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Advanced Drug Delivery Reviews Mar 2022Photoimaging and phototherapy have become major platforms for the diagnosis and treatment of various health complications. These applications require a photosensitizer... (Review)
Review
Photoimaging and phototherapy have become major platforms for the diagnosis and treatment of various health complications. These applications require a photosensitizer (PS) that is capable of absorbing light from a source and converting it into other energy forms for detection and therapy. While synthetic inorganic materials such as quantum dots and gold nanorods have been widely explored for their medical diagnosis and photodynamic (PDT) and photothermal (PTT) therapy capabilities, translation of these technologies has lagged, primarily owing to potential cytotoxicity and immunogenicity issues. Of the various photoreactive molecules, the naturally occurring endogenous compound heme, a constituent of red blood cells, and its derivatives, porphyrin, biliverdin and bilirubin, have shown immense potential as noteworthy candidates for clinically translatable photoreactive agents, as evidenced by previous reports. While porphyrin-based photomedicines have attracted significant attention and are well documented, research on photomedicines based on two other heme-derived compounds, biliverdin and bilirubin, has been relatively lacking. In this review, we summarize the unique photoproperties of heme-derived compounds and outline recent efforts to use them in biomedical imaging and phototherapy applications.
Topics: Diagnostic Imaging; Heme; Humans; Nanoparticle Drug Delivery System; Photochemotherapy; Photosensitizing Agents; Phototherapy; Porphyrins
PubMed: 35122881
DOI: 10.1016/j.addr.2022.114134 -
Angewandte Chemie (International Ed. in... Mar 2021Porphyrins and porphyrin derivatives have been widely explored for various applications owing to their excellent photophysical and electrochemical properties. However,... (Review)
Review
Porphyrins and porphyrin derivatives have been widely explored for various applications owing to their excellent photophysical and electrochemical properties. However, inherent shortcomings, such as instability and self-quenching under physiological conditions, limit their biomedical applications. In recent years, metal-organic frameworks (MOFs) have received increasing attention. The construction of porphyrin-based MOFs by introducing porphyrin molecules into MOFs or using porphyrins as organic linkers to form MOFs can combine the unique features of porphyrins and MOFs as well as overcome the limitations of porphyrins. This Review summarizes important synthesis strategies for porphyrin-based MOFs including porphyrin@MOFs, porphyrinic MOFs, and composite porphyrinic MOFs, and highlights recent achievements and progress in the development of porphyrin-based MOFs for biomedical applications in tumor therapy and biosensing. Finally, the challenges and prospects presented by this class of emerging materials for biomedical applications are discussed.
Topics: Animals; Biosensing Techniques; Drug Carriers; Humans; Immunotherapy; Metal-Organic Frameworks; Neoplasms; Photochemotherapy; Photosensitizing Agents; Photothermal Therapy; Porphyrins
PubMed: 31989749
DOI: 10.1002/anie.201909880 -
Accounts of Chemical Research May 2021Porphyrin derivatives are ubiquitous in nature and have important biological roles, such as in light harvesting, oxygen transport, and catalysis. Owing to their... (Review)
Review
Porphyrin derivatives are ubiquitous in nature and have important biological roles, such as in light harvesting, oxygen transport, and catalysis. Owing to their intrinsic π-conjugated structure, porphyrin derivatives exhibit characteristic photophysical and electrochemical properties. In biological systems, porphyrin derivatives are associated with various protein molecules through noncovalent interactions. For example, hemoglobin, which is responsible for oxygen transport in most vertebrates, consists of four subunits of a globular protein with an iron porphyrin derivative prosthetic group. Furthermore, noncovalently arranged porphyrin derivatives are the fundamental chromophores in light-harvesting systems for photosynthesis in plants and algae. These biologically important roles originate from the functional versatility of porphyrin derivatives. Specifically, porphyrins are excellent host compounds, forming coordination complexes with various metal ions that adds functionality to the porphyrin unit, such as redox activity and additional ligand binding at the central metal ion. In addition, porphyrins are useful building blocks for functional supramolecular assemblies because of their flat and symmetrical molecular architectures, and their excellent photophysical properties are typically utilized for the fabrication of bioactive functional materials. In this Account, we summarize our endeavors over the past decade to develop functional materials based on porphyrin derivatives using bioinspired approaches. In the first section, we discuss several synthetic receptors that act as artificial allosteric host systems and can be used for the selective detection of various chemicals, such as cyanide, chloride, and amino acids. In the second section, we introduce multiporphyrin arrays as mimics of natural light-harvesting complexes. The active control of energy transfer processes by additional guest binding and the fabrication of organic photovoltaic devices using porphyrin derivatives are also introduced. In the third section, we introduce several types of porphyrin-based supramolecular assemblies. Through noncovalent interactions such as metal-ligand interaction, hydrogen bonding, and π-π interaction, porphyrin derivatives were constructed as supramolecular polymers with formation of fiber or toroidal assembly. In the last section, the application of porphyrin derivatives for biomedical nanodevice fabrication is introduced. Even though porphyrins were good candidates as photosensitizers for photodynamic therapy, they have limitations for biomedical application owing to aggregation in aqueous media. We suggested ionic dendrimer porphyrins and they showed excellent photodynamic therapy (PDT) efficacy.
Topics: Amino Acids; Chlorides; Cyanides; Light-Harvesting Protein Complexes; Molecular Structure; Oxidation-Reduction; Porphyrins; Proteins
PubMed: 33891405
DOI: 10.1021/acs.accounts.1c00114 -
Molecules (Basel, Switzerland) Jul 2019The synthesis and application of porphyrins has seen a huge shift towards research in porphyrin bio-molecular based systems in the past decade. The preferential... (Review)
Review
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.
Topics: Animals; Glycoconjugates; Humans; Magnetic Resonance Imaging; Mice; Neoplasms; Photochemotherapy; Photosensitizing Agents; Porphyrins; Positron-Emission Tomography; Singlet Oxygen; Theranostic Nanomedicine; Water
PubMed: 31340553
DOI: 10.3390/molecules24142669 -
Journal of Materials Chemistry. B Nov 2022Inspired by the hierarchical chiral assembly of porphyrin-proteins in photosynthetic systems, the hierarchical self-assembly of porphyrin-amino acids/peptides provides a... (Review)
Review
Inspired by the hierarchical chiral assembly of porphyrin-proteins in photosynthetic systems, the hierarchical self-assembly of porphyrin-amino acids/peptides provides a novel strategy for constructing functional materials. How to artificially simulate the assembly of porphyrins, proteins, and other cofactors in the photosynthesis system to obtain persistent strong light capture, charge separation and catalytic reactions has become an important concern in the construction of biomimetic photosynthesis systems. This paper summarizes the different assembly strategies adopted in recent years, the effects of driving forces on self-assembly, and the application of porphyrin-peptides in catalysis and biomedicine, and briefly discusses the challenges and prospects for future research.
Topics: Porphyrins; Photosynthesis; Peptides; Amino Acids; Catalysis
PubMed: 36373597
DOI: 10.1039/d2tb01660e -
Topics in Current Chemistry (Cham) May 2021The four pyrrole rings and four meso carbons of tetrapyrrolic porphyrins can be arranged in different ways and the resulting porphyrin isomers exhibit very distinct... (Review)
Review
The four pyrrole rings and four meso carbons of tetrapyrrolic porphyrins can be arranged in different ways and the resulting porphyrin isomers exhibit very distinct electronic properties. The extensive research carried out on the porphyrins over the years has revealed that porphyrin can have several possible isomers and some of these have been identified and synthesized. Among the porphyrin isomers synthesized so far, porphycene and N-confused porphyrins have been investigated extensively whereas the other porphyrin isomers such as hemiporphycene, corrphycene and isoporphycene remain underdeveloped because of synthetic difficulties and their inherently unstable nature. Neoporphyrinoids are new members of the porphyrinoid family that were discovered serendipitously in 2011. Neoporphyrinoids are structural analogues of porphyrinoids with a confused pyrrole nitrogen linked to a meso carbon or the adjacent pyrrole carbon. Thus, neoporphyrinoids have an unusual structure in which pyrrole N is a part of a porphyrinoid framework and the lone pair of electrons on nitrogen participate in macrocyclic conjugation. It's been a decade since the discovery and different types of neoporphyrinoids, including regular, contracted and expanded neoporphyrinoids, have been synthesized by rational synthetic methodologies and their spectral, structural, aromatic and coordination properties have been studied. There is huge scope to develop different synthetic routes to produce new types of stable neoporphyrinoids to study their properties and potential applications. This article presents a brief overview of the synthesis, structure and properties of the neoporphyrinoids reported in this decade.
Topics: Models, Molecular; Molecular Structure; Porphyrins
PubMed: 34009495
DOI: 10.1007/s41061-021-00338-6 -
Chemical Society Reviews Aug 2022Porphyrins are variously substituted tetrapyrrolic macrocycles, with wide-ranging biological and chemical applications derived from metal chelation in the core and the... (Review)
Review
Porphyrins are variously substituted tetrapyrrolic macrocycles, with wide-ranging biological and chemical applications derived from metal chelation in the core and the 18π aromatic surface. Under suitable conditions, the porphyrin framework can deform significantly from regular planar shape, owing to steric overload on the porphyrin periphery or steric repulsion in the core, among other structure modulation strategies. Adopting this nonplanar porphyrin architecture allows guest molecules to interact directly with an exposed core, with guest-responsive and photoactive electronic states of the porphyrin allowing energy, information, atom and electron transfer within and between these species. This functionality can be incorporated and tuned by decoration of functional groups and electronic modifications, with individual deformation profiles adapted to specific key sensing and catalysis applications. Nonplanar porphyrins are assisting breakthroughs in molecular recognition, organo- and photoredox catalysis; simultaneously bio-inspired and distinctly synthetic, these molecules offer a new dimension in shape-responsive host-guest chemistry. In this review, we have summarized the synthetic methods and design aspects of nonplanar porphyrin formation, key properties, structure and functionality of the nonplanar aromatic framework, and the scope and utility of this emerging class towards outstanding scientific, industrial and environmental issues.
Topics: Porphyrins
PubMed: 35959748
DOI: 10.1039/d2cs00391k -
Molecules (Basel, Switzerland) Dec 2022This study presents the spectral characterization of TiO nanoparticles (NPs) functionalized with three porphyrin derivatives: 5,10,15,20-(Tetra-4-aminophenyl) porphyrin...
This study presents the spectral characterization of TiO nanoparticles (NPs) functionalized with three porphyrin derivatives: 5,10,15,20-(Tetra-4-aminophenyl) porphyrin (TAPP), 5,10,15,20-(Tetra-4-methoxyphenyl) porphyrin (TMPP), and 5,10,15,20-(Tetra-4-carboxyphenyl) porphyrin (TCPP). UV-Vis absorption and Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) spectroscopic studies of these porphyrins and their complexes with TiO NPs were performed. In addition, the efficiency of singlet oxygen generation, the key species in photodynamic therapy, was investigated. UV-Vis absorption spectra of the NPs complexes showed the characteristic bands of porphyrins. These allowed us to determine the loaded porphyrins on TiO NPs functionalized with porphyrins. FTIR-ATR revealed the formation of porphyrin-TiO complexes, suggesting that porphyrin adsorption on TiO may involve the pyrroles in the porphyrin ring, or the radicals of the porphyrin derivative. The quantum yield for singlet oxygen generation by the studied porphyrin complexes with TiO was higher compared to bare porphyrins for TAPP and TMPP, while for the TCPP-TiO NPs complex, a decrease was observed, but still maintained a good efficiency. The TiO NPs conjugates can be promising candidates to be tested in photodynamic therapy in vitro assays.
Topics: Porphyrins; Singlet Oxygen; Photochemotherapy; Spectroscopy, Fourier Transform Infrared; Nanoparticles; Photosensitizing Agents
PubMed: 36615512
DOI: 10.3390/molecules28010318 -
Chemical Research in Toxicology Dec 2022-Methyl protoporphyrin IX (NmePPIX) is a derivative of protoporphyrin IX (PPIX) and the lattice of heme. Certain xenobiotics strongly induce NmePPIX production in the... (Review)
Review
-Methyl protoporphyrin IX (NmePPIX) is a derivative of protoporphyrin IX (PPIX) and the lattice of heme. Certain xenobiotics strongly induce NmePPIX production in the liver. The existence of endogenous NmePPIX in untreated animal liver has also been reported. The detailed mechanisms of NmePPIX biosynthesis remain unclear, but cytochrome P450 enzymes are thought to be critical in xenobiotic-induced NmePPIX production. High levels of NmePPIX cause PPIX accumulation because NmePPIX is a potent inhibitor ( = 7 nM) of ferrochelatase, the last enzyme in the heme biosynthesis pathway that converts PPIX to heme. NmePPIX is also involved in several other physiological processes, including inhibition of nitric oxide production and promotion of lamin aggregation. Compared to the two well-characterized porphyrins, PPIX and heme, NmePPIX is understudied regarding the mechanism of formation, fate, and physiological functions. This Review summarizes the current understanding of NmePPIX and provides perspectives on areas of future research on NmePPIX.
Topics: Animals; Porphyrins; Protoporphyrins; Ferrochelatase; Heme
PubMed: 36459538
DOI: 10.1021/acs.chemrestox.2c00214 -
Journal of Materials Chemistry. B Jul 2023Porphyrins and their derivatives have excellent photophysical and electrochemical properties, which have attracted great interest in the fields of catalysis, biosensing,... (Review)
Review
Porphyrins and their derivatives have excellent photophysical and electrochemical properties, which have attracted great interest in the fields of catalysis, biosensing, gas storage, solar cells, biomedicine, However, the inherent limitations, such as self-quenching, weak absorption at biological spectral windows and poor photochemical stability, severely hinder their applications in biomedicine, especially in the field of photodynamic therapy (PDT). In recent years, metal-organic frameworks (MOFs) have received increasing attention as a class of hybrid porous coordination polymers assembled from metal ions/secondary building units (SBUs) and organic linkers. By introducing porphyrins into MOFs the encapsulation in the pores as well as grafting on the surface to form porphyrin@MOFs or using porphyrins as organic linkers to construct porphyrin-MOFs, not only the unique properties of porphyrins and MOFs are combined, but also the limitations of porphyrins are overcome and their applications are facilitated in the biomedicine field. This article reviews important synthetic strategies of forming porphyrin-based MOFs (including porphyrin@MOFs and porphyrin-MOFs), which focuses on the recent research achievements and progress in PDT and tumor therapy fields. Furthermore, by carefully designing the composition of MOFs (such as the modification of organic linkers), MOFs could respond to the tumor microenvironment for on-demand treatment. In addition, some other strategies, including chemotherapy, photothermal therapy (PTT) and the latest cancer immunotherapy, are also combined in the review. Finally, the challenges and prospects in biomedical applications of this class of emerging materials are discussed.
Topics: Metal-Organic Frameworks; Porphyrins; Photochemotherapy; Drug Carriers; Catalysis
PubMed: 37310273
DOI: 10.1039/d2tb02789e