22112-84-1Relevant articles and documents
Specific modification and self-transport of porphyrins and their multi-mechanism cooperative antitumor studies
Jia, Shuxin,Wang, Shaochen,Li, Shanshan,Hu, Peng,Yu, Shuling,Shi, Jiahua,Yuan, Jintao
, p. 3180 - 3191 (2021)
In order to reduce the toxicity and side effects of anti-tumor drugs and improve their therapeutic effect against cancer, photodynamic and chemical combination therapy has been exploited. However, the complicated preparation and metabolic toxicity of photosensitizer-loaded materials remain major obstacles for bioapplications. In this study, we designed and prepared a specific photosensitizer self-transporting drug-delivery system. First, 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphine (TAPP) was modified using specific molecules ofd-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) with a certain antitumor effect, to prepare a specific fluorescent amphiphilic system (TAPP-TPGS). Then, the drug-loaded fluorescence nanomicelle (TAPP-TPGS/PTX) was formedviaself-assembly using the amphiphilic system and the anticancer drug paclitaxel (PTX). The carrier material could be used as a drug tracer and cancer therapy reagent to synergistically trace the chemotherapy drug and treat cancers. The biocompatibility and the enhanced antitumor effect of TAPP-TPGS/PTX were confirmed byin vitroandin vivoexperiments. To detect the synergistic anticancer effect enhanced by TPGS, TAPP-mPEG synthesized with a similar method as TAPP-TPGS was used for a comparative analysis. The results showed that the excellent synergistic anticancer effect of the TAPP-TPGS/PTX was enhanced due to the introduction of TPGS. Thus, the specific porphyrin self-transporting nanomicelle is a very promising carrier material for applications in biomedicine.
High-yielding syntheses of hydrophilic conjugatable chlorins and bacteriochlorins
McCarthy, Jason R.,Bhaumik, Jayeeta,Merbouh, Nabyl,Weissleder, Ralph
, p. 3430 - 3436 (2009)
Next-generation photodynamic therapy agents based upon the conjugation of multiple photosensitizers to a targeting backbone will allow for more efficacious light-based therapies. To this end, we have developed glucose-modified chlorins and bacteriochlorins featuring a reactive carboxylic acid linker for conjugation to targeting moieties. The photosensitizers were synthesized in relatively high yields from meso-tetra(p-aminophenyl)porphyrin, and resulted in neutral, hydrophilic chromophores with superb absorption profiles in the far-red and near-infrared portions of the electromagnetic spectrum. In addition, conjugation of these photosensitizers to a model nanoscaffold (crosslinked dextran-coated nanoparticles) demonstrated that the inclusion of hydrophilic sugar moieties increased the number of dyes that can be loaded while maintaining suspension stability. The described compounds are expected to be particularly useful in the synthesis of a number of targeted nanotherapeutic systems.
Relative reactivities of activated carboxylic acids in amide-forming reactions employed for the synthesis of tetraphenylporphyrin libraries
Dombi, Kendra L.,Richert, Clemens
, p. 1265 - 1280 (2000)
Presented here is a method for rapidly testing the reactivity of carboxylic acids in amide-forming reactions. For this, a mixture of two acids, one a reference compound, and one acid whose reactivity is unknown, are coupled to an aminoacylated tetrakis(p-aminophenyl)porphyrin under typical peptide coupling conditions. The product distribution in the resulting library is analyzed via MALDI-TOF mass spectrometry to reveal the relative reactivity. This rapid reactivity test requires sub-nanomole quantities of acids, does not involve cleavage from a support or any potentially biasing work-up, and is automatable. Thus, it is well suited for testing building blocks for combinatorial syntheses. Further, it is demonstrated that step-wise coupling can produce near-statistically distributed libraries of porphyrins when acids of very different reactivity are employed.
Amino-metalloporphyrin polymers derived Fe single atom catalysts for highly efficient oxygen reduction reaction
Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Meng, Yuying,Sun, Qingdi,Xiao, Huajian,Zhang, Hao,Zhang, Ying
, p. 810 - 817 (2020)
Recently, nitrogen-doped porous carbon supported single atom catalysts (SACs) have become one of the most promising alternatives to precious metal catalysts in oxygen reduction reaction (ORR) due to their outstanding performance, especially those derived from porphyrin-based materials. However, most of them involve other metal residuals, which would cause the tedious pre- and/or post-treatment, even mislead the mechanistic investigations and active-site identification. Herein, we report a precursor-dilution strategy to synthesize Fe SACs through the Schiff-based reaction via co-polycondensation of amino-metalloporphyrin, followed by pyrolysis at high temperature. Systematic characterization results provide the compelling evidence of the dominant presence of atomically dispersed Fe-Nx species. Our catalyst shows superior ORR performance with positive half-wave potential (E1/2=0.85 V vs. RHE) in alkaline condition and moderate activity (E1/2=0.68 V vs. RHE) under the acidic condition, excellent methanol tolerance and good long-term stability. All the results indicate Fe SACs would be a promising candidate for replacing the precious Pt in metal-air batteries and fuel cells.
In situ bottom-up synthesis of porphyrin-based covalent organic frameworks
Tavakol, Elham,Kakekhani, Arvin,Kavani, Shayan,Tan, Peng,Ghaleni, Mahdi Mohammadi,Zaeem, Mohsen Asle,Rappe, Andrew M.,Nejati, Siamak
, p. 19560 - 19564 (2019)
Synthesis and processing of two-or three-dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electrochemical deposition of poly(5,10,15,20-tetrakis(4-aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. By adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py-POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.
Three-dimensional porphyrin-based covalent organic frameworks with tetrahedral building blocks for single-site catalysis
Liu, Yong,Yan, Xiaodong,Li, Tao,Zhang, Wen-Da,Fu, Qiu-Ting,Lu, Hui-Shu,Wang, Xuan,Gu, Zhi-Guo
, p. 16907 - 16914 (2019)
Two three-dimensional (3D) porphyrin covalent organic frameworks, PCOF-1 and PCOF-2, were synthesized via imine condensation of a planar porphyrin tetramine (TAPP or TABPP) and a rigid tetrahedral aldehyde based on the steric hindrance of 3,3′,5,5′-tetrakis(4-formylphenyl)bimesityl (TFBM). The structures of PCOF-1 and PCOF-2 were studied by FT-IR and 13C CP-MAS solid state NMR spectroscopy. Powder X-ray diffraction patterns revealed obvious crystallinity with two intense peaks at 3.28° and 3.75° for PCOF-1, and 2.63° and 2.98° for PCOF-2. Structural simulation confirmed their 3D rutile type (pts) topological structures with two different pore sizes. X-ray single crystal diffraction revealed a distorted tetrahedral structure for the building block TFBM with two dihedral angles of 119° and 107.8°, and a planar square structure for the model compound (MC) with an outspread angle of 176.5°. PCOF-1 and PCOF-2 exhibited Brunauer-Emmett-Teller (BET) surface areas of 316 and 234 m2 g-1, respectively. The morphologies of PCOF-1 and PCOF-2 were investigated by scanning electron microscopy and transmission electron microscopy methods. PCOF-1 and PCOF-2 showed a high thermal stability up to 420 °C without decomposition through thermogravimetric analysis (TGA), and high chemical stability with no obvious mass loss after three days of immersion in various solutions. Due to the large surface area and the appropriate pore size, PCOF-Fe exhibited excellent biocatalytic catalytic performance, while PCOF-Co exhibited good electrocatalytic activity towards oxygen evolution reactions. These results indicate that 3D porphyrin-based COFs constructed from the tetrahedral building block with steric hindrance are promising candidates for single-site catalysis.
Metalloporphyrin-based porous organic polymer as an efficient catalyst for cycloaddition of epoxides and CO2
Guo, Ding,Li, Cheng,Liu, Genyan,Luo, Xiaogang,Wu, Fengshou,Zhang, Juan
, (2021)
The chemical fixation of carbon dioxide to afford value added chemicals under solvent free and ambient conditions has gained considerable attentions. In this work, we successfully synthesized the porphyrin-based porous organic framework (PPOPs) through Schiff base reaction using 5,10,15,20-tetra(4-aminbiphenyl) porphyrin (TAPP) and 4,4′-biphenyldicarbaldehyde (BDA) as starting materials, which was then coordinated with cobalt to yield related metal complex (Co-PPOPs). The chemical structure and morphology of Co-PPOPs were characterized by absorption spectrum, FT-IR, X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and nitrogen physisorption. Co-PPOPs showed excellent catalytic activity towards the conversion of carbon dioxide to cyclic carbonates under ambient conditions. Furthermore, Co-PPOPs was recovered easily and could be used repeatedly (more than five times) without losing any catalytic activity. Thus, the as-prepared Co-PPOPs was a promising heterogeneous catalyst for carbon dioxide conversion, providing high turnover number than the previously reported catalysts.
Two self-assemblies of Schiff base porphyrins to modify titanium dioxide electrodes for supramolecular solar cells
Wu, Yu,Liu, Jia-Cheng,Cao, Jing,Li, Ren-Zhi,Jin, Neng-Zhi
, p. 6833 - 6842 (2015)
Abstract In this work, two Schiff base porphyrins have been successfully synthesized. The metal-ligand axial coordination assembling strategy has been used to organize two assemblies based on the two porphyrins appended isonicotinic acid ligands. Further, the assemblies were absorbed on the semiconducting TiO2 electrode surfaces by the carboxylic groups of isonicotinic acid ligands, and their photovoltaic performances were performed under irradiance of 100 mW cm-2 AM 1.5G sunlight. Photoelectrochemical studies show a significantly enhanced photovoltaic behavior for phenol-based zinc porphyrin assembly compared to pyridine-based zinc porphyrin assembly. The UV-Vis absorption, fluorescence spectra, molecular orbital patterns, and HOMO-LUMO energy gaps of the assemblies were also performed to further understand their photovoltaic features. In addition, the assembled modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by transmission electron microscopy.
A novel one-dimensional porphyrin-based covalent organic framework
Zhang, Miao,Zheng, Ruijin,Ma, Ying,Chen, Ruiping,Sun, Xun,Sun, Xuan
, (2019)
A novel one-dimensional covalent organic framework (COF-K) was firstly designed and synthesized through a Schiff-based reaction from a porphyrin building block and a nonlinear right-angle building block. The COF-K exhibited high BET surface area and narrow pore size of 1.25 nm and gave a CO2 adsorption capacity of 89 mg g?1 at 273K and 1bar.
Gigantic Porphyrinic Cages
Baik, Mu-Hyun,Cho, Dasol,Dhamija, Avinash,Hwang, In-Chul,Hwang, Wooseup,Kim, Ikjin,Kim, Kimoon,Kim, Seungha,Kim, Younghoon,Ko, Young Ho,Koo, Jaehyoung,Lee, Hochan,Mukhopadhyay, Rahul Dev,Song, Hayoung
, p. 3374 - 3384 (2020)
Due to the existing challenges in the synthesis of covalently linked large organic cages, the potential benefits of such gigantic structures have been less explored, comparatively. Here, we present a one-pot, template-free strategy to construct a porphyrin-based gigantic organic cage P12L24, built with 12 square-shaped porphyrins (P) and 24 bent linkers (L). Single crystal X-ray analysis of P12L24 revealed a cuboctahedron structure with a diameter of ～5.3 nm reminiscent of the COPII protein with a cuboctahedral geometry. To the best of our knowledge, it represents the largest, pure organic synthetic cage reported so far. By virtue of its large voids facilitating mass transport of substrates, 3a efficiently catalyzes the photooxidation of dihydroxynaphthalene derivatives in a heterogeneous setting, corroborating the benefits of these structures. Additionally, we demonstrate the insertion of a linear guest molecule into Zn-metallated cage Zn-3b in solution, which may facilitate the synthesis of multivariate gigantic cages in the future. A bottom-up self-assembly process has been a promising tool to mimic structurally complex natural architectures, e.g., the bacteriochlorophyll-based macrocyclic arrays in natural light-harvesting systems and gigantic hollow assemblies, such as ferritin, COPII cage, and other viral capsids. Nevertheless, there is still a long way to go before we can astutely program multiple building blocks to form predesigned structures. In this context, the reported examples related to atomically precise multiporphyrinic arrays and cages are limited by their tedious synthesis, poor yield and solubility, atomic-scale characterization, and small-sized cavities. Here, we report a strategy to synthesize gigantic porphyrinic cages (～5.3 nm) with 36 components and demonstrate its potential applications in processes such as heterogeneous photocatalysis and guest encapsulation. Our strategy may establish a cornerstone toward the construction of higher level, covalently bonded multiporphyrinic molecular containers. Porphyrin-based 3D molecular architectures encompassing a confined internal void have comparatively been less explored, despite their potential benefits. Here, we report a rational one-pot, template-free strategy for constructing a 5.3 nm porphyrin-based gigantic organic cage P12L24, which is reminiscent of the structure of COPII protein cuboctahedral cages. To the best of our knowledge, this is the largest purely organic cage reported so far. P12L24 efficiently catalyzes the photooxidation of dihydroxynaphthalene derivatives, thereby confirming the benefit of these gigantic structures with mesoscopic channels. Furthermore, we demonstrate the insertion of a long pillar linker (～4 nm in length) into Zn-P12L24 in solution. We believe that our strategy may establish a new direction toward the construction of higher level, covalently bonded multiporphyrinic cages.
Synthesis and spectroscopic characterization of meso-tetra (Schiff-base substituted phenyl) porphyrins and their zinc complexes
Wu, Ya-Hong,Chen, Lin,Yu, Jian,Tong, Shan-Ling,Yan, Yan
, p. 423 - 428 (2013)
In this work, a series of novel meso-tetra (Schiff-base substituted phenyl) porphyrins are reported from condensation of meso-tetra (p-aminopheny1) porphyrin with different substituted benzaldehydes. Their related zinc (II) complexes are also synthesized. These compounds have been characterized by spectroscopic determinations. Experimental results indicate that for the precursors, including meso-tetra (p-nitrophenyl) porphyrin and meso-tetra (p-aminophenyl) porphyrin, their substituted phenyls contribute obviously electronic effects on π-electron transition; while for meso-tetra (Schiff-base substituted phenyl) porphyrins, the secondary substituents in Schiff base groups provide weakly electronic effects on π-electron systems. These weak electronic effects are also observed in the electronic spectra of their zinc complexes. In fact the really electronic effect of secondary substituents should be considered as the contribution form the whole substituted phenyls in molecules of meso-tetra (Schiff-base substituted phenyl) porphyrin derivatives.
Novel nanostructured smart, photodynamic hydrogels based on poly(N-isopropylacrylamide) bearing porphyrin units in their crosslink chains: A potential sensitizer system in cancer therapy
Belali, Simin,Karimi, Ali Reza,Hadizadeh, Mahnaz
, p. 93 - 105 (2017)
Novel nanostructure, pH-thermo dual responsive photodynamic hydrogels based on poly(N-isopropylacrylamide) were successfully synthesized by in situ dispersion polymerization of NIPAAm with 5,10, 15, 20-tetrakis(4-N-carbonylacrylic aminophenyl)porphyrin (2% and 4% w/w) in the presence of methylene-bis-acrylamide (MBA) in water. 5, 10, 15, 20-tetrakis (4-N-carbonylacrylic aminophenyl)porphyrin (CAA-TPP) was designed and synthesized for the first time via reaction of tetrakis(4-aminophenyl)porphyrin (NH2-TPP) with maleic anhydrid and was applied as a crosslinker. The structure of the 5, 10, 15, 20-tetrakis(4-N-carbonylacrylic aminophenyl) porphyrin and hydrogels was thoroughly studied by a variety of techniques such as NMR, FT-IR and UV–visible spectrophotometer. The surface morphology of freeze-dried hydrogels using SEM showed one-dimensional nanostructured with uniform morphology of self-assembled interconnected nanofibers. Rheological measurement results were showed that the incorporation of porphyrin onto polymer structure can provide hydrogels without the loss of thermoresponsive viscoelastic properties. The lower critical solution temperatures (LCST) of P[NIPAAm-co-CAA-TPP] hydrogels in water were measured by the cloud point (CP) method. The LCST of P[NIPAAm-co-CAA-TPP (2%)] and P[NIPAAm-co-CAA-TPP (4%)] were at about 40 °C and 43 °C, respectively. The results showed that an increase in porphyrin content makes the LCSTs of the hydrogels increase. Swelling measurements of hydrogels indicated sensitivity to temperature and pH, suggesting that the P[NIPAAm-co-CAA-TPP]s were temperature/pH dual stimulus-responsive hydrogels. In this work, the efficiency of P[NIPAAm-co-CAA-TPP (2%)] and P[NIPAAm-co-CAA-TPP (4%)] as photodynamic therapy (PDT) systems were investigated. The production of reactive singlet oxygen, cytotoxity and phototoxicity of them were assessed. The study showed that the singlet oxygen production ability of P[NIPAAm-co-CAA-TPP (2%)] can be well controlled by irradiation time compared with free porphyrin. We tested these two hydrogels on A453 cells to compare their effectiveness. P[NIPAAm-co-CAA-TPP (2%)] and P[NIPAAm-co-CAA-TPP (4%)] exhibited cell viability over 97% and good photocytotoxity, indicating they are promising photodynamic systems for cancer therapy.
Aggregation of two carboxylic derivatives of porphyrin and their affinity to bovine serum albumin
Yin, Yao-Bing,Wang, Yi-Nong,Ma, Jian-Biao
, p. 1032 - 1038 (2006)
Aggregation of two porphyrin derivatives with carboxylic groups, 4-oxo-4-((4-(10,15,20-triphenyl-21H,23H-porphin-5-yl)phenyl)amino)butanoic acid (MAC) and 4,4′,4″,4?-[21H,23H-porphine-5,10,15,20-tetrayltetrakis(4,1-phenyleneimino)]tetrakis(4-oxo-butanoic acid) (TA4C), and their affinity to bovine serum albumin were investigated via absorption spectrometry, 1H NMR and fluorescence spectrometry. MAC and its complexes with β-cyclodextrin could form aggregates in an aqueous solution while TA4C was self-associated loosely. From the absorbance profiles of MAC in the titration of bovine serum albumin, hypochromicity was observed without any shift of the maximum absorbance wavelength. In both absorption spectra of TA4C in aqueous solutions and in solid state, three Q bands appeared in the visible region. In the measurements of absorption and fluorescence spectra upon titration of BSA, some spectral changes of TA4C were observed. The whole procedure of titration could be divided into three successive stages. The three-banded profiles of TA4C might be explained according to a loose dimer model.
La(OTf)3-catalyzed one-pot synthesis of meso-substituted porphyrinic thiazolidinones
Bhatt, Ranjan K.,Sharma, Satyasheel,Nath, Mahendra
, p. 309 - 316 (2012)
An improved synthetic procedure is developed for the regioselective nitration of a phenyl group of meso-tetraphenylporphyrin by using NaNO 2 in a mixture of trichloroacetic acid and AcOH. The meso-(4-nitro-phenyl)porphyrins are successfully reduced to corresponding meso-(4-aminophenyl)porphyrins by SnCl2 under acidic conditions. In addition, an efficient one-pot methodology for synthesizing a series of novel meso-substituted porphyrinic thiazolidinone conjugates is developed by reacting meso-(4-aminophenyl)porphyrins with various aromatic aldehydes and mercaptoacetic acid in refluxing toluene using La(OTf)3 as a catalyst. The products obtained are characterized on the basis of their spectral data. Preliminary photophysical properties of the newly synthesized compounds are reported.
Electrochemical doping and semiconductor properties of poly-5,10,15,20-tetrakis(p -aminophenyl)porphyrin films
Tesakova, Mariya V.,Parfenyuk, Vladimir I.
, p. 254 - 261 (2021/03/26)
Poly-5,10,15,20-tetrakis(p-aminophenyl)porphyrin films were obtained by interfacial polymerization and electropolymerization. According to the results of electron spectroscopy and IR spectroscopy it has been determined that oxidative polymerization of 5,10,15,20-tetrakis(p-aminophenyl)porphyrin, regardless of its type (chemical/electrochemical), proceeds through the formation of phenazine and dihydrophenazine fragments. It has been established that the film obtained by the electrochemical method is in the oxidized state, the supporting electrolyte anions are included in the film. The polyporphyrin films obtained by interfacial polymerization are non-conductive. As a result of doping the films obtained by the chemical method, due to the oxidation in the anodic potential region, the polymer acquires p-type semiconductor properties. It has been shown that electrochemical doping of poly-5,10,15,20-tetrakis(p-aminophenyl)porphyrin films can make them electroconductive. The obtained films can be recommended as elements of photovoltaic devices, the operation of which is based on the excitation of excitons under the action of light radiation, the redistribution of which leads to a change in the potential of the working electrode.
Synthesis method of tetra (4-aminophenyl) porphyrin metal complex
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Paragraph 0081-0083, (2021/06/13)
The invention discloses a synthesis method of a tetra (4-aminophenyl) porphyrin metal complex. The method comprises the following steps: 1) taking organic acid as a solvent and pyrrole and 4-halogen benzaldehyde as substrates, and carrying out condensation reaction to obtain a (4-halogen phenyl) porphyrin solid; 2) dissolving the (4-halogen phenyl) porphyrin solid in an organic solvent, adding a metal salt, and reacting to obtain a (4-halogen phenyl) porphyrin metal complex; and 3) taking the (4-halophenyl) porphyrin metal complex and ammonia water as substrates, and carrying out carbon-nitrogen coupling reaction in the presence of a catalyst and an organic solvent to obtain the tetra (4-aminophenyl) porphyrin metal complex. The method is mild in reaction condition, low in toxicity, green and environment-friendly.
