- Specific modification and self-transport of porphyrins and their multi-mechanism cooperative antitumor studies
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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.
- Jia, Shuxin,Wang, Shaochen,Li, Shanshan,Hu, Peng,Yu, Shuling,Shi, Jiahua,Yuan, Jintao
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- Further insight into aryl nitration of tetraphenylporphyrin
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We report an in-depth study on meso-aryl nitration of tetraphenylporphyrin. In contrast to previous studies, new evidence reveals that tetrakis(p- nitrophenyl) derivative can be obtained as a major product. Successful isolation of the barely soluble product toward a remarkable yield of nearly 90% has been reached by means of a solid phase extraction technique. Distribution of different nitro-porphyrin components is reassessed with respect to varying acid content in the reactions. An ortho-effect model is proposed to describe the formation mechanism.
- Xue, Zhi,Lee, Priscilla P.S.,Wang, Yanming,Kwong, Daniel W.J.,Li, Jing,Xin, John H.,Wong, Wai-Kwok,Cheuk, Kevin K.L.
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- High-yielding syntheses of hydrophilic conjugatable chlorins and bacteriochlorins
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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.
- McCarthy, Jason R.,Bhaumik, Jayeeta,Merbouh, Nabyl,Weissleder, Ralph
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- Synthesis and properties of 5,10,15,20-tetrakis[4-(3,5-dioctyloxybenzamido) phenyl]porphyrin and its metal complexes
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A novel 5,10,15,20-tetrakis[4-(3,5-dioctyloxybenzamido)phenyl]-porphyrin and its transition metal complexes are reported in this paper. Their molecular structures were characterized by elemental analysis as well as IR, 1H-NMR and UV-Vis spectroscopy. Their spectroscopic properties were studied by Raman and fluorescence spectroscopy, and X-ray photoelectron spectroscopy (XPS). The fluorescence quantum yields were measured at room temperature. The fluorescence intensity of the porphyrin ligand was stronger than the intensity of the complexes. There were large differences in the Raman spectrum of the porphyrin ligand and those of the metal complexes due to changes in the symmetry of porphyrin plane. In the XPS spectra, the replacement of the free-base protons by a metal ion to form the metalloporphyrin not only increases the symmetry of the molecule, but also introduces an electron withdrawing group into the center of the porphyrin ligand, which increases the N1S binding energy.
- Lian, Wenhui,Sun, Yuanyuan,Wang, Binbin,Shan, Ning,Shi, Tongshun
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- Relative reactivities of activated carboxylic acids in amide-forming reactions employed for the synthesis of tetraphenylporphyrin libraries
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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.
- Dombi, Kendra L.,Richert, Clemens
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- SYNTHESIS OF TETRAPHENYLPORPHINS WITH ACTIVE GROUPS IN THE PHENYL RINGS. 1. PREPARATION OF TETRAKIS(4-AMINOPHENYL)PORPHIN
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Condensation of p-nitrobenzaldehyde with pyrrole in propionic acid with added acetic anhydride gave tetrakis(4-nitrophenyl)porphin (24percent), by the reduction of which tetrakis(4-aminophenyl)porphin, which was also obtained by hydrolysis of tetrakis(4-acetamidophenyl)porphin, was synthesized.
- Semeikin, A. S.,Koifman, O. I.,Berezin, B. D.
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- Amino-metalloporphyrin polymers derived Fe single atom catalysts for highly efficient oxygen reduction reaction
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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.
- Gan, Tao,He, Qian,He, Xiaohui,Ji, Hongbing,Meng, Yuying,Sun, Qingdi,Xiao, Huajian,Zhang, Hao,Zhang, Ying
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- Novel graphene capsule-aminoporphyrin nanohybrids: Preparation and application in photodynamic therapy of cancer
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In this work, we firstly prepared new sealed graphene capsules (GCs) that were about 300 nm in size and had different morphologies using a simple reduction method. The quality of the graphene oxide (GO) sheets and the concentration of hydrazine hydrate are proposed to be influencing factors for the formation of sealed graphene capsules. GCs are covalently functionalized with 5,10,15,20-tetra-(4-aminophenyl)porphyrin, forming dispersible GC-aminoporphyrins in aqueous solution. The observed fluorescence quenching of the GCs by the aminoporphyrin indicated that the GCs are electron donors and electron transfer occurs from the GCs to the aminoporphyrin. This F?rster Resonance Energy Transfer (FRET) between the GCs and aminoporphyrins is probably the reason for the enhancement of 1O2 generation of the GC-aminoporphyrins. More importantly, the as-prepared GC-aminoporphyrin nanohybrids as novel photosensitizers (PSs) with a short excitation wavelength can be used as PDT reagents for the treatment of malignant melanoma A375 with high efficiency. We expect that GC-aminoporphyrins will be promising PSs in future cancer therapy.
- Liu, Guoli,Lv, Hongying,Zhao, Jing,Zhang, Shen,Sun, Shuqing
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- In situ bottom-up synthesis of porphyrin-based covalent organic frameworks
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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.
- Tavakol, Elham,Kakekhani, Arvin,Kavani, Shayan,Tan, Peng,Ghaleni, Mahdi Mohammadi,Zaeem, Mohsen Asle,Rappe, Andrew M.,Nejati, Siamak
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- Synthesis of novel porphyrin derivatives and their self-assemblies to enhance photocatalytic performance
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Three new porphyrin derivatives were synthesized from tetra (4-aminophenyl) porphyrin (TAPP), namely tetra[p-(4-cyanophenylmethylene imino)]phenyl porphyrin (TCyPPP), tetra[p-(P-benzylidene)]phenyl porphyrin (TbePPP) and tetra[p-(4-pyridylimethylene imino)]phenyl porphyrin (TPyPPP). Based on the principle of self-assembly, three kinds of porphyrin derivatives were self-assembled to prepare three kinds of monomers. The structures were characterized clearly by UV-vis, FT-IR, 1H NMR and SEM. The photocatalytic performance study shows that the self-assemblies of the three porphyrin derivatives have stronger photocatalytic performance than their monomers. Moreover, the self-assemblies and their monomers have good photocatalytic stability. This journal is
- Pei, Jinghe,Gao, Bo,Li, Yanhui,Duan, Qian
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- Three-dimensional porphyrin-based covalent organic frameworks with tetrahedral building blocks for single-site catalysis
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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.
- Liu, Yong,Yan, Xiaodong,Li, Tao,Zhang, Wen-Da,Fu, Qiu-Ting,Lu, Hui-Shu,Wang, Xuan,Gu, Zhi-Guo
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- Highly sensitive INHIBIT and XOR logic gates based on ICT and ACQ emission switching of a porphyrin derivative
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Fluorescence-switch-based logic devices are very sensitive compared with most of the reported devices based on UV/Vis absorption systems. Herein, we demonstrate that a simple molecule, 5,10,15,20-tetra-(4-amino-phenyl) porphyrin (TAPP), shows protonation-induced multiple emission switches through intramolecular charge transfer and/or aggregation-caused quenching. Highly sensitive INHIBIT and XOR logic gates can be achieved by combining the intermolecular assembly with the intramolecular photoswitching of diprotonated TAPP (TAPPH22+). In addition, molecular simulations have been performed by DFT for a better understanding of the emission-switching processes.
- Xu, Xiao-Ling,Lin, Fu-Wen,Xu, Wei,Wu, Jian,Xu, Zhi-Kang
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- Metalloporphyrin-based porous organic polymer as an efficient catalyst for cycloaddition of epoxides and CO2
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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.
- Guo, Ding,Li, Cheng,Liu, Genyan,Luo, Xiaogang,Wu, Fengshou,Zhang, Juan
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- Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction
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Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction (OER) is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin (Co-1-P) on carbon cloth (CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 mV. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.
- Zhang, Qingxin,Wang, Yabo,Wang, Yanzhi,Yang, Shujiao,Wu, Xuan,Lv, Bin,Wang, Ni,Gao, Yimei,Xu, Xiaoran,Lei, Haitao,Cao, Rui
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- Two self-assemblies of Schiff base porphyrins to modify titanium dioxide electrodes for supramolecular solar cells
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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.
- Wu, Yu,Liu, Jia-Cheng,Cao, Jing,Li, Ren-Zhi,Jin, Neng-Zhi
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- Porphyrin-vancomycin: A highly promising conjugate for the identification and photodynamic inactivation of antibiotic resistant Gram-positive pathogens
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The emergence of drug-resistant pathogens is a global public health problem. With the increasing antibiotic resistance of bacteria, there is an obvious need for the development for alternative therapeutics and materials that can effectively control this situation. In this work, a new conjugate, 5,10,15,20-tetrakis (para-aminophenyl) porphyrin-vancomycin was successfully explored for the identification and photoinactivation of antibiotic resistant Gram-positive pathogens. The minimum inhibitory concentration assay and photodynamic inactivation evaluation results revealed that the conjugate can effective inhibit the growth of 6 tested pathogenic strains under white light. The interaction intensity of the conjugate with Gram-positive and Gram-negative bacterial cells was evaluated by surface plasmon resonance, and the results showed that its activity toward Staphylococcus aureus was 14-fold larger than its activity toward Escherichia coli at 20 mM, indicating the conjugate selectively gathers in Gram-positive cells.
- Zhai, Le,Yang, Ke-Wu
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- A novel one-dimensional porphyrin-based covalent organic framework
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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.
- Zhang, Miao,Zheng, Ruijin,Ma, Ying,Chen, Ruiping,Sun, Xun,Sun, Xuan
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- Micellar cobaltporphyrin nanorods in alcohols
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Cobalt(II) meso-tetrakis(4-hexadecylamidophenyl)porphyrin self-assembles in ethanol/1-propanol 2/1 (v/v) to form a rodlike micelle with nanoscale dimensions; the nanorod is a face-to-face aggregate having a hydrophobic corona around a polar core and is thus characterized as a reverse micelle. Copyright
- Yuasa, Makoto,Oyaizu, Kenichi,Yamaguchi, Aritomo,Kuwakado, Michi
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- Gigantic Porphyrinic Cages
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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.
- 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
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- Effect of functional groups on sensitization of dye-sensitized solar cells (DSSCs) using free base porphyrins
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Dye-sensitized solar cells (DSSCs) were fabricated with six meso-substituted A3B and A4 free base porphyrin dyes having different functional groups, as sensitizers. The two step synthesis and the effect of different functional groups and their positions on the photosensitization properties of these porphyrin dyes are reported. The highest power conversion efficiencies (η) of 3.26%, 2.94% and 2.84% were achieved for the DSSC fabricated using 5,10,15-tris(4′-pyridyl)-20-(4′-carboxyphenyl)porphyrin (H2TriPyMCPP), 5,10,15,20-tetrakis(4′-aminophenyl)porphyrin (H2TAPP) and 5-(4′-pyridyl)-10,15,20-tris(4′-carboxyphenyl)porphyrin (H2MPyTriCPP) dyes, respectively. The electron donating amino group is shown to enhance the power conversion efficiency while pyridyl appended porphyrin sensitizers are shown to be superior sensitizers as compared to carboxyphenylporphyrins. The investigation of effect of functional group and position of functional group of porphyrin dye on DSSC can serve as an important tool to guide further selection and synthesis of potential candidates as sensitizers.
- Chaudhri, Nivedita,Sawhney, Nipun,Madhusudhan, Bijjam,Raghav, Anubhav,Sankar, Muniappan,Satapathi, Soumitra
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- Synthesis and spectroscopic characterization of meso-tetra (Schiff-base substituted phenyl) porphyrins and their zinc complexes
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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.
- Wu, Ya-Hong,Chen, Lin,Yu, Jian,Tong, Shan-Ling,Yan, Yan
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- Study of factors influencing the fabrication of Co-porphyrin porous coordination polymer via metal–organic gel intermediate
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In this work, 5, 10, 15, 20-Tetra-(4-aminophenyl) porphyrin (TAPP) was used as gelator to prepare metal-porphyrin porous coordination polymer (PCP) via solvothermal process, Soxhlet extraction and supercritical CO2 extraction. Firstly, the metal-porphyrin organic gel (MOG) was prepared as intermediate with solvothermal method. The generation of gels is associated with many factors. When four acetates [Co(Ac)2?4H2O, Zn(Ac)2?2H2O, Mn(Ac)2?4H2O and Ni(Ac)2?7H2O] reacted with TAPP, only the reaction between Co(Ac)2?4H2O and TAPP could form desired metal-porphyrin organic gel. The influences of solvent, concentration and anions were investigated in the gelation process. Secondly, the residual reactants and solvent molecules in MOG were removed through Soxhlet extraction and supercritical CO2 extraction. The Co-PCP is an amorphous material with a hierarchical porous structure can effectively catalyze the oxidation of ethylbenzene and also exhibits a strong adsorptive capacity for the strong-polar solvent molecules.
- Li, Jun,Zhao, Jiale,Cheng, Minglun,Yi, Jiajia,Yuan, Lin,Wang, Ning,Li, Jun
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- Novel nanostructured smart, photodynamic hydrogels based on poly(N-isopropylacrylamide) bearing porphyrin units in their crosslink chains: A potential sensitizer system in cancer therapy
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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.
- Belali, Simin,Karimi, Ali Reza,Hadizadeh, Mahnaz
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- Novel porphyrin-Schiff base conjugates: Synthesis, characterization and: In vitro photodynamic activities
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Three novel porphyrin-Schiff base conjugates derived from tetra(4-aminophenyl)porphyrin (TAPP), namely, tetra[4-(4-hydroxy benzylideneamino)]phenyl porphyrin (3a), tetra[4-(2-thienyldeneamino)]phenyl porphyrin (3b) and tetra[4-(2-pyridyldeneamino)]phenyl porphyrin (3c), were synthesized and characterized by IR, UV-vis, 1H NMR, HRMS and elementary analysis. Their biological activities against human epidermoid carcinoma (A431) cells were evaluated with an MTT assay. As we expected, the porphyrin conjugates showed negligible cytotoxicity to A431 cells in the absence of light, while their phototoxic activities were improved after irradiated with LED lamp (425 nm) and increased significantly with increased doses. The fluorescence microscope pictures revealed that the three porphyrin-Schiff conjugates could diffuse into skin cancer cells, demonstrating that these compounds are potential candidates for photodynamic therapy agents.
- Yao, Ya-Hong,Li, Jun,Yuan, Long-Fei,Zhang, Zeng-Qi,Zhang, Feng-Xing
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- Aggregation of two carboxylic derivatives of porphyrin and their affinity to bovine serum albumin
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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.
- Yin, Yao-Bing,Wang, Yi-Nong,Ma, Jian-Biao
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- A G-quadruplex ligand with 10000-fold selectivity over duplex DNA
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A cationic manganese porphyrin binds strongly and selectively to G-quadruplex DNA. This compound is the most selective G4-ligand reported to date. Copyright
- Dixon, Isabelle M.,Lopez, Frederic,Tejera, Agueda M.,Esteve, Jean-Pierre,Blasco, Maria A.,Pratviel, Genevieve,Meunier, Bernard
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- La(OTf)3-catalyzed one-pot synthesis of meso-substituted porphyrinic thiazolidinones
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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.
- Bhatt, Ranjan K.,Sharma, Satyasheel,Nath, Mahendra
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- Porphyrin-containing Polyimide with Enhanced Light Absorption and Photocatalysis Activity
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A series of porphyrin-containing polyimide (PI) photocatalysts were synthesized by a one-step solvothermal method. Characterization results revealed that porphyrin was uniformly coupled into the PI framework through covalent bonding and the visible-light absorption was greatly improved. The photodegradation activity of porphyrin-containing PIs for methyl orange (MO) under visible light was enhanced significantly, with the highest pseudo-first-order rate constant 35 times higher than that of neat porphyrin and 10 times higher than that of porphyrin-free PI. The enhancement is mainly attributed to an increased light harvesting accompanied by a varied HOMO level, which was clarified by control experiments, characterizations and theoretical calculations. This work provides an insight into multiple effects of dye molecules in dye-containing heterogeneous photocatalysts.
- Cui, Zhiwei,Zhou, Jun,Liu, Teng,Wang, Yicong,Hu, Yue,Wang, Ying,Zou, Zhigang
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- Electrochemical doping and semiconductor properties of poly-5,10,15,20-tetrakis(p -aminophenyl)porphyrin films
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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.
- Tesakova, Mariya V.,Parfenyuk, Vladimir I.
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p. 254 - 261
(2021/03/26)
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- Interfacially synthesized 2D COF thin film photocatalyst: efficient photocatalyst for solar formic acid production from CO2and fine chemical synthesis
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The targeted synthesis of an efficient, visible light active, recyclable, freestanding covalent organic framework thin film photocatalyst for multi-faceted photocatalysis is the essence of the proposed work. A simple, scalable, reagent free synthesis of a thin film at the interface of 5,10,15,20-tetra-(4-aminophenyl)porphyrin, 2-vinylbenzene-1,4-dicarbaldehyde in nitrobenzene and aqueous glyoxal affords centimetre sized continuous 2D thin film with substantial stability, flexibility and efficient visible light activity. Strikingly different from the regular imine based COF, the incorporation of the glyoxal unit as a modulator helps in band gap tuning and induces flexibility within the thin film. An interplay between time and concentration helps in achieving a thin film photocatalyst with efficient photocatalytic activity for 1,4-NADH regeneration and selective formic acid formation from CO2. The optimum band edge position of the thin film photocatalyst also enables solar fine chemical synthesisviareductive dehalogenation under visible light illumination with excellent recyclability. The present work gives insight into visible light active thin film formation en route to metal-free sustainable photocatalysis.
- Yadav, Dolly,Kumar, Abhishek,Kim, Jae Young,Park, No-Joong,Baeg, Jin-Ook
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supporting information
p. 9573 - 9580
(2021/04/26)
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- Synthesis method of tetra (4-aminophenyl) porphyrin metal complex
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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.
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Paragraph 0081-0083
(2021/06/13)
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- Controlling Oxygen Reduction Selectivity through Steric Effects: Electrocatalytic Two-Electron and Four-Electron Oxygen Reduction with Cobalt Porphyrin Atropisomers
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Achieving a selective 2 e? or 4 e? oxygen reduction reaction (ORR) is critical but challenging. Herein, we report controlling ORR selectivity of Co porphyrins by tuning only steric effects. We designed Co porphyrin 1 with meso-phenyls each bearing a bulky ortho-amido group. Due to the resulted steric hinderance, 1 has four atropisomers with similar electronic structures but dissimilar steric effects. Isomers αβαβ and αααα catalyze ORR with n=2.10 and 3.75 (n is the electron number transferred per O2), respectively, but ααββ and αααβ show poor selectivity with n=2.89–3.10. Isomer αβαβ catalyzes 2 e? ORR by preventing a bimolecular O2 activation path, while αααα improves 4 e? ORR selectivity by improving O2 binding at its pocket, a feature confirmed by spectroscopy methods, including O K-edge near-edge X-ray absorption fine structure. This work represents an unparalleled example to improve 2 e? and 4 e? ORR by tuning only steric effects without changing molecular and electronic structures.
- Apfel, Ulf-Peter,Cao, Rui,Guo, Kai,Jin, Xiaotong,Lei, Haitao,Li, Xialiang,Long, Ran,Lv, Bin,Ma, Jun,Wang, Fang,Wang, Yanzhi,Xiong, Yujie,Zhang, Qingxin,Zhang, Wei
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supporting information
p. 12742 - 12746
(2021/04/22)
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- Supramolecular Catalysis of Acyl Transfer within Zinc Porphyrin-Based Metal-Organic Cages
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To illustrate the supramolecular catalysis process in molecular containers, two porphyrinatozinc(II)-faced cubic cages with different sizes were synthesized and used to catalyze acyl-transfer reactions between N-acetylimidazole (NAI) and various pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC). A systemic investigation of the supramolecular catalysis occurring within these two hosts was performed, in combination with a host-guest binding study and density functional theory calculations. Compared to the reaction in a bulk solvent, the results that the reaction of 2-PC was found to be highly efficient with high rate enhancements (kcat/kuncat = 283 for Zn-1 and 442 for Zn-2), as well as the different efficiencies of the reactions with various ortho-substituted 2-PC substrates and NAI derivates should be attributed to the cages having preconcentrated and preoriented substrates. The same cage displayed different catalytic activities toward different PC regioisomers, which should be mainly attributed to different binding affinities between the respective reactant and product with the cages. Furthermore, control experiments were carried out to learn the effect of varying reactant concentrations and product inhibition. The results all suggested that, besides the confinement effect caused by the inner microenvironment, substrate transfer, including the encapsulation of the reactant and the release of products, should be considered to be a quite important factor in supramolecular catalysis within a molecular container.
- Li, Lili,Yang, Linlin,Li, Xuezhao,Wang, Jing,Liu, Xin,He, Cheng
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supporting information
p. 8802 - 8810
(2021/06/28)
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- Metalloporphyrin and Ionic Liquid-Functionalized Covalent Organic Frameworks for Catalytic CO2Cycloaddition via Visible-Light-Induced Photothermal Conversion
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We report the construction of a porphyrin and imidazolium-ionic liquid (IL)-decorated and quinoline-linked covalent organic framework (COF, abbreviated as COF-P1-1) via a three-component one-pot Povarov reaction. After post-synthetic metallization of COF-P1-1 with Co(II) ions, the metallized COF-PI-2 is generated. COF-PI-2 is chemically stable and displays highly selective CO2 adsorption and good visible-light-induced photothermal conversion ability (ΔT = 26 °C). Furthermore, the coexistence of Co(II)-porphyrin and imidazolium-IL within COF-PI-2 has guaranteed its highly efficient activity for CO2 cycloaddition. Of note, the needed thermal energy for the reactions is derived from the photothermal conversion of the Co(II)-porphyrin COF upon visible-light irradiation. More importantly, the CO2 cycloaddition herein is a "window ledge"reaction, and it can proceed smoothly upon natural sunlight irradiation. In addition, a scaled-up CO2 cycloaddition can be readily achieved using a COF-PI-2@chitosan aerogel-based fixed-bed model reactor. Our research provides a new avenue for COF-based greenhouse gas disposal in an eco-friendly and energy- and source-saving way.
- Ding, Luo-Gang,Yao, Bing-Jian,Wu, Wen-Xiu,Yu, Zhi-Gao,Wang, Xiao-Yu,Kan, Jing-Lan,Dong, Yu-Bin
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supporting information
p. 12591 - 12601
(2021/08/24)
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- Specific porphyrin self-transport nano carrier material and preparation method thereof
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The invention relates to a preparation method of a specific porphyrin self-transport nano carrier material. The method comprises the following steps of carrying out a mixed reaction on p-nitrobenzaldehyde, acetic anhydride, propionic acid and pyrrole to obtain purple solid tetra(4-nitrophenyl)porphyrin TNPP, and preparing tetra(4-aminophenyl)porphyrin TAPP; stirring TPGS, succinic anhydride, DMAP,triethylamine and 1,4-dioxane at room temperature, and performing dialysis to obtain carboxyl TPGS; and mixing the carboxyl TPGS, DMAP and PyBOP, adding DMF and TAPP, performing stirring at room temperature for 22-26 hours, performing dialysis, and freeze-drying dialysate to obtain the product TAPP-TPGS. The specific molecules TPGS are introduced into the carrier material, so that the carrier hasthe effect of assisting an anti-tumor drug in treating cancers, and the anti-tumor effect is improved through combined treatment of three modes of TPGS, PDT and chemotherapy.
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Paragraph 0015; 0016
(2021/01/04)
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- Encapsulation of Flavin Cofactor within a Manganese Porphyrin-Based Metal-Organic Polyhedron for Reductive Dioxygen Activation
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Encapsulation of flavin mononucleotide (FMN) in a porphyrinatomanganese(III)-based cubic cage allowed the fast reduction of manganese(III) porphyrin in the presence of nicotinamide adenine dinucleotide (NADH). This supramolecular system was capable of efficiently activating dioxygen and catalyzing the oxidation of benzyl alcohol. Control experiments suggested that the close proximity between FMN and manganese(III) porphyrins forced by the host-guest interaction might benefit the electron-transfer process from the FMN cofactor to the metal centers.
- Guo, Huimin,He, Cheng,Li, LiLi,Li, Xuezhao,Wang, Hailing,Yang, Linlin
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supporting information
p. 2636 - 2640
(2020/03/19)
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- Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect
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Several H?H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2. Understanding HER processes, especially controllable switching between homolytic and heterolytic H?H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.
- Apfel, Ulf-Peter,Cao, Rui,Ding, Shuping,Guo, Xiaojun,Li, Jianfeng,Li, Xialiang,Ren, Wanjie,Wang, Ni,Xu, Gelun,Zhang, Wei,Zhang, Zongyao,Zhao, Jianping
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supporting information
p. 8941 - 8946
(2020/04/22)
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- Donor-acceptor covalent organic frameworks of nickel(ii) porphyrin for selective and efficient CO2reduction into CO
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Donor-acceptor two-dimensional covalent organic frameworks, PD-COF-23 and PD-COF-23-Ni, are constructed and applied for selective CO2 reduction with CO conversion rates of 20.9 μmol g-1 h-1 and 40.0 μmol g-1 h-1, respectively, in the absence of any additional photosensitizers and noble metal co-catalysts within an operation time of 25 h. The multilayer nanosheet structure, efficient charge separation and transport, and internal reductive quenching cycle of the NiTAPP fragments of PD-COF-23-Ni result in its higher photocatalytic efficiency than that of PD-COF-23. This journal is
- Diao, Yingxue,Ke, Hanzhong,Qin, Xihao,Xu, Nanfeng,Xu, Zhengtao,Zhu, Xunjin
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supporting information
p. 15587 - 15591
(2020/11/24)
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- Photocatalytic Molecular Oxygen Activation by Regulating Excitonic Effects in Covalent Organic Frameworks
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Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+ in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O2 to 1O2 and O2?-, respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O2?-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in 1O2-mediated selective oxidation of organic sulfides. This work provides in-depth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
- Qian, Yunyang,Li, Dandan,Han, Yulan,Jiang, Hai-Long
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supporting information
p. 20763 - 20771
(2020/12/23)
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- Improved Photoreduction of CO2 with Water by Tuning the Valence Band of Covalent Organic Frameworks
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Porous covalent organic frameworks (COFs), as an emerging material, have the characteristics of high stability, large series of components, easy synthesis, modification, and adjustable amplitude. They have the potential to become good catalysts. Bromine, as a halogen, has attracted intensive interest for the modification of photocatalysts for photocatalytic reactions. It is feasible to enhance the activity and selectivity of the material by facile functionalization of the reticular parent structure′s electron-withdrawing groups. In addition, the conjugation effect of bromine, further delocalizing the electrons of the COF, is beneficial to the progress of many photocatalytic reactions. Reports on the modification of COFs by bromine functional groups to improve the catalytic performance have not been found so far. Here, TAPP [5,10,15,20-tetrakis(4-aminophenyl)porphyrin] and 2,5-dibromo-1,4-benzenedialdehyde instead of terephthalaldehyde were chosen to synthesize a porphyrin-based COF (TAPBB-COF) by the solvothermal method. As expected, the valence band (VB) of TAPBB-COF is thus adjusted to a more suitable position. Additionally, the CO production when using TAPBB-COF under full-wavelength light for 12 h was 295.2 μmol g?1, which was three times that of COF-366, and the new material has good recycling stability and selectivity (95.6 %). Theoretical calculations indicate that the nitrogen of the porphyrin ring and the Schiff base, and the bromine in TAPBB-COF contribute greatly to the activation of H2O and the conversion of CO2 in the photoreaction.
- Wang, Lu-jie,Wang, Rui-lei,Zhang, Xiao,Mu, Jing-lin,Zhou, Zi-yan,Su, Zhong-min
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p. 2973 - 2980
(2020/04/23)
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- Rational Design of Crystalline Covalent Organic Frameworks for Efficient CO2 Photoreduction with H2O
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Solar energy-driven conversion of CO2 into fuels with H2O as a sacrificial agent is a challenging research field in photosynthesis. Herein, a series of crystalline porphyrin-tetrathiafulvalene covalent organic frameworks (COFs) are synthesized and used as photocatalysts for reducing CO2 with H2O, in the absence of additional photosensitizer, sacrificial agents, and noble metal co-catalysts. The effective photogenerated electrons transfer from tetrathiafulvalene to porphyrin by covalent bonding, resulting in the separated electrons and holes, respectively, for CO2 reduction and H2O oxidation. By adjusting the band structures of TTCOFs, TTCOF-Zn achieved the highest photocatalytic CO production of 12.33 μmol with circa 100 % selectivity, along with H2O oxidation to O2. Furthermore, DFT calculations combined with a crystal structure model confirmed the structure–function relationship. Our work provides a new sight for designing more efficient artificial crystalline photocatalysts.
- Lu, Meng,Liu, Jiang,Li, Qiang,Zhang, Mi,Liu, Ming,Wang, Jin-Lan,Yuan, Da-Qiang,Lan, Ya-Qian
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supporting information
p. 12392 - 12397
(2019/08/16)
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- Covalently Copper(II) Porphyrin Cross-Linked Graphene Oxide: Preparation and Catalytic Activity
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Abstract: In this study, copper(II)-coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin (CuPPh) as a macrocyclic copper complex was covalently linked to the surface of graphene oxide (GO–CuPPh). This covalently cross-linked catalyst was characterized with various analysis such as FT-IR, SEM, TEM, EDS, ICP, TGA and UV–Vis. All analysis confirm the successful covalently immobilization of CuPPh on the GO. Then, the activity of catalyst has been tested for the preparation of propargylamine derivatives by the reaction of different aldehydes/ketones various amines and phenylacetylene via A3 and KA2 coupling reactions. The catalytic system indicated great catalytic activity in this reaction and the yields of the products were good to marvelous. The results of this work are hoped to aid the establishment of new class of heterogeneous catalysts as the high performance and low-cost candidates for industrial applications. Graphical Abstract: [Figure not available: see fulltext.].
- Khojastehnezhad, Amir,Bakavoli, Mehdi,Javid, Ali,Khakzad Siuki, Mohammad Mehdi,Moeinpour, Farid
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p. 713 - 722
(2019/02/03)
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- Zirconium (IV) porphyrin graphene oxide: a new and efficient catalyst for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones
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A covalently cross-linked graphene oxide (GO) as a catalyst was prepared by a cross-linking process using the nucleophilic reaction of zirconium (IV)-coordinated 5,10,15,20-tetrakis (aminophenyl)porphyrin (ZrPPh) with carboxyl groups of the edges of GO (GO-ZrPPh). The chemical structure of catalyst was characterized by different analyses such as FT-IR, SEM, TEM, EDS, ICP, TGA and UV. All analyses confirm the occurrence of successfully covalent immobilization of ZrPPh on the GO. Also, TEM and SEM images show that ZrPPh has been immobilized in the both of the edges and the basal plane of GO. The activity of the catalyst was studied for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones via Biginelli reaction. The cross-linked catalyst is able to catalyze the reaction in short reaction times and good to excellent yields.
- Ghadamyari, Zohreh,Shiri, Ali,Khojastehnezhad, Amir,Seyedi, Seyed Mohammad
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- New approach for the synthesis, docking of new porphyrins and their antitumor activity
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A new methodology for the synthesis of a new series of mesotetrakis[aryl]-21H,23H-porphyrin derivatives 5a-5d, 6a-6c, 7 and 8 is presented. Structures of new compounds were established based on both elemental and spectral data. Cytotoxicity activity of the newly synthesized compounds was investigated against two human cell lines MCF-7 and HepG2. Molecular docking was performed to investigate the binding between the most active porphyrin derivatives and Bcl-2 molecular biomarkers in HepG2 cells.
- Tawfik, Eman H.,Fadda, Ahmed A.,Soliman, Nanees N.,Abou-Zeid, Laila,Negm, Amr
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p. 251 - 259
(2019/02/24)
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- A porphyrin porous organic polymer with bicatalytic sites for highly efficient one-pot tandem catalysis
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A novel porphyrin-based porous organic polymer PPOP-1(Pd) with bifunctional catalytic sites was constructed via imine condensation of tetra(4-aminophenyl)porphyrin and acenaphthenequinone. PPOP-1(Pd) containing Pd(ii)-porphyrin and Pd(ii)-α-diimine moieties exhibits excellent catalytic activity and outstanding reusability for tandem catalytic reactions of C-H arylation and Suzuki coupling.
- Dai, Siyuan,Gu, Zhi-Guo,Li, Tao,Li, Yunxing,Liu, Yong,Shen, Rui,Yan, Xiaodong,Zhu, Wei
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supporting information
p. 822 - 825
(2019/01/21)
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- Synthesis, characterization, and investigation of catalytic activity of copper(II) porphyrin graphene oxide for azide–alkyne cycloaddition
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Abstract: A covalently cross-linked graphene oxide (GO) catalyst was prepared by a cross-linking process using nucleophilic reaction of copper(II)‐coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin (CuPPh) with carboxyl groups at the edges of GO (GO–CuPPh). The structure of the catalyst was characterized using different techniques such as Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive x-ray spectroscopy (EDS), thermogravimetric analysis (TGA), and inductively coupled plasma (ICP) spectroscopy. All analyses confirmed successful covalent immobilization of CuPPh on GO. The activity of the catalyst was then studied for synthesis of 1,4-disubstituted 1,2,3-triazoles derivatives by reaction of various aryl azides and different terminal alkynes in mild reaction condition with good to excellent yield. Graphical abstract: [Figure not available: see fulltext.].
- Khojastehnezhad, Amir,Bakavoli, Mehdi,Javid, Ali,Khakzad Siuki, Mohammad Mehdi,Shahidzadeh, Mansour
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p. 4473 - 4485
(2019/05/17)
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- In silico study, synthesis, and cytotoxic activities of porphyrin derivatives
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Five known porphyrins, 5,10,15,20-tetrakis(p-tolyl)porphyrin (TTP), 5,10,15,20-tetrakis(pbromophenyl) porphyrin (TBrPP), 5,10,15,20-tetrakis(p-aminophenyl)porphyrin (TAPP), 5,10,15- tris(tolyl)-20-mono(p-nitrophenyl)porphyrin (TrTMNP), 5,10,15-tris(tolyl)-20-mono(paminophenyl) porphyrin (TrTMAP), and three novel porphyrin derivatives, 5,15-di-[bis(3,4- ethylcarboxymethylenoxy)phenyl]-10,20-di(p-tolyl)porphyrin (DBECPDTP), 5,10-di-[bis(3,4- ethylcarboxymethylenoxy)phenyl]-15,20-di-(methylpyrazole-4-yl)porphyrin (cDBECPDPzP), 5,15-di- [bis(3,4-ethylcarboxymethylenoxy)phenyl]-10,20-di-(methylpyrazole-4-yl)porphyrin (DBECPDPzP), were used to study their interaction with protein targets (in silico study), and were synthesized. Their cytotoxic activities against cancer cell lines were tested using 3-(4,5-dimetiltiazol-2-il)-2,5- difeniltetrazolium bromide (MTT) assay. The interaction of porphyrin derivatives with carbonic anhydrase IX (CAIX) and REV-ERBβ proteins were studied by molecular docking and molecular dynamic simulation. In silico study results reveal that DBECPDPzP and TrTMNP showed the highest binding interaction with REV- ERBβ and CAIX, respectively, and both complexes of DBECPDPzPREV- ERBβ and TrTMNP-CAIX showed good and comparable stability during molecular dynamic simulation. The studied porphyrins have selective growth inhibition activities against tested cancer cells and are categorized as marginally active compounds based on their IC50.
- Kurniawan, Fransiska,Miura, Youhei,Kartasasmita, Rahmana Emran,Mutalib, Abdul,Yoshioka, Naoki,Tjahjono, Daryono Hadi
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- Electrochemical hydrogen evolution by cobalt (II) porphyrins: Effects of ligand modification on catalytic activity, efficiency and overpotential
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Electrochemical H2 evolution of a series of cobalt(II) porphyrins with electron-withdrawing (EW) and electron-donating (ED) substituents at the para positions of the meso-phenyl rings has been investigated in DMSO using acetic acid as a proton source. Our study showed that the nature of substituents significantly influences catalytic activity, efficiency, and the potential at which catalysis occurs. Faradaic efficiencies (FE) ranging from 44 to 99%, turnover numbers (TONs) from 1.5 to 104 (～11 h electrolysis), turnover frequencies (TOFs) from 0.23 to 9.1 h?1, and onset overpotentials from 25 to 445 mV were obtained by tuning the porphyrinic substituents. Cobalt porphyrins with -SO3H, -COOH, or -NH2 groups as the substituents showed high activity and efficiency with more positive onset potentials as compared to the parent [Co(TPP)]. Supports also from the low hydrogen generation activities for complexes with -COOMe, -OMe and -OH groups as the substituents suggest that the acidity of the meso-phenyl substituent plays a key role in enhancing the hydrogen evolution activities during the catalytic processes.
- Beyene, Belete B.,Mane, Sandeep B.,Hung, Chen-Hsiung
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p. H481 - H487
(2018/07/06)
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- Synthesis, characterization and first application of covalently immobilized nickel-porphyrin on graphene oxide for Suzuki cross-coupling reaction
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In this study, nickel(ii)-coordinated 5,10,15,20-tetrakis(aminophenyl)porphyrin (NiTAPP) as a macrocyclic complex was covalently grafted to the edge of graphene oxide (GO). The prepared nanocatalyst was well characterized by various techniques such as FT-IR, Raman, XRD, TEM, SEM, EDX, TGA, ICP-OES, UV and XPS. All analyses confirmed the successful immobilization of NiTAPP on GO. The synthesized catalyst was applied to evaluate its performance in the Suzuki-Miyaura cross-coupling reaction. GO/NiTAPP exhibited good catalytic efficiency with a high yield of products. Moreover, the suggested catalyst could be recycled for five consecutive cycles without a noticeable decrease in its catalytic activity or metal leaching.
- Keyhaniyan, Mahdi,Shiri, Ali,Eshghi, Hossein,Khojastehnezhad, Amir
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p. 19433 - 19441
(2018/12/13)
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- Method for synthesizing TNPP and TAPP at high yield and high efficiency
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The invention provides a method for synthesizing TNPP and TAPP at high yield and high efficiency and belongs to the technical field of chemical synthesis. The method provided by the invention is characterized in that a small amount of acetic anhydride or propionic anhydride is added to serve as a catalyst in the reaction process of nitrobenzaldehyde and pyrrole, so that the reaction speed is effectively improved and the reaction is performed rightwards to the maximum extent; hot pyrrole is adopted for dissolving and purifying the TNPP to obtain a TNPP product with high purity; in the process of synthesizing the TAPP, a strong reducer tin chloride is adopted for ammonifying the TNPP, and trichloromethane capable of dissolving the TAPP is adopted for efficiently separating the TAPP from an organic phase by adopting a Soxhlet extraction method, so that the purity and the yield of the TAPP are effectively improved.
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Paragraph 0021; 0022
(2017/09/02)
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- Selective Reduction of Nitroarenes with Silanes Catalyzed by Nickel N-Heterocyclic Carbene Complexes
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An efficient catalytic system for the reduction of nitroarenes to amines was developed using a well-defined nickel–NHC (N-heterocyclic carbene) complex as catalyst and phenylsilane as reducing agent. The excellent activity of the catalyst provides access to anilines containing a wide array of reactive functionalities at 20 °C, and without using any base or additive. Notably, the catalytic system allows the reduction of 5,10,15,20-tetra-(nitrophenyl)porphyrin (TNPP) and CuII β-nitroporphyrin to the corresponding aminoporphyrins.
- Lopes, Rita,Pereira, Mariette M.,Royo, Beatriz
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p. 3073 - 3077
(2017/08/15)
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- Tetramine monomer of hyperbranched polyimide containing porphyrin structure, hyperbranched polyimide polymer, preparation method and application
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The invention discloses a tetramine monomer of hyperbranched polyimide containing a porphyrin structure, a hyperbranched polyimide polymer, a preparation method and an application and belongs to the technical field of preparation of hyperbranched polyimide. The anhydride-terminated or amino-terminated hyperbranched polyimide material is synthesized from TAPP serving as polyamine and dianhydride. The TAPP has a large conjugated molecule system to form a two-dimensional coplanar structure, can form a stable spatial network structure with dianhydride easily and has great application prospects as a photoelectrical material. Besides, the hyperbranched polyimide formed by TAPP and dianhydride can be applied to the field of porous adsorbent materials.
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Paragraph 0041; 0043; 0044
(2017/09/02)
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- PH-sensitive fluorescent dye and its preparation method and application
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The invention discloses pH sensitive fluorochrome and a preparation method and application thereof. The molecule in the pH sensitive fluorochrome contains two fluorophores responded to pH, the molecular structural formula of the pH sensitive fluorochrome is shown in the formula I, M is selected from NH2 or -COOH, R is selected from -(CH2)n- or -Ph-, and n is larger than or equal to 2 and is smaller than or equal to 4. The pH sensitive fluorochrome is prepared by connecting a naphthalimide derivative with a porphyrin derivative through a Schiff base reaction. When M is -NH2, aliphatic dialdehyde or aromatic dialdehyde is used as a connection bridge; when M is -COOH, aliphatic linear chain diamide or p-phenyl diamide is used as a connection bridge. The pH sensitive fluorochrome can be used for manufacturing a fluorescence ratio sensor. The pH sensitive fluorochrome is high in sensitivity, good in selectivity, photo-stable and high in quantum yield.
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- Synthetic method of porphyrin and porphyrin derivative
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The invention discloses a synthetic method of porphyrin and a porphyrin derivative. According to the method, a reaction separation synchronous reactor is used to prepare porphyrin and the porphyrin derivative. The reaction separation synchronous reactor includes a stirring reaction tower and a constant-temperature settlement tower connected to the bottom of the stirring reaction tower. The method comprises: adding a mixed raw material of pyrrole, a benzaldehydes compound, organic carboxylic acid and DMF in the reaction separation synchronous reactor till the reaction zone of the constant-temperature settlement tower and the stirring reaction tower is filled with the mixed raw material, controlling the temperature in the stirring reaction tower in a range of 130-155 DEG C and controlling the temperature of the constant-temperature settlement tower in a range of 50-80 DEG C, and obtaining the porphyrin or porphyrin derivative precipitation from the constant-temperature settlement tower. According to the method, no complicated separation means is adopted, and high-purity porphyrin is obtained at a high yield. The method allows industrial production to be easily achieved.
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Paragraph 0039-0040
(2017/07/21)
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- Synthesis, characterization and in vitro photodynamic antimicrobial activity of basic amino acid-porphyrin conjugates
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Photodynamic antimicrobial chemotherapy (PACT), as a novel and effective modality for the treatment of infection with the advantage of circumventing multidrug resistance, receives great attention in recent years. The photosensitizer is the crucial element in PACT, and cationic porphyrins have been demonstrated to usually be more efficient than neutral and negatively charged analogues towards bacteria in PACT. In this work, three native basic amino acids, l-lysine, l-histidine and l-arginine, were conjugated with amino porphyrins as cationic auxiliary groups, and 13 target compounds were synthesized. This paper reports their syntheses, structural characterizations, oil-water partition coefficients, singlet oxygen generation yields, photo-stability, as well as their photo inactivation efficacies against methicillin-resistant Staphylococcus aureus (MRSA), Escherichia coli and Pseudomonas aeruginosa in vitro. The preliminary structure-activity relationship was discussed. Compound 4i, with porphyrin bearing four lysine moieties, displays the highest photo inactivation efficacy against the tested bacterial strains at 3.91 1/4M with a low light dose (6 J/cm2), and it is stable in serum and lower cytotoxicity to A929 cells. These basic amino acid-porphyrin conjugates are potential photosensitizers for PACT.
- Meng, Shuai,Xu, Zengping,Hong, Ge,Zhao, Lihui,Zhao, Zhanjuan,Guo, Jianghong,Ji, Haiying,Liu, Tianjun
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supporting information
p. 35 - 48
(2015/02/19)
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- Effects of substituents on the photophysical properties of symmetrical porphyrins
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Porphyrin compounds having groups that mimic the phenolic moiety of m- and p-isomers of 5,10,15,20-tetrakis(hydroxyphenyl) porphyrin (THPP) have been synthesized along with 5,10,15,20-tetrakis(heteroaryl) porphyrins bearing 2-thienyl and 5-thiazolyl groups. Absorption and fluorescence spectroscopy, including fluorescence lifetime (τf) and quantum yield (Φf) measurements, were employed to characterize the singlet excited state of all compounds, using 5,10,15,20-tetraphenylporphyrin (H 2TPP) as a standard (Φf = 0.12 in DMF). The generation of singlet oxygen by each porphyrin photosensitizer was measured as the singlet oxygen quantum yield (ΦΔ), using H2TPP as a standard (ΦΔ = 0.64 in DMF). Partition coefficients were determined using 2-octanol as the organic phase and PBS solution as the aqueous phase. Fluorescence quantum yields ranged from 0.01 to 0.18 for all compounds, with heteroaryl porphyrins having the lowest values. Singlet oxygen quantum yields ranged from 0.40 to 0.65, with heteroaryl porphyrins having the highest values, showing them to be better sensitizers than m- and p-THPP. Log P values were all >1 showing higher solubility in the 2-octanol layer.
- Ormond, Alexandra B.,Freeman, Harold S.
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p. 440 - 448
(2013/02/23)
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- USE OF METALLOPORPHYRINS AND SALEN COMPLEXES FOR THE CATALYTIC OXIDATION OF ORGANIC COMPOUNDS
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A method of decomposing an organic substrate includes identifying an organic substrate or its constituents having one or more desired or undesired properties; and contacting the organic substrate with an oxidizing agent and a catalyst selected from the group consisting of sterically hindered and electronically activated metallotetraphenylporphyrms, metallophthalocyanines and metallosalen complexes in an aqueous or aqueous-organic solution to produce a treated composition comprising one or more degradation products, wherein the degradation products have one or more desired properties and/or lack the undesired properties of the organic substrate.
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Paragraph 0123
(2013/08/28)
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- Spectroscopy of protonated tetraphenylporphyrins with amino/carbomethoxy substituents: Hyperporphyrin effects and evidence for a monoprotonated porphyrin
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Spectrophotometric titrations for a full series of para-amino/carbomethoxy- substituted tetraphenylporphyrins were carried out using methanesulfonic acid in DMSO to study the hyperporphyrin effect across different substitution patterns. The series included zero, one, two (cis and trans), three, and four amino groups, with the remaining para substituents carbomethoxy groups. With increasing numbers of aminophenyl groups, the relative basicity increased and the hyperporphyrin effect increased, marked by a strong red band and a split Soret band. The cis diamino derivative showed a stronger hyperporphyrin effect compared to the trans isomer, which can be explained based on simple resonance forms. For the monoamino derivative, an initial increase in the Soret band upon acid titration along with well-defined isosbestic points provided evidence for a monoprotonated porphyrin, distinct from the diprotonated and triprotonated states. The relative stability of this unusual intermediate is proposed to be due to charge delocalization of the first cation to the single amino group and destabilization of the second protonation by the electron-withdrawing carbomethoxy substituents.
- Rudine, Alexander B.,Delfatti, Brian D.,Wamser, Carl C.
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p. 6040 - 6049
(2013/07/26)
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