Synthesis Of Porphyrins Research Articles

Remote template effect in the synthesis of bipyridine-strapped porphyrins.

A bipyridine-strapped porphyrin was prepared using a remote template effect of alkali or transition metal cations in the bipyridine subunit to enhance the yield 10-fold. The flexibility of the bipyridine-strap also allowed the synthesis of a doubly strapped porphyrin.

Keggin type heteropolyacid-mediated novel green protocol for the synthesis of porphyrins

Phosphovanadotungstic acid mediated novel strategy employs mild reaction conditions without use of halogenated solvents/oxidising agents and affords a commendable spectroscopic yield of 12–39%.

Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems

AbstractFor the first time, the simultaneous synthesis and deposition of heterometallic porphyrin conjugated polymer thin films from a simple and scalable gas‐phase approach are reported. The oxidative chemical vapor deposition (oCVD) reaction of 5,15‐(diaryl) porphyrins chelated with different metal cations (M = Co(II), Ni(II), Zn(II), Cu(II), Pd(II)) readily yields the formation of new hetero‐metalated fused porphyrin tapes, such as evidenced by in‐depth high‐resolution mass spectrometry studies. The impact of the coreactants on the regioselectivity of the intermolecular dehydrogenative coupling reaction and the formation of double or triple bonds between the porphyrin units is demonstrated. The oCVD reaction of multiple porphyrins brings the possibility to easily engineer the chemical features and the electronic and optoelectronic properties of these highly conjugated porphyrin polymers. Particularly, it is demonstrated that porphyrin conjugated polymers having different chelated metal cations can achieve higher electrical conductivities and promote narrower bandgaps. The gas‐phase approach presented herein overcomes the main limitations of the conventional solution‐based approaches and opens the path to the engineering of a novel class donor–acceptor heterometallic polymers with high interest in several fields including multimetallic electrocatalysis, photocatalysis, sensing, and nonlinear optics applications.

Synthesis and study of water-soluble asymmetric cationic porphyrins as potential photoinactivators of pathogens

Synthesis and study of water-soluble asymmetric cationic porphyrins as potential photoinactivators of pathogens

Iron porphyrin with appended guanidyl group for significantly improved electrocatalytic carbon dioxide reduction activity and selectivity in aqueous solutions

AbstractIron porphyrins have high activity and selectivity for electrocatalytic CO2 reduction reaction (CO2RR) in nonaqueous solutions, but they usually display poor or moderate selectivity for CO2RR in aqueous solutions because of the competitive hydrogen evolution reaction. Using water as the electrocatalytic reaction solvent is more favored because not only it is cheap, green and abundant but also it can sufficiently provide protons required for CO2RR. Therefore, developing Fe porphyrins as electrocatalysts for efficient and selective CO2RR in aqueous solutions is of both fundamental and practical significance. Herein, we report the design and synthesis of Fe porphyrin 1 with an appended guanidyl group and its electrocatalytic features for CO2RR in both nonaqueous and aqueous solutions. In acetonitrile, Fe porphyrin 1 and its guanidyl-free analogue, tetrakis(3,4,5-trimethoxyphenyl)porphyrin 2, are both efficient for electrocatalytic CO2-to-CO conversion, but the turnover frequency with 1 (3.9 × 105 s−1) is one order of magnitude larger than that with 2 (1.7 × 104 s−1), showing the critical role of the appended guanidyl group in improving electrocatalytic CO2RR activity. More importantly, in 0.1 mol L−1 KHCO3 aqueous solutions, 1 showed very high selectivity for electrocatalytic CO2-to-CO conversion with a Faradaic efficiency of 96%, while 2 displayed a Faradaic efficiency of 65% for the CO2-to-CO conversion. This work is of significance to show the effect of appended guanidyl group on improving both activity and selectivity of Fe porphyrins for CO2RR electrocatalysis.

Synthesis of water-soluble porphyrin with tyrosine fragments and study of its interaction with S-protein of SARS-CoV-2.

The multistage purposeful synthesis of 5,15-bis(4'-l-N-tyrosinylamidophenyl)-10,20-bis(N-methylpyridin-3'-yl)porphine diiodide was carried out, and the optimum synthesis conditions were determined. 5,15-Bis(4'-nitrophenyl)-10,20-bis(pyridin-3'-yl)porphine served as the starting porphyrin. The structure, individual character, and purity of the target compound were proved by electron spectroscopy, 1H NMR spectroscopy, mass spectrometry (MALDI TOF), and TLC. Specific features of the interaction of the synthesized porphyrin with S-protein of SARS-CoV-2 were studied using spectral and thermochemical methods, including conditions of photoirradiation. The photoirradiation of the synthesized porphyrin in a complex with the SARS-CoV-2 S-protein can result in the partial oxidation of amino acid residues of the protein and distort its primary and secondary structures. The photoirradiation of the S-protein complex with the porphyrin decreases its thermal resistance to melting by 15 °C compared to the free S-protein and causes porphyrin release.

Rational Synthesis of Benzoheterole-fused Porphyrins and π-System Switching by Central Metal Ion

Abstract We developed a rational synthetic approach for benzoheterole-fused porphyrins and demonstrated the synthesis of benzothiophene- and indole-fused porphyrins using the approach. The fused porphyrins exhibited red-shifted absorption and fluorescence due to the effective π-expansion through heterole-fused structures. In addition, the π-circuit of indole-fused porphyrin can be switched by a central metal ion.

Synthesis and Functionalization of Challenging meso-Substituted Aryl Bis-pocket Porphyrins Accessed via Suzuki-Miyaura Cross-Coupling.

Herein we report an investigation into the synthesis, metalation, and functionalization of bis-pocket porphyrins using the Suzuki–Miyaura cross-coupling reaction. Steric limitations to accessing bis-pocket porphyrins were overcome by using this Pd-catalyzed C–C-bond-forming strategy to introduce steric bulk after macrocyclization: 2,6-dibromo-4-trimethylsilybenzaldehyde was condensed with pyrrole, and a variety of boronic acids were coupled to the resulting porphyrin in up to 95% yield. Furthermore, we show that these porphyrins can be metalated with a variety of metals and sulfonated to create water-soluble bis-pocket porphyrins.

Progress of antiaromatic ring-contracted porphyrinoids

<p indent="0mm">Antiaromatic ring-contracted porphyrinoids have fewer pyrrole units or <italic>meso</italic> carbons than standard 18π-conjugated aromatic porphyrins and exhibit a 4<italic>n</italic> π-conjugation system, with representative molecules including 16π-conjugated norcorrole, corrole, and triphyrin. Antiaromatic ring-contracted porphyrins exhibit great molecular rigidity, excellent stability, and simplicity of functionalization, as well as intense paratropic induced ring current, strong magnetic shielding effect, small highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gap, and high charge transfer capability. This review introduces recent advances in the synthesis and functionalization of antiaromatic ring-contracted porphyrins, and highlights their promising utility in electronic materials based on aromatic-antiaromatic conversion, rechargeable battery electrode materials, and supramolecular conductive materials.

Synthesis, photophysical properties and theoretical evaluation of alkyl-linked porphyrin – BODIPY dyads

Novel porphyrin-BODIPY Dyads linked by alkyl chains of different lengths as molecular conjugates were prepared and their intramolecular energy transfer properties have been investigated. Steady-state absorption and emission spectra have shown the successful intramolecular energy transfer (FRET) from BODIPY to porphyrin units approved with the calculated Förster radii and FRET efficiencies. Alkyl chain shortening has revealed an explicit increase in energy transfer as it could be expected. Further, DFT and TD-DFT studies for the synthesized dyads were carried out and frontier molecular orbital energies were investigated at the HSEH1PBE/6-31+G** theory level. Strongly electron-withdrawing C6F5- substituents on the porphyrin periphery extended the HOMO-LUMO gap in contrast to the 4-CF3C6H4- substituent from ca. 2.37 eV to ca. 2.50 eV. Open-circuit voltage values (Voc), reorganization energies (λe and λh), ionization potentials, and adiabatic electron affinities were calculated to evaluate the optical and electronic behaviors of Dyads. Calculated Voc values exceeding 1.00 V, and low reorganization energies of the Dyads indicate that they are promising structures for developing new photovoltaics.

Versatile Synthesis of Multivalent Porphyrin-Peptide Conjugates by Direct Porphyrin Construction on Resin.

Multifunctional porphyrin–peptide conjugates with different propensities for self‐assembly into various supramolecular nanoarchitectures play important roles in advanced materials and biomedical research. However, preparing prefunctionalized core porphyrins by traditional low‐yielding statistical synthesis and purifying them after peptide ligation through many rounds of HPLC purification is tedious and unsustainable. Herein, we report a novel integrated solid‐phase synthetic protocol for the construction of porphyrin moieties from simple aldehydes and dipyrromethanes on resin‐bound peptides directly to form mono‐, cis/trans‐di‐, and trivalent porphyrin–peptide conjugates in a highly efficient and controllable manner; moreover, only single final‐stage HPLC purification of the products is needed. This efficient strategy enables the rapid, greener, and substrate‐controlled diversity‐oriented synthesis of multivalent porphyrin–(long) peptide conjugate libraries for multifarious biological and materials applications.

Versatile Synthesis of Multivalent Porphyrin–Peptide Conjugates by Direct Porphyrin Construction on Resin

AbstractMultifunctional porphyrin–peptide conjugates with different propensities for self‐assembly into various supramolecular nanoarchitectures play important roles in advanced materials and biomedical research. However, preparing prefunctionalized core porphyrins by traditional low‐yielding statistical synthesis and purifying them after peptide ligation through many rounds of HPLC purification is tedious and unsustainable. Herein, we report a novel integrated solid‐phase synthetic protocol for the construction of porphyrin moieties from simple aldehydes and dipyrromethanes on resin‐bound peptides directly to form mono‐, cis/trans‐di‐, and trivalent porphyrin–peptide conjugates in a highly efficient and controllable manner; moreover, only single final‐stage HPLC purification of the products is needed. This efficient strategy enables the rapid, greener, and substrate‐controlled diversity‐oriented synthesis of multivalent porphyrin–(long) peptide conjugate libraries for multifarious biological and materials applications.

New Avenues of Heme Synthesis Regulation.

During erythropoiesis, there is an enormous demand for the synthesis of the essential cofactor of hemoglobin, heme. Heme is synthesized de novo via an eight enzyme-catalyzed pathway within each developing erythroid cell. A large body of data exists to explain the transcriptional regulation of the heme biosynthesis enzymes, but until recently much less was known about alternate forms of regulation that would allow the massive production of heme without depleting cellular metabolites. Herein, we review new studies focused on the regulation of heme synthesis via carbon flux for porphyrin synthesis to post-translations modifications (PTMs) that regulate individual enzymes. These PTMs include cofactor regulation, phosphorylation, succinylation, and glutathionylation. Additionally discussed is the role of the immunometabolite itaconate and its connection to heme synthesis and the anemia of chronic disease. These recent studies provide new avenues to regulate heme synthesis for the treatment of diseases including anemias and porphyrias.

Therapy Follows Diagnosis: Old and New Approaches for the Treatment of Acute Porphyrias, What We Know and What We Should Know.

Heme, iron protoporphyrin IX, is one of life’s most central molecules. Hence, availability of the enzymatic machinery necessary for its synthesis is crucial for every cell. Consequently, inborn errors of porphyrin metabolism that compromise normal synthesis, namely the family of porphyrias, undermine normal cellular metabolism given that heme has functions in catalytic centers, signal transduction and functional regulation and its synthesis is fully integrated into the center of intermediary metabolism. Very often, diagnosis of porphyrias is difficult and therefore delayed. Therapy can be as complicated. Over the last 50 years, several strategies have been developed: because of its integration with other parts of intermediary metabolism, the infusion of glucose (glucose effect) was one of the first attempts to counterbalance the dysregulation of porphyrin synthesis in porphyrias. Since heme synthesis is impaired, infusional replacement of heme was the next important therapeutic step. Recently, siRNA technology has been introduced in order to downregulate 5-ALA-synthase 1, which contributes to the patho-physiology of these diseases. Moreover, other novel therapies using enzyme protein replacement, mRNA techniques or proteostasis regulators are being developed.

Bioinspired iron porphyrins with appended poly-pyridine/amine units for boosted electrocatalytic CO2 reduction reaction

Developing highly efficient electrocatalysts for the CO2 reduction reaction (CO2RR) has attracted increasing interest in the past decade. Herein, we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2-picolyl)ethylenediamine (DPEN) unit that boosts electrocatalytic activity for CO2-to-CO conversion in acetonitrile with water as the proton source. By mimicking carbon monoxide dehydrogenase (CODH), 1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer. The protonated and positively charged DPEN unit can also stabilize CO2 reduction intermediates through electrostatic and hydrogen-bonding interactions. These factors make 1 a highly active electrocatalyst for the CO2RR by achieving a TOFmax of 5.0 ​× ​104 ​s−1 with water providing the protons. These critical roles of the DPEN unit in the CO2RR are further supported by theoretical studies. This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.

Studies on Synthesis of Porphyrins – β ‐Substituted with Multiple Nitrogen‐containing Groups

The preparation of highly β-substituted amino-/nitro-porphyrins is described. They were formed in two-step transformation: electrophilic nitration/nucleophilic amination via attractive substitution of hydrogen reaction (VNS). This type of porphyrins, bearing up to four nitrogen groups, are practically not available by alternative methods. They are valuable starting materials in the synthesis of more complex moieties, e. g. anticancer PDT agents.

Risk of Hepatocellular Carcinoma in Patients with Porphyria: A Systematic Review.

Simple SummaryPorphyria is a metabolic condition which leads to reduced heme production. While it involves multiple organs systems, porphyria affecting the liver can lead to elevations in hepatic enzymes, progressive fibrosis, cirrhosis and eventually malignancy. Our study looked at the prevalence of liver cancer in patients with porphyria. Overall, we found that patients with porphyria are at increased risk of developing hepatic malignancy. As a result, patients with porphyria should undergo routine surveillance for detecting primary liver malignancy.Acute porphyrias are a group of metabolic disorders resulting in defective porphyrin synthesis and reduced heme production, which carries a risk of malignancy. Porphyrias are inborn defects in the heme biosynthesis pathway resulting in neurovisceral manifestations and cutaneous photosensitivity attacks with multi-systemic involvement. Its estimated prevalence nears 5 per 100,000 patients worldwide. Subclinical liver disease is common, which can progress into transaminitis, fibrosis, cirrhosis, and malignancy. However, data on the incidence of primary liver cancer are lacking. We aim to determine the risk of hepatocellular carcinoma (HCC) in patients with porphyria. A systematic review and pooled analysis were conducted through 2021 on studies assessing blood tests, imaging, cancer development, liver transplant, surgical resection, and outcomes in porphyria. In total, 19 studies, which included 7381 patients with porphyria (3476 females), were considered for the final review. In eight studies, alpha-fetoprotein levels were elevated between 200 and 1000 IU/mL. Of the total cohort of patients with porphyria, primary liver cancer was diagnosed in 351 patients (4.8%), of whom 243 (3.3% of the total) were found to have HCC. A subset of patients was found to have cholangiocarcinoma (n = 18; 0.3% of the total). Interestingly, advanced liver disease or cirrhosis was not a prerequisite for the formation of HCC in a small group of patients. Of the total cohort, 30 patients underwent liver resection, 48 patients underwent liver transplantation, and 327 patients died. Patients with porphyria are at risk of developing primary liver malignancy. Further studies should aim to develop diagnostic and prognostic models aimed at the early detection of HCC in porphyria.

Synthesis of porphyrin(2.1.2.1) with embedded naphthalene

Expanded nonaromatic stable porphyrins(2.1.2.1) were successfully synthesized by 2,3-di(1H-pyrrol-2-yl)naphthalene as buliding blocks and aromatic aldehydes under acid catalyzed condensation conditions in acceptable isolated yields. NMR, X-ray diffraction analysis, absorption, electrochemical, and density functional theory revealed these macrocycles to be non-aromatic due to highly saddle-shaped molecular structures of dinaphthoporphyrin(2.1.2.1). The saddle-shaped dinaphthoporphyrins(2.1.2.1) with embedded naphthalene units as [Formula: see text]-conjugation units show perturbations to molecular structure, optical and electronic properties. The dinaphthoporphyrins(2.1.2.1) are effective macrocyclic ligands giving copper(II) and nickel(II) complexes.

Synthesis of zinc porphyrin with fluorophenyl group and applications in dye sensitized solar cells

To fabricate highly efficient porphyrin dyes, we designed and synthesized two dyes with different numbers of fluorine atoms, dyes ZnF1 and ZnF2, respectively. These dyes were then connected to TiO2 electrode surface to build dye sensitized solar cells, and we studied the relationship between porphyrins dyes with different numbers of fluorine atoms and the performance of dye-sensitized solar cells. Our results indicate that solar cells with fewer fluorine atoms show higher photocurrent conversion efficiency (PCE). In particular, the ZnF1 solar cell containing one fluorine atom exhibits relatively high short-circuit current density ([Formula: see text] due to its low band gap and remarkable light collection capability. ZnF1 solar cells showed relatively higher short circuit current density ([Formula: see text] due to their low energy band gap and significant light collection ability. With the purpose to further improve the efficiencies, cosensitized with chenodeoxycholic acid (CDCA) dyes approaches were employed. As a result, the efficiencies have been successfully elevated to 2.71%. Additionally, the UV-vis absorption, density functional theory (DFT) calculations, electrochemical impedance spectra (EIS) and HOMO-LUMO energy gaps are used to further verify the test results of the sensitized solar cells.

Chemisorption Role of Clay Surfaces in the Synthesis of Porphyrins from its Raw Materials via Room Temperature Reactions

Chemisorption Role of Clay Surfaces in the Synthesis of Porphyrins from its Raw Materials via Room Temperature Reactions