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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 -
ChemMedChem Dec 2023Photodynamic therapy (PDT) efficiently induces apoptosis through visible-light irradiation of photosensitizers (PSs) within tumors and microbial cells. Porphyrin... (Review)
Review
Photodynamic therapy (PDT) efficiently induces apoptosis through visible-light irradiation of photosensitizers (PSs) within tumors and microbial cells. Porphyrin analogues serve as widely utilized photosensitizing agents with their therapeutic abilities being governed by molecular structures and central metal ions. However, these macrocyclic compounds tend to agglutinate and form stacks in aqueous environments, resulting in a loss of photochemical activity. To overcome this limitation, encapsulation within liposomes and polymer micelles enables the dispersion of porphyrins as monomolecular entities in aqueous solutions, preventing undesirable deactivation. Recently, the use of reconstituted hemoproteins containing various metal-porphyrins and protein cages incorporating porphyrins has garnered significant interest as a new generation of biocompatible PSs. In this concept paper, we provide a comprehensive review of recent developments and trends of protein-porphyrin complex PSs for applications in anticancer and antimicrobial PDTs.
Topics: Photosensitizing Agents; Porphyrins; Photochemotherapy; Light; Anti-Infective Agents
PubMed: 37821798
DOI: 10.1002/cmdc.202300373 -
Chemistry (Weinheim An Der Bergstrasse,... Sep 2015Silylation of peripherally lithiated porphyrins with silyl electrophiles has realized the first synthesis of a series of directly silyl-substituted porphyrins. The...
Silylation of peripherally lithiated porphyrins with silyl electrophiles has realized the first synthesis of a series of directly silyl-substituted porphyrins. The meso-silyl group underwent facile protodesilylation, whereas the β-silyl group was entirely compatible with standard work-up and purification on silica gel. The meso-silyl group caused larger substituent effects to the porphyrin compared with the β-silyl group. Silylation of β-lithiated porphyrins with 1,2-dichlorodisilane furnished β-to-β disilane-bridged porphyrin dimers. A doubly β-to-β disilane-bridged Ni(II)-porphyrin dimer was also synthesized from a β,β-dilithiated Ni(II)-porphyrin and characterized by X-ray crystallographic analysis to take a steplike structure favorable for interporphyrinic interaction. Denickelation of β-silylporphyrins was achieved upon treatment with a 4-tolylmagnesium bromide to yield the corresponding freebase porphyrins.
Topics: Crystallography, X-Ray; Metalloporphyrins; Molecular Structure; Nickel; Porphyrins; Silanes
PubMed: 26356498
DOI: 10.1002/chem.201502563 -
Biomedicine & Pharmacotherapy =... Aug 2023Photodynamic therapy (PDT) and sonodynamic therapy (SDT) are non-invasive treatment methods with obvious inhibitory effect on tumors and have few side effects, which... (Review)
Review
Photodynamic therapy (PDT) and sonodynamic therapy (SDT) are non-invasive treatment methods with obvious inhibitory effect on tumors and have few side effects, which have been widely concerned and explored by researchers. Sensitizer is the main factor in determining the therapeutic effect of PDT and SDT. Porphyrins, a group of organic compounds widespread in nature, can be activated by light or ultrasound and produce reactive oxygen species. Therefore, porphyrins as sensitizers in PDT have been widely explored and investigated for many years. Herein, we summarize the classical porphyrin compounds and their applications and mechanisms in PDT and SDT. The application of porphyrin in clinical diagnosis and imaging is also discussed. In conclusion, porphyrins have good application prospects in disease treatment as an important part of PDT or SDT, and in clinical diagnosis and imaging.
Topics: Humans; Porphyrins; Photochemotherapy; Ultrasonic Therapy; Neoplasms; Reactive Oxygen Species
PubMed: 37236030
DOI: 10.1016/j.biopha.2023.114933 -
Nanoscale Jul 2016Porphyrins have been used as pioneering theranostic agents not only for the photodynamic therapy, sonodynamic therapy and radiotherapy of cancer, but also for diagnostic... (Review)
Review
Porphyrins have been used as pioneering theranostic agents not only for the photodynamic therapy, sonodynamic therapy and radiotherapy of cancer, but also for diagnostic fluorescence imaging, magnetic resonance imaging and photoacoustic imaging. A variety of porphyrins have been developed but very few of them have actually been employed in clinical trials due to their poor selectivity to tumorous tissue and high accumulation rates in the skin. In addition, most porphyrin molecules are hydrophobic and form aggregates in aqueous media. Nevertheless, the use of nanoparticles as porphyrin carriers shows great promise to overcome these shortcomings. Encapsulating or attaching porphyrins to nanoparticles makes them more suitable for tissue delivery because we can create materials with a conveniently specific tissue lifetime, specific targeting, immune tolerance, and hydrophilicity as well as other characteristics through rational design. In addition, various functional components (e.g. for targeting, imaging or therapeutic functions) can be easily introduced into a single nanoparticle platform for cancer theranostics. This review presents the current state of knowledge on porphyrin-loaded nanoparticles for the interwined imaging and therapy of cancer. The future trends and limitations of prophyrin-loaded nanoparticles are also outlined.
Topics: Humans; Nanoparticles; Neoplasms; Photochemotherapy; Porphyrins; Theranostic Nanomedicine
PubMed: 26730838
DOI: 10.1039/c5nr07849k -
Chemical Reviews Feb 2017Porphyrins, called the pigments of life, have been studied for decades. However, the first constitutional isomer of porphyrin, porphycene, was not synthesized until... (Review)
Review
Porphyrins, called the pigments of life, have been studied for decades. However, the first constitutional isomer of porphyrin, porphycene, was not synthesized until 1986. This milestone marked the beginning of a new era in the field of porphyrinoids and presented opportunities for the creation of an abundance of new pigments. The unique structural and electronic features of these compounds give rise to interesting physical and optical properties with applications in biomedicine and materials science. This review focuses on the synthetic methodologies available for the preparation of porphycenes (functionalized porphycenes, extended porphycenes, benzoporphycenes, naphthoporphycenes, and heteroanalogues) and the other known isomers, namely, corrphycene, hemiporphycene, and isoporphycene. Although the classical synthetic approaches are discussed, particular emphasis is placed on improvements to the known methodologies and recent advances in the field.
Topics: Isomerism; Porphyrins
PubMed: 27958722
DOI: 10.1021/acs.chemrev.6b00345 -
Chemical Reviews Feb 2017The heteroatom-containing porphyrin analogues or core-modified porphyrins that resulted from the replacement of one or two pyrrole rings with other five-membered... (Review)
Review
The heteroatom-containing porphyrin analogues or core-modified porphyrins that resulted from the replacement of one or two pyrrole rings with other five-membered heterocycles such as furan, thiophene, selenophene, tellurophene, indene, phosphole, and silole are highly promising macrocycles and exhibit quite different physicochemical properties compared to regular azaporphyrins. The properties of heteroporphyrins depend on the nature and number of different heterocycle(s) present in place of pyrrole ring(s). The heteroporphyrins provide unique and unprecedented coordination environments for metals. Unlike regular porphyrins, the monoheteroporphyrins are known to stabilize metals in unusual oxidation states such as Cu and Ni in +1 oxidation states. The diheteroporphyrins, which are neutral macrocycles without ionizable protons, also showed interesting coordination chemistry. Thus, significant progress has been made in last few decades on core-modified porphyrins in terms of their synthesis, their use in building multiporphyrin arrays for light-harvesting applications, their use as ligands to form interesting metal complexes, and also their use for several other studies. The synthetic methods available in the literature allow one to prepare mono- and diheteroporphyrins and their functionalized derivatives, which were used extensively to prepare several covalent and noncovalent heteroporphyrin-based multiporphyrin arrays. The methods are also developed to synthesize different hetero analogues of porphyrin derivatives such as heterocorroles, heterochlorins, heterocarbaporphyrinoids, heteroatom-substituted confused porphyrins, and so on. This Review summarizes the key developments that have occurred in heteroporphyrin chemistry over the last four decades.
Topics: Porphyrins
PubMed: 27813402
DOI: 10.1021/acs.chemrev.6b00496 -
Bioconjugate Chemistry Dec 2023Porphyrins have been vastly explored and applied in many cutting-edge fields with plenty of encouraging achievements because of their excellent properties. As important... (Review)
Review
Porphyrins have been vastly explored and applied in many cutting-edge fields with plenty of encouraging achievements because of their excellent properties. As important derivatives of porphyrins, porphyrin-based amphiphiles (PBAs) not only maintain the advanced properties of porphyrins (catalysis, imaging, and energy transfer) but also possess self-assembly and encapsulation capability in aqueous solution. Accordingly, PBAs and their self-assembles have had important roles in diagnosing and treating tumors and inflammation lesions , but not limited to these. In this article, we introduce the research progress of PBAs, including their constitution, structure design strategies, and performances in tumor and inflammation lesion diagnosis and treatments. On that basis, the defects of synthesized PBAs during their application and the possible effective strategies to overcome the limitations are also proposed. Finally, perspectives on PBAs exploration are updated based on our knowledge. We hope this review will bring researchers from various domains insights about PBAs.
Topics: Humans; Porphyrins; Nanostructures; Neoplasms; Inflammation
PubMed: 37955349
DOI: 10.1021/acs.bioconjchem.3c00432 -
Chemical Society Reviews Apr 2021Porphyrins feature prominently in nature, be it as enzymatic cofactors, electron and exciton shuffles, as photoactive dyes, or as signaling substances. Their involvement... (Review)
Review
Porphyrins feature prominently in nature, be it as enzymatic cofactors, electron and exciton shuffles, as photoactive dyes, or as signaling substances. Their involvement in the generation, storage and use of oxygen is pivotal to life, while their photochemical properties are central to the biochemical functioning of plants. When complexed to metals, porphyrins can engage in a multitude of contemporary applications ranging from solar energy generation to serving as catalysts for important chemical reactions. They are also able to function as useful theranostic agents, and as novel materials for a wide range of applications. As such, they are widely considered to be highly valuable molecules, and it almost goes without saying that synthetic organic chemistry has dramatically underpinned all the key advances made, by providing reliable access to them. In fact, strategies for the synthesis of functionalized porphyrins have now reached a state of refinement where pretty well any desired porphyrin can successfully be synthesized with the approaches that are available, including a cornucopia of related macrocycle-modified porphyrinoids. In this review, we are going to illustrate the development of this exciting field by discussing a number of classic syntheses of porphyrins. Our coverage will encompass the natural protoporphyrins and chlorophylls, while also covering general strategies for the synthesis of unsymmetrical porphyrins and chlorins. Various industrial syntheses of porphyrins will also be discussed, as will other routes of great practical importance, and avenues to key porphyrinoids with modified macrocycles. A range of selected examples of contemporary functionalization reactions will be highlighted. The various key syntheses will be described and analyzed from a traditional mechanistic organic chemistry perspective to help student readers, and those who are new to this area. The aim will be to allow readers to mechanistically appreciate and understand how many of these fascinating ring-systems are built and further functionalized.
Topics: Molecular Structure; Porphyrins
PubMed: 33623938
DOI: 10.1039/c7cs00719a -
Molecules (Basel, Switzerland) May 2022Metal-Organic Frameworks (MOFs) are hybrid multifunctional platforms that have found remarkable applications in cancer treatment and diagnostics. Independently, these... (Review)
Review
Metal-Organic Frameworks (MOFs) are hybrid multifunctional platforms that have found remarkable applications in cancer treatment and diagnostics. Independently, these materials can be employed in cancer treatment as intelligent drug carriers in chemotherapy, photothermal therapy, and photodynamic therapy; conversely, MOFs can further be used as diagnostic tools in fluorescence imaging, magnetic resonance imaging, computed tomography imaging, and photoacoustic imaging. One essential property of these materials is their great ability to fine-tune their composition toward a specific application by way of a judicious choice of the starting building materials (metal nodes and organic ligands). Moreover, many advancements were made concerning the preparation of these materials, including the ability to downsize the crystallites yielding nanoporous porphyrin MOFs (NMOFs) which are of great interest for clinical treatment and diagnostic theranostic tools. The usage of porphyrins as ligands allows a high degree of multifunctionality. Historically these molecules are well known for their reactive oxygen species formation and strong fluorescence characteristics, and both have proved helpful in cancer treatment and diagnostic tools. The anticipation that porphyrins in MOFs could prompt the resulting materials to multifunctional theranostic platforms is a reality nowadays with a series of remarkable and ground-breaking reports available in the literature. This is particularly remarkable in the last five years, when the scientific community witnessed rapid development in porphyrin MOFs theranostic agents through the development of imaging technologies and treatment strategies for cancer. This manuscript reviews the most relevant recent results and achievements in this particular area of interest in MOF chemistry and application.
Topics: Humans; Ligands; Magnetic Resonance Imaging; Metal-Organic Frameworks; Neoplasms; Porphyrins; Precision Medicine
PubMed: 35630585
DOI: 10.3390/molecules27103111