Synthesis Of Porphyrins Research Articles

C-glycosylated pyrroles and their application in dipyrromethane and porphyrin synthesis

Pyrrole C-glycosylated in either the 2- or the 3-position could be prepared by the acid-catalyzed reaction between trichloroacetimidate glycosyl donors and pyrrole, or [Formula: see text]-phenyl-tri?uoroacetimidate glucosyl donor and [Formula: see text]-TIPS pyrrole, respectively. Pyrroles carrying glucose, mannose, galactose and lactose in the 2-position, and glucose in the 3-position were obtained. The configurations of the products could be assigned using a combination of 1D and 2D NMR spectroscopy. A number of undesired background reactions yielding a variety of stereo- and regioisomers were identified; in several cases these could be eliminated. Glycosylpyrroles could be incorporated into mono- and diglycosylated dipyrromethanes, a diglycosylated BODIPY dye, and a monoglycosylated Zn(II) porphyrin without damaging the sugar unit.

RNA Interference by Ingested Dsrna-Expressing Bacteria to Study Porphyrin Pigmentation in Crassostrea gigas

Porphyrins are a widespread group of pigments in nature which are believed to contribute to shell colors in mollusks. Previous studies have provided candidate genes for porphyrin shell coloration, however, the linkage analysis between functional genes and porphyrin pigmentation remains unclear in mollusks. RNA interference is a powerful molecular tool for analyzing the loss of functions of genes in vivo and alter gene expression. In this study, we used unicellular alga Platymonas subcordiformis and Nitzschia closterium f. minutissima as vectors to feed oysters with Escherichia coli strain HT115 engineered to express double-stranded RNAs targeting specific genes involved in porphyrin synthesis. A strain of Crassostrea gigas with orange shell was used to target key haem pathway genes expression using the aforementioned approach. We show here that feeding the oysters with E. coli, containing dsRNA targeting pigmentation genes, can cause changes in the color of the newly deposited shell. For example, the RNAi knockdown of CgALAS and CgPBGD resulted in the loss of uroporphyrin pigmentation from the shell due to the accumulation of the pigment in the oyster’s mantle. The study probed the crucial role of ALAS and PBGD genes potential functions of uroporphyrin production and shell color pigmentation in C. gigas.

Integration of Dual Stress Transcriptomes and Major QTLs from a Pair of Genotypes Contrasting for Drought and Chronic Nitrogen Starvation Identifies Key Stress Responsive Genes in Rice

We report here the genome-wide changes resulting from low N (N-W+), low water (N+W-)) and dual stresses (N-W-) in root and shoot tissues of two rice genotypes, namely, IR 64 (IR64) and Nagina 22 (N22), and their association with the QTLs for nitrogen use efficiency. For all the root parameters, except for root length under N-W+, N22 performed better than IR64. Chlorophyll a, b and carotenoid content were higher in IR64 under N+W+ treatment and N-W+ and N+W- stresses; however, under dual stress, N22 had higher chlorophyll b content. While nitrite reductase, glutamate synthase (GS) and citrate synthase assays showed better specific activity in IR64, glutamate dehydrogenase showed better specific activity in N22 under dual stress (N-W-); the other N and C assimilating enzymes showed similar but low specific activities in both the genotypes. A total of 8926 differentially expressed genes (DEGs) were identified compared to optimal (N+W+) condition from across all treatments. While 1174, 698 and 903 DEGs in IR64 roots and 1197, 187 and 781 in N22 roots were identified, nearly double the number of DEGs were found in the shoot tissues; 3357, 1006 and 4005 in IR64 and 4004, 990 and 2143 in N22, under N-W+, N+W- and N-W- treatments, respectively. IR64 and N22 showed differential expression in 15 and 11 N-transporter genes respectively, under one or more stress treatments, out of which four showed differential expression also in N+W- condition. The negative regulators of N- stress, e.g., NIGT1, OsACTPK1 and OsBT were downregulated in IR64 while in N22, OsBT was not downregulated. Overall, N22 performed better under dual stress conditions owing to its better root architecture, chlorophyll and porphyrin synthesis and oxidative stress management. We identified 12 QTLs for seed and straw N content using 253 recombinant inbred lines derived from IR64 and N22 and a 5K SNP array. The QTL hotspot region on chromosome 6 comprised of 61 genes, of which, five were DEGs encoding for UDP-glucuronosyltransferase, serine threonine kinase, anthocyanidin 3-O-glucosyltransferase, and nitrate induced proteins. The DEGs, QTLs and candidate genes reported in this study can serve as a major resource for both rice improvement and functional biology.

Synthesis of Hetaryl-Substituted Asymmetric Porphyrins and Their Affinity to SARS-CoV-2 Helicase.

Novel porphyrin compounds containing benzothiazole, benzoxazole, and benzimidazole moieties have been prepared and their structures have been confirmed. Molecular docking of non-symmetric hetaryl-substituted porphyrins and chlorin e6 with SARS-CoV-2 helicase has been carried out. The affinity of hetaryl-substituted porphyrins to this protein has been found significantly higher than that of the drugs approved by the FDA and chlorin e6. The structure of the complexes of SARS-CoV-2 helicase with the considered macroheterocyclic compounds has been analyzed. Possible ways to inhibit and photoinactivate SARS-CoV helicase have been suggested basing on the localization of porphyrins and chlorin e6 in the helicase domains.

Synthesis of Chiral Carbazole-Based Porphyrins and Bodipys

We have explored the synthesis and functionalization of carbazole-based porphyrins and BODIPYs showing NIR absorption and solid-state fluorescence. Here, we synthesized chiral carbazole-based porphyrins and BODIPYs. The former showed Cotton effect in the NIR region, while the latter showed CPL both in solution and in the solid state. In this presentation, chiroptical properties of this chiral dyes are reported.

Synthesis, Spectral and Electrochemical Studies of β-Trisubstituted Porphyrins and Monobenzoporphyrins

Meso-Tetraarylporphyrins having electron-withdrawing substituents viz. nitro, formyl, acyl, or bromo groups is the key precursor to expand the chemistry of β-functionalized porphyrins.1 These β-functionalized porphyrins have been utilized in nonlinear optics, anion sensing, gas storage, photodynamic therapy (PDT), and dye-sensitized solar cells (DSSC).2 Modulating the degree of π-conjugation and introducing suitable donor-acceptor substituents at β-positions result red-shifted electronic spectral features, low HOMO-LUMO gap and high ground state dipole moment which are essentials for enhanced nonlinear optical behavior. Benzoporphyrin derivatives are currently under investigation as photosensitizers for PDT.3 Herein, we synthesized unsymmetrically functionalized trisubstituted porphyrins and monobenzoporphyrins in one step and characterized by various spectroscopic techniques viz. UV-vis, fluorescence, NMR, MALDI-TOF mass spectrometry and electrochemical studies.The synthesized trisubstituted porphyrins and monobenzoporphyrins were significantly red-shifted as compared to their precursor porphyrins. Further, these porphyrins exhibited a large anodic shift in reduction and cathodic shift in oxidation potentials due to extended π-conjugation and electron-withdrawing β-substituents. In this presentation, we will present the facile synthesis, photophysical and intriguing electrochemical redox properties of π-extended porphyrins. Figure 1. Molecular structures, absorption spectral profile and cyclic voltammograms of synthesized porphyrins.

Supramolecular Architecturing of Quantum Box Arrays from Functionalized Porphyrins and Exploring Their Quantum States

Our research is based on the analysis of structure-function correlations for a broad spectrum of functionalized porphyrins and phthalocyanines in their propensity to create increasingly complex and functional on surface architectures. [1] Thereby we use porphyrin and phthalocyanine functionalization and synthesis, ‘by design’, or ‘on-surface-supramolecular chemistry’ to create structures with specific physical properties towards e.g. future quantum devices.By using a fluoro-bi-phenyl functionalized porphyrin to create a stable, porous organic network, we manufacture arrays of identical quantum boxes. These boxes contain a specific quantum well state arising from the confinement of the electronic (Shockley) surface state within the pores. We show that the electronic quantum box state as well as the interbox coupling can be modified locally by adsorbates, e.g. C60, interacting with the barrier. In view of the wealth of available and differently acting adsorbates, this approach allows for the engineering of quantum states in on-surface network architectures. Thus, by their dance on the nose of the ‘devil’ [3], porphyrins and phthalocyanines justify the emergence of ‘on-surface supramolecular physics’ as reflected by ongoing and future research work.Fig. 1) Adsorbate-induced modification of the confining barriers in a quantum box array formed by a functionalized fluoro-bi-phenyl porphyrin on Ag(111). (Taken from [2])[1] N. Wintjes et al. Two-dimensional phase behavior of a bimolecular porphyrin system at the solid-vacuum interface, J. Am. Chem. Soc. 2010, 132, 21, 7306-7311; N. Wintjes et al., Supramolecular synthons on surfaces: Controlling dimensionality and periodicity of tetraarylporphyrin assemblies by the interplay of cyano and alkoxy substituents Chem. Eur. J. 2008, 14, 5794.[2] S. Nowakowska et al., Adsorbate-induced modification of the confining barriers in a quantum box array, ACS Nano 2018, 12, 768.[3] W. Pauli “God made the bulk; surfaces were invented by the devil.” Quoted, e.g. in the Preface of A. Zangwill, Physics at Surfaces, Cambridge University Press, 1988. ISBN 978-0-521-34752-5 Figure 1

Photoinactivation of mycobacteria to combat infection diseases: current state and perspectives.

The spread of multi-drug-resistant bacterial strains causing serious infectious diseases dictates the development of new approaches to combat these diseases. In addition to drug resistance, the important causative agent of tuberculosis (Mycobacterium tuberculosis (Mtb)) is able to persist asymptomatically in individuals for many years, causing latent forms of tuberculosis. In such a dormant state, Mtb cells are also resistant to known antibiotics. In this regard, photodynamic inactivation (PDI) could be an effective alternative to antibiotics as its action is based on the generation of active forms of oxygen independently on the presence of specific antibiotic targets, thereby inactivating both drug-resistant and dormant bacteria. In this review, we summarise examples of the application of PDI for the elimination of representatives of the genus Mycobacteria, both in vitro and in vivo. According to published results, including photosensitisers in the PDI regime results in a significantly higher lethal effect. Such experiments were mainly performed using chemically synthesised photosensitisers, which need to be transported to the areas of bacterial infections, limiting PDI usage by surface (skin) diseases. In this regard, endogenous photosensitisers (mainly porphyrins) could be used to solve the problem of transportation. In vitro experiments demonstrate the effective application of PDI for mycobacteria, including Mtb, using endogenous porphyrins; the intracellular contents of these substances can be elevated by administration of 5-aminolevulenic acid, a precursor of porphyrin synthesis. Photodynamic inactivation can also be used for dormant mycobacteria, which are characterised by high levels of endogenous porphyrins. Thus, PDI can effectively eliminate drug-resistant mycobacteria. The exploitation of modern light-transmitting techniques opens new possibilities to use PDI in clinical settings.Key points •The potential effects of photodynamic inactivation of mycobacteria are critically reviewed. •Approaches to photoinactivation of mycobacteria using exogenous and endogenous photosensitisers are described. •Prospects for the use of photodynamic inactivation in the treatment of tuberculosis are discussed.

Syn-Diarylphthalimidoporphyrins: Effects of Symmetry Breaking on Two-Photon Absorption and Linear Photophysical Properties

Aromatically π-extended porphyrins possess exceptionally intense one-photon (1P) and sometimes two-photon (2P) absorption bands, presenting interest for construction of optical imaging probes and photodynamic agents. Here we investigated how breaking the molecular symmetry affects linear and 2PA properties of π-extended porphyrins. First, we developed the synthesis of porphyrins fused with two phthalimide fragments, termed syn-diarylphthalimidoporphyrins (DAPIP). Second, the photophysical properties of H2, Zn, Pd, and Pt DAPIP were measured and compared to those of fully symmetric tetraarylphthalimidoporphyrins (TAPIP). The data were interpreted using DFT/TDDFT calculations and sum-over-states (SOS) formalism. Overall, the picture of 2PA in DAPIP was found to resemble that in centrosymmetric porphyrins, indicating that symmetry breaking, even as significant as by syn-phthalimido-fusion, induces a relatively small perturbation to the porphyrin electronic structure. Collectively, the compact size, versatile synthesis, high 1PA and 2PA cross sections, and bright luminescence make DAPIP valuable chromophores for construction of imaging probes and other bioapplications.

Utility of dipyrromethane in the synthesis of some new A2B2 porphyrin and their related porphyrin like derivatives with their evaluation as antimicrobial and antioxidant agents

In this work, the dipyrromethane derivatives 2a,b were synthesized from an aldehyde and excess of pyrrole at room temperature in solvent-free conditions. The reaction of dipyrromethanes 2a,b with different aromatic aldehydes in the presence of hydrochloric acid or p-toluenesulfonic acid as a catalyst afforded some new porphyrin like and A2B2 porphyrin derivatives 4a-g and 5a-d, respectively. Biological evaluation of the newly synthesized compounds 4a-g and 5a-d showed promising activity as antimicrobial and antioxidant agents. Compounds 4c,4e,4g,5c, and 5d exhibited the highest antimicrobial activity, whereas, compounds 4a,4f,5a,5b, and 5d recorded the highest antioxidant activity.

Synthesis, characterization, and photocatalytic disinfection studies of porphyrin dimer/TiO2-based photocatalyst

In this research, we synthesized a novel panchromatic absorption dimer porphyrin and designed a dimer molecule with maximum absorption in the visible and NIR regions. The work was followed and monitored by its photocatalytic function with anatase TiO2 and brookite-rutile TiO2, and preliminarily compared and tested its photocatalytic disinfection of gram-negative bacteria Escherichia coli (E. coli) in visible light conditions toward the potential of future studies. The finding results were compared with the bare anatase TiO2 and brookite-rutile TiO2. The prepared structure of molecules was confirmed by SEM, EDS, XRD, XPS, and solid-state diffuse reflectance spectral studies.

Amphiphilic axially modified cationic indium-porphyrins linked to hydrophilic magnetic nanoparticles for photodynamic antimicrobial chemotherapy against gram-negative strain; Escherichia coli

In this study, we report on the synthesis, characterization, and application of indium porphyrins linked to silver core-shell magnetic nanoparticles for in vitro photodynamic antimicrobial chemotherapy (PACT) against gram-negative strain, E. coli. This work compares the photophysicochemical and PACT activities of InCl 5-p-carboxyphenyl-10-15-20-(tris-4-methylpyridinium)-triiodide porphyrin (1), InCl 5-p-carboxyphenyl-10-15-20-(tris-4-hexylpyridinium)-triiodide porphyrin (2), In (para-aminophenyl) 5,10,15,20-tetrakis(4-methylpyridinium)-tetraiodide porphyrin (3), and In (para-aminophenyl) 5,10,15,20-tetrakis(4-hexylpyridinium)-tetraiodide porphyrin (4). The comparisons were based on the structure and number of charges. Hydrophilic and hydrophobic characters of the amphiphilic porphyrins were studied by comparing the effect of the different alkyl halides (iodomethane and iodohexane) quaternizing agents. The porphyrin complexes were further linked to magnetic nanoparticles to facilitate antimicrobial synergy and recovery of the complexes after use. High Log reduction values ranging from 7.19 to 9.58 were obtained for the quaternized complexes.

Porphyrin- and porphyrinoid-based covalent organic frameworks (COFs): From design, synthesis to applications

• Porphyrin and porphyrinoid-based covalent organic frameworks (COFs) are reviewed. • The design and synthesis of porphyrin and porphyrinoid-based COFs are discussed. • Recent advances in applications of porphyrin and porphyrinoid-based COFs are examined. • Perspectives and challenges for their future development are provided. Covalent organic frameworks (COFs), constructed with the light atoms such as carbon, nitrogen, oxygen, borane etc. via covalent bonds, represent a promising class of structurally ordered, highly crystalline functional porous materials possessing a large surface area to volume ratio. Recently there is a rapidly growing interest in tetrapyrrolic macrocycle-based COFs in which naturally occurring porphyrin and the synthetic analogs of porphyrin such as corroles and phthalocyanines, generally referred to as porphyrinoids, are employed as building blocks. Due to the intriguing properties of porphyrin and porphyrinoid units, the resulting COFs have found applications in different areas such as in gas absorption, storage of energy, optoelectronics, and catalysis. Herein, we review the research progress achieved in these areas over the past 5 years. The design and synthesis of porphyrin and porphyrinoid COFs will first be discussed, and is followed by an examination of the recent advances in their applications. The prospects and challenges for the further development of porphyrin and porphyrinoid COFs from design to applications will be highlighted.

Addressing Environmental Challenges of Porphyrin Mixtures Obtained from Statistical Syntheses

AbstractSyntheses of complex molecular mixtures on the preparative scale are often challenging steps for chemists, which go hand in hand with expensive purification steps. Herein, the preparation and isolation of unsymmetrically substituted porphyrins, obtained from statistical reactions between two benzaldehydes, were investigated. Therefore, a semi‐automated modular process was developed to lower the consumable costs, save time, and reduce waste production. We utilized a monomode microwave reactor equipped with an autosampler, and a medium pressure liquid chromatography (MPLC) flash purification device, equipped with a UV/Vis detector and a re‐usable glass column packed with SiO2. With this method, it was possible to synthesize and purify several statistical porphyrin mixtures, while simultaneously reducing the environmental factor (E‐factor) significantly, compared to conventionally performed porphyrin syntheses. Our approach shows that a sustainable investigation of academically relevant low‐symmetrical porphyrins can be carried out feasibly, without sacrificing invested time.

Classic highlights in porphyrin and porphyrinoid total synthesis and biosynthesis.

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.

Synthesis, characterization, and cellular investigations of porphyrin- and chlorin-indomethacin conjugates for photodynamic therapy of cancer.

Indomethacin is a potent non-steroidal anti-inflammatory drug (NSAID) with a strong selective inhibitor activity towards cyclooxygenase-2 (COX-2), an enzyme that is highly overexpressed in various tumour cells, being involved in tumourigenesis. Concomitantly, porphyrins have gained much attention as promising photosensitizers (PSs) for the non-invasive photodynamic therapy (PDT) of cancer. Herein, we report the design, and determine the singlet oxygen generation capacity and in vitro cellular toxicity of porphyrin- and chlorin-indomethacin conjugates (P2-Ind and C2-Ind). Both the conjugates were obtained in high yields and were characterized by 1H, 19F and 13C NMR as well as by high resolution mass spectrometry. The singlet oxygen generation properties were assessed by the 1,3-diphenylisobenzofuran singlet oxygen trap method, which showed that C2 and C2-Ind are the best singlet oxygen photosensitizers. In addition, it was found that the presence of indomethacin did not influence the singlet oxygen generation of porphyrin or chlorin. Cytotoxicity studies of the conjugate in human HEp2 cells revealed that the porphyrin- and chlorin-indomethacin conjugates have similar dark cytotoxicities, while chlorin C2 was shown to be the most phototoxic. Despite having lower cellular uptake than C2-Ind after 24 hours, chlorin C2 had a broad localization in HEp2 cells while the chlorin-indomethacin conjugate C2-Ind could be detected in the form of small aggregates. DFT calculations were performed to shed light on the reaction energy involved in the formation of the indomethacin conjugates and to compare the relative stability of selected isomers in solution. Moreover, the calculated energy of their first excited triplet state structures confirmed their use as suitable photosensitizers to generate singlet oxygen for PDT.

Synthesis of (E)-1,2-Bis[4-[di(1H-pyrrol-2-yl)methyl]phenyl]ethene as a New Bis(dipyrromethane) Building Block

Dipyrromethanes are useful intermediates in the synthesis of porphyrins and their analogs. In this paper, we report the synthesis of a new bis(dipyrromethane) {(E)-1,2-bis[4-[di(1H-pyrrol-2- yl)methyl]phenyl]ethene}, from (E)-4,4'-1,2-ethenediylbis(benzaldehyde), showing a long resonance chain with improved UV spectrometric properties. This product has high potential in the synthesis of new bis(porphyrins) or other related compounds.

Efficient Photoinduced Energy Transfer in Porphyrin-Based Nanomaterials

Synthesis, characterization, and ultrafast dynamics of porphyrin- and zinc porphyrin-based nanomaterials are reported. Spherical nanoparticles composed of a group of uniform materials based on orga...

Physiological and molecular responses in halotolerant Dunaliella salina exposed to molybdenum disulfide nanoparticles

Molybdenum disulfide nanoparticles (MoS2 NPs) has emerged as the promising nanomaterial with a wide array of applications in the biomedical, industrial and environmental field. However, the potential effect of MoS2 NPs on marine organisms has yet to be reported. In this study, the effect of MoS2 NPs on the physiological index, subcellular morphology, transcriptomic profiles of the marine microalgae Dunaliella salina was investigated for the first time. exhibited “doping-like” effects on marine microalgae; Growth stimulation was 193.55%, and chlorophyll content increased 1.61-fold upon the addition of 50 μg/L MoS2 NPs. Additionally, exposure to MoS2 NPs significantly increased the protein and carbohydrate content by 2.03- and 1.56-fold, respectively. The antioxidant system was activated as well to eliminate the adverse influence of reactive oxygen species (ROS). Transcriptomic analysis revealed that genes involved in porphyrin synthesis, glycolysis/gluconeogenesis, tricarboxylic acid cycle and DNA replication were upregulated upon MoS2 NPs exposure, which supports the mechanistic role of MoS2 NPs in improving cellular growth and photosynthesis. The “doping-like” effects on marine algae suggest that the low concentration of MoS2 NPs might change the rudimentary ecological composition in the ocean.

Recent advances in the production of high-value products of porphyrin metabolism pathways and their microbial synthesis

<p indent=0mm>Porphyrins are a class of macrocyclic compounds that contain substituents in the porphyrin ring. Some intermediate metabolites of the metabolism pathways of porphyrins, such as 5-aminolevulinic acid, heme, chlorophyll, and vitamin B12, have many important physiological and metabolic functions and are widely used in the field of medicine, agriculture, food, and industry. Microbial fermentation, when compared with chemical synthesis, is an ideal method to produce porphyrins. This paper focuses on the latest research developments in metabolic engineering and synthetic biology for promoting the abiotic synthesis of high value-added chemicals, such as 5-aminolevulinic acid, heme, chlorophyll, and vitamin B12, based on a systematic introduction of the pathway for <italic>in vivo</italic> porphyrin biosynthesis and discusses the challenges and possible solutions for further high-efficiency biological porphyrin synthesis.