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The Journal of Physical Chemistry. A Dec 2020Recent advances in laser technology have made three-photon (3P) microscopy a real possibility, raising interest in the phenomenon of 3P absorption (3PA). Understanding...
Recent advances in laser technology have made three-photon (3P) microscopy a real possibility, raising interest in the phenomenon of 3P absorption (3PA). Understanding 3PA of organic chromophores is especially important in view of those imaging applications that rely on exogenous probes, whose optical properties can be manipulated and optimized. Here, we present measurements and theoretical analysis of the degenerate 3PA spectra of several phosphorescent metalloporphyrins, which are used in the construction of biological oxygen probes. The effective 3PA cross sections (σ) of these porphyrins near 1700 nm, a new promising biological optical window, were found to be on the order of 1000 GM3 (1 GM3 = 10 cm s), therefore being among the highest values reported to date for organic chromophores. To interpret our data, we developed a qualitative four-state model specific for porphyrins and used it in conjunction with quantitative analysis based on the time-dependent density functional theory (TDDFT)/ Tamm-Dancoff approximation (ATDA)/sum-over-states (SOS) formalism. The analysis revealed that B (Soret) state plays a key role in the enhancement of 3PA of porphyrins in the Q band region, while the low-lying two-photon (2P)-allowed gerade states interfere negatively and diminish the 3PA strength. This study features the first systematic examination of 3PA properties of porphyrins, suggesting ways to improve their performance and optimize them for imaging and other biomedical applications.
Topics: Lasers; Models, Molecular; Molecular Structure; Photoelectron Spectroscopy; Porphyrins
PubMed: 33337890
DOI: 10.1021/acs.jpca.0c08334 -
Molecules (Basel, Switzerland) Nov 2021Colorectal cancer (CRC) is a leading cause of cancer-related death. The demand for new therapeutic approaches has increased attention paid toward therapies with high... (Review)
Review
Colorectal cancer (CRC) is a leading cause of cancer-related death. The demand for new therapeutic approaches has increased attention paid toward therapies with high targeting efficiency, improved selectivity and few side effects. Porphyrins are powerful molecules with exceptional properties and multifunctional uses, and their special affinity to cancer cells makes them the ligands par excellence for anticancer drugs. Porphyrin derivatives are used as the most important photosensitizers (PSs) for photodynamic therapy (PDT), which is a promising approach for anticancer treatment. Nevertheless, the lack of solubility and selectivity of the large majority of these macrocycles led to the development of different photosensitizer complexes. In addition, targeting agents or nanoparticles were used to increase the efficiency of these macrocycles for PDT applications. On the other hand, gold tetrapyrrolic macrocycles alone showed very interesting chemotherapeutic activity without PDT. In this review, we discuss the most important porphyrin derivatives, alone or associated with other drugs, which have been found effective against CRC, as we describe their modifications and developments through substitutions and delivery systems.
Topics: Colorectal Neoplasms; Humans; Nanoparticles; Photochemotherapy; Photosensitizing Agents; Porphyrins
PubMed: 34885849
DOI: 10.3390/molecules26237268 -
Cellular and Molecular Gastroenterology... 2019Porphyrias are caused by porphyrin accumulation resulting from defects in the heme biosynthetic pathway that typically lead to photosensitivity and possible end-stage...
BACKGROUND & AIMS
Porphyrias are caused by porphyrin accumulation resulting from defects in the heme biosynthetic pathway that typically lead to photosensitivity and possible end-stage liver disease with an increased risk of hepatocellular carcinoma. Our aims were to study the mechanism of porphyrin-induced cell damage and protein aggregation, including liver injury, where light exposure is absent.
METHODS
Porphyria was induced in vivo in mice using 3,5-diethoxycarbonyl-1,4-dihydrocollidine or in vitro by exposing human liver Huh7 cells and keratinocytes, or their lysates, to protoporphyrin-IX, other porphyrins, or to δ-aminolevulinic acid plus deferoxamine. The livers, cultured cells, or porphyrin exposed purified proteins were analyzed for protein aggregation and oxidation using immunoblotting, mass spectrometry, and electron paramagnetic resonance spectroscopy. Consequences on cell-cycle progression were assessed.
RESULTS
Porphyrin-mediated protein aggregation required porphyrin-photosensitized singlet oxygen and porphyrin carboxylate side-chain deprotonation, and occurred with site-selective native protein methionine oxidation. Noncovalent interaction of protoporphyrin-IX with oxidized proteins led to protein aggregation that was reversed by incubation with acidified n-butanol or high-salt buffer. Phototoxicity and the ensuing proteotoxicity, mimicking porphyria photosensitivity conditions, were validated in cultured keratinocytes. Protoporphyrin-IX inhibited proteasome function by aggregating several proteasomal subunits, and caused cell growth arrest and aggregation of key cell proliferation proteins. Light-independent synergy of protein aggregation was observed when porphyrin was applied together with glucose oxidase as a secondary peroxide source.
CONCLUSIONS
Photo-excitable porphyrins with deprotonated carboxylates mediate protein aggregation. Porphyrin-mediated proteotoxicity in the absence of light, as in the liver, requires porphyrin accumulation coupled with a second tissue oxidative injury. These findings provide a potential mechanism for internal organ damage and photosensitivity in porphyrias.
Topics: Aminolevulinic Acid; Animals; Carcinoma, Hepatocellular; Cell Line; Deferoxamine; Heme; Hepatocytes; Humans; Liver; Liver Neoplasms; Male; Mice; Mice, Inbred C57BL; Oxygen; Photosensitivity Disorders; Photosensitizing Agents; Porphyrias; Porphyrins; Protein Aggregates; Protein Conformation; Protoporphyrins
PubMed: 31173894
DOI: 10.1016/j.jcmgh.2019.05.010 -
Molecules (Basel, Switzerland) Jul 2017Phthalocyanine and porphyrin were among the first organic compounds investigated by means of electronic spectroscopy in superfluid helium nanodroplets. Superfluid helium... (Review)
Review
Phthalocyanine and porphyrin were among the first organic compounds investigated by means of electronic spectroscopy in superfluid helium nanodroplets. Superfluid helium nanodroplets serve as a very gentle host system for preparing cold and isolated molecules. The uniqueness of helium nanodroplets is with respect to the superfluid phase which warrants the vanishing viscosity and, thus, minimal perturbation of the dopant species at a temperature as low as 0.37 K. These are ideal conditions for the study of molecular spectra in order to analyze structures as well as dynamic processes. Besides the investigation of the dopant species itself, molecular spectroscopy in helium droplets provides information on the helium droplet and in particular on microsolvation. This article, as part of a special issue on phthalocyanines and porphyrins, reviews electronic spectroscopy of phthalocyanine and porphyrin compounds in superfluid helium nanodroplets. In addition to the wide variety of medical as well as technical and synthetical aspects, this article discusses electronic spectroscopy of phthalocyanines and porphyrins in helium droplets in order to learn about both the dopant and the helium environment.
Topics: Helium; Indoles; Isoindoles; Nanoparticles; Photoelectron Spectroscopy; Porphyrins
PubMed: 28757568
DOI: 10.3390/molecules22081244 -
Journal of Postgraduate Medicine 2023Porphyrias are a rare group of inborn errors of metabolism due to defects in the heme biosynthetic pathway. The biochemical hallmark is the overproduction of porphyrin...
Porphyrias are a rare group of inborn errors of metabolism due to defects in the heme biosynthetic pathway. The biochemical hallmark is the overproduction of porphyrin precursors and porphyrin species. Afflicted patients present with a myriad of symptoms causing a diagnostic odyssey. Symptoms often overlap with those of common diseases and may be overlooked unless there is heightened clinical suspicion. We are reporting clinical features and diagnostic challenges in four pediatric patients having variegate porphyria, congenital erythropoietic porphyria, acute intermittent porphyria, and erythropoietic protoporphyria (EPP), who presented with diverse multisystem manifestations. This case series illustrates a logical analysis of symptoms and judicious selection of investigations and the role of genotyping in successfully diagnosing porphyrias.
Topics: Child; Humans; Porphyrias; Porphyria, Acute Intermittent; Porphyrins
PubMed: 37082991
DOI: 10.4103/jpgm.jpgm_698_22 -
International Journal of Molecular... May 2020The application of porphyrins and their derivatives have been investigated extensively over the past years for phototherapy cancer treatment. Phototherapeutic Porphyrins... (Review)
Review
The application of porphyrins and their derivatives have been investigated extensively over the past years for phototherapy cancer treatment. Phototherapeutic Porphyrins have the ability to generate high levels of reactive oxygen with a low dark toxicity and these properties have made them robust photosensitizing agents. In recent years, Porphyrins have been combined with various nanomaterials in order to improve their bio-distribution. These combinations allow for nanoparticles to enhance photodynamic therapy (PDT) cancer treatment and adding additional nanotheranostics (photothermal therapy-PTT) as well as enhance photodiagnosis (PDD) to the reaction. This review examines various porphyrin-based inorganic nanoparticles developed for phototherapy nanotheranostic cancer treatment over the last three years (2017 to 2020). Furthermore, current challenges in the development and future perspectives of porphyrin-based nanomedicines for cancer treatment are also highlighted.
Topics: Animals; Biocompatible Materials; Carbon; Humans; Magnetic Iron Oxide Nanoparticles; Mammary Neoplasms, Experimental; Metal Nanoparticles; Mice; Nanoparticles; Neoplasms; Photochemotherapy; Porphyrins; Quantum Dots; Silicon Dioxide; Theranostic Nanomedicine
PubMed: 32397477
DOI: 10.3390/ijms21093358 -
Angewandte Chemie (International Ed. in... Nov 2017Carbon monoxide (CO) outcompetes oxygen when binding to the iron center of hemeproteins, leading to a reduction in blood oxygen level and acute poisoning. Harvesting the...
Carbon monoxide (CO) outcompetes oxygen when binding to the iron center of hemeproteins, leading to a reduction in blood oxygen level and acute poisoning. Harvesting the strong specific interaction between CO and the iron porphyrin provides a highly selective and customizable sensor. We report the development of chemiresistive sensors with voltage-activated sensitivity for the detection of CO comprising iron porphyrin and functionalized single-walled carbon nanotubes (F-SWCNTs). Modulation of the gate voltage offers a predicted extra dimension for sensing. Specifically, the sensors show a significant increase in sensitivity toward CO when negative gate voltage is applied. The dosimetric sensors are selective to ppm levels of CO and functional in air. UV/Vis spectroscopy, differential pulse voltammetry, and density functional theory reveal that the in situ reduction of Fe to Fe enhances the interaction between the F-SWCNTs and CO. Our results illustrate a new mode of sensors wherein redox active recognition units are voltage-activated to give enhanced and highly specific responses.
Topics: Biosensing Techniques; Carbon Monoxide; Density Functional Theory; Electrochemical Techniques; Limit of Detection; Nanotubes, Carbon; Porphyrins; Spectrophotometry, Ultraviolet
PubMed: 28952172
DOI: 10.1002/anie.201707491 -
Advanced Science (Weinheim,... May 2024Photoacoustic imaging (PAI)-guided photothermal therapy (PTT) in the second near-infrared (NIR-II, 1000-1700 nm) window has been attracting attention as a promising...
Photoacoustic imaging (PAI)-guided photothermal therapy (PTT) in the second near-infrared (NIR-II, 1000-1700 nm) window has been attracting attention as a promising cancer theranostic platform. Here, it is reported that the π-extended porphyrins fused with one or two nanographene units (NGP-1 and NGP-2) can serve as a new class of NIR-responsive organic agents, displaying absorption extending to ≈1000 and ≈1400 nm in the NIR-I and NIR-II windows, respectively. NGP-1 and NGP-2 are dispersed in water through encapsulation into self-assembled nanoparticles (NPs), achieving high photothermal conversion efficiency of 60% and 69%, respectively, under 808 and 1064 nm laser irradiation. Moreover, the NIR-II-active NGP-2-NPs demonstrated promising photoacoustic responses, along with high photostability and biocompatibility, enabling PAI and efficient NIR-II PTT of cancer in vivo.
Topics: Porphyrins; Theranostic Nanomedicine; Photoacoustic Techniques; Mice; Animals; Nanoparticles; Graphite; Humans; Infrared Rays; Disease Models, Animal; Photothermal Therapy; Cell Line, Tumor; Neoplasms; Phototherapy
PubMed: 38430537
DOI: 10.1002/advs.202309131 -
Molecules (Basel, Switzerland) Aug 2022The emergence of metal-organic frameworks (MOFs) in recent years has stimulated the interest of scientists working in this area as one of the most applicable archetypes... (Review)
Review
The emergence of metal-organic frameworks (MOFs) in recent years has stimulated the interest of scientists working in this area as one of the most applicable archetypes of three-dimensional structures that can be used as promising materials in several applications including but not limited to (photo-)catalysis, sensing, separation, adsorption, biological and electrochemical efficiencies and so on. Not only do MOFs have their own specific versatile structures, tunable cavities, and remarkably high surface areas, but they also present many alternative procedures to overcome emerging obstacles. Since the discovery of such highly effective materials, they have been employed for multiple uses; additionally, the efforts towards the synthesis of MOFs with specific properties based on planned (template) synthesis have led to the construction of several promising types of MOFs possessing large biological or bioinspired ligands. Specifically, metalloporphyrin-based MOFs have been created where the porphyrin moieties are either incorporated as struts within the framework to form porphyrinic MOFs or encapsulated inside the cavities to construct porphyrin@MOFs which can combine the peerless properties of porphyrins and porous MOFs simultaneously. In this context, the main aim of this review was to highlight their structure, characteristics, and some of their prominent present-day applications.
Topics: Adsorption; Catalysis; Metal-Organic Frameworks; Metalloporphyrins; Porphyrins
PubMed: 35956867
DOI: 10.3390/molecules27154917 -
Scientific Reports Oct 2022This study presents the synthesis and doping of reduced graphene oxide (rGO) with synthesized porphyrin (5,15-bisdodecyl porphyrin, C12P) nanoparticles to fabricate...
This study presents the synthesis and doping of reduced graphene oxide (rGO) with synthesized porphyrin (5,15-bisdodecyl porphyrin, C12P) nanoparticles to fabricate reduced graphene oxide-porphyrin (rGO-P) nanocomposite as well as demonstrates their outstanding removal activity of azo dye and antimicrobial potential. The synthesized porphyrin, rGO, and rGO-P nanocomposites were characterised using SEM, HRTEM, Raman spectroscopy, XRD, H-NMR, mass spectrometry, and UV-Visible spectroscopy. The ability of the synthesized rGO-P nanocomposite was then investigated (as catalyst and/or adsorbent) to impact its removal efficacy against Congo red (CR) as a well-known toxic, mutagenic and carcinogenic synthetic dye. The findings indicated that 0.01 g of rGO-P nanocomposite achieved 78.0% removal of CR at pH 3.0. Besides, the removal efficacy was evaluated while studying many aspects i.e. pH, CR initial concentration, and rGO-P nanocomposite amount. Moreover, the minimum inhibitory concentration (MIC) and zone of inhibition (ZOI) of antimicrobial activity against pathogenic bacteria and yeast were evaluated. The antimicrobial results showed that rGO-P nanocomposite revealed the greatest antimicrobial activity against Candida albicans, Enterococcus faecalis, and Staphylococcus aureus with ZOI values of 24.3, 21.8, and 22.1 mm, respectively. Consequently, it demonstrates the substantial potential of rGO-P nanocomposite in the effective removal of pollutant dyes as well as significant antibacterial and antifungal properties.
Topics: Anti-Bacterial Agents; Antifungal Agents; Azo Compounds; Coloring Agents; Congo Red; Environmental Pollutants; Graphite; Nanocomposites; Porphyrins; Water Purification
PubMed: 36224230
DOI: 10.1038/s41598-022-21360-8