Phthalocyanine Nanoparticles Research Articles

Trifluoromethyl-pyrrolidone phthalocyanine nanoparticles for targeted lipid droplet imaging and in vitro photodynamic therapy in breast cancer cells

Lipid droplets (LDs) serve as vital subcellular organelles, crucial for the maintenance of lipid and energy homeostasis within cells. Their visualization is of significant value for elucidating the intricate interactions between LDs and other cellular organelles. Despite the importance of LDs, the literature on the utilization of phthalocyanine-based photosensitizers for targeted LD imaging and two-photon imaging-guided photodynamic therapy (PDT) remains sparse. In this study, we have designed and synthesized trifluoromethyl-pyrrolidone silicon phthalocyanine (PyCF3SiPc). To enhance the water solubility of PyCF3SiPc and improve its tumor cells accumulation, we employed 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000] (DSPE-mPEG2000) as a nanocarrier, thereby formulating DSPE@PyCF3SiPc nanoparticles. Our in vitro experiments in MCF-7 cells demonstrated that DSPE@PyCF3SiPc selectively targets and visualizes LDs, offering a reliable tool for tracking their dynamic movement. Moreover, DSPE@PyCF3SiPc demonstrates considerable phototoxicity against MCF-7 cells subjected to PDT underscoring its potential as an effective therapeutic agent. In conclusion, DSPE@PyCF3SiPc presents itself as a promising novel probe for the dual purpose of monitoring the dynamic movement of LDs and guiding imaging-assisted PDT. The development of this nanoparticle system not only advances our understanding of LD biology but also paves the way for innovative therapeutic strategies in oncology.

Synergistic effect of iron phthalocyanine and ultrafine cobalt nanoparticles for efficient CO2 electroreduction to syngas

Developing efficient electrocatalysts for CO2 electroreduction to syngas with a specific H2/CO ratio over a wide potential window is desperately required but still challenging. In this work, a series of dual-site catalysts composed of iron phthalocyanine (FePc) and ∼18 nm Cobalt nanoparticles (Co NPs) anchored on N-doped carbon matrix has been constructed from zeolitic imidazolate framework-67 (ZIF-67). Benefiting from the synergistic effect of FePc and Co NPs, the derived FePc/Co@N–C catalyst shows impressive capability for CO2 electrolysis to syngas. By varying the pyrolysis temperatures (600–800 °C) of ZIF-67 and the mass ratio of Co@N–C to FePc (1–3), an adjustable H2/CO ratio of 2–4 is obtained, and the value can be maintained stable within a potential window of −0.66 to −0.86 V vs. RHE in an H-type cell. Moreover, this electrocatalyst exhibits favorable stability without distinct performance decay. When conducted in a flow cell, an enhanced catalytic activity is demonstrated with an industrial current density (>100 mA cm−2) at −0.8 V vs. RHE and a steady H2/CO ratio of 2 from −0.4 to −0.6 V vs. RHE. This work provides a promising strategy of designing bifunctional electrocatalysts for syngas generation with stable H2/CO ratio across a wide potential range.

S-scheme heterojunction phthalocyanine/TiO2 photoelectrochemical sensor for innovative glutathione detection.

A novel photoelectrochemical sensor, employing an S-scheme heterojunction of phthalocyanine and TiO2 nanoparticles, has been developed to enable highly sensitive determination of glutathione. By integrating the favorable stability, environmental benignity, and electronic properties of the TiO2 matrix with the unique photoactivity of phthalocyanine species, the designed sensor presents a substantial linear dynamic range and a low detection limit for the quantification of glutathione. The sensitivity is attributed to efficient charge transfer and separation across the staggered heterojunction energy levels, which generates measurable photocurrent signals. Systematic variation of phthalocyanine content reveals an optimal composition that balances light harvesting capacity and electron-hole recombination rates. The incorporation of phosphotungstic acid (PTA) in sample preparation effectively minimizes interference from compounds like L-cysteine and others. Consequently, this leads to an improvement in accuracy through the reduction of impurity levels. Appreciable photocurrent enhancements are observed upon introduction of both oxidized and reduced glutathione at the optimized composite photoanode. Coupled with advantageous features of photoelectrochemical transduction such as simplicity, cost-effectiveness, and resistance to fouling, this sensor holds great promise for practical applications in complex biological media.

Synthesis of (2-(4-methylthiazol-5-yl) ethoxy)-substituted silicon phthalocyanine and novel green silver nanoparticles: DSSC targets

ABSTRACT In this study, designed as a dye-sensitive solar cell material which, bis-(2-(4-methylthiazol-5-yl) ethoxy) phthalocyaninato silicon (IV) compound (3) was obtained from the chemical reaction of SiPcCl2 and 4-methyl-5-thiazoleethanol. Silver nanoparticles (AgNPs) were synthesized using environmentally friendly and cost-effective green methods using leaf and flower extracts of Corydalis cava(CoV) and Nonea pulla(NP) plants. For the characterization of phthalocyanine compound and silver nanoparticles, Transmission electron microscopy (TEM), 1H NMR, 13C NMR, X-Ray Diffraction (XRD), UV-visible, FT-IR and Mass spectrum devices were used. The power conversion efficiency of without doping compound 3 is 1.20. After doping this compound with CoVAgNPs and NPAgNPs, the power conversion efficiencies increased to 1.74 and 2.10. From this it is clearly seen that silver nanoparticles are effective. It is concluded that better photovoltaic materials can be created by using phthalocyanine and silver nanoparticles together.

Carbon nanotube-interconnected ruthenium phthalocyanine nanoparticles used for real-time monitoring of nitric oxide released from vascular endothelial barrier model

Real-time monitoring of nitric oxide (NO) is of great importance in diagnosing the physiological functions of neurotransmission, cardiovascular, and immune systems. This study reports the carbon nanotube-interconnected ruthenium phthalocyanine nanoparticle nanocomposite and its applicability in construction of an electrochemical platform, which could real-time detect NO released from the vascular endothelial barrier (VEB) model in cell culture medium. The nanocomposite exhibits regular morphology, uniform particle size, and excellent electro-catalytic activity to electrochemical oxidation of NO. Under optimal conditions, the electrochemical device has high sensitivity (0.871 μA μM−1) and can selectively detect NO down to the concentration of 6 × 10−10 M. The human brain microvascular endothelial cells were cultured onto the Transwell support to construct the VEB model. Upon stimulated by L-arginine, NO produced by the VEB diffuses into the bottom chamber of the Transwell, and is real-time monitored by the electrochemical device. Moreover, evaluation of the NO inhibition by drug is realized using the electrochemical device-Transwell platform. This simple and sensitive platform would be of great interesting for evaluating the endothelial function or its pathological states, and screening the related drugs or chemicals.

Theranostic Phthalocyanine and Naphthalocyanine Nanoparticles for Photoacoustic Imaging and Photothermal Therapy of Tumors.

Background: Phthalocyanine (PC) and naphthalocyanine (NC) dyes have long garnered interest as theranostic agents for optical imaging and phototherapy due to their near-infrared absorbance, photostability, imaging contrast, and proven safety in clinical trials. Yet, only a small fraction of these dyes has been evaluated as photothermal therapy (PTT) agents for cancer treatment. Methods: Nearly 40 distinct NC and PC dyes were encapsulated within polymeric PEG-PCL micelles via oil-in-water emulsions. The optimal NC/PC-loaded micelle formulations for PTT and photoacoustic (PA) imaging were identified through in vivo and in vitro studies. Results: The most promising candidate, CuNC(Octa)-loaded micelles, demonstrated a strong PA signal with a peak absorbance at ~870 nm, high photothermal efficiency, and photostability. The CuNC(Octa)-loaded micelles exhibited heat generation as good or better than gold nanorods/nanoshells and >10-fold higher photoacoustic signals. Micelle preparation was reproducible/scalable, and the CuNC(Octa)-loaded micelles are highly stable under physiological conditions. The CuNC(Octa)-loaded micelles localize within tumors via enhanced permeability and retention and are readily detectable by PA imaging. In a syngeneic murine tumor model of triple-negative breast cancer, CuNC(Octa)-loaded micelles demonstrate efficient heat generation with PTT, leading to the complete eradication of tumors. Conclusions: CuNC(Octa)-loaded micelles represent a promising theranostic agent for PA imaging and PTT. The ability to utilize conventional ultrasound in combination with PA imaging enables the simultaneous acquisition of information about tumor morphology and micelle accumulation. PTT with CuNC(Octa)-loaded micelles can lead to the complete eradication of highly invasive tumors.

Real-time investigation of reactive oxygen species and radicals evolved from operating Fe-N-C electrocatalysts during the ORR: potential dependence, impact on degradation, and structural comparisons.

Improving the stability of platinum-group-metal-free (PGM-free) catalysts is a critical roadblock to the development of economically feasible energy storage and conversion technologies. Fe-N-C catalysts, the most promising class of PGM-free catalysts, suffer from rapid degradation. The generation of reactive oxygen species (ROS) during the oxygen reduction reaction (ORR) has been proposed as a central cause of this loss of activity. However, there is insufficient understanding of the generation and dynamics of ROS under catalytic conditions due to the difficulty of detecting and quantifying short-lived ROS such as the hydroxyl radical, OH˙. To accomplish this, we use operando scanning electrochemical microscopy (SECM) to probe the production of radicals by a commercial pyrolyzed Fe-N-C catalyst in real-time using a redox-active spin trap methodology. SECM showed the monotonic production of OH˙ which followed the ORR activity. Our results were thoroughly backed using electron spin resonance confirmation to show that the hydroxyl radical is the dominant radical species produced. Furthermore, OH˙ and H2O2 production followed distinct trends. ROS studied as a function of catalyst degradation also showed a decreased production, suggesting its relation to the catalytic activity of the sample. The structural origins of ROS production were also probed using model systems such as iron phthalocyanine (FePc) and Fe3O4 nanoparticles, both of which showed significant generation of OH˙ during the ORR. These results provide a comprehensive insight into the critical, yet under-studied, aspects of the production and effects of ROS on electrocatalytic systems and open the door for further mechanistic and kinetic investigation using SECM.

Nanocomposite of nickel phthalocyanine nanoparticles and detonation nanodiamonds for enhanced electrocatalysis

This work reports on nickel phthalocyanines nanoparticles (NPs)-detonation nanodiamonds (DNDs) as potential platforms for electrocatalytic detection of nitrite in 0.2 M sodium hydroxide solution. The electrode surfaces were analysed using cyclic voltammetry and electrochemical impedance which showed enhanced electron transfer after modification, with (1)-NPs-DNDs showing relatively better electron tranter ability. The electrocatalytic performance of modified surfaces was investigated towards nitrite electrooxidation. The results demonstrated that tetrakis [4-(4-(4,5-dichloro-1H-benzo[d]imidazole-2-yl) phenoxy] phthalocyanato nickel (II) (1)-NPs-DNDs gave more negative oxidation potential (0.87 V), highest background corrected current (120.3 μA), highest electrocatalytic rate constant (2.84 × 104 M−1 s−1) and lowest limit of detection of (0.098 nM). These factors rendered (1)-NPs-DNDs electrode surface better than others studied here making it a promising sensor for nitrite.

Preparation of Manganese Phthalocyanine Nanoparticles by Laser Ablation in Liquid and Application to Bioimaging

Preparation of Manganese Phthalocyanine Nanoparticles by Laser Ablation in Liquid and Application to Bioimaging

A novel boronate-linked polydopamine-poloxamer 407 loaded zinc phthalocyanine nanoparticles for photothermal and photodynamic synergy therapy

A novel boronate-linked polydopamine-poloxamer 407 loaded zinc phthalocyanine nanoparticles for photothermal and photodynamic synergy therapy

Fluorinated triphenylamine silicon phthalocyanine nanoparticles with two-color imaging guided in vitro photodynamic therapy through lysosomal dysfunction

Lysosome-targeting therapy has emerged as a promising strategy for combating drug-resistant tumors. However, the synthesis of nanodrugs to achieve efficient lysosome targeting remains a challenging task. In this study, a nanoparticle DSPE@TPA-FBPA-SiPc was developed for lysosome targeting therapy. The nanoparticle was prepared by loading 2-[4-(diphenylamino)-1-diphenicacid-1-carbobenzoxy-4-(1,1,1,3,3,3-hexafluoropropane-4-phenoxy) silicon phthalocyanine (TPA-FBPA-SiPc) into 1,2-distearoyl-sn‑glycero-3-phosphoethanolamine-N-[succinyl(polyethyleneglycol)-2000] (DSPE). DSPE@TPA-FBPA-SiPc demonstrated remarkable capabilities such as two-color imaging, lysosome targeting and in vitro photodynamic therapy functions. The results revealed that DSPE@TPA-FBPA-SiPc efficiently accumulated in lysosomes, leading to generation of a high amount of reactive oxygen species upon irradiation. This induced apoptosis in MCF-7 cells by disrupting lysosomal function. Consequently, DSPE@TPA-FBPA-SiPc holds great potential as a photosensitizer for photodynamic therapy, utilizing the lysosomal-mediated cell death pathway.

Morpholinyl silicon phthalocyanine nanoparticles with lysosome cell death and two-photon imaging functions for in vitro photodynamic therapy of cancer cells.

The lysosome is an important target for realizing antitumor therapy. Lysosomal cell death exerts significant therapeutic effects on apoptosis and drug-resistance. The development of lysosome-targeting nanoparticles to obtain efficient cancer treatment is challenging. In this article, nanoparticles composed of DSPE@M-SiPc and possessing bright two-photon fluorescence, lysosome targeting ability, and photodynamic therapy multifunctionalities are prepared by encapsulating morpholinyl-substituted silicon phthalocyanine (M-SiPc) with 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(poly(ethylene glycol))-2000] (DSPE). Two photon fluorescence bioimaging showed that M-SiPc and DSPE@M-SiPc mainly locate in lysosomes after cellular internalization. Upon irradiation, DSPE@M-SiPc effectively generates reactive oxygen species and damages the function of lysosome, subsequently leading to lysosomal cell death. DSPE@M-SiPc is a promising photosensitizer for cancer treatment.

A membrane/mediator-free high-power density dual-photoelectrode PFC aptasensor for lincomycin detection in milk and chicken

Over use of lincomycin (LIN) as antibiotic in animals can lead to multiple harmful impacts to public health, thus detection of LIN at trace level in milk and chicken sample matrixes is vital. In this work, Zinc phthalocyanine nanoparticles sensitized MoS2 (ZnPc/MoS2) was firstly developed as a novel photocathode material combined with nitrogen-doped graphene-loaded TiO2 nanoparticles (TiO2/NG) as photoanode material to construct a dual-photoelectrode photofuel cell (PFC). The as-prepared membrane/mediator-free PFC achieved excellent output performance that the maximum power density (Pmax) reached 11.83 μW cm−2. Specific aptamers are adopted as LIN recognition elements, the as-proposed self-powered aptasensor for LIN exhibited a linear scope in 10−11 –10−5 mol L−1 along with a low detection limit (3S/N) of 3.33 pmol L−1. Consequently, such high-power density dual-photoelectrode PFC aptasensor may be a reassuring candidate electrochemical sensor for the detection of trace contamination in food samples.

Theranostic Properties of Crystalline Aluminum Phthalocyanine Nanoparticles as a Photosensitizer.

The study of phthalocyanines, known photosensitizers, for biomedical applications has been of high research interest for several decades. Of specific interest, nanophotosensitizers are crystalline aluminum phthalocyanine nanoparticles (AlPc NPs). In crystalline form, they are water-insoluble and atoxic, but upon contact with tumors, immune cells, or pathogenic microflora, they change their spectroscopic properties (acquire the ability to fluoresce and become phototoxic), which makes them upcoming agents for selective phototheranostics. Aqueous colloids of crystalline AlPc NPs with a hydrodynamic size of 104 ± 54 nm were obtained using ultrasonic dispersal and centrifugation. Intracellular accumulation and localization of AlPc were studied on HeLa and THP-1 cell cultures and macrophages (M0, M1, M2) by fluorescence microscopy. Crystallinity was assessed by XRD spectroscopy. Time-resolved spectroscopy was used to obtain characteristic fluorescence kinetics of AlPc NPs upon interaction with cell cultures. The photodynamic efficiency and fluorescence quantum yield of AlPc NPs in HeLa and THP-1 cells were evaluated. After entering the cells, AlPc NPs localized in lysosomes and fluorescence corresponding to individual AlPc molecules were observed, as well as destruction of lysosomes and a rapid decrease in fluorescence intensity during photodynamic action. The photodynamic efficiency of AlPc NPs in THP-1 cells was almost 1.8-fold that of the molecular form of AlPc (Photosens). A new mechanism for the occurrence of fluorescence and phototoxicity of AlPc NPs in interaction with cells is proposed.

Electrochemical Sensor Based on Iron(II) Phthalocyanine and Gold Nanoparticles for Nitrite Detection in Meat Products.

Nitrites are widely used in the food industry, particularly for the preservation of meat products. Controlling the nitrate content in food is an important task to ensure people’s health is not at risk; therefore, the search for, and research of, new materials that will modify the electrodes in the electrochemical sensors that detect and control the nitrate content in food products is an urgent task. In this paper, we describe the electrochemical behavior of a glass carbon electrode (GCE), modified with a Fe(II) tetra-tert-butyl phthalocyanine film (FePc(tBu)4/GCE), and decorated with gold nanoparticles (Au/FePc(tBu)4/GCE); this electrode was deposited using gas-phase methods. The composition and morphology of such electrodes were examined using spectroscopy and electron microscopy methods, whereas the main electrochemical characteristics were determined using cyclic voltammetry (CV) and amperometry (CA) methods in the linear ranges of CV 0.25–2.5 mM, CA 2–120 μM in 0.1 M phosphate buffer (pH = 6.8). The results showed that the modification of bare GCEs, with a Au/FePc(tBu)4 heterostructure, provided a high surface-to-volume ratio, thus ensuring its high sensitivity to nitrite ions of 0.46 μAμM−1. The sensor based on the Au/FePc(tBu)4/GCE has a low limit of nitrite detection at 0.35 μM, good repeatability, and stability. The interference study showed that the proposed Au/FePc(tBu)4/GCE exhibited a selective response in the presence of interfering anions, and the analytical capability of the sensor was demonstrated by determining nitrite ions in real samples of meat products.

π-Conjugated Copper Phthalocyanine Nanoparticles as Highly Sensitive Sensor for Colorimetric Detection of Biomarkers.

Though numerous nanomaterials with enzyme-like activities have been utilized as probes and sensors for detecting biological molecules, it is still challenging to construct highly sensitive detectors for biomarkers using polymeric materials. Benefiting from the π-d delocalization effect of electrons, excellent metal-chelating property, high electron transferability, and good chemical stability of π-conjugated phthalocyanine, the design of the copper phthalocyanine-based conjugated polymer nanoparticles (Cu-PcCP NPs) as a colorimetric sensor for a variety of biomarkers is reported. The Cu-PcCP NPs are synthesized through a simple microwave-assisted polymerization, and their chemical structures are thoroughly characterized. The colorimetric results of Cu-PcCP NPs demonstrate excellent peroxidase-like detecting activity and also great substrate selectivity than most of the reported Cu-based nanomaterials. The Cu-PcCP NPs can achieve a detection limit of 4.88 μM for the H2 O2 , 4.27 μM for the L-cysteine, and 21.10 μM for the glucose via a cascade catalytic system, which shows comparable detecting sensitivity as that of many earlier reported enzyme-like nanomaterials. Moreover, Cu-PcCP NPs present remarkable resistance to harsh conditions, including high temperature, low pH, and excessive salts. These highly specific π-conjugated copper-phthalocyanine nanoparticles not only overcome the current limitation of polymeric material-based sensors but also provide a new direction for designing next-generation enzyme-like nanomaterial-based colorimetric biosensors.

Intensification of photocatalytic wastewater treatment using a novel continuous microcapillary photoreactor irradiated by visible LED lights

This paper presents a novel multi microcapillary photoreactor capped with two transparent poly (methyl methacrylate) (PMMA) plates irradiated by a 60 W visible LED SMD lamp for intensified degradation of methyl orange (MO). Copper phthalocyanine doped Bi2O3-ZnO nanophotocatalysts (CuPc-Bi2O3-ZnO) were coated on inner walls of the microcapillaries. XRD and FESEM-EDX analyses confirmed highly dispersion of copper phthalocyanine, Bi2O3 and ZnO nanoparticles with approximate size of 41 nm on the inner walls of the microcapillary tubes. DRS analysis indicated CuPc doping resulted in red shift of the light absorption region and reduction of the bandgap energy to 2.68 eV. Photocatalytic space-time yield for the fabricated intensified microphotoreactor was obtained 3.74 × 10−2 m3 wastewater/m3 reactor.day.kW, while this benchmark was 4 orders of magnitude lower, 7.5 × 10−6 m3 wastewater/m3 reactor.day.kW, for a studied batch photoreactor, and 2.17 × 10−2 m3 wastewater/m3 reactor.day.kW, for a tubular flow photoreactor, revealing positive effect of process intensification on efficiency of the photocatalytic degradation of MO. MO degradation percent in the fabricated microphotoreactor, the studied batch photoreactor, and the tubular flow photoreactor was obtained 90.83%, 58.6%, and 65.33%, respectively, as well. Study on the effect of length (30, 45, 60 mm) and diameter (400, 850 μm) of the microcapillary tubes illustrated MO conversion decreased from 94.19% (30 mm length, 850 μm diameter) to 58.01 % (45 mm length, 400 μm diameter) because according to laser analysis and COMSOL simulations with narrowing and elongating tubes, photon loss, pressure drop, and turbulence in tubes increased.

INFLUENCE OF PHTHALOCYANINE NANOSTRUCTURES ON OPTICAL AND PHOTOVOLTAIC CHARACTERISTICS OF A POLYMER SOLAR CELL

Nanocomposite polymer solar cells were obtained. Nanostructures of phthalocyanines were added to a mixture of photoactive layer at a concentration of 0.5%. The photoactive layer was applied by centrifugation at a rotation speed of 1500 rpm. Atomic force microscope images of the surface of the films were measured. Absorption spectra of composite films were measured. It was found that the introduction of phthalocyanine nanostructures into the photoactive photoactive layer leads to a broadening of the spectrumand an increase in the optical density at the absorption maximum by 2.1 times for nanorods and 1.9 times for nanoparticles. The current-voltage characteristics of composite organic solar cells were measured. To do this, an aluminum electrode with a thickness of 100 nm was sprayed onto the surface of the photoactive layer at 10-5Torr. It is shown that when the photoactive layer was doped with nanorods and phthalocyanine nanoparticles, the short-circuit current density of the current-voltage characteristics increased by 8% and 5%, respectively, and the efficiency value increased to 4.58% and 4.51%, respectively. The impedance spectra of composite organic solar cells were measured. Analysis of hodographs of nanocomposite films showed that doping of the photoactive layer with nanorods and phthalocyanine nanoparticles leads to an increase in the diffusion length by 2.2 times and 1.8 times, respectively, and an increase in the mobility of charge carriers by 1.4 times and 1.2 times.

Liposomal Composition Based on Hydroxyaluminum Phthalocyanine and Gold Nanoparticles for Combined Photodynamic and Photothermal Therapy

Liposomal Composition Based on Hydroxyaluminum Phthalocyanine and Gold Nanoparticles for Combined Photodynamic and Photothermal Therapy

Voltammetric sensing using an array of modified SPCE coupled with machine learning strategies for the improved identification of opioids in presence of cutting agents

This work reports the use of modified screen-printed carbon electrodes (SPCEs) for the identification of three drugs of abuse and two habitual cutting agents, caffeine and paracetamol, combining voltammetric sensing and chemometrics. In order to achieve this goal, codeine, heroin and morphine were subjected to Square Wave Voltammetry (SWV) at pH 7, in order to elucidate their electrochemical fingerprints. The optimized SPCEs electrode array, which have a differentiated response for the three oxidizable compounds, was derived from Carbon, Prussian blue, Cobalt (II) phthalocyanine, Copper (II) oxide, Polypyrrole and Palladium nanoparticles ink-modified carbon electrodes. Finally, Principal Component Analysis (PCA) coupled with Silhouette parameter assessment was used to select the most suitable combination of sensors for identification of drugs of abuse in presence of cutting agents.