Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 1.086
Filtrar
1.
Molecules ; 26(4)2021 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-33672044

RESUMO

In spite of unique structural, spectroscopic and redox properties, the synthetic variants of the planar, antiaromatic hexaphyrin (1.0.1.0.1.0) derivatives 2, has been limited due to the low yields and difficulty in access to the starting material. A chemical modification of the meso-substituents could be good alternative overcoming the synthetic barrier. Herein, we report a regio-selective nucleophilic aromatic substitution (SNAr) of meso-pentafluorophenyl group in rosarrin 2 with catechol. The reaction afforded benzodioxane fused rosarrin 3 as single product with high yield. The intrinsic antiaromatic character of the starting rosarrin 2 retained throughout the reactions. Clean, two electron reduction was achieved by treatment of 3 with SnCl2•2H2O affording 26π-electron aromatic rosarrin 4. The synthesized compounds exhibited noticeable changes in photophysical and redox properties compared with starting rosarrin 2.


Assuntos
Porfirinas/química , Porfirinas/síntese química , Técnicas Eletroquímicas , Espectrofotometria Ultravioleta , Estereoisomerismo
2.
Molecules ; 26(4)2021 Feb 20.
Artigo em Inglês | MEDLINE | ID: mdl-33672630

RESUMO

Despite advances achieved over the last decade, infections caused by multi-drug-resistant bacterial strains are increasingly becoming important societal issues that need to be addressed. New approaches have already been developed in order to overcome this problem. Photodynamic antimicrobial chemotherapy (PACT) could provide an alternative to fight infectious bacteria. Many studies have highlighted the value of cationic photosensitizers in order to improve this approach. This study reports the synthesis and the characterization of cationic porphyrins derived from methylimidazolium and phenylimidazolium porphyrins, along with a comparison of their photophysical properties with the well-known N-methylpyridyl (pyridinium) porphyrin family. PACT tests conducted with the tetracationic porphyrins of these three families showed that these new photosensitizers may offer a good alternative to the classical pyridinium porphyrins, especially against S.aureus and E.coli. In addition, they pave the way to new cationic photosensitizers by the means of derivatization through amide bond formation.


Assuntos
Antibacterianos/farmacologia , Imidazóis/farmacologia , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/farmacologia , Piridinas/farmacologia , Antibacterianos/síntese química , Antibacterianos/química , Relação Dose-Resposta a Droga , Escherichia coli/efeitos dos fármacos , Imidazóis/síntese química , Imidazóis/química , Testes de Sensibilidade Microbiana , Estrutura Molecular , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Porfirinas/síntese química , Porfirinas/química , Pseudomonas aeruginosa/efeitos dos fármacos , Piridinas/síntese química , Piridinas/química , Staphylococcus aureus/efeitos dos fármacos
3.
Eur J Med Chem ; 213: 113184, 2021 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-33497889

RESUMO

tetracationic (TMPyP) and tricationic porphyrin (TriMPyCOOHP) derivatives were synthesized, characterized and investigated for binding with DNA by Isothermal Titration Calorimetry as well as by UV-Vis spectroscopy in order to study the effect of structural variation on tumor targeting efficacy of cationically charged porphyrin derivatives. Fluorescence cell imaging studies performed in cancer cell lines corroborated the findings of aforementioned studies. Photocytotoxicity experiments in A549 cell lines revealed relatively higher light dependent cytotoxic effects exerted by TMPyP compared to TriMPyCOOHP. In-vivo experiments in tumor bearing animal model revealed relatively longer retention of 68Ga-TMPyP in tumorous lesion compared to that of 68Ga-TriMPyCOOHP. The study reveals that removal of one of the positive charges of the tetracationic porphyrin derivatives significantly reduces their DNA binding ability and cytotoxicity as well as brings changes in the pharmacokinetic pattern and tumor retention in small animal model.


Assuntos
Antineoplásicos/farmacologia , Fibrossarcoma/diagnóstico por imagem , Fibrossarcoma/tratamento farmacológico , Fotoquimioterapia , Porfirinas/farmacologia , Tomografia por Emissão de Pósitrons , Células A549 , Animais , Antineoplásicos/síntese química , Antineoplásicos/química , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Modelos Animais de Doenças , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Camundongos , Estrutura Molecular , Porfirinas/síntese química , Porfirinas/química , Relação Estrutura-Atividade , Células Tumorais Cultivadas
4.
Nat Commun ; 11(1): 1724, 2020 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-32265490

RESUMO

Vesicular photothermal therapy agents (PTAs) are highly desirable in photothermal therapy (PTT) for their excellent light-harvesting ability and versatile hollow compartments. However, up to now, the reported vesicular PTAs are generally self-assembled from small molecules like liposomes, and polymer vesicles have seldom been used as PTAs due to the unsatisfactory photothermal conversion efficiency resulting from the irregular packing of chromophores in the vesicle membranes. Here we report a nano-sized polymer vesicle from hyperbranched polyporphyrins with favorable photothermal stability and extraordinarily high photothermal efficiency (44.1%), showing great potential in imaging-guided PTT for tumors through in vitro and in vivo experiments. These excellent properties are attributed to the in situ supramolecular polymerization of porphyrin units inside the vesicle membrane into well-organized 1D monofilaments driven by π-π stacking. We believe the supramolecular polymerization-enhanced self-assembly process reported here will shed a new light on the design of supramolecular materials with new structures and functions.


Assuntos
Sobrevivência Celular/efeitos dos fármacos , Hipertermia Induzida/métodos , Nanopartículas/química , Fototerapia/métodos , Polímeros/química , Porfirinas/química , Animais , Dicroísmo Circular , Feminino , Humanos , Interações Hidrofóbicas e Hidrofílicas , Células MCF-7 , Membranas Artificiais , Camundongos , Camundongos Nus , Microscopia Eletrônica de Varredura , Simulação de Dinâmica Molecular , Células NIH 3T3 , Nanopartículas/uso terapêutico , Nanopartículas/ultraestrutura , Polimerização , Polímeros/síntese química , Polímeros/farmacocinética , Polímeros/uso terapêutico , Porfirinas/síntese química , Porfirinas/farmacocinética , Porfirinas/uso terapêutico , Ratos , Espectrometria de Fluorescência , Temperatura , Transplante Heterólogo
5.
J Fluoresc ; 30(2): 397-406, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-32088851

RESUMO

New porphyrin analogues have been designed and synthesized using pyrrole, various aldehydes and propionic acid. The formation of desired compounds was analyzed by utilizing the spectral analysis such as IR, NMR and Mass spectroscopy. The studies on absorption and fluorescence emission of synthesized porphyrins were used to evaluate photophysical characteristics such as molar excitation coefficient and Stokes shift. The estimated values of fluorescence lifetime and fluorescence quantum yield of synthesized porphyrins were found to be variable due to the presence of change in the electron donating and withdrawing characters. The efficiency of generation of singlet oxygen by each synthesized porphyrin as photosensitizer was measured in terms of singlet oxygen quantum yield through photooxidation of 9,10-dimethylantharacene. The obtained singlet oxygen quantum yield values were found to be higher in case of porphyrins those have more electron withdrawing characters rather than donating characters as compared to reference 5,10,15,20-tetraphenylporphyrin (H2TPP). The singlet oxygen quantum yield values of synthesized porphyrins varied from 0.52 to 0.66. Pleasingly, some of synthesized porphyrins are found to be photostable and competent to discover as PDT agents as compared to reference H2TPP.


Assuntos
Desenho de Fármacos , Fotoquimioterapia , Fármacos Fotossensibilizantes/síntese química , Porfirinas/síntese química , Estrutura Molecular , Fármacos Fotossensibilizantes/química , Porfirinas/química , Espectrometria de Fluorescência
6.
Chem Commun (Camb) ; 56(25): 3617-3620, 2020 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-32108215

RESUMO

Herein, we developed fluorinated nanoemulsions with significantly enhanced in vitro and in vivo129Xe hyper-CEST MRI, 19F MRI and fluorescence imaging signals for selective and sensitive tumor detection and NIR-activated photodynamic therapy.


Assuntos
Imagem Multimodal , Neoplasias/diagnóstico por imagem , Fotoquimioterapia , Compostos Policíclicos/química , Porfirinas/química , Nanomedicina Teranóstica , Emulsões/síntese química , Emulsões/química , Humanos , Imageamento por Ressonância Magnética , Neoplasias/tratamento farmacológico , Imagem Óptica , Compostos Policíclicos/síntese química , Porfirinas/síntese química
7.
Molecules ; 25(3)2020 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-31972976

RESUMO

Natural and synthetic macrocycles like porphyrins, corroles and phthalocyanines are considered strong candidates to be used in different fields, such as catalysis, sensing, medicine, materials science, or in the development of advanced biomimetic models. All these applications are strongly dependent on the availability of compounds with adequate and specific structural features. This Special Issue has collected 13 contributions which consolidate and expand our knowledge on the application of these macrocycles in different fields accompanied by innovative synthetic methodologies to afford and to functionalize this type of compounds.


Assuntos
Compostos Macrocíclicos/síntese química , Tetrapirróis/síntese química , Catálise , Compostos Macrocíclicos/química , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/síntese química , Porfirinas/química , Telomerase/metabolismo , Tetrapirróis/química
8.
Eur J Med Chem ; 189: 112049, 2020 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-31945666

RESUMO

Photodynamic therapy (PDT) has been developed as a promising therapeutic method in cancer treatment. The discovery of effective photosensitizer, which is the key factor of PDT, is highly desired. This paper reports the synthesis of novel chlorin derivatives, 5,10,15,20-tetraphenyl-[2:3]-[(methoxycarbonyl, carboxy)methano] chlorin I and 5,10,15,20-tetraphenyl-[2:3]- {[methoxycarbonyl, (2-hydroxyethyl)amide]methano}chlorin II. Their structures were characterized with UV-vis, 1HNMR, 13CNMR and HRMS spectroscopies. Photophysical and photochemical experiments results showed that compound I and II had an absorption maximum around 650 nm, with molar extinction coefficients of 1 × 104 M-1 cm-1. They had strong fluorescence emission in 650-660 nm upon excitation with 419-422 nm light. ESR showed that singlet oxygen was produced upon irradiation of compounds with 650 nm light in the presence of molecular oxygen. The photo-bleaching test indicated that the structure of compounds was stable. These new compounds exhibit excellent anti-tumor effects and lower toxicity compared to m-THPC in vitro and in vivo. Compound I and II had high tumor selectivity, which could induced tumor cells shrinkage and necrosis under 650 nm laser irradiation. Flow cytometry revealed that the compounds might mediate PDT effect at late apoptotic phase. These results make these compound I and II promising candidates for future study in photo-diagnosis and photodynamic therapy of cholangiocarcinoma.


Assuntos
Antineoplásicos/farmacologia , Neoplasias dos Ductos Biliares/tratamento farmacológico , Colangiocarcinoma/tratamento farmacológico , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/farmacologia , Animais , Antineoplásicos/síntese química , Antineoplásicos/efeitos da radiação , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Feminino , Humanos , Luz , Masculino , Camundongos Endogâmicos BALB C , Camundongos Endogâmicos ICR , Camundongos Nus , Necrose/induzido quimicamente , Fotoquimioterapia , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/efeitos da radiação , Porfirinas/síntese química , Porfirinas/efeitos da radiação , Ensaios Antitumorais Modelo de Xenoenxerto
9.
Int J Mol Sci ; 21(1)2020 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-31948078

RESUMO

In this work, we studied the anthracene oxidation by hydroxyl radicals. Hydroxyl radical was generated by reaction of 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin Fe (III) (TPPFe) with hydrogen peroxide under visible radiation at a nitrogen atmosphere. The TPPFe was synthesized by Adler Method followed by metal complexation with Fe (III) chloride hexahydrate. Hydroxyl radical was detected by fluorescence emission spectroscopy and we studied kinetic of anthracene selective oxidation by hydroxyl radicals through the differential method. The TPPFe was characterized by UV-Vis spectrophotometry, Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM) measurements. The results indicated that TPPFE was compound by micro-particles with a size distribution of around 2500 nm. Kinetic results showed that the apparent rate constant for the oxidation of anthracene increased exponentially on as temperature increases, furthermore, the activation energy for the Anthracene oxidation by hydroxyl radicals under visible irradiation was 51.3 kJ/mol. Finally, anthraquinone was the main byproduct generated after oxidation of anthracene by TPP-Fe under visible irradiation.


Assuntos
Antracenos/química , Radical Hidroxila/química , Antracenos/efeitos da radiação , Difusão Dinâmica da Luz , Compostos Férricos/síntese química , Compostos Férricos/química , Peróxido de Hidrogênio/química , Cinética , Luz , Microscopia Eletrônica de Varredura , Nitrogênio , Oxirredução , Porfirinas/síntese química , Porfirinas/química , Porfirinas/efeitos da radiação , Espectrometria de Fluorescência
10.
Molecules ; 25(2)2020 Jan 09.
Artigo em Inglês | MEDLINE | ID: mdl-31936458

RESUMO

Taxol is one of the potential anticancer drugs; however, the yield of Taxol and its cytotoxicity are common challenges. Thus, manipulating the Taxol biosynthetic pathway from endophytic fungi, in addition to chemical modification with biocompatible polymers, is the challenge. Four fungal isolates, namely, Aspergillus flavipes, A. terreus, A. flavus, and A. parasiticus, were selected from our previous study as potential Taxol producers, and their potency for Taxol production was evaluated in response to fluconazole and silver nitrate. A higher Taxol yield was reported in the cultures of A. flavipes (185 µg/L) and A. terreus (66 µg/L). With addition of fluconazole, the yield of Taxol was increased 1.8 and 1.2-fold for A. flavipes and A. terreus, respectively, confirming the inhibition of sterol biosynthesis and redirecting the geranyl phosphate pool to terpenoids synthesis. A significant inhibition of ergosterol biosynthesis by A. flavipes with addition of fluconazole was observed, correlating with the increase on Taxol yield. To increase the Taxol solubility and to reduce its cytotoxicity, Taxol was modified via chemical conjugation with porphyrin, and the degree of conjugation was checked from the Thin layer chromatography and UV spectral analysis. The antiproliferative activity of native and modified Taxol conjugates was evaluated; upon porphyrin conjugation, the activity of Taxol towards HepG2 was increased 1.5-fold, while its cytotoxicity to VERO cells was reduced 3-fold.


Assuntos
Antineoplásicos/química , Proliferação de Células/efeitos dos fármacos , Paclitaxel/química , Porfirinas/química , Animais , Antineoplásicos/síntese química , Antineoplásicos/farmacologia , Aspergillus/química , Chlorocebus aethiops , Células Hep G2 , Humanos , Paclitaxel/síntese química , Paclitaxel/isolamento & purificação , Paclitaxel/farmacologia , Porfirinas/síntese química , Porfirinas/farmacologia , Células Vero
11.
J Med Chem ; 63(3): 1245-1260, 2020 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-31930916

RESUMO

Designing small molecules able to break down G4 structures in mRNA (RG4s) offers an interesting approach to cancer therapy. Here, we have studied cationic porphyrins (CPs) bearing an alkyl chain up to 12 carbons, as they bind to RG4s while generating reactive oxygen species upon photoirradiation. Fluorescence-activated cell sorting (FACS) and confocal microscopy showed that the designed alkyl CPs strongly penetrate cell membranes, binding to KRAS and NRAS mRNAs under low-abundance cell conditions. In Panc-1 cells, alkyl CPs at nanomolar concentrations promote a dramatic downregulation of KRAS and NRAS expression, but only if photoactivated. Alkyl CPs also reduce the metabolic activity of pancreatic cancer cells and the growth of a Panc-1 xenograft in SCID mice. Propidium iodide/annexin assays and caspase 3, caspase 7, and PARP-1 analyses show that these compounds activate apoptosis. All these data demonstrate that the designed alkyl CPs are efficient photosensitizers for the photodynamic therapy of ras-driven cancers.


Assuntos
Antineoplásicos/uso terapêutico , Carcinoma Ductal Pancreático/tratamento farmacológico , Quadruplex G/efeitos dos fármacos , Neoplasias Pancreáticas/tratamento farmacológico , Fármacos Fotossensibilizantes/uso terapêutico , Porfirinas/uso terapêutico , Animais , Antineoplásicos/síntese química , Apoptose/efeitos dos fármacos , Sequência de Bases , Linhagem Celular Tumoral , Regulação para Baixo/efeitos dos fármacos , Feminino , GTP Fosfo-Hidrolases/genética , Genes ras/efeitos dos fármacos , Humanos , Proteínas de Membrana/genética , Camundongos SCID , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/síntese química , Porfirinas/síntese química , Proteínas Proto-Oncogênicas p21(ras)/genética , RNA/química , RNA/genética , Espécies Reativas de Oxigênio/metabolismo
12.
J Photochem Photobiol B ; 202: 111703, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31810036

RESUMO

Despite the continuous development of medicine, there is still a lack of effective and fully safe protocols for the treatment of neoplastic diseases. The drug-drug conjugates approach seems to give a chance to obtain more efficient molecules. New alkoxy and metronidazole substituted porphyrins were synthesized. Novel porphyrins were purified by flash column chromatography and characterized using NMR, MS, UV-Vis and HPLC. The Nuclear Magnetic Resonance study was performed to annotate experimentally observed 1H NMR and 13C NMR signals of new compounds. The 2D NMR techniques such as 1H-1H COSY (Correlation Spectroscopy), 1H-13C HSQC (Heteronuclear Single Quantum Correlation) and 1H-13C HMBC (Heteronuclear Multiple Bond Correlation) were used for the structure elucidation of the new compounds. In the range of 250-450 nm of the absorption spectra, the Soret band was observed, whereas the Q band was noted in the range of 500-650 nm. Compounds revealed a fluorescence quantum yield in the range 0.03-0.12. Singlet oxygen generation quantum yields up to 0.54 were determined. Electrochemical properties has also been studied. It has been noticed electropolymerization of compound bearing 5-nitroimidazole substituents. The photodynamic activity of the studied porphyrins against A549 and HEK001/HPV16 cancer cells were examined. The most active against A549 and HEK 001/HPV16 was light-excited trioxanonylporphyrin with the values of IC50 equal to 0.49 µM and 50 nM respectively.


Assuntos
Nitroimidazóis/química , Fármacos Fotossensibilizantes/química , Porfirinas/química , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Técnicas Eletroquímicas , Humanos , Luz , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/síntese química , Porfirinas/farmacologia , Oxigênio Singlete/química , Oxigênio Singlete/metabolismo
13.
Int J Biol Macromol ; 145: 244-251, 2020 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-31870869

RESUMO

BACKGROUND: The G-quadruplex-forming sequence within the KRAS proto-oncogene P1 promoter is a promising target for anticancer therapy. Porphyrin derivatives are among the most rewarding G-quadruplex binders. They can also behave as photosensitizers. METHODS: Three water-soluble, positively charged porphyrin-like compounds were synthesized and tested for their interaction with the KRAS G-quadruplex by circular dichroism, fluorescence, and molecular docking calculations. For a comparison of ligands binding affinity and selectivity, TMPyP4 was taken as a reference. RESULTS: One out of the three tested compounds proved biological activity and selectivity for G-quadruplex over duplex DNA. It also showed to discriminate between different G-quadruplex topologies, with a preference for the parallel over antiparallel conformation. Molecular docking studies suggested a preferential binding to the 3'-end of the KRAS G-quadruplex driven through π-π stacking interactions. Biological assays also revealed a good photodynamic-induced cytotoxicity on HeLa cells. CONCLUSIONS: The reported results show that these porphyrin-like compounds could actually give the basis for the development of G-quadruplex ligands with effective photodynamic-induced cytotoxicity on cancer cells. GENERAL SIGNIFICANCE: The possibility of obtaining photosensitizers with improved physico-chemical features and able to selectively target G-quadruplexes is a very interesting perspective to develop new therapeutic agents.


Assuntos
Quadruplex G/efeitos dos fármacos , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/farmacologia , Regiões Promotoras Genéticas , Proteínas Proto-Oncogênicas p21(ras)/genética , Quadruplex G/efeitos da radiação , Células HeLa , Humanos , Sequências Repetidas Invertidas , Ligantes , Luz , Simulação de Acoplamento Molecular , Oligonucleotídeos/síntese química , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/síntese química , Porfirinas/síntese química , Proteínas Proto-Oncogênicas p21(ras)/metabolismo , Solubilidade , Água
14.
Biomolecules ; 9(12)2019 12 10.
Artigo em Inglês | MEDLINE | ID: mdl-31835568

RESUMO

Photosensitizers (PSs) represent a group of molecules capable of generating reactive oxygen species (ROS), such as singlet oxygen (SO); thus, they are considered to be promising agents for anti-cancer therapy. The enhancement of the photodynamic efficiency of these compounds requires increasing the PS activity in the cancer cell milieu and exactly at the target cells. In the present work, we report the synthesis, lipid membrane binding and photodynamic activity of three novel cationic PSs based on ß-imidazolyl-substituted porphyrin and its Zn(II) and In(III) complexes (1H2, 1Zn and 1In). Comparison of the behavior of the investigated porphyrins at the bilayer lipid membrane (BLM) demonstrated the highest adsorption for the 1In complex and the lowest one for 1Zn. The photodynamic efficiency of these porphyrins was evaluated by determining the oxidation rate of the styryl dye, di-4-ANEPPS, incorporated into the lipid membrane. These rates were proportional to the surface density (SD) of the porphyrin molecules at the BLM and were roughly the same for all three porphyrins. This indicates that the adsorption of these porphyrins at the BLM determines their photodynamic efficiency rather than the extinction or quantum yield of singlet oxygen.


Assuntos
Imidazóis/química , Bicamadas Lipídicas/química , Compostos Organometálicos/química , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Porfirinas/química , Adsorção , Concentração de Íons de Hidrogênio , Compostos Organometálicos/síntese química , Fármacos Fotossensibilizantes/síntese química , Porfirinas/síntese química , Propriedades de Superfície
15.
ACS Nano ; 13(11): 13304-13316, 2019 11 26.
Artigo em Inglês | MEDLINE | ID: mdl-31689082

RESUMO

Despite the excellent photodynamic and photothermal properties of organic molecular photosensitizers (PSs) and photothermal agents (PTAs), such as porphyrin and naphthalocyanine, their poor water solubility severely impedes their biological applications. Covalent organic frameworks (COFs), as an emerging class of organic crystalline porous materials, possess free active end groups (bonding defects) and large inner pores, which make them an ideal type of nanocarriers for loading hydrophobic organic molecular PSs and PTAs by both bonding defect functionalization (BDF) and guest encapsulation approaches to obtain multifunctional nanomedicines for PDT/PTT combination therapy. In this work, we report a nanoscale COF (NCOF) prepared via a facile synthetic approach under ambient conditions. Furthermore, a dual-modal PDT/PTT therapeutic nanoagent, VONc@COF-Por (3), is successfully fabricated by stepwise BDF and guest encapsulation processes. The covalently grafted porphyrinic PS (Por) and the noncovalently loaded naphthalocyanine PTA (VONc) are independently responsible for the PDT and PTT functionalities of the nanoagent. Upon visible (red LED) and NIR (808 nm laser) irradiation, VONc@COF-Por (3) displayed high 1O2 generation and photothermal conversion ability (55.9%), consequently providing an excellent combined PDT/PTT therapeutic effect on inhibiting MCF-7 tumor cell proliferation and metastasis, which was well evidenced by in vitro and in vivo experiments. We believe that the results obtained herein can significantly promote the development of NCOF-based multifunctional nanomedicines for biomedical applications.


Assuntos
Antineoplásicos/farmacologia , Estruturas Metalorgânicas/farmacologia , Nanopartículas/química , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Proliferação de Células/efeitos dos fármacos , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Interações Hidrofóbicas e Hidrofílicas , Células MCF-7 , Estruturas Metalorgânicas/síntese química , Estruturas Metalorgânicas/química , Compostos Organometálicos/síntese química , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Tamanho da Partícula , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Porosidade , Porfirinas/síntese química , Porfirinas/química , Porfirinas/farmacologia , Propriedades de Superfície
16.
Photochem Photobiol Sci ; 18(11): 2792-2803, 2019 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-31626259

RESUMO

We report the first exocyclically metallated tetrapyridinoporphyrazine, [tetrakis-(trans-Pt(NH3)2Cl)-tetra(3,4-pyrido)porphyrazine-zinc(ii)](NO3)4 (4), synthesized in a multistep synthesis starting from 3,4-pyridinedicarbonitrile (1). The synthetic procedure involved a platination reaction of the intermediate tetra(3,4-pyrido)porphyrazine-zinc(ii) (2), whereby the zinc(ii) enhanced the solubility of the intermediate enabling the platination reaction. A similar approach to synthesize [tetrakis-(trans-Pt(NH3)2Cl)-tetra(3,4-pyrido)porphyrazine](NO3)4 (5) failed due to the unsuitable solubility properties of the intermediate tetra(3,4-pyrido)porphyrazine (3). The final product 4 and the intermediates were characterized, the photochemical and photophysical properties were determined and the photocytotoxicities were investigated. We demonstrate that the platinated tetra-pyridinoporphyrazine 4 is a potential photosensitizer for photodynamic therapy (PDT).


Assuntos
Fármacos Fotossensibilizantes/química , Porfirinas/química , Zinco/química , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Humanos , Luz , Neoplasias/tratamento farmacológico , Neoplasias/patologia , Fotoquimioterapia , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/síntese química , Porfirinas/farmacologia , Espécies Reativas de Oxigênio/metabolismo , Espectrometria de Fluorescência , Estereoisomerismo
17.
Anal Chim Acta ; 1089: 66-77, 2019 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-31627820

RESUMO

The dehydration reaction of tetraamino porphyrin and 4,4'-biphenyldicarboxaldehyde was performed for the synthesis of a novel covalent organic framework (COF), which was decorated on magnetic Fe3O4 to obtain core-shell structured Fe3O4@COFs nanospheres for the first time, for effective extraction and enrichment of sulfonamides (SAs). The morphology and structure of the synthesized nanospheres were characterized through various methods. The extraction conditions for six SAs including sulfadiazine, sulfamerazine, sulfamethazine, sulfamonomethoxine, sulfamethoxazole, sulfadimethoxine were systematically optimized. Fe3O4@COFs nanospheres were evaluated for magnetic solid-phase extraction. By coupling with high-performance liquid chromatography, a facile and sensitive method was established for the quantitation analysis of six SAs. The method showed good linearity ranging from 1 to 500 ng mL-1 with R2 > 0.99, high sensitivity with LODs in the range of 0.2-1 ng mL-1, and high precision with RSDs≤6.3%. This method was further applied into determination of SAs in environmental water and food samples, with recoveries in the range of 65.3%-107.3% and RSDs≤6.7%. These successful applications suggest that the core-shell structured Fe3O4@COFs nanospheres could be used as a potential adsorbent for efficient extraction and analysis of trace SAs.


Assuntos
Contaminação de Alimentos/análise , Nanopartículas de Magnetita/química , Estruturas Metalorgânicas/química , Porfirinas/química , Sulfonamidas/análise , Poluentes Químicos da Água/análise , Adsorção , Animais , Galinhas , Lagos/análise , Limite de Detecção , Estruturas Metalorgânicas/síntese química , Leite/química , Penaeidae , Carne de Porco/análise , Porfirinas/síntese química , Frutos do Mar/análise , Extração em Fase Sólida/métodos
18.
Biosens Bioelectron ; 146: 111734, 2019 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-31586759

RESUMO

Highly-conductive two-dimensional covalent organic framework (COF) displays prominent applications in various fields of science and technology. This paper reports the design and liquid-liquid interface synthesis of a novel Zr-coordinated amide porphyrin-based 2D COF (Zr-amide-Por-based 2D COF). The COF adopts a graphene-like multilayer structure with the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) band gap of 1.6 eV. The ordered multilayer structure of the amide COF was confirmed through a series of characterization techniques, including scanning electron microscopy, high-resolution transmission electron microscopy, atomic force microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. In particular, the inherent-ordered structure of Zr-amide-Por-based 2D COF with Zr as the catalytically active center confers several distinct advantages to the material, such as high conductivity and high electrocatalysis performance. A molecularly imprinted tetracycline electrochemiluminescence sensor was constructed based on the Zr-amide-Por-based 2D COF, and gate control effect was used as a signal-generation mechanism. Under optimal conditions, the sensor showed a good linear relationship with tetracycline in the concentration range of 5-60 pM, with a detection limit of 2.3 pM. Because the sensor is rapid, cost-efficient, highly sensitive, and specific, it can be considered as a viable platform for veterinary drug residue monitoring.


Assuntos
Antibacterianos/análise , Estruturas Metalorgânicas/química , Porfirinas/química , Tetraciclina/análise , Zircônio/química , Animais , Técnicas Eletroquímicas/métodos , Análise de Alimentos/métodos , Estruturas Metalorgânicas/síntese química , Leite/química , Porfirinas/síntese química , Difração de Raios X
19.
Molecules ; 24(17)2019 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-31480572

RESUMO

A simple and straightforward synthesis of diporphyrins and pentaporphyrins is reported here. The supramolecular interactions of the new porphyrin derivatives with C60 and PyC60 (a pyridyl [60]fulleropyrrolidine) were evaluated by absorption and fluorescence titrations in toluene. While no measurable modifications of the absorption and fluorescence spectra were observed upon addition of C60 to the porphyrin derivatives, the addition of PyC60 to the corresponding mono-Zn(II) porphyrins resulted in the formation of Zn(porphyrin)-PyC60 coordination complexes and the binding constants were calculated. Results show that the four free-base porphyrin units in pentaporphyrin 6 have a significant contribution in the stabilization of the 6-PyC60 complex. The crystal and molecular features of the pentaporphyrin Zn5 were unveiled using single-crystal X-ray diffraction studies.


Assuntos
Fulerenos/química , Substâncias Macromoleculares/química , Porfirinas/síntese química , Cinética , Substâncias Macromoleculares/síntese química , Modelos Moleculares , Porfirinas/química , Espectrometria de Fluorescência , Tolueno/química
20.
Int J Nanomedicine ; 14: 7065-7078, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31507320

RESUMO

Background:  Metal-free, water-soluble and highly stable meso-tetra-(4-sulfonatophenyl) porphyrin (TPPS4) has been studied for their singlet oxygen quantum yield. However, TPPS4 suffers from inherent shortcomings. To address these, TPPS4 was conjugated to ternary copper indium sulphide/ zinc sulphide (CuInS2/ZnS) quantum dots (QDs). Purpose:  We herein report for the first time the synthesis of TPPS4-CuInS/ZnS QDs conjugate as an improved photosensitizer. Methods:  Water-soluble TPPS4 was synthesized from tetraphenylporphyrin (TPPH2) after silica-gel purification. The CuInS/ZnS QDs were synthesized by hydrothermal method at a Cu:In ratio of 1:4. The porphyrin-QDs conjugate was formed via the daggling sulfonyl bond of the porphyrin and amine bond of the QDs. The effect of pH on the optical properties of TPPS4 was evaluated. The effect of Zn:Cu + In ratio on the ZnS shell passivation was examined to reduce structural defects on the as-synthesized QDs. Results : Various spectroscopic techniques were used to confirm the successful conversion of the organic TPPH2 to water-soluble TPPS4. The singlet oxygen generation evaluation shows an improved singlet oxygen quantum yield from 0.19 for the porphyrin (TPPS4) alone to 0.69 after conjugation (CuInS/ZnS-TPPS4) with an increase in the reaction rate constant (k (s-1)).


Assuntos
Cobre/química , Índio/química , Porfirinas/síntese química , Porfirinas/farmacologia , Pontos Quânticos/química , Sulfetos/síntese química , Compostos de Zinco/síntese química , Concentração de Íons de Hidrogênio , Fenômenos Ópticos , Fármacos Fotossensibilizantes , Porfirinas/química , Pontos Quânticos/ultraestrutura , Oxigênio Singlete/química , Espectroscopia de Infravermelho com Transformada de Fourier , Sulfetos/química , Temperatura , Compostos de Zinco/química
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...