at 100 to 400 mW with an energy density of 20 to 30 J/cm 2 in continuous wave mode, combined with five interim-sessions of PBMT using a 635 nm diode laser at 200 to 300 mW with an energy density of 6 to 10 J/cm 2 in continuous wave, the patient reported relief of burning sensation beside remission of lesions without any complications. Conclusion: The wide-spreading recalcitrant OLP with burning sensation can be managed by combining PDT and PBMT.


Asunto(s)
Liquen Plano Oral , Terapia por Luz de Baja Intensidad , Mucosa Bucal , Fotoquimioterapia , Humanos , Masculino , Adulto , Fotoquimioterapia/métodos , Liquen Plano Oral/tratamiento farmacológico , Liquen Plano Oral/terapia , Liquen Plano Oral/radioterapia , Liquen Plano Oral/patología , Mucosa Bucal/patología , Terapia por Luz de Baja Intensidad/métodos , Terapia Combinada , Ácido Aminolevulínico/uso terapéutico , Ácido Aminolevulínico/análogos & derivados
13.
Artículo en Inglés | MEDLINE | ID: mdl-38919078

RESUMEN

Platinum (II) drugs, including cisplatin, carboplatin, and oxaliplatin, have achieved significant clinical success in cancer treatment. However, their clinical application has been greatly hindered by various adverse factors such as non-specific activation and drug resistance. Compared with Pt(II) drugs, the axial ligands within Pt(IV) compounds can improve the pharmacokinetic properties, selectivity, and biological activity, implementing alternative cytotoxic mechanisms beyond DNA cross-linking and partially overcoming drug resistance. The controlled conversion of Pt(IV) prodrugs into Pt(II) agents at the tumor site has been extensively explored internationally. In this review, Pt(IV) prodrug modification strategies are first summarized, next the development of the predominant external and internal photosensitizers is listed. Finally, three representative photoreduction mechanisms and strategies for developing corresponding Pt(IV) prodrugs are discussed. This work provides constructive instruction for the subsequent molecular design of Pt(IV) prodrugs.

.

14.
Photodiagnosis Photodyn Ther ; 48: 104249, 2024 Jun 17.
Artículo en Inglés | MEDLINE | ID: mdl-38897530

RESUMEN

BACKGROUND: This study aimed to evaluate the impact of photodynamic therapy (PDT) using two photosensitizers, methylene blue and indocyanine green, on the microtensile bond strength of a universal adhesive to caries-affected dentin. METHODS: The occlusal enamel of 60 third molars was cut to expose the inner one-third of the dentin. Artificial caries were induced through a pH cycling process. The samples were divided into three groups: M (Methylene blue+ diode laser), I (Indocyanine green agents+ diode laser irradiation), and control. Each group was further divided into two subgroups according to the adhesive protocol (self-etch, total-etch). After restoring with Gradia composite resin, teeth were sectioned and exposed to 5000 thermal cycles. Microtensile bond strength was measured using a universal testing machine. The data were subjected to two- and one-way ANOVA and paired comparisons were performed by the Tamhane and Tukey tests. RESULTS: The study found significant effects of the photosensitizer, etching pattern, and their interactions on the microtensile bond strength of composite resin to caries-affected dentin (P < 0.001). In the self-etching mode, PDT with indocyanine green exhibited significantly higher bond strength values compared to PDT with methylene blue (P = 0.001) and the control groups (P < 0.001). However, no significant differences were observed in the total-etch mode. (P = 0.54). CONCLUSIONS: The etching mode played a more significant role in the bond strength when using the universal adhesive alongside PDT with methylene blue and indocyanine green. Employing two photosensitizers in PDT during the self-etch mode significantly increased the bond strength values.

15.
Colloids Surf B Biointerfaces ; 241: 114018, 2024 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-38865868

RESUMEN

The pressing need for highly efficient antibacterial strategies arises from the prevalence of microbial biofilm infections and the emergence of rapidly evolving antibiotic-resistant strains of pathogenic bacteria. Photodynamic therapy represents a highly efficient and compelling antibacterial approach, offering promising prospects for effective control of the development of bacterial resistance. However, the effectiveness of many photosensitizers is limited due to the reduced generation of reactive oxygen species (ROS) in hypoxic microenvironment, which commonly occur in pathological conditions such as inflammatory and bacteria-infected wounds. Herein, we designed and prepared two phenothiazine-derived photosensitizers (NB-1 and NB-2), which can effectively generate superoxide anion radicals (O2●-) through the type I process. Both photosensitizers demonstrate significant efficacy in vitro for the eradication of broad-spectrum bacteria. Moreover, NB-2 possesses distinct advantages including strong membrane binding and strong generation of O2●-, rendering it an exceptionally efficient antibacterial agent against mature biofilms. In addition, laser activated NB-2 could be applied to treat MRSA-infected wound in vivo, which offers new opportunities for potential practical applications.

16.
Int J Mol Sci ; 25(11)2024 May 25.
Artículo en Inglés | MEDLINE | ID: mdl-38891937

RESUMEN

Modular supramolecular complexes, where different proteins are assembled to gather targeting capability and photofunctional properties within the same structures, are of special interest for bacterial photodynamic inactivation, given their inherent biocompatibility and flexibility. We have recently proposed one such structure, exploiting the tetrameric bacterial protein streptavidin as the main building block, to target S. aureus protein A. To expand the palette of targets, we have linked biotinylated Concanavalin A, a sugar-binding protein, to a methylene blue-labelled streptavidin. By applying a combination of spectroscopy and microscopy, we demonstrate the binding of Concanavalin A to the walls of Gram-positive S. aureus and Gram-negative E. coli. Photoinactivation is observed for both bacterial strains in the low micromolar range, although the moderate affinity for the molecular targets and the low singlet oxygen yields limit the overall efficiency. Finally, we apply a maximum entropy method to the analysis of autocorrelation traces, which proves particularly useful when interpreting signals measured for diffusing systems heterogeneous in size, such as fluorescent species bound to bacteria.


Asunto(s)
Pared Celular , Concanavalina A , Escherichia coli , Staphylococcus aureus , Concanavalina A/química , Concanavalina A/metabolismo , Escherichia coli/metabolismo , Staphylococcus aureus/metabolismo , Pared Celular/metabolismo , Estreptavidina/química , Estreptavidina/metabolismo , Proteínas Bacterianas/metabolismo , Unión Proteica
17.
Angew Chem Int Ed Engl ; : e202408064, 2024 Jun 09.
Artículo en Inglés | MEDLINE | ID: mdl-38853147

RESUMEN

Tumor-specific activatable long-wavelength (LW) photosensitizers (PSs) show promise in overcoming the limitations of traditional photodynamic therapy (PDT), such as systemic phototoxicity and shallow tissue penetration. However, their insufficient LW light absorption and low singlet oxygen quantum yield (F1O2) usually require high laser power density to produce thermal energy and synergistically enhance PDT. The strong photothermal radiation causing acute pain significantly reduces patient compliance and hinders the broader clinical application of LW PDT. Through the exciton dynamics dissection strategy, we have developed a series of pH-activatable cyanine-based LW PSs (LET-R, R = H, Cl, Br, I), among which the activated LET-I exhibits strong light absorption at 808 nm and a remarkable 3.2-fold enhancement in F1O2 compared to indocyanine green. Transient spectroscopic analysis and theoretical calculations confirmed its significantly promoted intersystem crossing and simultaneously enhanced LW fluorescence emission characteristics. These features enable the activatable fluorescence and photoacoustic dual-modal imaging-escorted complete photodynamic eradication of tumors by the folic acid (FA)-modified LET-I probe (LET-I-FA), under the ultralow 808 nm laser power density (0.2 W cm-2) for irradiation, without the need for photothermal energy synergy. This research presents a novel strategy of dissecting exciton dynamics to screen activatable LW PSs for traceable PDT.

18.
Chemistry ; : e202401483, 2024 Jun 09.
Artículo en Inglés | MEDLINE | ID: mdl-38853431

RESUMEN

Herein, we report a novel flavin analogue as singular chemical component for lysosome bioimaging and inherited photosensitizer capability of the flavin core was demonstrated as a promising candidate for photodynamic therapy (PDT) application. Fine-tuning the flavin core with the incorporation of methoxy naphthyl appendage provides an appropriate chemical design, thereby offering greater photostability, selectivity, and lysosomal colocalization, along with the aggregation-induced emissive nature, making it suitable for lysosomal bioimaging, applications. Additionally, photosensitization capability of the flavin core with photostable nature of the synthesized analogue has shown remarkable capacity for generating reactive oxygen species (ROS) within cells making it a promising candidate for photodynamic therapy (PDT) application.

19.
Environ Sci Technol ; 58(24): 10817-10827, 2024 Jun 18.
Artículo en Inglés | MEDLINE | ID: mdl-38832598

RESUMEN

Direct photoreduction of FeIII is a widely recognized route for accelerating FeIII/FeII cycle in photo-Fenton chemistry. However, most of the wavelengths covering the full spectral range are insufficient to supply enough photon energy for the direct reduction process. Herein, the hitherto neglected mechanism of FeIII reduction that the FeIII indirect reduction pathway initiated by light energy-dependent reactivity variation and reactive excited state (ES) was explored. Evolution of excited-state FeIII species (*FeIII) resulting from metal-centered charge excitation (MCCE) of FeIII is experimentally verified using pulsed laser femtosecond transient absorption spectroscopy with UV-vis detection and theoretically verified by quantum chemical calculation. Intense photoinduced intravalence charge transition was observed at λ = 380 and 466 nm, revealing quartet 4MCCE and doublet 2MCCE and their exponential processes. Light energy-dependent variation of *FeIII reactivity was kinetically certified by fitting the apparent rate constant of the radical-chain sequence of photo-Fenton reactions. Covalency is found to compensate for the intravalence charge separation following photoexcitation of the metal center in the MCCE state of Fenton photosensitizer. The *FeIII is established as a model, demonstrating the intravalence hole delocalization in the ES can be leveraged for photo-Fenton reaction or other photocatalytic schemes based on electron transfer chemistry.


Asunto(s)
Hierro , Hierro/química , Oxidación-Reducción , Peróxido de Hidrógeno/química , Cinética
20.
Environ Sci Technol ; 58(25): 11096-11104, 2024 Jun 25.
Artículo en Inglés | MEDLINE | ID: mdl-38865480

RESUMEN

Hydrogen peroxide (H2O2) plays a crucial role as an oxidizing agent within the tropospheric environment, making a substantial contribution to sulfate formation in hydrated aerosols and cloud and fog droplets. Field observations show that high levels of H2O2 are often observed in heavy haze events and polluted air. However, the source of H2O2 remains unclear. Here, using the droplets formed in situ by the deliquescence of hygroscopic compounds under a high relative humidity (RH), the formation of H2O2 by the photochemistry of imidazole-2-carbaldehyde (2-IC) under ultraviolet irradiation was explored. The results indicate that 2-IC produces IM-C•-OH and IM-C•═O radicals via H transfer itself to its excited triplet state and generates H2O2 and organic peroxides in the presence of O2, which has an evident oxidizing effect on SO2, suggesting the potential involvement of this pathway in the formation of atmospheric sulfate. H2O2 formation is limited in acidic droplets or droplets containing ammonium ions, and no H2O2 is detected in droplets containing nitrate, whereas droplets containing citric acid have an obvious promotion effect on H2O2 formation. These findings provide valuable insights into the behaviors of atmospheric photosensitizers, the source of H2O2, and the formation of sulfate in atmospheric droplets.


Asunto(s)
Peróxido de Hidrógeno , Oxidación-Reducción , Peróxido de Hidrógeno/química , Imidazoles/química , Fotoquímica , Dióxido de Azufre/química , Contaminantes Atmosféricos/química , Rayos Ultravioleta
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