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1.
Chembiochem ; 25(17): e202400329, 2024 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-38926093

RESUMO

Photodynamic therapy (PDT) is a noninvasive approach to cancer treatment, wherein cell death is initiated by singlet oxygen (1O2) production via energy transfer from excited photosensitizers to ground-state O2. Effective clinical photosensitizers necessitate water solubility for in vivo administration. Hydrophobic dyes, such as phthalocyanines, cannot be used directly as photosensitizers. Herein, we synthesized a myoglobin-(human serum albumin) fusion protein reconstituted with zinc-phthalocyanine (ZnPc), termed ZnPcMb-HSA. The photophysical properties of ZnPcMb-HSA closely resemble those of ZnPc-substituted Mb. Notably, ZnPc dissociates from ZnPcMb-HSA and selectively accumulates within cancer cells, while the protein components remain extracellular. Treatment of four distinct cell lines with ZnPcMb-HSA, followed by red-light irradiation, effectively induced apoptosis. The half-maximal inhibitory concentrations (IC50) against these cancer cell lines ranged between 0.1-0.5 µM. Reconstituted Mb-HSA emerges as a promising carrier for transporting various water-insoluble porphyrinoid photosensitizer to target cancer cells in PDT applications.


Assuntos
Indóis , Isoindóis , Mioglobina , Compostos Organometálicos , Fotoquimioterapia , Fármacos Fotossensibilizantes , Compostos de Zinco , Humanos , Indóis/química , Indóis/farmacologia , Mioglobina/química , Mioglobina/metabolismo , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/síntese química , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Compostos Organometálicos/síntese química , Compostos de Zinco/química , Linhagem Celular Tumoral , Albumina Sérica Humana/química , Albumina Sérica Humana/metabolismo , Proteínas Recombinantes de Fusão/química , Proteínas Recombinantes de Fusão/farmacologia , Proteínas Recombinantes de Fusão/metabolismo , Apoptose/efeitos dos fármacos , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Neoplasias/tratamento farmacológico , Neoplasias/patologia
2.
Nanomedicine ; 61: 102768, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-38945506

RESUMO

Nanophotothermolysis (NPhT) effect is considered to be an approach for the development of highly selective modalities for anticancer treatment. Herein, we evaluated an antitumor efficacy of NPhT with intravenously injected zinc phthalocyanine particles (ZnPcPs) in murine subcutaneous syngeneic tumor models. In S37 sarcoma-bearing mice a biodistribution of ZnPcPs was studied and the high antitumor efficacy of ZnPcPs-mediated NPhT was shown, including a response of metastatic lesions. The morphological investigation showed the main role of a local NPhT-induced vascular damage in the tumor growth and tumor spread inhibition. Murine tumors of different histological origin were not equally sensitive to the treatment. The results demonstrate a potential of ZnPcPs-mediated NPhT for treatment of surface tumors.


Assuntos
Indóis , Isoindóis , Compostos Organometálicos , Compostos de Zinco , Animais , Compostos de Zinco/química , Indóis/química , Camundongos , Compostos Organometálicos/química , Compostos Organometálicos/administração & dosagem , Compostos Organometálicos/farmacologia , Linhagem Celular Tumoral , Nanopartículas/química , Distribuição Tecidual , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/administração & dosagem , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/administração & dosagem , Humanos , Feminino
3.
Lasers Med Sci ; 39(1): 133, 2024 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-38771549

RESUMO

BACKGROUND: Tooth discoloration is a common concern in antimicrobial photodynamic therapy (aPDT) using various photosensitizers (PS). Toluidine Blue (TB), Methylene Blue (MB), Phthalocyanine (Pc), and 2-mercaptopyridine-substituted zinc phthalocyanine (TM-ZnPc) are among those studied, but their relative impacts on tooth discoloration remain unclear. AIM: This study aimed to compare the effects of TB, MB, Pc, and TM-ZnPc in aPDT on tooth discoloration, utilizing a controlled experimental setup. MATERIALS AND METHODS: The study comprised seventy-five single-rooted incisors with root canals. Following meticulous preparation, a standardized area on the crown surface was designated for examination, and precise measurements of the initial tooth colors were recorded. Samples were randomly divided into five groups: Negative control, MB, TM, Pc, and TM-ZnPc. Photoactivation was performed using LED light, and color measurements were taken at multiple time points up to 90 days. Data were converted to Lab* color values of the CIE Lab* color system (International Commission on Illumination, Vienna, Austria), and ΔE values were calculated. Statistical analysis was performed using Two-way ANOVA and Post-Hoc Tukey tests (p < 0.05). RESULTS: At day 7 and 30, TM-ZnPc and Pc caused less discoloration compared to MB and TB. TM-ZnPc caused more tooth discoloration compared to Pc (p < 0.05). Compared to baseline, MB and TM-ZnPc caused more tooth discoloration at 30 days and TB caused more tooth discoloration at 90 days (p < 0.05). No significant difference was observed in terms of tooth discoloration at all periods evaluated after Pc application (p > 0.05). All photosensitizers tested in the study caused tooth coloration. CONCLUSION: All PS induced clinically detectable tooth discoloration, with TB and MB causing more significant discoloration compared to Pc and TM-ZnPc at certain time points. TM-ZnPc and Pc demonstrated more stable coloration levels over time, suggesting their potential reliability in aPDT applications. This study highlights the importance of selecting appropriate PS to minimize tooth discoloration in aPDT, with Pc showing promise in this regard.


Assuntos
Isoindóis , Azul de Metileno , Fotoquimioterapia , Fármacos Fotossensibilizantes , Espectrofotometria , Cloreto de Tolônio , Descoloração de Dente , Fotoquimioterapia/métodos , Fotoquimioterapia/efeitos adversos , Fármacos Fotossensibilizantes/administração & dosagem , Humanos , Descoloração de Dente/induzido quimicamente , Azul de Metileno/administração & dosagem , Compostos de Zinco , Indóis/efeitos adversos , Indóis/administração & dosagem , Compostos Organometálicos/administração & dosagem , Compostos Organometálicos/efeitos adversos
4.
J Biol Inorg Chem ; 28(5): 495-507, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37452218

RESUMO

Metallo-phthalocyanines (MPc) are common photosensitizers with ideal photophysical and photochemical properties. Also, these molecules have shown to interact with non-canonical nucleic acid structures, such as G-quadruplexes, and modulate oncogenic expression in cancer cells. Herein, we report the synthesis and characterisation of two metallo-phthalocyanines containing either zinc (ZnPc) or nickel (NiPc) in the central aromatic core and four alkyl ammonium lateral chains. The interaction of both molecules with G-quadruplex DNA was assessed by UV-Vis, fluorescence and FRET melting experiments. Both molecules bind strongly to G-quadruplexes and stabilise these structures, being NiPc the most notable G-quadruplex stabiliser. In addition, the photosensitizing ability of both metal complexes was explored by the evaluation of the singlet oxygen generation and their photoactivation in cells. Only ZnPc showed a high singlet oxygen generation either by direct observation or by indirect evaluation using a DPBF dye. The cellular evaluation showed mainly cytoplasmic localization of ZnPc and a decrease of the IC50 values of the cell viability of ZnPc upon light activation of two orders of magnitude. Two metallo-phthalocyanines containing zinc and nickel within the aromatic core have been investigated as G-quadruplex stabilizers and photosensitizers. NiPc shows a high G4 binding but negligible photosensitizing ability while ZnPc exhibits a moderate binding to G-quadruplex together with a high potency to generate singlet oxygen and photocytotoxicity. The interaction with G4s and capacity to be photosensitized is associated with the geometry adopted by the central metal core of the phthalocyanine scaffold.


Assuntos
Antineoplásicos , Quadruplex G , Compostos Organometálicos , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Oxigênio Singlete/química , Níquel , Antineoplásicos/química , Compostos Organometálicos/química , Zinco/química , Compostos de Zinco
5.
Nano Lett ; 22(3): 1032-1038, 2022 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-35001635

RESUMO

Future photonic devices require efficient, multifunctional, electrically driven light sources with directional emission properties and subwavelength dimensions. Electrically driven plasmonic nanoantennas have been demonstrated as enabling technology. Here, we present the concept of a nanoscale organic light-emitting antenna (OLEA) as a color- and directionality-switchable point source. The device consists of laterally arranged electrically contacted gold nanoantennas with their gap filled by the organic semiconductor zinc phthalocyanine (ZnPc). Since ZnPc shows preferred hole conduction in combination with gold, the recombination zone relocates depending on the polarity of the applied voltage and couples selectively to either of the two antennas. Thereby, the emission characteristics of the device also depend on polarity. Contrary to large-area OLEDs where recombination at metal contacts significantly contributes to losses, our ultracompact OLEA structures facilitate efficient radiation into the far-field rendering transparent electrodes obsolete. We envision OLEA structures to serve as wavelength-scale pixels with tunable color and directionality for advanced display applications.

6.
Sensors (Basel) ; 22(24)2022 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-36560314

RESUMO

Rapid and accurate detection of lethal volatile compounds is an emerging requirement to ensure the security of the current and future society. Since the threats are becoming more complex, the assurance of future sensing devices' performance can be obtained solely based on a thorough fundamental approach, by utilizing physics and chemistry together. In this work, we have applied thermal desorption spectroscopy (TDS) to study dimethyl methylophosphate (DMMP, sarin analogue) adsorption on zinc phthalocyanine (ZnPc), aiming to achieve the quantification of the sensing mechanism. Furthermore, we utilize a novel approach to TDS that involves quantum chemistry calculations for the determination of desorption activation energies. As a result, we have provided a comprehensive description of DMMP desorption processes from ZnPc, which is the basis for successful future applications of sarin ZnPc-based sensors. Finally, we have verified the sensing capability of the studied material at room temperature using impedance spectroscopy and took the final steps towards demonstrating ZnPc as a promising sarin sensor candidate.


Assuntos
Substâncias para a Guerra Química , Compostos Organometálicos , Substâncias para a Guerra Química/análise , Sarina , Compostos Organometálicos/química , Compostos de Zinco
7.
Nano Lett ; 21(12): 5006-5012, 2021 06 23.
Artigo em Inglês | MEDLINE | ID: mdl-34061553

RESUMO

We demonstrate that nanocavity plasmons generated a few nanometers away from a molecule can induce molecular motion. For this, we study the well-known rapid shuttling motion of zinc phthalocyanine molecules adsorbed on ultrathin NaCl films by combining scanning tunneling microscopy (STM) and spectroscopy (STS) with STM-induced light emission. Comparing spatially resolved single-molecule luminescence spectra from molecules anchored to a step edge with isolated molecules adsorbed on the free surface, we found that the azimuthal modulation of the Lamb shift is diminished in case of the latter. This is evidence that the rapid shuttling motion is remotely induced by plasmon-molecule coupling. Plasmon-induced molecular motion may open an interesting playground to bridge the nanoscopic and mesoscopic worlds by combining molecular machines with nanoplasmonics to control directed motion of single molecules without the need for local probes.


Assuntos
Microscopia de Tunelamento , Nanotecnologia , Luminescência , Análise Espectral
8.
Chemistry ; 27(12): 4159-4167, 2021 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-33372312

RESUMO

Whether chemical bonding can regulate the excited-state and optoelectronic properties of donor-acceptor dyads has been largely elusive. In this work, we used electronic structure and nonadiabatic dynamics methods to explore the excited-state properties of covalently bonded zinc phthalocyanine (ZnPc)-fullerene (C60 ) dyads with a 6-6 (or 5-6) bonding configuration in which ZnPc is bonded to two carbon atoms shared by the two hexagonal rings (or a pentagonal and a hexagonal ring) in C60 . In both cases, the locally excited (LE) states on ZnPc are spectroscopically bright. However, their different chemical bonding differentiates the electronic interactions between ZnPc and C60 . In the 5-6 bonding configuration, the LE states on ZnPc are much higher in energy than the LE states on C60 . Thus, the excitation energy transfer from ZnPc to C60 is thermodynamically favorable. On the other hand, in the 6-6 bonding configuration, such a process is inhibited because the LE states on ZnPc are the lowest ones. More detailed mechanisms are elucidated from nonadiabatic dynamics simulations. In the 6-6 bonding configuration, no excitation energy transfer was observed. In contrast, in the 5-6 bonding configuration, several LE and charge-transfer (CT) excitons were shown to participate in the energy-transfer process. Further analysis reveals that the photoinduced energy transfer is mediated by a CT exciton, such that electron- and hole-transfer processes take place in a concerted but asynchronous manner in the excitation energy transfer. It is also found that high-level electronic structure methods including exciton effects are indispensable to accurately describe photoinduced energy- and electron-transfer processes. Furthermore, this work opens up new avenues for regulating the excited-state properties of molecular donor-acceptor dyads by means of chemical bonding.

9.
Biotechnol Lett ; 43(4): 781-790, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33387115

RESUMO

In the present work, we propose the synthesis of novel nicotinamide subsituted phthlocyanine photosensitizer (PS) and characterized by FTIR, UV-visible, H-NMR and MALDI Toff spectroscopy. Nicotinamide plays a vital rule in the central nervous system and its potential as a therapeutic for neurodegenerative disease. Nicotinamide substituted PS (3) efficiently produced ROS via type-1 process as measured by DCF assay. We observed that our PS after red light illumination (22 J/cm2) killed gram positive S. aureus upto 3 log reduction. Furher the addition of Potassium Iodide (100 mM) significantly potentiated PS at lower concentrations and enhanced the bacterial killing upto 6 log reduction against the S. aureus. We further found that the synergistic effect of PS and KI also eradicated the gram negative E. coli strain at lower concentraion of PS and found to killed E. coli upto 5 log reduction under the red light illumination at 22 J/cm2 of light dose. The conjugation of such biologically important form of vitamin B3 with PS would be a great addition and could pav the way for the novel photodynamic agent in the treatement of cancer and infectious diseases. A new symmetrical Nicotinamide tetrasubstituted zinc phthalocyanine (3) was synthesized. Upon addition of potassium Iodide with PS, the PS exhibited significant photodynamic activity with 5-6 logs reduction in bacterial load was achieved.


Assuntos
Escherichia coli/crescimento & desenvolvimento , Isoindóis/síntese química , Niacinamida/química , Iodeto de Potássio/farmacologia , Staphylococcus aureus/crescimento & desenvolvimento , Sinergismo Farmacológico , Escherichia coli/efeitos dos fármacos , Isoindóis/química , Isoindóis/farmacologia , Testes de Sensibilidade Microbiana , Viabilidade Microbiana/efeitos dos fármacos , Fotoquimioterapia , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Staphylococcus aureus/efeitos dos fármacos
10.
Int J Mol Sci ; 22(18)2021 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-34575942

RESUMO

Colorectal cancer (CRC) is an aggressive cancer that remains a challenge to diagnose and treat. Photodynamic diagnosis (PDD) and therapy (PDT) are novel alternative techniques, which can enhance early diagnosis, as well as elicit tumor cell death. This is accomplished through photosensitizer (PS) mediated fluorescence and cytotoxic reactive oxygen species activation upon laser light irradiation excitation at specific low and high range wavelengths, respectively. However, the lack of PS target tumor tissue specificity often hampers these techniques. This study successfully fabricated a bioactive nanoconjugate, ZnPcS4-AuNP-S-PEG5000-NH2-Anti-GCC mAb (BNC), based upon a polyethylene glycol-gold nanoparticle, which was multi-functionalized with a fluorescent PDT metalated zinc phthalocyanine PS, and specific anti-GCC targeting antibodies, to overcome CRC PDD and PDT challenges. The BNC was found to be stable and showed selectively improved subcellular accumulation within targeted CRC for improved PDD and PDT outcomes in comparison to healthy in vitro cultured cells. Additionally, the BNC reported significantly higher late apoptotic PDT-induced CRC cell death rates (34% ***) when compared to PDT PS administration alone (15% *). These results indicated that the improved PDD and PDT outcomes were due to the specific PS accumulation in CRC cells through nanoparticle carriage and bioactive anti-GCC targeting.


Assuntos
Neoplasias Colorretais/terapia , Imunoconjugados/farmacologia , Imunoterapia , Nanopartículas Metálicas/uso terapêutico , Antineoplásicos/farmacologia , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Neoplasias Colorretais/diagnóstico , Neoplasias Colorretais/imunologia , Neoplasias Colorretais/patologia , Ouro/química , Humanos , Imunoconjugados/química , Imunoconjugados/imunologia , Indóis/química , Indóis/farmacologia , Nanopartículas Metálicas/química , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Fotoquimioterapia , Espécies Reativas de Oxigênio/metabolismo
11.
Molecules ; 26(22)2021 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-34833970

RESUMO

Photodynamic therapy (PDT) is a light-based cancer therapy approach that has shown promising results in treating various malignancies. Growing evidence indicates that cancer stem cells (CSCs) are implicated in tumor recurrence, metastasis, and cancer therapy resistance in colorectal cancer (CRC); thus, targeting these cells can ameliorate the prognosis of affected patients. Based on our bioinformatics results, SOX2 overexpression is significantly associated with inferior disease-specific survival and worsened the progression-free interval of CRC patients. Our results demonstrate that zinc phthalocyanine (ZnPc)-PDT with 12 J/cm2 or 24 J/cm2 irradiation can substantially decrease tumor migration via downregulating MMP9 and ROCK1 and inhibit the clonogenicity of SW480 cells via downregulating CD44 and SOX2. Despite inhibiting clonogenicity, ZnPc-PDT with 12 J/cm2 irradiation fails to downregulate CD44 expression in SW480 cells. Our results indicate that ZnPc-PDT with 12 J/cm2 or 24 J/cm2 irradiation can substantially reduce the cell viability of SW480 cells and stimulate autophagy in the tumoral cells. Moreover, our results show that ZnPc-PDT with 12 J/cm2 or 24 J/cm2 irradiation can substantially arrest the cell cycle at the sub-G1 level, stimulate the intrinsic apoptosis pathway via upregulating caspase-3 and caspase-9 and downregulating Bcl-2. Indeed, our bioinformatics results show considerable interactions between the studied CSC-related genes with the studied migration- and apoptosis-related genes. Collectively, the current study highlights the potential role of ZnPc-PDT in inhibiting stemness and CRC development, which can ameliorate the prognosis of CRC patients.


Assuntos
Neoplasias Colorretais/tratamento farmacológico , Isoindóis/farmacologia , Células-Tronco Neoplásicas/efeitos dos fármacos , Compostos Organometálicos/farmacologia , Fármacos Fotossensibilizantes/farmacologia , Compostos de Zinco/farmacologia , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Movimento Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Neoplasias Colorretais/patologia , Humanos , Células-Tronco Neoplásicas/patologia , Fotoquimioterapia
12.
Mol Pharm ; 17(1): 190-201, 2020 01 06.
Artigo em Inglês | MEDLINE | ID: mdl-31804837

RESUMO

Nitric oxide (NO) can play both prosurvival and prodeath roles in photodynamic therapy (PDT). The generation efficiency of peroxynitrite anions (ONOO-), by NO and superoxide anions (O2•-), significantly influenced the outcome. Reports indicated that such efficiency is closely related to the distance between NO and O2•-. Thus, in this manuscript, l-arginine (Arg) ethyl ester-modified zinc phthalocyanine (Arg-ZnPc) was designed and synthesized as a photosensitizer (PS) and NO donor. Post light irradiation, the guanido of Arg-ZnPc can be effectively oxidized by the generated reactive oxygen species (ROS) in the PDT process to release NO. Such a strategy could ensure O2•- and NO generation in the same place at the same time to guarantee effective ONOO- formation. In addition, NO has other multiple synergistic cancer treatment functions, including tumor tissue vasodilatation for drug extravasation promotion, P-glycoprotein (P-gp) downregulation for drug efflux inhibition, and glutathione depletion for cancer cell endogenous antioxidant defense destruction. In vitro and in vivo results indicated that the effective ONOO- formation and multiple functions of Arg-ZnPc could synergistically enhance its PDT activity and ensure satisfactory cancer treatment outcome.


Assuntos
Indóis/química , Indóis/farmacologia , Neoplasias/tratamento farmacológico , Óxido Nítrico/farmacologia , Compostos Organometálicos/química , Compostos Organometálicos/farmacologia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacologia , Superóxidos/farmacologia , Membro 1 da Subfamília B de Cassetes de Ligação de ATP/metabolismo , Animais , Apoptose/efeitos dos fármacos , Apoptose/efeitos da radiação , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Sinergismo Farmacológico , Feminino , Fluorescência , Glutationa/metabolismo , Humanos , Indóis/síntese química , Indóis/efeitos da radiação , Isoindóis , Camundongos , Neoplasias/metabolismo , Óxido Nítrico/química , Compostos Organometálicos/síntese química , Compostos Organometálicos/efeitos da radiação , Ácido Peroxinitroso/química , Espécies Reativas de Oxigênio/química , Superóxidos/química , Distribuição Tecidual/efeitos dos fármacos , Distribuição Tecidual/efeitos da radiação , Ensaios Antitumorais Modelo de Xenoenxerto , Compostos de Zinco
13.
Luminescence ; 35(5): 667-672, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31916376

RESUMO

This study reports the influence of CdSe-ZnS core-shell quantum dots (QDs) for formation of singlet oxygen using zinc-phthalocyanine (ZnPc) dyes in colloidal solutions. Using a microluminescence surface scan technique it was possible to measure accurately the photon diffusion length, or photon mean free path, inside the medium. Analyses were performed for a range of QD concentrations. Photon diffusion length was assigned to the bimolecular singlet oxygen emission at 707 nm. Related singlet oxygen emission was predicted by observing quenching of the photon diffusion length measured at the specific oxygen emission as a function of QD concentration, being a nontrivial phenomenon related to the QD donors. Diffusion length measured at 707 nm increased with QD concentration; in the absence of QDs, as in pure ZnPc samples, the emission peak at 707 nm was not observed.


Assuntos
Corantes Fluorescentes/química , Indóis/química , Compostos Organometálicos/química , Pontos Quânticos/química , Oxigênio Singlete/química , Compostos de Cádmio/química , Transferência de Energia , Isoindóis , Compostos de Selênio/química , Espectrometria de Fluorescência , Sulfetos/química , Compostos de Zinco/química
14.
Nano Lett ; 19(12): 8605-8611, 2019 12 11.
Artigo em Inglês | MEDLINE | ID: mdl-31738569

RESUMO

We investigate electroluminescence of single molecular emitters on NaCl on Ag(111) and Au(111) with submolecular resolution in a low-temperature scanning probe microscope with tunneling current, atomic force, and light detection capabilities. The role of the tip state is studied in the photon maps of a prototypical emitter, zinc phthalocyanine (ZnPc), using metal and CO-metal tips. CO-functionalization is found to have an impact on the resolution and contrast of the photon maps due to the localized overlap of the p-orbitals on the tip with the molecular orbitals of the emitter. The possibility of using the same CO-functionalized tip for tip-enhanced photon detection and high resolution atomic force is demonstrated. We study the electroluminescence of ZnPc, induced by charge carrier injection at sufficiently high bias voltages. We propose that the distinct level alignment of the ZnPc frontier orbitals with the Au(111) and Ag(111) Fermi levels governs the primary excitation mechanisms as the injection of electrons and holes from the tip into the molecule, respectively. These findings put forward the importance of the tip status in the photon maps and contribute to a better understanding of the photophysics of organic molecules on surfaces.

15.
Chemistry ; 25(43): 10123-10132, 2019 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-31264744

RESUMO

Directly linked to promote strong intramolecular interactions, donor-acceptor dyads and a donor-acceptor-donor triad featuring zinc phthalocyanine (ZnPc) as electron donor and perylenediimide (PDI) as electron acceptor have been synthesized and characterized. Owing to complementary absorption features of the entities, improved light absorption was witnessed in these conjugates. The optimized geometry and electronic structures showed the majority of the highest occupied molecular orbital (HOMO) on the ZnPc entity, whereas the lowest unoccupied molecular orbital (LUMO) was on the PDI entity, suggesting that the charge-separated states would be ZnPc+ -PDI. - . The electrochemical and free-energy calculations suggested exothermic energy and/or electron transfer processes via the singlet states of PDI or ZnPc entities depending on the excitation wavelength of the laser used. The measured rates using femtosecond pump-probe spectroscopy coupled with global analysis of transient data revealed ultrafast energy transfer from 1 PDI* to ZnPc followed by charge separation. However, when ZnPc was selectively excited, only electron transfer was witnessed wherein the time constants for forward and reverse electron transfer processes followed Marcus predictions. The absorption in a wide section of the solar spectrum and the ultrafast charge separation suggest the usefulness of these systems as good photosynthetic models.

16.
Microsc Microanal ; 25(6): 1416-1421, 2019 12.
Artigo em Inglês | MEDLINE | ID: mdl-31130144

RESUMO

The drive to replace scarce and expensive Pt-based electrocatalysts for oxygen reduction reaction (ORR) has led to the development of a group of electrocatalysts composed of transition-metal ion centers coordinated with four nitrogen groups (M-N4). Among these, metal phthalocyanines (MPcs), due to low cost of preparation, highly conjugated structure as well as high thermal and chemical stability, have received a great interest. The catalytic activity of MPcs can be improved by employing conducting supports. Here, in this report, we have solvothermally synthesized graphene-supported zinc phthalocyanine nanostructures, and their ORR kinetics and mechanism have been investigated in neutral solution (pH = 7) by using the rotating disk electrode technique. The as-synthesized nanocomposite followed a 4e- reduction pathway. The onset potential (-0.04 V versus Ag/AgCl) found in this work can be comparable with other state-of-the-art material, demonstrating good performance in neutral solution. The fascinating performance leads the nanocomposite material toward future energy applications.

17.
Int J Mol Sci ; 20(13)2019 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-31269724

RESUMO

Photodynamic therapy (PDT) is a cancer treatment modality that utilizes three components: light (λ 650-750 nm), a photosensitizer (PS) and molecular oxygen, which upon activation renders the modality effective. Colorectal cancer has one of the highest incident rates as well as a high mortality rate worldwide. In this study, a zinc (Zn) metal-based phthalocyanine (ZnPcSmix) PS was used to determine its efficacy for the treatment of colon adenocarcinoma cells (DLD-1 and Caco-2). Photoactivation of the PS was achieved by laser irradiation at a wavelength of 680 nm. Dose responses were performed to establish optimal PS concentration and irradiation fluence. A working combination of 20 µM ZnPcSmix and 5 J/cm2 was used. Biochemical responses were determined after 1 or 24 h incubation post-treatment. Since ZnPcSmix is localized in lysosomes and mitochondria, mitochondrial destabilization analysis was performed monitoring mitochondrial membrane potential (MMP). Cytosolic acidification was determined measuring hydrogen peroxide (H2O2) levels in the cytoplasm. Having established apoptotic cell death induction, an apoptosis PCR array was performed to establish the apoptotic mechanism. In DLD-1 cells, expression of genes included 3 up-regulated and 20 down-regulated genes while in Caco-2 cells, there were 16 up-regulated and 22 down-regulated genes. In both cell lines, in up-regulated genes, there was a combination of pro- and anti-apoptotic genes that were significantly expressed. Gene expression results showed that more tumorigenic cells (DLD-1) went through apoptosis; however, they exhibit increased risk of resistance and recurrence, while less tumorigenic Caco-2 cells responded better to PDT, thus being suggestive of a better prognosis post-PDT treatment. In addition, the possible apoptotic mechanisms of cell death were deduced based on the genetic expression profiling of regulatory apoptotic inducing factors.


Assuntos
Adenocarcinoma/tratamento farmacológico , Neoplasias Colorretais/tratamento farmacológico , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Indóis/farmacologia , Compostos Organometálicos/farmacologia , Fármacos Fotossensibilizantes/farmacologia , Adenocarcinoma/genética , Células CACO-2 , Linhagem Celular Tumoral , Neoplasias Colorretais/genética , Humanos , Isoindóis , Fotoquimioterapia , Compostos de Zinco
18.
J Fluoresc ; 28(3): 827-838, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29961202

RESUMO

Various sizes of graphene quantum dots (GQDs) denoted as GQD2, GQD6 and GQD10 (increasing in size) were non-covalently attached to 2,9,16,23-tetrakis[4-(N-methylpyridyloxy)]-phthalocyanine (ZnTPPcQ) to form GQDs-ZnTPPcQ nanoconjugates. X-ray photoelectron spectroscopy (XPS) showed that increasing sizes of GQDs decreases the atomic concentrations of oxygen, which leads to blue shift in spectra of the GQDs. Relative to Pcs alone (0.03), the presence of GQDs improved the singlet oxygen quantum yields with the following values: GQD2-ZnTPPcQ (0.17), GQD6-ZnTPPcQ (0.27) and GQD10-ZnTPPcQ (0.11). GQD2-ZnTPPcQ nanoconjugate system had the most ZnTPPcQ loading, but did not generate the most singlet oxygen species due to aggregation. This study shows that, the quantity of oxygen, size and quality of GQDs as well as amount of Pc loading are amongst the vital properties to consider when constructing GQD-nanoconjugate systems with optimal singlet oxygen quantum yields.

19.
Nanomedicine ; 14(4): 1099-1110, 2018 06.
Artigo em Inglês | MEDLINE | ID: mdl-29462663

RESUMO

Zinc phthalocyanine (ZnPc) is a highly potent second-generation photosensitizer for cancer photodynamic therapy (PDT) with attractive photo-physical and photo-chemical properties. However, poor solubility and strong trend of crystallization prevent it from loading in most of drug delivery systems and hamper its further application. Herein, to overcome this problem, an amphiphilic block copolymer poly(ethylene glycol)-poly[2-(methylacryloyl)ethylnicotinate] (PEG-PMAN) with aromatic nicotinate is used to load ZnPc for their π-π interactions. The formed PEG-PMAN/ZnPc nanoparticle (PPZ) dramatically increases reactive oxygen species production in osteosarcoma cells after light irradiation, causes mitochondrial injury and promotes cell cycle arrest at G2/M, leading to a 100-fold cytotoxicity improvement comparing with free ZnPc. The excellent therapeutic effectiveness and safety of PPZ are also proved by in vivo experiments operating on osteosarcoma model. The finding above indicates that PPZ has promising clinical applications as a next-generation photosensitizer in PDT of osteosarcoma.


Assuntos
Indóis/química , Compostos Organometálicos/química , Osteossarcoma/terapia , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/química , Polímeros/química , Animais , Linhagem Celular Tumoral , Humanos , Isoindóis , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Camundongos , Micelas , Nanopartículas/química , Compostos de Zinco
20.
Lasers Med Sci ; 33(9): 1969-1978, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-30143924

RESUMO

Regarding post-complication of convenient therapies against breast cancer, the emergence of effective approaches is essential. Photodynamic therapy is touted as a novel invasive therapeutic approach by the application of a photosensitizer promoted by laser irradiation. This study aimed to investigate the combined regime of low-level laser irradiation with zinc phthalocyanine in human breast cancer ZR-75-1 cell line. Cells were treated with 0.01 and 5 µg/ml of ZnPc for 24 h and exposed to radiation (70 mW) for 60 s. Cell viability was evaluated by MTT and flow cytometry. Cell migration capacity was monitored by scratch test, Transwell migration insert, and gelatin zymography. The function of MDR in treated cells was examined by Rhodamine 123 exclusion test. The level of GALNT11 was measured by ELISA. The expression of Bax and Bcl-2 genes was evaluated by real-time PCR. Laser irradiation and zinc phthalocyanine induced cell cytotoxicity in a dose-dependent manner. Flow cytometry analysis showed the induction of apoptotic and necrotic changes in treated cells. We found a reduction in migration rate and MMP-9 activity in cells undergoing the experimental procedure (p < 0.05). Immunofluorescence imaging revealed the intracellular accumulation of Rhodamine 123 coincided with a reduction in the level of GALNT11 in treated cells, showing the reduction of MDR activity and tumor cell resistance. Similar to flow cytometry assay, the reduction of Bcl-2 (approximately twofold) and upregulation of Bax genes were found in treated cells. Photodynamic therapy could be as an effective and alternative method for the treatment of breast cancer in a human.


Assuntos
Neoplasias da Mama/patologia , Indóis/farmacologia , Luz , Compostos Organometálicos/farmacologia , Subfamília B de Transportador de Cassetes de Ligação de ATP/metabolismo , Apoptose/efeitos dos fármacos , Contagem de Células , Linhagem Celular Tumoral , Movimento Celular/efeitos dos fármacos , Movimento Celular/efeitos da radiação , Sobrevivência Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos da radiação , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Feminino , Humanos , Isoindóis , Metaloproteinase 9 da Matriz/metabolismo , N-Acetilgalactosaminiltransferases/metabolismo , Necrose , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Rodamina 123/metabolismo , Compostos de Zinco , Proteína X Associada a bcl-2/metabolismo
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