Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 1.066
Filtrar
Mais filtros










Base de dados
Intervalo de ano de publicação
1.
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
2.
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
3.
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
4.
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
5.
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
6.
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
7.
Molecules ; 24(16)2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31434280

RESUMO

The synthesis and surface self-assembly behavior of two types of metal-porphyrin dimers is described. The first dimer type consists of two porphyrins linked via a rigid conjugated spacer, and the second type has an alkyne linker, which allows rotation of the porphyrin moieties with respect to each other. The conjugated dimers were equipped with two copper or two manganese centers, while the flexible dimers allowed a modular built-up that also made the incorporation of two different metal centers possible. The self-assembly of the new porphyrin dimers at a solid-liquid interface was investigated at the single-molecule scale using scanning tunneling microscopy (STM). All dimers formed monolayers, of which the stability and the internal degree of ordering of the molecules depended on the metal centers in the porphyrins. While in all monolayers the dimers were oriented coplanar with respect to the underlying surface ('face-on'), the flexible dimer containing a manganese and a copper center could be induced, via the application of a voltage pulse in the STM setup, to self-assemble into monolayers in which the porphyrin dimers adopted a non-common perpendicular ('edge-on') geometry with respect to the surface.


Assuntos
Porfirinas/química , Cobre/química , Dimerização , Manganês/química , Microscopia de Tunelamento , Porfirinas/síntese química , Imagem Individual de Molécula/métodos
8.
Anticancer Res ; 39(8): 4199-4206, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31366506

RESUMO

BACKGROUND/AIM: We previously synthesized a glucose-conjugated chlorin compound e6 (G-chlorin e6), and reported that it has very strong antitumor effects. The aim of the present study was to synthesize acetylated glucose-conjugated chlorin (AcN003HP) and evaluate its antitumor effect and excretion. MATERIALS AND METHODS: To evaluate the antitumor effect of AcN003HP, its IC50 was calculated as well as its accumulation in cancer cells was examined by flow cytometry. Confocal microscopy was used to observe the intracellular localization of AcN003HP. The excretion and antitumor effects of AcN003HP were also evaluated in vivo. RESULTS: AcN003HP showed stronger antitumor effects and accumulation into cancer cells compared to talaporfin sodium, a conventional photosensitizer. AcN003HP was localized in the endoplasmic reticulum. In a xenograft tumor mouse model, AcN003HP showed longer excretion time from the body than G-chlorin e6, and photodynamic therapy using AcN003HP showed very strong antitumor effects. CONCLUSION: The safety, improved controllability, and robust antitumor effects suggest AcN003HP as a good next-generation photosensitizer.


Assuntos
Neoplasias Gastrointestinais/terapia , Glucose/administração & dosagem , Fotoquimioterapia , Fármacos Fotossensibilizantes/administração & dosagem , Acetilação/efeitos dos fármacos , Animais , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Retículo Endoplasmático/efeitos dos fármacos , Citometria de Fluxo , Neoplasias Gastrointestinais/patologia , Glucose/síntese química , Glucose/química , Humanos , Camundongos , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Porfirinas/administração & dosagem , Porfirinas/síntese química , Porfirinas/química , Ensaios Antitumorais Modelo de Xenoenxerto
9.
Chem Commun (Camb) ; 55(65): 9590-9605, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31334709

RESUMO

The study of artificial receptor molecules with the intention to mimic enzyme-substrate binding processes and catalysis in nature has always been a traditional area of research in supramolecular chemistry. Along this line, our group has developed a family of porphyrin cage compounds based on glycoluril and employed these in host-guest binding studies, as components of allosterically controlled self-assembled processes, in which structural changes in the cage upon complexation of a guest or a ligand change binding equilibria, and as enzyme mimics in supramolecular catalysis. In a recently started research program aimed at developing a new molecular approach to long-term data storage, porphyrin cage compounds are studied as molecular machines to encode information into synthetic polymer chains. In this Feature Article we will give an overview of the above aspects of our porphyrin cage compounds and place them in the context of related systems reported in the literature.


Assuntos
Alquinos/química , Materiais Biomiméticos/química , Imidazóis/química , Porfirinas/química , Receptores Artificiais/química , Materiais Biomiméticos/síntese química , Catálise , Imidazóis/síntese química , Ligantes , Metaloporfirinas/síntese química , Metaloporfirinas/química , Nanotecnologia/métodos , Porfirinas/síntese química , Receptores Artificiais/síntese química , Estereoisomerismo , Termodinâmica
10.
J Chromatogr A ; 1607: 460387, 2019 Dec 06.
Artigo em Inglês | MEDLINE | ID: mdl-31358296

RESUMO

In this work, porphyrin-functionalized graphene oxide nanosheets (GO@meso-tetrakis(4-hydroxyphenyl)porphyrin) were synthesized and employed as the sorbent. Porphyrins owing to their unique structures and tunable terminal functional groups are expected to be promising media for extraction of the desired analytes. Also, GO with a high specific surface area has exhibited good potential for the extraction purposes. Inspired by these intriguing properties, the combination of GO and porphyrin can benefit both of these amazing features. The synthesized sorbent was utilized for micro solid phase extraction of non-steroidal anti-inflammatory drugs followed by HPLC-UV. Optimization of the experimental factors including sorbent amount, sample pH, sample and eluent flowrates, eluent volume, and the number of desorption cycles were performed with the aid of central composite design. Under the optimal conditions, the calibration curves were linear within the range of 2.0-600 ng mL-1 and limits of detection were found between 0.5-2.0 ng mL-1. The preconcentration factors and absolute recoveries were obtained in the range of 4.80-9.79 and 29%-59%, respectively. The matrix effect for the urine samples varied between 81.9%-91.6% at two concentrations of 50 and 300 ng mL-1, respectively. Intra- and inter-day RSD% (n = 3) of the spiked urine samples at three level concentrations of 25, 100, and 300 ng mL-1 were less than 10%. The relative recoveries of the urine samples were calculated in the range of 85.2-98.6%. Eventually, the method exhibits proper sensitivity, excellent repeatability, high reusability, and acceptable precision and accuracy.


Assuntos
Anti-Inflamatórios não Esteroides/urina , Grafite/química , Nanoestruturas/química , Porfirinas/química , Microextração em Fase Sólida/métodos , Adsorção , Adulto , Anti-Inflamatórios não Esteroides/química , Cromatografia Líquida de Alta Pressão , Feminino , Humanos , Limite de Detecção , Masculino , Pessoa de Meia-Idade , Nanoestruturas/ultraestrutura , Porfirinas/síntese química , Espectroscopia de Infravermelho com Transformada de Fourier , Adulto Jovem
11.
Spectrochim Acta A Mol Biomol Spectrosc ; 223: 117314, 2019 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-31280126

RESUMO

A series of novel porphyrin-cinnamic acid (porphyrin/CA) conjugates (4a-4c) have been synthesized by condensation of 5-(4-Hydroxyphenyl)-10,15,20-triphenyl- porphyrin (1) with different substituted cinnamic acids (CAs) through an alkyl linker due to the biological activities of CAs and the application of porphyrins in photodynamic therapy (PDT) of cancer. Their related zinc (II) complexes (5a-5c) were also prepared. These novel compounds have been fully characterized by 1H NMR, Infrared (IR), Mass spectra (Ms) and Elemental analysis. The photophysical properties of these target molecules were studied by absorption and Fluorescence spectroscopy. In solution, the effect of pH, ionic strength in acid media and concentration on the aggregation behaviors of 4a has also been investigated by UV-Vis spectra. The broadened and red shifted Soret band indicated the formation of J-aggregates when the pH value was up to 2.0 in THF-aqueous solution. Furthermore, the higher ionic strength of 0.3 M NaCl in acid media resulted in the generation of J-aggregates in THF-aqueous solution. And the significant blue shift of Soret band also demonstrated the formation of H-aggregates of 4a at 1.1 × 10-4 M in THF.


Assuntos
Cinamatos/química , Cinamatos/síntese química , Porfirinas/química , Porfirinas/síntese química , Concentração de Íons de Hidrogênio , Concentração Osmolar , Espectroscopia de Prótons por Ressonância Magnética , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta , Espectroscopia de Infravermelho com Transformada de Fourier
12.
Molecules ; 24(14)2019 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-31340553

RESUMO

The synthesis and application of porphyrins has seen a huge shift towards research in porphyrin bio-molecular based systems in the past decade. The preferential localization of porphyrins in tumors, as well as their ability to generate reactive singlet oxygen and low dark toxicities has resulted in their use in therapeutic applications such as photodynamic therapy. However, their inherent lack of bio-distribution due to water insolubility has shifted research into porphyrin-nanomaterial conjugated systems to address this challenge. This has broadened their bio-applications, viz. bio-sensors, fluorescence tracking, in vivo magnetic resonance imaging (MRI), and positron emission tomography (PET)/CT imaging to photo-immuno-therapy just to highlight a few. This paper reviews the unique theranostic role of porphyrins in disease diagnosis and therapy. The review highlights porphyrin conjugated systems and their applications. The review ends by bringing current challenges and future perspectives of porphyrin based conjugated systems and their respective applications into light.


Assuntos
Glicoconjugados/síntese química , Neoplasias/diagnóstico por imagem , Neoplasias/terapia , Fármacos Fotossensibilizantes/síntese química , Porfirinas/síntese química , Animais , Glicoconjugados/farmacocinética , Glicoconjugados/farmacologia , Humanos , Imagem por Ressonância Magnética/métodos , Camundongos , Neoplasias/patologia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacocinética , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/farmacocinética , Porfirinas/farmacologia , Tomografia por Emissão de Pósitrons/métodos , Oxigênio Singlete/química , Oxigênio Singlete/metabolismo , Nanomedicina Teranóstica/métodos , Água/química , Água/metabolismo
13.
J Photochem Photobiol B ; 197: 111548, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31288120

RESUMO

The visible light combined with photosensitizers (PSs) is exploited in both antitumoral and antimicrobial fields inducing a photo-oxidative stress within the target cells. Among the different PSs, porphyrins belong to the family of the most promising compounds to be used in clinical photodynamic applications. Although in the last years many porphyrins have been synthesised and tested, only a few reports concern the in vitro effects of the 5,15-diarylporphyrins. In this work, the activity of four 5,15-diarylporphyrins (compounds 7-10), bearing alkoxy-linked pyridinium appendixes, have been tested on cancer cell lines and against bacterial cultures. Among the synthetized PSs, compounds 7 and 9 are not symmetrically substituted porphyrins showing one cationic charge tethered at the end of one 4C or 8C carbon chains, respectively. On the other hand, compounds 8 and 10 are symmetrically substituted and show two chains of C4 and C8 carbons featuring a cationic charge at the end of both chains. The dicationic 8 and 10 were more hydrophilic than monocationic 7 and 9, outlining that the presence of two pyridinium salts have a higher impact on the solubility in the aqueous phase than the lipophilic effect exerted by the length of the alkyl chains. Furthermore, these four PSs showed a similar rate of photobleaching, irrespective of the length and number of chains and the number of positive charges. Among the eukaryotic cell lines, the SKOV3 cells were particularly sensitive to the photodynamic activity of all the tested diarylporphyrins, while the HCT116 cells were found more sensitive to PSs bearing C4 chain (7 and 8), regardless the number of cationic charges. The photo-induced killing effect of these porphyrins was also tested against two different bacterial cultures. As expected, the Gram positive Bacillus subtilis was more sensitive than the Gram negative Escherichia coli, and the dicationic porphyrin 8, bearing two C4 chains, was the most efficient on both microorganisms. In conclusion, the new compound 8 seems to be an optimal candidate to deepen as versatile anticancer and antibacterial photosensitizer.


Assuntos
Antibacterianos/química , Antineoplásicos/química , Fármacos Fotossensibilizantes/química , Porfirinas/química , Antibacterianos/síntese química , Antibacterianos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/farmacologia , Cátions/química , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Proliferação de Células/efeitos da radiação , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Humanos , Luz , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/síntese química , Porfirinas/farmacologia , Espécies Reativas de Oxigênio/metabolismo
14.
Mater Sci Eng C Mater Biol Appl ; 102: 192-199, 2019 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-31146990

RESUMO

The preparation of light-activated hybrid antibacterial agent combining the porphyrin molecules, bound to the silver nanoparticles (AgNPs) surface is reported. AgNPs were synthesized by N-methyl-2-pyrrolidone-initiated reduction without additional reducing agents. The chemical structure of protoporphyrin IX was modified with the aim to introduce thiol groups. The size distribution and shape features of AgNPs were checked using TEM and HRTEM microscopies. The introduction of thiol groups into the porphyrin was proved by IR spectroscopy. The AgNPs-porphyrin binding was performed in solution and confirmed by fluorescence quenching, Raman spectroscopy and energy-filtered transmission electron microscopy (EFTEM). The antibacterial tests were performed against S. epidermidis and E. coli upon to LED illumination and in the dark. The synergetic effect of AgNPs and porphyrin as well as light activation of the created antibacterial conjugates were observed.


Assuntos
Antibacterianos/síntese química , Antibacterianos/farmacologia , Nanopartículas Metálicas/química , Porfirinas/síntese química , Porfirinas/farmacologia , Prata/farmacologia , Escherichia coli/efeitos dos fármacos , Luminescência , Nanopartículas Metálicas/ultraestrutura , Testes de Sensibilidade Microbiana , Porfirinas/química , Prata/química , Staphylococcus epidermidis/efeitos dos fármacos
15.
Molecules ; 24(11)2019 Jun 08.
Artigo em Inglês | MEDLINE | ID: mdl-31181809

RESUMO

Multifunctionalized materials are expected to be versatile probes to find specific interactions between a ligand and a target biomaterial. Thus, efficient methods to prepare possible combinations of the functionalities is desired. The concept of dynamic combinatorial chemistry (DCC) is ideal for the generation of any possible combination, as well as screening for target biomaterials. Here, we propose a new molecular design of multitopic probes for ligand discovery in DCC. We synthesized a new Gable Porphyrin, GP1, having prop-2-yne groups as a scaffold to introduce various functional groups. GP1 is a bis(imidazolylporphyrinatozinc) compound connected through a 1,3-phenylene moiety, and it gives macrocycles spontaneously and quantitatively by strong imidazole-to-zinc complementary coordination. Some different types of functional groups were introduced into GP1 in high yields. Formation of heterogeneous macrocycles composed of GP1 derivatives having different types of substituents was accomplished under equilibrium conditions. These results promise that enormous numbers of macrocycles having various functional groups can be provided when the kinds of GP components increase. These features are desirable for DCC, and the present system using GP1 is a potential candidate to provide a dynamic combinatorial library of multitopic probes to discover specific interactions between a ligand and a biomaterial.


Assuntos
Técnicas de Química Combinatória/métodos , Descoberta de Drogas , Sondas Moleculares/química , Dimerização , Isomerismo , Ligantes , Modelos Moleculares , Porfirinas/síntese química , Porfirinas/química , Espectroscopia de Prótons por Ressonância Magnética , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta , Zinco/química
16.
Eur J Med Chem ; 177: 144-152, 2019 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-31132530

RESUMO

Effective photosensitizers are particularly important factor in clinical photodynamic therapy (PDT). However, there is a scarcity of photosensitizers for simultaneous cancer photo-diagnosis and targeted PDT. Herein, two novel dimethyl 2-(guanidinyl)ethylamino chlorin e6 photosensitizers were synthesized and their efficacy in PDT in A549 tumor was investigated. It was shown that compounds 3 and 4 have a long absorption wavelength in the near infrared region and strong fluorescence emission with slow photo-bleaching rate and markedly strong ability of 1O2 generation. They exhibited lower cytotoxicity and higher photo-cytotoxicity in vitro compared to the known anticancer drug m-THPC in MTT assay in A549 lung cancer cell lines. Compound 4 exhibit better inhibition effect than compound 3 and the IC50 value of compound 4 was 0.197 µM/L under 2 J/cm2 laser irradiation, while compound 3 showed better anti-tumor effects compared to compound 4 in vivo. Intracellular ROS generation was found to be responsible for apoptotic cell death in DCFDA assay. Subcellular localization confirmed the damage site of compounds 3 and 4 in PDT. These findings suggest that the two novel photosensitizers might serve as potential photosensitizers for improved therapeutic efficiency of PDT.


Assuntos
Antineoplásicos/farmacologia , Guanidinas/farmacologia , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/farmacologia , Células A549 , Adenocarcinoma Bronquioloalveolar/patologia , Animais , Antineoplásicos/síntese química , Apoptose/efeitos dos fármacos , Retículo Endoplasmático/metabolismo , Feminino , Guanidinas/síntese química , Humanos , Neoplasias Pulmonares/patologia , Lisossomos/metabolismo , Masculino , Camundongos Endogâmicos BALB C , Mitocôndrias/metabolismo , Necrose , Fármacos Fotossensibilizantes/síntese química , Porfirinas/síntese química , Oxigênio Singlete/metabolismo , Ensaios Antitumorais Modelo de Xenoenxerto
17.
Int J Mol Sci ; 20(10)2019 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-31121942

RESUMO

The post-functionalization of 5,10,15-tris(1-methylpyridinium-4-yl)-20-(pentafluorophenyl)porphyrin tri-iodide, known as a highly efficient photosensitizer (PS) for antimicrobial photodynamic therapy (aPDT), in the presence of 3- or 4-mercaptobenzoic acid, afforded two new tricationic porphyrins with adequate carboxylic pending groups to be immobilized on chitosan or titanium oxide. The structural characterization of the newly obtained materials confirmed the success of the porphyrin immobilization on the solid supports. The photophysical properties and the antimicrobial photodynamic efficacy of the non-immobilized porphyrins and of the new conjugates were evaluated. The results showed that the position of the carboxyl group in the mercapto units or the absence of these substituents in the porphyrin core could modulate the action of the photosensitizer towards the bioluminescent Gram-negative Escherichia coli bacterium. The antimicrobial activity was also influenced by the interaction between the photosensitizer and the type of support (chitosan or titanium dioxide). The new cationic porphyrins and some of the materials were shown to be very stable in PBS and effective in the photoinactivation of E. coli bacterium. The physicochemical properties of TiO2 allowed the interaction of the PS with its surface, increasing the absorption profile of TiO2, which enables the use of visible light, inactivating the bacteria more efficiently than the corresponding PS immobilized on chitosan.


Assuntos
Antibacterianos/química , Quitosana/análogos & derivados , Fármacos Fotossensibilizantes/química , Porfirinas/química , Titânio/química , Antibacterianos/síntese química , Antibacterianos/farmacologia , Cátions/síntese química , Cátions/química , Cátions/farmacologia , Quitosana/síntese química , Quitosana/farmacologia , Escherichia coli/efeitos dos fármacos , Infecções por Escherichia coli/tratamento farmacológico , Humanos , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/síntese química , Porfirinas/farmacologia , Titânio/farmacologia
18.
Carbohydr Polym ; 213: 168-175, 2019 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-30879656

RESUMO

Porphyrins are widely used in anticancer photodynamic therapy (PDT). However, low physiological solubility and lack of selectivity towards cancer cells are the main limitations of their clinical use. Nanoparticles are being intensively explored as photosensitizer carriers for PDT to overcome these limitations. The aims of this work are to synthesize core-shell hybrid nanoparticles formed by a silica core and xylan carrying a 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin (TPPOH) shell, and evaluate their anticancer activity. To afford drug-controlled incorporation and enhance blood circulation, TPPOH was covalently linked to xylan. Different xylans with degrees of substitution in TPPOH ranging from 0.034 to 1.11, were obtained and characterized. Then, the xylan-TPPOH conjugate (PX) was used to coat the silica nanoparticles (PX SNPs). The obtained nano-objects were characterized and their therapeutic potential for photodynamic therapy evaluated against colorectal cancer cell lines. in vitro analysis showed that PX SNPs were 40-fold and 10-fold more effective against HCT116 cells and HT-29 cells respectively compared to free TPPOH.


Assuntos
Antineoplásicos/farmacologia , Nanopartículas/química , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/química , Dióxido de Silício/química , Xilanos/química , Antineoplásicos/síntese química , Antineoplásicos/química , Apoptose/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Portadores de Fármacos/química , Ensaios de Seleção de Medicamentos Antitumorais , Células HCT116 , Células HT29 , Humanos , Estrutura Molecular , Tamanho da Partícula , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Porfirinas/síntese química , Propriedades de Superfície
19.
ACS Appl Mater Interfaces ; 11(14): 13158-13167, 2019 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-30901194

RESUMO

Photosensitizer is one of the most important elements of photodynamic therapy (PDT). Herein, we reported a novel strategy to prepare a new series of composite photosensitizers. The composite photosensitizer was prepared by simply mixing DNA G-quadruplexes with a hydrophilic porphyrin (TMPipEOPP)4+·4I-. Compared with the conventional porphyrin photosensitizers, the excitation wavelength of the composite one has been ∼50 nm redshifted (from 650 to 700 nm), which is beneficial to the penetration of the light. Moreover, the composite photosensitizer showed an about 7.4-fold increase of light absorption efficiency, thus greatly enhancing the singlet oxygen (1O2) generation capacity and PDT efficacy. What is more, the introduction of nucleic acids in the composite photosensitizer could also provide some extra charming properties, such as the targeted recognition ability conferred by aptamer and high capability to assemble with various drug carriers. We demonstrated that the composite photosensitizer could be easily assembled with MnO2 nanosheet. The obtained nanodevice integrated the merits of a composite photosensitizer and MnO2 nanosheet, thus showing strong near-infrared absorption, high 1O2 generation efficiency, avoidance of nonideal 1O2 consumption by glutathione, and in situ O2 generation to relieve tumor hypoxia. This nanodevice showed greatly improved PDT efficacy both in vitro and in vivo, presenting a huge potential for applications in clinical therapy for tumors.


Assuntos
Quadruplex G , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Piperidinas/química , Porfirinas/química , Portadores de Fármacos/química , Glutationa/química , Glutationa/metabolismo , Humanos , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/uso terapêutico , Piperidinas/síntese química , Piperidinas/uso terapêutico , Porfirinas/síntese química , Porfirinas/uso terapêutico , Oxigênio Singlete/química
20.
Molecules ; 24(5)2019 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-30818765

RESUMO

The synthesis, chromatographic isolation, and structure elucidation of ß,ß-substituted isomers of dinitro-5,10,15,20-tetraphenylporphyrin complexes are described. meso-Tetraphenyl-porphyrin chelates (CuII, NiII, CoII) upon reaction wit e.g., itric acid (yellow HNO3, d = 1.52, diluted to 25⁻50%) in CHCl3 formed a mixture of nitro-derivatives with combined yields of ca 80%. This nitration (under optimized conditions: 25⁻30% HNO3, 30⁻40 min, r.t.) can be carried out selectively to give mainly ß,ß-dinitro-compounds in yields of up to 73%. From the above mixtures of five possible regioisomers that can be formed, usually two or three of them were isolated, for which the structures were assigned on the basis of ¹H NMR spectra including COSY and NOESY measure-ments. These types of products are attractive starting materials for synthesis of potential anticancer PDT agents with unique structures, being practically unavailable by any other alternative method.


Assuntos
Porfirinas/química , Porfirinas/síntese química , Isomerismo , Espectroscopia de Ressonância Magnética , Estrutura Molecular
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA