cas 917-23-7, Tetraphenylporphyrin | Articles data

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Physicochemical Basis for the Creation of Liquid-Phase Sensor Materials Based on Tetraaryldithiaporphyrins
Abstract: Basic properties of 5,10,15,20-tetraaryl-21-thia- and 5,10,15,20-tetraaryl-21,23-dithiaporphyrins in acetonitrile were examined spectrophotometrically. The geometry of the heteroporphyrins was optimized in the DFT approximation (hybrid functiona
Ivanova, Yu. B.,Kiselev, A. N.,Pukhovskaya, S. G.,Syrbu, S. A.
p. 231 - 240
(2022/03/18)

Method for synthesizing tetraphenylporphyrin by using return pipe type reactor
The invention discloses a method for synthesizing tetraphenylporphyrin by using a return pipe type reactor, wherein the method comprises the steps: carrying out condensation reaction on benzaldehyde and pyrrole in an equal molar ratio in the presence of a
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Paragraph 0032-0036; 0038-0042; 0044-0048; 0050-0054

(2021/02/06)

Tetraphenylporphyrin covalent functionalized titanium disulfide nonlinear nanometer hybrid material and preparation thereof
The invention relates to a tetraphenylporphyrin covalent functionalized titanium disulfide nonlinear nanometer hybrid material and a preparation method thereof, wherein the hybrid material is prepared from tetraphenylporphyrin diazonium salt TPP-N. 2
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Paragraph 0041-0044

(2021/12/07)

The construction of C(sp3)–O bond via copper porphyrin catalyzed cross-dehydrogenative coupling reaction: Substituent and electronic effect of the catalysts
The push-pull electronic and steric effect of copper porphyrin catalysts on the cross-dehydrogenative coupling (CDC) reaction between the hydroxyl group of phenol substrates and C(sp3)-H bond have been investigated. Results showed that copper porphyrin bearing electron-withdrawing, bulky steric hindrance or heteroatom of pyridyl groups could increase the catalytic activity in the reaction. 5,10,15,20-(tetrakis(4-pyridyl)porphyrin)copper (CuTPyP) was found the best among all tested catalysts. Phenol substrates bearing various functional groups afforded moderate to excellent yields (99%). Significantly, as compared to other tested copper porphyrins, CuTPyP not only exhibited remarkable higher activity but also could shorten the reaction time from 12 to 6 h.
Wang, Feng-Hua,Liu, Zheng-Yan,Yang, Shuang,Shi, Lei,Lin, Dong-Zi,Liu, Hai-Yang,Yuan, Gao-Qing
supporting information
p. 2053 - 2062
(2021/05/26)

Multifunctional Porphyrin-based dyes for cations detection in solution and thermoresponsive low-cost materials
Two β-pyrrolic substituted porphyrinic dyes 3 and 4, have been synthesized and fully characterized. Both compounds showed spectral alterations upon metal interaction indicating the complexation of the inner nitrogens in the porphyrin moiety by the metal i
Capelo, José Luis,Cheptene, Victoria,Lodeiro, Carlos,Moura, Nuno M. M.,Neves, M. Gra?a P. M. S.,Oliveira, Elisabete,Pucci, Andrea,Valentini, Simone
(2020/10/18)

Poly(L-Glutamic Acid)-Drug Conjugates for Chemo- and Photodynamic Combination Therapy
Despite the polymeric vascular disrupting agent (poly(L-glutamic acid)-graft-methoxy poly(ethylene glycol)/combretastatin A4) nanoparticles can efficiently inhibit cancer growth, their further application is still a challenge owing to the tumor
Yu, Haiyang,Bao, Yanli,Xu, Caina,Chen, Li,Tang, Zhaohui
(2020/10/14)

Quick and Easy Method to Dramatically Improve the Electrochemical CO2 Reduction Activity of an Iron Porphyrin Complex
The development of artificial molecular catalysts for CO2 reduction is the key to solving energy and environmental problems. Although chemical modifications can generally improve the catalytic activity of this class of compounds, they often req
Kondo, Mio,Kosugi, Kento,Masaoka, Shigeyuki
supporting information
p. 22070 - 22074
(2021/08/30)

Porphyrin bearing phenothiazine pincers as hosts for fullerene bindingviaconcave-convex complementarity: synthesis and complexation study
In this work, we synthesized free base porphyrin hosts,m-(PTZ)4-H2Pandp-(PTZ)4-H2P, that are functionalized with four phenothiazine moieties at themeso-positionviaa flexible ethoxy phenyl linker. The rigid and n
Chitta, Raghu,Duvva, Naresh,Giribabu, Lingamallu,Jain, Kanika,Roy, Tapta Kanchan
supporting information
p. 19691 - 19703
(2021/11/12)

A series of asymmetric and symmetric porphyrin derivatives: one-pot synthesis, nonlinear optical and optical limiting properties
In this work, a series of asymmetric and symmetric porphyrin derivatives (structure types: A4, A3B1,trans-A2B2,cis-A2B2, A1B3, and B4) have been synthesizedviaa one-pot method and characterized by TLC, HPLC, FT-IR,1H-NMR and UV-Vis to identify their structures and properties. The porphyrin derivatives withtrans-A2B2andcis-A2B2structures are visually distinguishedviasingle-crystal X-ray diffraction; the crystal morphology oftrans-A2B2is a needle-like structure. All porphyrin derivatives (I-VI) have excellent nonlinear optical (NLO) and optical limiting (OL) properties, and are investigated using the standardZ-scan technique. Porphyrin derivativeIIIexhibits the maximum nonlinear absorption, nonlinear refraction coefficients and optical limitation threshold, and the values are 3.7 × 10?9m W?1, ?17 × 10?17m2W?1and 0.11 J cm?2, respectively. The results demonstrate that the introduction of different substituent numbers (mono-, di- and tri-, tetra-) and substituent sites (trans-A2B2andcis-A2B2) in the porphyrins could influence the NLO and OL properties. Structure regulation of porphyrin can lead to the adjustment of NLO and OL properties, and affect its practical NLO application in the future.
Bao, Changjiang,Chen, Changshun,Duan, Qian,Li, Yanhui,Li, Yanwei,Si, Zhenjun,Wang, Lei,Zhang, Yanru
p. 16030 - 16038
(2021/09/22)

K2S2O8mediated synthesis of 5-Aryldipyrromethanes and meso-substituted A4-Tetraarylporphyrins
The synthesis of dipyrromethanes from pyrrole and arylglyoxylic acids in the presence of K2S2O8at 90 C is reported affording dipyrromethanes in very good yields. Unlike an excess pyrrole traditionally used in dipyrromethane synthesis, the current method uses a stoichiometric amount of pyrrole avoiding any use of Br?nsted or Lewis acid. A gram scale synthesis of 5-phenyldipyrromethane is also achieved demonstrating potential scale up of dipyrromethanes using this method feasible. Subsequently, dipyrromethanes were converted to A4tetraarylporphyrins also in the presence of K2S2O8at 90C. A direct synthesis of A4-tetraphenylporphyrin from excess pyrrole and phenylglyoxylic acid in the presence of K2S2O8 at 90C is also reported.
Laha, Joydev K.,Hunjan, Mandeep Kaur
p. 664 - 673
(2021/06/03)

Combining metalloporphyrins and cyclometalated complexes – A luminous pair?
Cyclometalation is investigated as a method to modulate the photophysical properties of phosphorescent (benzo)porphyrins. For cyclometalation with Pt(II), 2-pyridyl groups were incorporated into three Pd(II) porphyrin complexes. Integration of the freely rotating cyclometalated 2-phenylpyridyl based motif in meso-position does not lead to notable spectral changes and only affects the luminescence decay time (about 2-fold decrease) in solution at room temperature. The decay times, however, are not affected in frozen glass at 77 K or immobilized into a rigid polystyrene matrix. In contrast, cyclometalation involving a 2-pyridyl unit in meso-position and the β-H of the porphyrin results in a large bathochromic shift (～ 1900 cm?1) of Q-bands in the absorption spectrum and the phosphorescence peak. A drastic decrease of the phosphorescence lifetime (about 20-fold) also is observed. Cyclometalation is accompanied by an increase of the singlet oxygen quantum yield to 85 % making the new dye a powerful red-light excitable 1O2 photosensitizer.
Borisov, Sergey M.,Moritz, Yvonne,Steinegger, Andreas
(2020/12/04)

Pd-porphyrin complex-catalyzed allylation of indole with allylic alcohols through C3–C2 coupling
Appropriate and efficient way for the preparation of 3-allyl-2,3-dihydro-2,3′-bisindoles has been developed via homocoupling of N–H indole. Pd-porphyrin-catalyzed allylation of indoles with allylic alcohols in the presence of PBr3 and a base is developed. The reaction involves dimerization at the C3 and C2 positions of the indoles, giving 2-allylated 3-(indolin-2-yl)-1H-indoles in moderate to good yields. 3-(Indolin-2-yl)-1H-indole derivatives serve as intermediates for the synthesis of pharmaceutically active molecules.
Atia, Alaa A.,Kimura, Masanari
supporting information

(2021/05/19)

Synthesis of meso-substituted corroles and porphyrins using iodine as a catalyst
Abstract: Different types of corroles and porphyrins are synthesized from substituted aldehydes and pyrrole. The current synthetic method involves iodine as catalyst and proceeds at room temperature itself. By varying the amounts of reactants (i.e., pyrrole and aldehydes), the corrole and porphyrins were obtained in good to excellent yields. These products were characterized by 1H-NMR, UV-visible, and HRMS techniques. The reaction approach utilizes the readily available pyrrole and substituted aldehydes as starting materials and makes this reaction highly attractive in diversity-oriented synthesis. Graphic abstract: Different types of porphyrins and corroles are synthesized from substituted aldehydes and pyrrole using iodine as a catalyst and the reaction proceeds at room temperature itself. By varying the amount of reactants (i.e. pyrrole and aldehydes), the porphyrins and corroles are obtained in good to excellent yields.[Figure not available: see fulltext.]
Chauhan, Shive M S,Dandia, Anshu
(2020/10/02)

Comparative in vitro Studies of the Topoisomerase I Inhibition and Anticancer Activities of Metallated N-Confused Porphyrins and Metallated Porphyrins
Using the original approach, a series of metallated N-confused porphyrins and metallated porphyrins have been synthesized and characterized. For all the synthesized porphyrins, in vitro studies of cytotoxic activity against K562, U937, HL-60, Jurkat, A549 and HeLa cancer cell lines, the ability to induce apoptosis and effects on the cell cycle as well as the kinetics of proliferative activity of porphyrins and their respective metallated complexes in real time have been developed. The inhibitory activity of metallated porphyrins against human topoisomerase I and the possible mechanism of inhibition have been carried out by modelling using molecular docking.
D'yakonov, Vladimir A.,Dzhemilev, Usein M.,Dzhemileva, Lilya U.,Halder, Nyancy,Ramazanov, Ilfir R.,Rath, Harapriya
(2020/03/24)

Tuning on and off chemical- And photo-activity of exfoliated MoSe2nanosheets through morphologically selective "soft" covalent functionalization with porphyrins
The covalent functionalization of 2D transition metal dichalcogenides (TMDCs) with organic molecules exploiting the thiol conjugation approach is still a very controversial topic. We have synthesized thiolated tetraphenyl porphyrins, with and without hydr
Agnoli, Stefano,Blanco, Matías,Bortoli, Marco,Girardi, Leonardo,Granozzi, Gaetano,Lunardon, Marco,Mosconi, Dario,Orian, Laura
supporting information
p. 11019 - 11030
(2020/08/19)

Preparation of TSPP and application of TSPP in detection of content of sulfur ions
The invention provides preparation of 5,10,15,20-(tetrasulfonic acid) tetraphenylporphyrin (TSPP) and an application of the TSPP in detection of the content of sulfur ions. When riboflavin is introduced into a TSPP solution, TSPP fluorescence intensity at
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Paragraph 0041-0045; 0106; 0108-0109

(2020/12/15)

Rare earth–porphyrin complex catalysts for transforming CO2 into cyclic carbonate under mild conditions
A series of rare earth metal complexes RE(TPP)(acac) (RE = NdIII, YbIII, EuIII, ErIII, PrIII, and LuIII; TPP = 5,10,15,20-tetraphenylporphyrin) were synthesized and characterized via UV–vis
Wang, Wenzhen,Fan, Wei,Jia, Xingang,Li, Leilei
p. 1380 - 1386
(2020/03/10)

Elucidating the Electroreduction Mechanism of the Monoprotonated Octaethylporphyrin. A Comparative Study with the Diprotonated Octaethyl- A nd meso-Tetraphenyl-porphyrins
The electrochemical reduction mechanisms of diprotonated tetraphenylporphyrin (H2TPP) and mono- A nd diprotonated octaethylporphyrin (H2OEP) were studied in tetrabutylammonium perchlorate/benzonitrile. The diprotonated forms of both porphyrins undergo two
Arias-Aranda, Leslie R.,Castro-Cruz, Hiram M.,Farfán, Norberto,MacIás-Ruvalcaba, Norma A.,Xochitiotzi-Flores, Elba
(2020/09/03)

Modification of porous lignin with metalloporphyrin as an efficient catalyst for the synthesis of cyclic carbonates
The conversion of carbon dioxide into useful chemical raw materials is a necessary development for advancing carbon dioxide capture and storage technology. In this work, a Friedel–Crafts reaction of lignin and metalloporphyrin was used to produce a lignin
Song, Kunpeng,Tang, Cheng,Zou, Zhijuan,Wu, Yundang
p. 111 - 119
(2019/11/19)

Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes
Porphyrins are cornerstone functional materials that are useful in a wide variety of settings, ranging from molecular electronics to biology and medicine. Their applications are often hindered, however, by poor solubilities that result from their extended
Adler, Marc J.,Bismillah, Aisha N.,Hussein, Burhan A.,Mcgonigal, Paul R.,Pia, Julia E.,Pilkington, Melanie,Shakeel, Zainab,Turley, Andrew T.,Wolfstadt, Kody M.
supporting information
p. 13533 - 13541
(2020/10/02)

Synthesis and pharmacological evaluation of chlorin derivatives for photodynamic therapy of cholangiocarcinoma
Photodynamic therapy (PDT) has been developed as a promising therapeutic method in cancer treatment. The discovery of effective photosensitizer, which is the key factor of PDT, is highly desired. This paper reports the synthesis of novel chlorin derivativ
Gao, Ying-Hua,Li, Man-Yi,Sajjad, Faiza,Wang, Jin-Hai,Meharban, Faiza,Gadoora, Malaz Abdelazeem,Yan, Yi-Jia,Nyokong, Tebello,Chen, Zhi-Long
(2020/01/21)

Synthesis, characterization and photodynamic activity against bladder cancer cells of novel triazole-porphyrin derivatives
Novel triazole-porphyrin derivatives (TZ-PORs) were synthesized through the Heck reaction and then incorporated into polyvinylpyrrolidone (PVP) micelles. After verifying that this incorporation did not compromise the photophysical and chemical features of
Gomes, Ana T.P.C.,Fernandes, Rosa,Ribeiro, Carlos F.,Tomé, Jo?o P.C.,Neves, Maria G.P.M.S.,da Silva, Fernando de C.,Ferreira, Vítor F.,Cavaleiro, José A.S.
(2020/04/10)

Porphyrin derivative with red aggregation-induced emission characteristic as well as preparation method and application of porphyrin derivative
The invention discloses a porphyrin derivative with a red aggregation-induced emission characteristic, and a preparation method and application thereof. Porphyrin molecules are modified through a tetraphenyl vinyl group, and due to introduction of a prope
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Paragraph 0031-0034

(2020/05/29)

Guanidino-aryl derivatives: Protonation and structure tuning for spectrophotometric recognition of ds-DNA and ds-RNA
A series of aryl-substituted guanidines revealed a pKa of about 10 in aqueous medium, thus positioning themselves between the more basic aliphatic guanidines (pKa > 13) and the acidic guanidinocarbonyl-pyrrole (pKa 6). The study revealed that for the bior
?ud, Mateja,Glasovac, Zoran,Margeti?, Davor,Piantanida, Ivo
supporting information
p. 11537 - 11545
(2020/07/27)

Peroxynitrite (ONOO-) generation from the HA-TPP@NORM nanoparticles based on synergistic interactions between nitric oxide and photodynamic therapies for elevating anticancer efficiency
Due to biological safety and negligible toxicity, nitric oxide (NO) therapy has gained increasing interest in the field of cancer therapy during the past few years. However, individual NO cancer therapy normally exhibited limited therapeutic efficiency. In order to acquire satisfactory therapeutic outcomes, the NO therapy is usually combined with other therapeutic treatments, mostly chemotherapy. Herein, we constructed HA-TPP@NORM nanoparticles based on the co-assembly of an NO donor (NORM) and tetraphenylporphyrin (TPP)-modified hyaluronic acid, which can efficiently generate a highly biocidal molecule of peroxynitrite (ONOO-) via the synergistic interactions of the nitric oxide (NO) therapy and photodynamic therapy (PDT) to enhance the cancer therapeutic efficiency. In addition, MTT results exhibited that without light irradiation, the HA-TPP@NORM nanoparticles have favourable biocompatibility with the cell viability above 95% at the maximum TPP concentration (20 μg mL-1). Under simultaneous irradiation with 365 nm and 650 nm light, ONOO- can be efficiently produced in cancer cells via the direct coupling reaction of the generated NO and superoxide anion radical (O2-), which significantly enhanced the anticancer effect, when compared with individual NO therapy or PDT therapy. Therefore, the HA-TPP@NORM nanoparticles may provide a new insight into the design of efficiently NO-related cancer therapeutic systems.
Jiang, Dawei,Yue, Tao,Wang, Guichen,Wang, Chaochao,Cao, Hongliang,Gao, Yun,Chen, Chao
supporting information
p. 162 - 170
(2019/12/26)

Oxidation of toluene to benzoic acid via VOTPP catalyst synthesized with an improved method
Abstract: In this paper, two-step method was used to synthesize 5,10,15,20-tetraphenyl-21H,23H-porphine vanadium(IV) oxide (VOTPP) and toluene catalytic oxidation was explored. The result showed that this catalyst led to benzoic acid as the main product and successfully simulated the reaction of toluene oxidation with the catalytic center of P-450 enzyme. Through testing the reaction conditions including used catalyst amount, temperature, pressure, and reaction time, the optimum reaction conditions were: 0.3 g VOTPP in 100 cm3 of toluene, 145 °C, 0.8 MPa, and 4 h. The conversion of toluene was 23.0% and the selectivity of benzoic acid could reach 86.0%. Its benefits lie in no solvent, mild reaction conditions, and no toxic acidic waste, making toluene oxidation a green process. Graphic abstract: [Figure not available: see fulltext.].
Chen, Xi,Jia, Jiaojiao,Niu, Yulan,Zhai, Lijun
p. 1549 - 1555
(2020/10/19)

Unusually Large Singlet Oxygen (1O2) Production by Very Weakly Emissive Pyrene-Functionalized Iridium(III) Complex: Interplay between Excited 3ILCT/3IL and 3MLCT States
The photophysical properties of a few Ir(III) and Rh(III) complexes have been attempted to be correlated (1–4) with their 1O2 generation efficiencies. A very weakly emissive pyrene-functionalized Ir(III) complex (1) produces 1O2 more efficiently than the other more emissive Ir(III) complexes. All of them have excited triplet state lifetimes (τT) in the microsecond regime. However, the pyrene-functionalized Ir(III) complex possesses the largest τT and has reasonable HOMO (highest occupied molecular orbital) energy (1O2 production. 1–4 emit mostly from the 3MLCT state. The lowest triplet emissive state of 3 and 4 is the 3MLCT state while it is the 3ILCT/3IL state for 1 which is mostly non-emissive. However, the large excited state lifetime and the small energy gap between the 3ILCT/3IL states and the ground electronic state for complex 1 facilitates efficient energy transfer to molecular 3O2 producing 1O2.
Seth, Sourav Kanti,Purkayastha, Pradipta
supporting information
p. 2990 - 2997
(2020/07/04)

Interaction between meso-Phenyl-Substituted Porphirinioids and Carboxylic Acids, and a Thermal Analysis of Their Cationic Salts
Abstract: Thermogravimetry and quantum chemistry, including NBO analysis, are used to study the thermal stability and NH acidity of single and double protonated forms of tetrapyrrole macroheterocyclic ligands (porphyrins, their inverted and N-substituted analogs, and corroles). The temperature ranges of the destruction of porphyrinium acetates and trifluoroacetates, the enthalpies of evaporation of acid molecules from the crystalline phase, and the composition of cationic salts are calculated. The structures of protonated forms of macrocycles are optimized. The energies of porphyrin–acid interaction and the values of charge transfer ??during the formation of bonds are calculated.
Likhonina,Krest’yaninov,Morshnev,Kritskii,Kudayarova,Berezin
p. 110 - 118
(2020/03/24)

A new synthesis of porphyrins: Via a putative trans-manganese(iv)-dihydroxide intermediate
A new method for the synthesis of meso-substituted porphyrins was developed. In this two-step methodology, the first step involves the condensation of pyrroles/dipyrromethanes with aldehydes in a water-methanol mixture under acidic conditions. The second step involves manganese induced cyclization followed by oxidation via PhIO/O2. This methodology has been useful for the synthesis of a wide range of trans-A2B2 porphyrins and also symmetric porphyrins in moderate to good yields. A detailed investigation of the manganese induced cyclization reaction has allowed us to characterize a Mn-porphyrinogen complex. A series of analytical and spectroscopic techniques and DFT calculations have led us to the conclusion that the putative intermediate species are trans-manganese(iv)-dihydroxide complexes. EPR and magnetic susceptibility measurements helped us to assign the oxidation state of the manganese complexes in their native state. The assumption of trans-manganese(iv)-dihydroxide as the true intermediate for this porphyrin synthesis has been authenticated via in situ UV-Vis experiments. This new methodology is certainly different from other previously reported methodologies in many aspects and most importantly these reactions can be easily performed on a gram scale for the synthesis of porphyrins.
Biswal, Himansu S.,Jena, Subhrakant,Kar, Sanjib,Mondal, Sruti,Patra, Bratati,Sahu, Kasturi
p. 1424 - 1432
(2020/02/15)

Porphyrin synthesis using mechanochemistry: Sustainability assessment
Looking for sustainable synthetic methodologies, mechanochemistry as a new tool for one-step and two-step approaches for the synthesis of meso-substituted porphyrins was explored. The best results were obtained in a two-step procedure, under liquid-assisted grinding in the oxidation step using 2-methyltetrahydrofuran, an environmentally acceptable solvent, and MnO2 as a heterogeneous oxidant. The sustainability was assessed using two sustainability metrics, E-factor and EcoScale, which allow comparison between procedures and methods.
Gomes, Carla,Peixoto, Mariana,Pineiro, Marta
p. 889 - 897
(2019/08/12)

Conformational-Switch Based Strategy Triggered by [18] π Heteroannulenes toward Reduction of Alpha Synuclein Oligomer Toxicity
A water-soluble meso-carboxy aryl substituted [18] heteroannulene (porphyrin) and its Zn-complex have been found to be viable in targeting α-Syn aggregation at all its key microevents, namely, primary nucleation, fibril elongation, and secondary nucleation, by converting the highly heterogeneous and cytotoxic aggresome into a homogeneous population of minimally toxic off-pathway oligomers, that remained unexplored until recently. With the EC50 and dissociation constants in the low micromolar range, these heteroannulenes induce a switch in the secondary structure of toxic prefibrillar on-pathway oligomers of α-Syn, converting them into minimally toxic nonseeding off-pathway oligomers. The inhibition of the aggregation and the reduction of toxicity have been studied in vitro as well as inside neuroblastoma cells.
Chakraborty, Ritobrita,Sahoo, Sumit,Halder, Nyancy,Rath, Harapriya,Chattopadhyay, Krishnananda
p. 573 - 587
(2018/10/31)

Synthesis, spectral and redox properties of closely spaced pyrrole-β-position-linked porphyrin-fullerene dyads
Two free base meso-tetraphenylporphyrin-fullerene dyads, H2PMe-C60, H2POMe-C60, and their zinc complexes, ZnPMe-C60 and ZnPOMe-C60, which the para positions of the meso-tetrasubstituted phenyl groups of the porphyrin core were substituted by methyl(-Me) and methoxyl(-OMe) groups respectively, were synthesized. The porphyrin unit in the synthesized dyads is directly linked to the fullerene entity through the pyrrole-β- position rather than through the traditionally meso-substituted phenyl group, which may be more favorable for electron communication between the donor and the acceptor. They are fully characterized by mass spectrometry, nuclear magnetic resonance, infrared spectroscopy and ultraviolet visible spectroscopy. Experimental results obtained from steady-state fluorescence spectroscopy and cyclic voltammetry show that the coordination of the zinc ions lead to an increase in the singlet excited state energy of the metallated porphyrin unit by about 0.15 eV, and to a reduce in the HOMO level and in the HOMO-LUMO energy gap. The molecular reorganization energy decreases after the electron-donating groups of -Me or -OMe attaching to the para position of the meso-phenyl group of the porphyrin moiety. The results of the energy calculations show that photoinduced electron transfer is thermodynamically favorable for the synthesized porphyrin-C60 dyads. There exists a competition between the photoinduced electron transfer and energy transfer processes from the first singlet excited state of porphyrin core to fullerene moiety. The photoinduced electron transfer rate constant of the dyads were calculated according to Marcus theory. The results indicate that the coordination of metal zinc ions lead to great increase in the electron transfer rate constant. Further, the photoinduced electron transfer rate constant increases in the order ZnP-C60, ZnPMe-C60, ZnPOMe-C60.
Wu, Zhen-Yi,Yang, Sheng-Yan
p. 244 - 254
(2019/04/17)

Water-soluble sulfonate porphyrin functionalized hyaluronic acid with comb-like structure: Potential photosensitizers for photodynamic therapy
A water-soluble comb-like porphyrin polymer based on hyaluronic acid (HA) as the main chain and sulfonate substituted tetraphenylporphyrin (TASP) as side groups, named as HA-g-NH-TPP-(SO3Na) [(HA-g-TASP)], was designed and synthesized, which co
Cui, Xu,Li, Yanhui,Li, Yanwei,Qiu, Baoguo,Duan, Qian
p. 237 - 243
(2019/02/03)

A chain porphyrin polymer and its synthesis method (by machine translation)
A chain porphyrin polymer is composed of two amino phenyl porphyrin and terephthalic formaldehyde aldehyde ammonia condensation polymerization through the alternate link, so as to form a chain structure of the polymer, this chain porphyrin polymer and its
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Paragraph 0020-0022

(2019/10/22)

A ruthenium porphyrin-based porous organic polymer for the hydrosilylative reduction of CO2 to formate
A ruthenium porphyrin-based porous organic polymer (POP) was synthesized, characterized, and used to reduce CO2 to a formate salt. We demonstrate that Ru-BBT-POP can be utilized to reduce CO2 to a silyl formate and then converted to potassium formate with a respectable turnover number and frequency.
Eder, Grace M.,Pyles, David A.,Wolfson, Eric R.,McGrier, Psaras L.
supporting information
p. 7195 - 7198
(2019/07/02)

A Br-regulated transition metal active-site anchoring and exposure strategy in biomass-derived carbon nanosheets for obtaining robust ORR/HER electrocatalysts at all pH values
A novel Br-regulated "Transition Metal Active-site Anchoring and Exposure" (TMAAE) strategy is reported, for the first time, to fabricate a hierarchical porous Co/N-doped bio-carbon bifunctional electrocatalyst (CoTBrPP?bio-C) for an all-pH ORR and HER by using a simple one-pot co-pyrolysis over a mushroom (MR) template with adsorbed Br-substituted porphyrinato cobalt (CoTBrPP). Introduction of CoTBrPP onto the MR template not only leads to a larger specific area of 604 m2 g-1 in CoTBrPP?bio-C relative to that of CoTPP?bio-C (CoTPP = Br-free CoTBrPP), 98 m2 g-1, but more importantly also regulates the oriented distribution of pores precisely which promotes effective exposure of multiple active sites depending on the departure of Br-species attached to the Co-N4 macrocycle periphery. Impressively, CoTBrPP?bio-C with a Co loading down to 0.77 at% exhibits higher all-pH ORR and HER performance compared to CoTPP?bio-C with a Co loading of 3.5 at%. An efficient TMAAE makes CoTBrPP?bio-C possess higher onset and half-wave potentials of 0.93 and 0.85 V for the ORR, and a smaller Tafel slope of 80 mV dec-1 for the HER in an alkaline medium. CoTBrPP?bio-C also had a superior all-pH long-term stability and outstanding methanol tolerance, surpassing commercial Pt/C and most non-precious-metal catalysts reported to date. Furthermore, Zn-air batteries assembled with CoTBrPP?bio-C exhibited a higher peak power density of 100 mW cm-2 and excellent durability than Pt/C.
Lv, Xuehui,Chen, Yanli,Wu, Yanling,Wang, Haoyuan,Wang, Xinlong,Wei, Chuangyu,Xiao, Zuoxu,Yang, Guangwu,Jiang, Jianzhuang
supporting information
p. 27089 - 27098
(2019/12/11)

Metalloporphyrin complex and organic electroluminescent device thereof
The invention provides a metalloporphyrin complex and an organic electroluminescent device thereof, and belongs to the technical field of organic photoelectric materials. The invention discloses a metalloporphyrin complex, which contains a porphyrin-conta
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Paragraph 0048-0052

(2020/01/08)

Diaqua-β-octaferrocenyltetraphenylporphyrin: A multiredox-active and air-stable 16π non-aromatic species
Herein the synthesis and properties of the first β-octaferrocenyltetraphenylporphyrin, {TPPFc8(H2O)2}, in its extraordinary stable and non-aromatic 16π form are reported, showing seven separate reversible redox events. As oxidation progresses, the neighbouring ferrocenyls of the pyrrole subunits display moderate electronic coupling, while electron transfer along the 16π porphyrin cycle was, due to its non-aromatic nature, not observed.
Al-Shewiki, Rasha K.,Korb, Marcus,Hildebrandt, Alexander,Zahn, Stefan,Naumov, Sergej,Buschbeck, Roy,Rüffer, Tobias,Lang, Heinrich
supporting information
p. 1578 - 1585
(2019/02/07)

Crystallographic identification of a series of manganese porphyrin complexes with nitrogenous bases
Studying the axial ligation behavior of metalloporphyrins with nitrogenous bases helps to better understand not only the biological function of heme-based protein systems, but also the catalytic properties of porphyrin-based reaction sites in other biomim
Lahanas, Nicole,Kucheryavy, Pavel,Lalancette, Roger A.,Lockard, Jenny V.
p. 304 - 312
(2019/02/20)

Nickel(II) Tetraphenylporphyrin as an Efficient Photocatalyst Featuring Visible Light Promoted Dual Redox Activities
Nickel(II) tetraphenylporphyrin (NiTPP) is presented as a robust, cost-effective and efficient visible light induced photoredox catalyst. The ground state electrochemical data (CV) and electronic absorption (UV-Vis) spectra reveal the excited state redox potentials for [NiTPP]*/[NiTPP].? and NiTPP].+/[NiTPP]* couples as +1.17 V and ?1.57 V vs SCE respectively. The potential values represent NiTPP as a more potent photocatalyst compare to the well-explored [Ru(bpy)3]2+. The non-precious photocatalyst exhibits excited state redox reactions in dual fashions, i. e., it is capable of undergoing both oxidative as well as reductive quenching pathways. Such versatility of a photocatalyst based on first-row transition metals is very scarce. This unique phenomenon allows one to perform diverse types of redox reactions by employing a single catalyst. Two different sets of chemical reactions have been performed to represent the synthetic utility. The catalyst showed superior efficiency in both carbon-carbon and carbon-heteroatom bond-forming reactions. Thus, we believe that NiTPP is a valuable addition to the photocatalyst library and this study will lead to more practical synthetic applications of earth-abundant-metal-based photoredox catalysts. (Figure presented.).
Mandal, Tanumoy,Das, Sanju,De Sarkar, Suman
supporting information
p. 3200 - 3209
(2019/05/16)

Wavelength-Dependent Energy and Charge Transfer in MOF: A Step toward Artificial Porous Light-Harvesting System
Chromophore assemblies within well-defined porous coordination polymers, such as metal-organic frameworks (MOFs), can emulate the functionality of the antenna rings of chlorophylls in light-harvesting complexes (LHCs). The chemical, electronic, and structural diversities define MOFs as a promising platform where photogenerated excitons can be displaced to redox catalysts similar to the reaction center of the LHC. The precise positioning of the pigments and complementary redox units enables us to understand the charge/energy-transfer process within these crystalline solid compositions. In this study, we postsynthetically anchored tetraphenylporphyrinato zinc(II) (TPPZn)-derived complementary pigment within the 1D pores of 1,3,6,8-tetrakis(p-benzoicacid)pyrene (H4TBAPy)-derived NU-1000 MOF to form a high-density donor-acceptor system. The ground- and excited-state redox potentials of the donor and acceptor were chosen to facilitate an energy transfer (EnT) from the excited MOF (i.e., NU-1000*) to TPPZn and a charge transfer (CT) from excited porphyrin (i.e., TPPZn*). Thus, the processes depend on the excitation wavelength. The energy transfer process was spectroscopically probed by excitation-emission mapping: MOF emission was completely quenched at 460 nm, where the pyrene-centered emission was expected. Instead, the excited MOF efficiently transfers the energy to manifest a TPPZn-centered emission at 670 nm (kEnT ≈ 4.7 × 1011 s-1). The excited TPPZn pigment, with a neighboring TBAPy linker, forms an artificial "special-pair"-like system driving the charge-separation process (kCT = 1.2 × 1010 s-1). The findings demonstrate a synthetic MOF-based artificial LHC system where their well-defined structure will open up new possibilities as the separated charge can hop along the 1D pore channel for further mechanistic understanding and future developments.
Li, Xinlin,Yu, Jierui,Gosztola, David J.,Fry, H. Christopher,Deria, Pravas
supporting information
p. 16849 - 16857
(2019/10/17)

Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins
Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.
Atoyebi, Adewole O.,Brückner, Christian
supporting information
p. 9631 - 9642
(2019/03/26)

Through the challenging synthesis of tetraphenylporphyrin derivatives bearing nitroxide moieties
Tetraphenylporphyrin derivatives a synthetic heterocycles with convenient preparation and a richness of properties which make them attractive in broad fields such as energy, life and materials sciences. Thus, in the quest for new radical architectures, tetraphenylporphyrins are prime candidates. To this end, we designed free-base tetraphenylporphyrins bearing nitronyl and imino nitroxide moieties covalently bonded to the para-position of the meso-phenyl substituent. Their detailed synthesis and characterization are reported here.
?nal, Emel,Fidan, Ismail,Luneau, Dominique,Hirel, Catherine
p. 584 - 588
(2019/05/15)

Synthesis and photophysical properties of novel pyrene-metalloporphyrin dendritic systems
A novel series of dendronized porphyrins bearing pyrene units in the periphery (Porph-O-Gn) and their metal complexes (M-[Porph-O-Gn]) are reported. The pyrene-containing Frechet-type dendrons up to the first generation were synthesized and further reacted with 5-phenol-10,15,20-triphenylporphyrin via an esterification reaction to afford the desired pyrene-labeled dendronized porphyrins. Later, these compounds were used as ligands to produce the corresponding complexes of Zn2+, Cu2+, Mg2+ and Mn3+. With the compounds in hand, the optical and photophysical properties of the dendritic metalloporphyrins were studied by absorption and fluorescence spectroscopy. The quantum yields, F?rster radius and efficiency of energy transfer were determined and discussed as a function of the structure and the donor-acceptor distances, finding an efficient energy transfer from the pyrene moiety to the metallated porphyrin core in each case.
Rojas-Montoya, Sandra M.,Vonlanthen, Mireille,Porcu, Pasquale,Flores-Rojas, Gabriel,Ruiu, Andrea,Morales-Morales, David,Rivera, Ernesto
p. 10435 - 10447
(2019/07/22)

Neutral Porphyrin Derivative Exerts Anticancer Activity by Targeting Cellular Topoisomerase i (Top1) and Promotes Apoptotic Cell Death without Stabilizing Top1-DNA Cleavage Complexes
Camptothecin (CPT) selectively traps topoisomerase 1-DNA cleavable complexes (Top1cc) to promote anticancer activity. Here, we report the design and synthesis of a new class of neutral porphyrin derivative 5,10-bis(4-carboxyphenyl)-15, 20-bis(4-dimethylaminophenyl)porphyrin (compound 8) as a potent catalytic inhibitor of human Top1. In contrast to CPT, compound 8 reversibly binds with the free enzyme and inhibits the formation of Top1cc and promotes reversal of the preformed Top1cc with CPT. Compound 8 induced inhibition of Top1cc formation in live cells was substantiated by fluorescence recovery after photobleaching (FRAP) assays. We established that MCF7 cells treated with compound 8 trigger proteasome-mediated Top1 degradation, accumulate higher levels of reactive oxygen species (ROS), PARP1 cleavage, oxidative DNA fragmentation, and stimulate apoptotic cell death without stabilizing apoptotic Top1-DNA cleavage complexes. Finally, compound 8 shows anticancer activity by targeting cellular Top1 and preventing the enzyme from directly participating in the apoptotic process.
Das, Subhendu K.,Ghosh, Arijit,Paul Chowdhuri, Srijita,Halder, Nyancy,Rehman, Ishita,Sengupta, Souvik,Sahoo, Krushna Chandra,Rath, Harapriya,Das, Benu Brata
p. 804 - 817
(2018/02/17)

One-Pot Approach to Chlorins, Isobacteriochlorins, Bacteriochlorins, and Pyrrocorphins
A Diels-Alder strategy is reported to synthesize the complete set of hydroporphyrins: chlorins, bacteriochlorins, isobacteriochlorins, and pyrrocorphins. Porphyrins and Ni-porphyrins react with isobenzofuran in very high yields at 70 °C to form the corres
Peters, Morten K.,R?hricht, Fynn,N?ther, Christian,Herges, Rainer
supporting information
p. 7879 - 7883
(2019/01/14)

A four-phenyl porphine preparation method
The invention discloses a preparation method of meso-tetraphenylchlorin. The preparation method comprises the steps that 1, a mixed solution of pyrrole and aromatic aldehyde is prepared for standby; 2, a solvent is added into a polymerization reactor, nitrogen displacement is conducted till the concentration of tail oxygen is lower than 1%, the solvent is heated to backflow, the mixed solution obtained in the first step starts to be dropwise added, a reaction is started, after the mixed solution is dropwise added completely, the reaction is continuously conducted for 0.05 h to 0.5 h, and then the reaction is stopped; 3, oxygen-containing gas with the oxygen volume fraction ranging from 5% to 100% is fed into the polymerization reactor for oxidation, cooling is conducted after the oxidation is completed, filtration is conducted to obtain a filter cake and filtrate, and a product is obtained after the filter cake is washed and dried. The preparation method of the meso-tetraphenylchlorin has the advantages that the yield is high, safety and environmental protection are achieved, separation and purification are easy, and the product quality is stable.
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Paragraph 0058-0060

(2018/03/26)

A four-phenyl porphine production method (by machine translation)
The invention discloses a production method for tetraphenyl porphin. The production method includes the steps that 1, pyrrole and aromatic aldehyde are prepared into a mixed solution for standby application; 2, solvent is added into a polymerization reactor, the pressure of the polymerization reactor is maintained at 1-5 atm, the mixed solution obtained in the step 1 starts to be dripped to start a polymerization reaction, after the reaction is finished, reaction products are cooled to normal temperature, and filter liquor and a filter cake are obtained through filtration; 3, the filter cake obtained in the step 2 and propionic acid are added into an oxidation reactor, oxygen-containing gas is introduced to carry out an oxidation reaction, cooling is carried out after oxidation is finished, a solid and filter liquor are obtained through filtration, and the solid is washed and dried to obtain the tetraphenyl porphin. The production method has the advantages of being high in yield, safe and environmentally friendly, separation and purification are easy, and the production quality is stable.
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Paragraph 0059-0062

(2020/02/07)

Optochemical properties of gas-phase protonated tetraphenylporphyrin investigated using an optical waveguide NH3 sensor
5,10,15,20-Tetraphenylporphyrin (TPP) was synthesized, and a glass optical waveguide (OWG, which restricts and maintains the light energy in a specific, narrow space and propagates along the space axially) was coated with a gas-phase protonated TPP thin f
Tuerdi, Gulimire,Nizamidin, Patima,Kari, Nuerguli,Yimit, Abliz,Wang, Fu
p. 5614 - 5621
(2018/04/30)

Bifunctional metal-free photo-organocatalysts for enantioselective aerobic oxidation of β-dicarbonyl compounds
A series of bifunctional metal-free photo-organocatalysts have been developed by grafting the photosensitizer to cinchona-derived phase-transfer catalysts. Using air as a green oxidant and visible light as the driving force, these catalysts are applied to the oxidation of a range of β-dicarbonyl compounds in good yields (up to 97%) and enantioselectivities (up to 93:7 er).
Tang, Xiao-fei,Feng, Shi-hao,Wang, Ya-kun,Yang, Fan,Zheng, Ze-hao,Zhao, Jing-nan,Wu, Yu-feng,Yin, Hang,Liu, Guang-zhi,Meng, Qing-wei
p. 3624 - 3633
(2018/05/25)