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1.
Naturwissenschaften ; 111(1): 6, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38300300

RESUMO

Pigmentary coloration is widespread in animals. Its evolutionary and ecological features are often attributed to the property of predominant pigments; therefore, most research has focused on predominant pigments such as carotenoids in carotenoid-based coloration. However, coloration results from predominant pigments and many other minority pigments, and the importance of the latter is overlooked. Here, we focused on porphyrin, an "uncommon" pigment found in bird feathers, and investigated its importance in the context of feather color changes in the barn swallow Hirundo rustica. We found that the "pheomelanin-based coloration" of the barn swallow faded after the irradiation of UV light, and this effect was particularly strong in the feathers of young swallows (nestlings and fledglings, here). We also found that it is not the predominant pigment, pheomelanin, but protoporphyrin IX pigment that showed the same pattern of depigmentation after the irradiation of UV light, particularly in the feathers of young swallows. In fact, the abovementioned age-dependent feather color change was statistically explained by the amount of porphyrin in the feathers. The current study demonstrates that a minority pigment, porphyrin, explains within-season dynamic color change, an ecological feature of feather coloration. The porphyrin-mediated rapid color change would benefit young birds, in which feather coloration affects the parental food allocation during a few weeks before independence, but not later. Future studies should not ignore these minor but essential pigments and their evolutionary and ecological functions.


Assuntos
Plumas , Porfirinas , Animais , Raios Ultravioleta , Evolução Biológica , Carotenoides
2.
ACS Appl Mater Interfaces ; 16(7): 8403-8416, 2024 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-38334116

RESUMO

Cancer immunotherapy is expected to achieve tumor treatment mainly by stimulating the patient's own immune system to kill tumor cells. However, the low immunogenicity of the tumor and the poor efficiency of tumor antigen presentation result in a variety of solid tumors that do not respond to immunotherapy. Herein, we designed a proton-gradient-driven porphyrin-based liposome (PBL) with highly efficient Toll-like receptor 7 (TLR7) agonist (imiquimod, R837) encapsulation (R837@PBL). R837@PBL rapidly released R837 in the acid microenvironment to activate the TLR in the endosome inner membrane to promote bone-marrow-derived dendritic cell maturation and enhance antigen presentation. R837@PBL upon laser irradiation triggered immunogenic cell death of tumor cells and tumor-associated antigen release after subcutaneous injection, activated TLR7, formed in situ tumor nanoadjuvants, and enhanced the antigen presentation efficiency. Photoimmunotherapy promoted the infiltration of cytotoxic T lymphocytes into tumor tissues, inhibited the growth of the treated and abscopal tumors, and exerted highly effective photoimmunotherapeutic effects. Hence, our designed in situ tumor nanoadjuvants are expected to be an effective treatment for treated and abscopal tumors, providing a novel approach for synergistic photoimmunotherapy of tumors.


Assuntos
Neoplasias , Porfirinas , Humanos , Imiquimode/farmacologia , Lipossomos/farmacologia , Receptor 7 Toll-Like/agonistas , Prótons , Porfirinas/farmacologia , Neoplasias/terapia , Imunoterapia , Adjuvantes Imunológicos/farmacologia , Antígenos de Neoplasias , Microambiente Tumoral , Linhagem Celular Tumoral
3.
ACS Appl Bio Mater ; 7(2): 1204-1213, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38211352

RESUMO

Here, we report that a mesoporous silica nanoparticle (MSN) coated with a fluoresceine-labeled bovine serum albumin (F-BSA) hydrogel layer works as a temperature-responsive nanocarrier for tetrakis-N-methylpyridyl porphyrin (TMPyP) and as a fluorescence ratiometric pH probe. F-BSA hydrogel-coated MSN containing TMPyP (F-BSA/MSN/TMPyP) was synthesized by thermal gelation of denatured F-BSA on the external surface of MSN. The F-BSA hydrogel layer was composed of an inner hard corona layer and an outer soft layer and was stable under physiological conditions. F-BSA/MSN/TMPyP exhibited temperature-dependent exponential release of TMPyP. In this release profile, the MSN was found to be a suitable host for stable encapsulation of tetracationic TMPyP by electrostatic interactions, and the F-BSA hydrogel layer mediated the diffusion of TMPyP from the MSN pore interior into the solution phase. Increasing temperature promoted partitioning of TMPyP from the pore interior to the F-BSA hydrogel layer, from where it was spontaneously released into the bulk solution phase by cation exchange. F-BSA/MSN/TMPyP also gave a linear ratiometric fluorescence response (1.3 per pH unit) in the pH range from 6.1 to 8.9.


Assuntos
Nanopartículas , Porfirinas , Dióxido de Silício , Fluorescência , Hidrogéis , Soroalbumina Bovina , Concentração de Íons de Hidrogênio , Cátions
4.
Anal Chem ; 96(4): 1427-1435, 2024 01 30.
Artigo em Inglês | MEDLINE | ID: mdl-38226591

RESUMO

Although porphyrins make up a promising class of electrochemiluminescence (ECL) luminophors, their aggregation-caused quenching (ACQ) characteristics lead to inferior ECL efficiency (ΦECL). Furthermore, current application of porphyrins is limited to cathodic emission. This work creatively exploited a cage-like porous complex (referred to as SWU-1) as the microreactor to recede the ACQ effect while modulating dual ECL emission of meso-tetra(4-carboxyphenyl)porphine (TCPP), which self-assembled with SWU-1 to form TCPP@SWU-1 nanocapsules (TCPP@SWU-1 NCs). As the microreactor, SWU-1 not only effectively constrained TCPP aggregation to improve electron-hole recombination efficiency but also improved stability of anion and cation radicals, thus significantly enhancing the dual emission of TCPP. Compared with TCPP aggregates, the resulting TCPP@SWU-1 NCs exhibited significantly enhanced anodic and cathodic emission, and their ΦECL was increased by 8.7-fold and 3.9-fold, respectively. Furthermore, black hole quencher-2 (BHQ2) can simultaneously quench anodic and cathodic signals. TCPP@SWU-1 NCs coupling BHQ2 conveniently achieved an ECL ratio detection of miRNA-126, and the limit of detection (S/N = 3) was 4.1 aM. This work pioneered the development of the cage-like porous complex SWU-1 as the microreactor to alleviate defects of the ACQ effect and mediate dual emission of TCPP. The coupling of dual-emitting TCPP@SWU-1 NCs and dual-function moderator BHQ2 created a novel single-luminophor-based ratio system for bioanalysis and provided a promising ECL analysis approach for miRNA-126.


Assuntos
Técnicas Biossensoriais , MicroRNAs , Porfirinas , Porosidade , Fotometria , Medições Luminescentes/métodos , Técnicas Eletroquímicas/métodos
5.
ACS Appl Bio Mater ; 7(2): 1250-1259, 2024 Feb 19.
Artigo em Inglês | MEDLINE | ID: mdl-38253544

RESUMO

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


Assuntos
Cárie Dentária , Fulerenos , Porfirinas , alfa-Amilases Salivares , Humanos , Fulerenos/química , Amido/metabolismo , Microscopia Eletrônica de Varredura
6.
Biomater Sci ; 12(4): 964-977, 2024 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-38168803

RESUMO

Biofilms pose significant threats to public health by causing persistent clinical infections. The development of innovative antibacterial approaches for eliminating biofilms is an urgent necessity. In this study, we developed amphiphilic Janus nanoparticles (JNPs), loaded with hydrophobic chlorin e6 (Ce6) and hydrophilic S-nitrosoglutathione (GSNO), denoted as Ce6-PDA/CaP-GSNO, with the aim to effectively eradicate biofilms and combat methicillin-resistant Staphylococcus aureus (MRSA) infections through nitric oxide (NO) synergistic photodynamic therapy (PDT). Ce6-PDA/CaP-GSNO demonstrated remarkable biofilm penetration ability, efficiently reaching the acidic inner layers, which triggered the rapid release of GSNO, resulting in the generation of an abundant supply of NO. NO not only exhibited potent bactericidal activity but also effectively lowered the GSH level of the biofilm, leading to enhanced efficacy of Ce6. Additionally, the interaction between NO and reactive oxygen species (ROS) resulted in the generation of reactive nitrogen species (RNS), further enhancing PDT efficacy both in vitro and in vivo. In summary, Ce6-PDA/CaP-GSNO demonstrated remarkable biofilm penetration capacity and effective reduction of the GSH level in the biofilms, leading to enhanced PDT efficacy at low photosensitizer doses and laser intensities, thereby minimizing adverse effects on normal tissues. These findings highlight the promising potential of our approach for combating biofilm-related infections.


Assuntos
Staphylococcus aureus Resistente à Meticilina , Nanopartículas Multifuncionais , Nanopartículas , Fotoquimioterapia , Porfirinas , Fotoquimioterapia/métodos , Óxido Nítrico , Fármacos Fotossensibilizantes/química , Porfirinas/química , Biofilmes , Nanopartículas/química
7.
J Photochem Photobiol B ; 251: 112847, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38241947

RESUMO

The bovine tick Rhipicephalus microplus, a primary ectoparasite of veterinary concern, contributes significantly to disease transmission and reduced cattle productivity, resulting in substantial economic losses. The overuse of chemical acaricides has led to the emergence of resistant strains, posing a considerable challenge to veterinary medicine. Consequently, the development of alternative parasite control methods is essential to ensure livestock quality and enhance food safety worldwide. Our study introduces an innovative approach to photodynamic inactivation (PDI) of the bovine tick, harnessing natural daylight for a potential field application. Reproductive parameters (female and egg mass, egg production index, and larval hatch) were evaluated in engorged female ticks under photodynamic action using the hematoporphyrin (HP) and tetra-cationic porphyrins free-base meso-tetra-ruthenated (4-pyridyl) (RuTPyP) and its zinc(II) complex (ZnRuTPyP) as photosensitizers (PS). The results showed that there was no significant difference between the groups treated with tetra­ruthenium porphyrins and the control group. However, HP exhibits a control percentage of 97.9% at a concentration of 2.5 µmol.L-1, aligning with the expected control rates achieved by conventional chemical acaricides. Photophysical and physicochemical parameters such as the number of singlet oxygen produced and lipophilicity were discussed for each PS and related to tick control percentages. Furthermore, the interaction between HP and chitin, an important macromolecule presents in the tick's cuticle, considered as the primary target tick structure during PDI was observed by the absorption and fluorescence emission spectroscopic techniques. Therefore, the results presented here extend the potential for controlling R. microplus through photodynamic inactivation while utilizing sunlight as a source of natural irradiation.


Assuntos
Acaricidas , Porfirinas , Rhipicephalus , Animais , Feminino , Bovinos , Acaricidas/farmacologia , Rhipicephalus/fisiologia , Porfirinas/farmacologia , Reprodução
8.
Biochim Biophys Acta Biomembr ; 1866(3): 184270, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38211647

RESUMO

Transition of Mycolicibacterium smegmatis (Msm) and Mycobacterium tuberculosis to dormancy in vitro is accompanied by an accumulation of free methylated forms of porphyrins (tetramethyl coproporphyrin - TMC) localized in the cell wall of dormant bacteria. A study of the fluorescence anisotropy of BODIPY based fluorescent probes on individual cell level using confocal microscope revealed significant changes in this parameter for BODIPY FL C16 from 0.05 to 0.22 for vegetative and dormant Msm cells correspondingly. Similarly, the increase of TMC concentration in vegetative Msm cells grown in the presence of 5-aminolevulinic acid (a known inducer of porphyrin synthesis) resulted in an increase of BODIPY FL C16 anisotropy. These changes in TMC concentration and membrane fluidity were accompanied by an inhibition of the activity of the respiratory chain measured by oxygen consumption and a reduction of the DCPIP redox acceptor. During the first 8 h of the reactivation of the dormant Msm cells, the porphyrin content and probe fluorescent anisotropy returned to the level for vegetative bacteria. We suggested that upon transition to dormancy, an accumulation of TMC in membranes leads to a decrease in membrane fluidity, resulting in an inhibition of the respiratory chain activity. However, direct interactions of TMC with membrane bound enzymes cannot also be excluded. This, in turn, may result in the down regulation of many metabolic energy-dependent reactions as a part of mechanisms accompanying the transition to a hypometabolic state of mycobacteria.


Assuntos
Compostos de Boro , Porfirinas , Transporte de Elétrons , Fluidez de Membrana , Ácidos Palmíticos/metabolismo , Mycobacterium smegmatis/metabolismo
9.
Sci Rep ; 14(1): 846, 2024 01 08.
Artigo em Inglês | MEDLINE | ID: mdl-38191600

RESUMO

Mycobacterium tuberculosis (Mtb) is able to transition into a dormant state, causing the latent state of tuberculosis. Dormant mycobacteria acquire resistance to all known antibacterial drugs and can survive in the human body for decades before becoming active. In the dormant forms of M. tuberculosis, the synthesis of porphyrins and its Zn-complexes significantly increased when 5-aminolevulinic acid (ALA) was added to the growth medium. Transcriptome analysis revealed an activation of 8 genes involved in the metabolism of tetrapyrroles during the Mtb transition into a dormant state, which may lead to the observed accumulation of free porphyrins. Dormant Mtb viability was reduced by more than 99.99% under illumination for 30 min (300 J/cm2) with 565 nm light that correspond for Zn-porphyrin and coproporphyrin absorptions. We did not observe any PDI effect in vitro using active bacteria grown without ALA. However, after accumulation of active cells in lung macrophages and their persistence within macrophages for several days in the presence of ALA, a significant sensitivity of active Mtb cells (ca. 99.99%) to light exposure was developed. These findings create a perspective for the treatment of latent and multidrug-resistant tuberculosis by the eradication of the pathogen in order to prevent recurrence of this disease.


Assuntos
Mycobacterium tuberculosis , Porfirinas , Tuberculose , Humanos , Ácido Aminolevulínico/farmacologia , Macrófagos , Zinco
10.
ACS Appl Mater Interfaces ; 16(5): 5683-5695, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38261396

RESUMO

Photosensitizers have been widely used to cause intratumoral generation of reactive oxygen species (ROS) for cancer therapy, but they are easily disturbed by the autophagy pathway, a self-protective mechanism by mitigating oxidative damage. Hereby, we reported a simple and effective strategy to construct a carrier-free nanodrug, Ce6@CQ namely, based on the self-assembly of the photosensitizer chlorin e6 (Ce6) and the autophagy inhibitor chloroquine (CQ). Specifically, Ce6@CQ avoided the unexpected toxicity caused by the regular nanocarrier and also ameliorated its stability in different conditions. Light-activated Ce6 generated cytotoxic ROS and elicited part of the immunogenic cell death (ICD). Moreover, CQ induced autophagy dysfunction, which hindered self-healing in tumor cells and enhanced photodynamic therapy (PDT) to exert a more potent killing effect and more efficient ICD. Also, Ce6@CQ could effectively accumulate in the xenograft breast tumor site in a mouse model through the enhanced permeability and retention (EPR) effect, and the growth of breast tumors was effectively inhibited by Ce6@CQ with light. Such a carrier-free nanodrug provided a new strategy to improve the efficacy of PDT via the suppression of autophagy to digest ROS-induced toxic substances.


Assuntos
Neoplasias da Mama , Nanopartículas , Fotoquimioterapia , Porfirinas , Animais , Camundongos , Humanos , Feminino , Neoplasias da Mama/tratamento farmacológico , Neoplasias da Mama/patologia , Espécies Reativas de Oxigênio/metabolismo , Linhagem Celular Tumoral , Morte Celular Imunogênica , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/uso terapêutico , Autofagia , Porfirinas/farmacologia , Porfirinas/uso terapêutico
11.
J Colloid Interface Sci ; 660: 1021-1029, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38295540

RESUMO

Multifunctional nanomaterials with potential applications in both bioimaging and photodynamic-sonodynamic therapy have great advantages in cancer theranostic, but the design and preparation of "all-in-one" type of multifunctional nanomaterials with single component remains challenging. Herein the "all-in-one" type of Mn-PpIX (Protoporphyrin IX) coordination polymers (MnPPs) was reported as efficient nano-photo/sonosensitizers. The MnPPs had an average size of âˆ¼ 110 nm. Upon light/US (ultrasound) irradiation for 5 min, 61.8 % (light) and 32.4 % (US) of DPBF (1.3-diphenyl isobenzofuran) was found to be oxidized by MnPPs, which showed effective ROS (reactive oxygen species) generation for photodynamic/sonodynamic therapy (PDT/SDT). In addition, MnPPs revealed excellent biosafety and could be engulfed by cells to produce intracellular ROS under light/US excitation for efficient killing tumor cells. When MnPPs was injected into mice, the tumor could be monitored via MRI (magnetic resonance imaging). In addition, tumor growth could be significantly inhibited by the synergistic PDT-SDT. Therefore, the present study not only represents MnPPs as an "all-in-one" type of multifunctional nanomaterials for MRI-guided PDT-SDT therapy, but also provides some insights for designing other PpIX-related molecules with the similar structure for bioapplication.


Assuntos
Neoplasias , Porfirinas , Terapia por Ultrassom , Camundongos , Animais , Terapia por Ultrassom/métodos , Espécies Reativas de Oxigênio , Polímeros/farmacologia , Imageamento por Ressonância Magnética , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico , Linhagem Celular Tumoral
12.
Mol Pharm ; 21(2): 609-621, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-38189667

RESUMO

The development of targeted drug delivery mechanisms in the human body is a matter of growing interest in medical science. The selective release of therapeutic agents at a specific target site can increase the therapeutical efficiency and at the same time reduce the side effects. Light-sensitive liposomes can release a drug by an externally controlled light trigger. Liposomes containing photosensitizers that can be activated in the longer wavelength range (650-800 nm) are particularly intriguing for medical purposes. This is because light penetration into a tissue is more efficient within this wavelength range, increasing their potential applications. For this study, liposomes with an encapsulated amphiphilic photosensitizer, the porphyrin 5,10-DiOH (5,10-di(4-hydroxyphenyl)-15,20-diphenyl-21,23H-porphyrin), its chlorin (5,10-DiOH-chlorin) and its bacteriochlorin (5,10-DiOH-bacteriochlorin) were synthesized. The porphyrin 5,10-DiOH showed previously effective cargo release after liposomal encapsulation when irradiated at a wavelength of 420 nm. The new synthesized chlorin and bacteriochlorin photosensitizers show additional absorption bands in the longer wavelength range, which would enable excitation in deeper layers of tissue. Effective cargo release with chlorin at a longer wavelength of 650 nm and bacteriochlorin at 740 nm was possible. Irradiation of chlorin allowed more than 75% of the cargo to be released and more than 60% for bacteriochlorin. The new liposomes would enable selective drug release in deeper tissue layers and expand the range of possible applications.


Assuntos
Lipossomos , Porfirinas , Humanos , Fármacos Fotossensibilizantes
13.
ACS Nano ; 18(4): 3161-3172, 2024 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-38227816

RESUMO

Designing and constructing supramolecular photosensitizer nanosystems with highly efficient photodynamic therapy (PDT) is vital in the nanomedical field. Despite recent advances in forming well-defined superstructures, the relationship between molecular arrangement in nanostructures and photodynamic properties has rarely been involved, which is crucial for developing stable photosensitizers for highly efficient PDT. In this work, through a microemulsion-assisted self-assembly approach, indium porphyrin (InTPP) was used to fabricate a series of morphology-controlled self-assemblies, including nanorods, nanospheres, nanoplates, and nanoparticles. They possessed structure-dependent 1O2 generation efficiency. Compared with the other three nanostructures, InTPP nanorods featuring strong π-π stacking, J-aggregation, and high crystallinity proved to be much more efficient at singlet oxygen (1O2) production. Also, theoretical modeling and photophysical experiments verified that the intermolecular π-π stacking in the nanorods could cause a decreased singlet-triplet energy gap (ΔEST) compared with the monomer. This played a key role in enhancing intersystem crossing and facilitating 1O2 generation. Both in vitro and in vivo experiments demonstrated that the InTPP nanorods could trigger cell apoptosis and tumor ablation upon laser irradiation (635 nm, 0.1 W/cm2) and exhibited negligible dark toxicity and high phototoxicity. Thus, the supramolecular self-assembly strategy provides an avenue for designing high-performance photosensitizer nanosystems for photodynamic therapy and beyond.


Assuntos
Nanoestruturas , Fotoquimioterapia , Porfirinas , Fármacos Fotossensibilizantes/química , Porfirinas/farmacologia , Porfirinas/química , Índio , Nanoestruturas/química , Oxigênio Singlete/química
14.
Org Biomol Chem ; 22(7): 1484-1494, 2024 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-38289387

RESUMO

The development of photodynamic therapy requires access to smart photosensitizers which combine appropriate photophysical and biological properties. Interestingly, supramolecular and dynamic covalent chemistries have recently shown their ability to produce novel architectures and responsive systems through simple self-assembly approaches. Herein, we report the straightforward formation of porphyrin-peptide conjugates and cage compounds which feature on their surface chemical groups promoting cell uptake and specific organelle targeting. We show that they self-assemble, in aqueous media, into positively-charged nanoparticles which generate singlet oxygen upon green light irradiation, while also undergoing a chemically-controlled disassembly due to the presence of reversible covalent linkages. Finally, the biological evaluation in cells revealed that they act as effective photosensitizers and promote synergistic effects in combination with Doxorubicin.


Assuntos
Nanopartículas , Fotoquimioterapia , Porfirinas , Porfirinas/farmacologia , Porfirinas/química , Fármacos Fotossensibilizantes/química , Oxigênio Singlete , Nanopartículas/química , Peptídeos/farmacologia
15.
Eur J Med Chem ; 265: 116102, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-38176359

RESUMO

Study on corrole photosensitizers (PSs) for photodynamic therapy (PDT) has made remarkable progress. Targeted delivery of PSs is of great significance for enhancing therapeutic efficiency, decreasing the dosage, and reducing systemic toxicity during PDT. The development of PSs that can be specifically delivered to the subcellular organelle is still an attractive and challenging work. Herein, we synthesize a series of azide-modified corrole phosphorus and gallium complex PSs, in which phosphorus corrole 2-P could not only precisely target the endoplasmic reticulum (ER) with a Pearson correlation coefficient (PCC) up to 0.92 but also possesses the highest singlet oxygen quantum yields (ΦΔ = 0.75). This renders it remarkable PDT activity at a very low dosage (IC50 = 23 nM) towards HepG2 tumor cell line while ablating solid tumors in vivo with excellent biosecurity. Furthermore, 2-P exhibits intense red fluorescence (ΦF = 0.25), outstanding photostability, and a large Stokes shift (190 nm), making it a promising fluorescent probe for ER. This study provides a clinically potential photosensitizer for cancer photodynamic therapy and a promising ER fluorescent probe for bioimaging.


Assuntos
Neoplasias , Fotoquimioterapia , Porfirinas , Azidas , Fluorescência , Fósforo , Corantes Fluorescentes/farmacologia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacologia , Retículo Endoplasmático , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico
16.
Appl Microbiol Biotechnol ; 108(1): 68, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-38194135

RESUMO

Heme is an iron-containing porphyrin compound widely used in the fields of healthcare, food, and medicine. Compared to animal blood extraction, it is more advantageous to develop a microbial cell factory to produce heme. However, heme biosynthesis in microorganisms is tightly regulated, and its accumulation is highly cytotoxic. The current review describes the biosynthetic pathway of free heme, its fermentation production using different engineered bacteria constructed by metabolic engineering, and strategies for further improving heme synthesis. Heme synthetic pathway in Bacillus subtilis was modified utilizing genome-editing technology, resulting in significantly improved heme synthesis and secretion abilities. This technique avoided the use of multiple antibiotics and enhanced the genetic stability of strain. Hence, engineered B. subtilis could be an attractive cell factory for heme production. Further studies should be performed to enhance the expression of heme synthetic module and optimize the expression of heme exporter and fermentation processes, such as iron supply. KEY POINTS: • Strengthening the heme biosynthetic pathway can significantly increase heme production. • Heme exporter overexpression helps to promote heme secretion, thereby further promoting excessive heme synthesis. • Engineered B. subtilis is an attractive alternative for heme production.


Assuntos
Heme , Porfirinas , Animais , Fermentação , Antibacterianos , Ferro
17.
J Mater Chem B ; 12(3): 720-729, 2024 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-38165308

RESUMO

Nanoarchitectonics, an emerging strategy, presents a promising alternative for developing highly efficient next-generation functional materials. Multifunctional materials developed using nanoarchitectonics help to mimic biological molecules. Porphyrin-based molecules can be effectively utilized to design such assemblies. Metal nanocluster is one of the functional materials that can shed more insight into developing nanoarchitectonic materials. Herein, an inherently near-infrared (NIR) fluorescing copper nanocluster (CuC)-mediated structural assembly via protoporphyrin IX (PPIX) and doxorubicin (Dox) is demonstrated as the functional material. Dox-loaded porphyrin-mediated CuC assembly shows singlet oxygen generation and 66% drug release at 15 min. Furthermore, the efficacy of this material is tested for cancer diagnosis and bimodal therapeutic strategy due to the fluorescing ability of the cluster and loading of PPIX as well as the drug, respectively. The nanoarchitecture exhibits targeted imaging and 83% cell death in HeLa cells upon laser irradiation with 10 nmoles and 20 nmoles of PPIX and Dox, respectively.


Assuntos
Neoplasias , Porfirinas , Humanos , Cobre/química , Porfirinas/farmacologia , Células HeLa , Medicina de Precisão , Doxorrubicina/química , Neoplasias/diagnóstico por imagem , Neoplasias/tratamento farmacológico
18.
ACS Nano ; 18(5): 4539-4550, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38261792

RESUMO

Photocatalytic materials are some of the most promising substitutes for antibiotics. However, the antibacterial efficiency is still inhibited by the rapid recombination of the photogenerated carriers. Herein, we design a cationic covalent organic framework (COF), which has a symmetrical localized built-in electric field due to the induced polarization effect caused by the electron-transfer reaction between the Zn-porphyrin unit and the guanidinium unit. Density functional theory calculations indicate that there is a symmetrical electrophilic/nucleophilic region in the COF structure, which results from increased electron density around the Zn-porphyrin unit. The formed local electric field can further inhibit the recombination of photogenerated carriers by driving rapid electron transfer from Zn-porphyrin to guanidinium under light irradiation, which greatly increases the yield of reactive oxygen species. This COF wrapped by DSPE-PEG2000 can selectively target the lipoteichoic acid of Gram-positive bacteria by electrostatic interaction, which can be used for selective discrimination and imaging of bacteria. Furthermore, this nanoparticle can rapidly kill Gram-positive bacteria including 99.75% of Staphylococcus aureus and 99.77% of Enterococcus faecalis at an abnormally low concentration (2.00 ppm) under light irradiation for 20 min. This work will provide insight into designing photoresponsive COFs through engineering charge behavior.


Assuntos
Estruturas Metalorgânicas , Porfirinas , Antibacterianos/farmacologia , Bactérias , Guanidina , Íons , Estruturas Metalorgânicas/farmacologia , Zinco/química
19.
Food Chem ; 442: 138420, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38237294

RESUMO

This study presents a novel fluorescence imaging method for the real-time monitoring of beef quality deterioration and freshness. The fluorescence property of porphyrin in the form of heme can be used to characterize quality changes in beef during storage. Therefore, a fluorescence imaging system with an excitation light source of 440 nm and a CCD camera with a specific wavelength filter of 595 nm was constructed, and the porphyrin fluorescence images of beef samples stored at different temperatures were then collected. The quantitative model for predicting the microbial freshness indicator (TVC) of beef was built with the support vector machine regression (SVR) algorithm and produced satisfactory results with Rc2 and Rp2 of 0.858 and 0.812, respectively. The classification model based on the support vector machine (SVM) algorithm classified beef freshness into "fresh" and "spoiled", with calibration and prediction accuracy of 100 % and 90.9 %, respectively.


Assuntos
Porfirinas , Carne Vermelha , Animais , Bovinos , Carne Vermelha/análise , Temperatura , Algoritmos , Máquina de Vetores de Suporte
20.
J Mater Chem B ; 12(5): 1317-1329, 2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38229564

RESUMO

Bacterial biofilm infection is a serious obstacle to clinical therapeutics. Photodynamic therapy (PDT) plays a dynamic role in combating biofilm infection by utilizing reactive oxygen species (ROS)-induced bacterial oxidation injury, showing advantages of mild side effects, spatiotemporal controllability and little drug resistance. However, superfluous glutathione (GSH) present in biofilm and bacteria corporately reduces ROS levels and seriously affects PDT efficiency. Herein, we have constructed a Cu2+-infused porphyrin metal-organic framework (MOF@Cu2+) for the enhanced photodynamic combating of biofilm infection by the maximum depletion of GSH. Our results show that the released Cu2+ from porphyrin MOF@Cu2+ could not only oxidize GSH in biofilm but also consume GSH leaked from ROS-destroyed bacteria, thus greatly weakening the antioxidant system in biofilm and bacteria and dramatically improving the ROS levels. As expected, our dual-enhanced PDT nanoplatform exhibits a strong biofilm eradication ability both in vitro and in an in vivo biofilm-infected mouse model. In addition, Cu2+ can promote biofilm-infected wound closing by provoking cell immigration, collagen sediment and angiogenesis. Besides, no apparent toxicity was detected after treatment with MOF@Cu2+. Overall, our design offers a new paradigm for photodynamic combating biofilm infection.


Assuntos
Fotoquimioterapia , Porfirinas , Animais , Camundongos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/uso terapêutico , Cobre/farmacologia , Porfirinas/farmacologia , Espécies Reativas de Oxigênio , Glutationa , Bactérias , Biofilmes
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