21211-65-4Relevant articles and documents
Chiral and achiral basket-handle porphyrins: Short synthesis and stereostructures of these versatile building blocks
Gehrold, Andreas C.,Bruhn, Torsten,Schneider, Heidi,Radius, Udo,Bringmann, Gerhard
, p. 210 - 213 (2015)
Both, chiral and achiral basket-handle porphyrins were synthesized via a short, reliable, and efficient route in multigram quantities. Standard synthetic protocols such as metalation of the macrocycle, halogenation, and borylation of the porphyrin core or alkyl- and arylation with lithium organyls were successfully adapted. The planar-chiral representatives were resolved into their enantiomers, whose absolute configurations were determined by comparison of experimental CD spectra with TDCAM-B3LYP calculated ones.
A Porphyrin-Based Conjugated Polymer for Highly Efficient In Vitro and In Vivo Photothermal Therapy
Guo, Bing,Feng, Guangxue,Manghnani, Purnima Naresh,Cai, Xiaolei,Liu, Jie,Wu, Wenbo,Xu, Shidang,Cheng, Xiamin,Teh, Cathleen,Liu, Bin
, p. 6243 - 6254 (2016)
Conjugated polymers have been increasingly studied for photothermal therapy (PTT) because of their merits including large absorption coefficient, facile tuning of exciton energy dissipation through nonradiative decay, and good therapeutic efficacy. The high photothermal conversion efficiency (PCE) is the key to realize efficient PTT. Herein, a donor–acceptor (D–A) structured porphyrin-containing conjugated polymer (PorCP) is reported for efficient PTT in vitro and in vivo. The D–A structure introduces intramolecular charge transfer along the backbone, resulting in redshifted Q band, broadened absorption, and increased extinction coefficient as compared to the state-of-art porphyrin-based photothermal reagent. Through nanoencapsulation, the dense packing of a large number of PorCP molecules in a single nanoparticle (NP) leads to favorable nonradiative decay, good photostability, and high extinction coefficient of 4.23 × 104m?1 cm?1 at 800 nm based on porphyrin molar concentration and the highest PCE of 63.8% among conjugated polymer NPs. With the aid of coloaded fluorescent conjugated polymer, the cellular uptake and distribution of the PorCP in vitro can be clearly visualized, which also shows effective photothermal tumor ablation in vitro and in vivo. This research indicates a new design route of conjugated polymer-based photothermal therapeutic materials for potential personalized theranostic nanomedicine.
Selective oxidation of alcohols by porphyrin-based porous polymer-supported manganese heterogeneous catalysts
Chen, Jian,Zhang, Yan,Zhu, Dajian,Li, Tao
, (2020)
A series of porphyrin-based porous polymers to support Mn heterogeneous catalysts (Mn/TFP-DPM, Mn/TFP-DPM-2, Mn/TFP-DPM-3, and Mn/TFP-DPM-4) in the selective oxidation of alcohols were designed. TFP-DPM and TFP-DPM-2 demonstrated micro/nanoscale spherical morphology, whereas TFP-DPM-3 and TFP-DPM-4 exhibited nanosheets structure. According to surface area and porosity analysis results, the specific surface areas of these catalysts were less than 300 m2 g–1. Thermogravimetric analysis indicated that the synthesized catalysts maintain their stability even at 300 °C. Catalysts Mn/TFP-DPM and Mn/TFP-DPM-3, which had the smallest and largest specific surface area among the four catalysts, respectively, were used to perform selective oxidation reaction of alcohols, with experimental results indicating that both have excellent catalytic performance. As these catalysts possess good catalytic performance despite their low specific surface area, we suggest that porphyrin-based porous polymer-supported Mn heterogeneous catalysts are promising materials for selective oxidation of alcohols.
Structure-charge transport relationship of 5,15-dialkylated porphyrins
Zhou, Li,Xu, Zong-Xiang,Zhou, Ye,Feng, Yan,Zhou, Xiang-Ge,Xiang, Hai-Feng,Roy
, p. 5139 - 5141 (2012)
5,15-Dialkyl-substituted porphyrins that are symmetrically capped with ethyl (C2-Por), butyl (C4-Por) and hexyl (C 6-Por) were synthesized and characterized. Molecular structure versus physical property relationship has been established through the analysis of planar charge transport using thin film transistor (TFT) structure.
Remarkable isolation, structural characterisation and electrochemistry of unexpected scrambling analogues of 5-ferrocenyl-10,20-diphenylporphyrin
Auger, Aurelien,Muller, Alfred J.,Swarts, Jannie C.
, p. 3623 - 3633 (2007)
Selective condensation of 5-ferrocenyldipyrromethane, 1, and dipyrromethane, 2, with benzaldehyde, 3, led to 5-ferrocenyl-10,20- diphenylporphyrin, 5. During the condensation, an unusually large amount of scrambling was observed which led to the isolation of two further ferrocenylated porphyrin analogues 6 and 7. The structure of 6 was confirmed by a single-crystal X-ray study. A mechanism is proposed for this atypical scrambling which is likely to involve acid-catalysed reversion of the dipyrromethane synthesis. 1H NMR further elucidated the structures of each complex and showed the existence of atropisomerism. An electrochemical study (cyclic voltammetry, Osteryoung square wave and linear sweep voltammetry) showed that there exists a linear relationship between the sum of the group electronegativities of meso substituents of the obtained porphyrins and the formal reduction potentials of the two observed ring-centred reduction processes, the meso substituent ferrocenyl-based oxidation process and the first ring-centred oxidation wave. These four relationships could be mathematically quantified. Due to the strong electron-withdrawing properties of the oxidised ferrocenium group, the second ring centred oxidation wave fell outside the potential window of dichloromethane as solvent. The Royal Society of Chemistry.
Nonlinear optical properties of symmetrical and asymmetrical porphyrin derivatives with click chemistry modification
Liu, Xiong,Wang, Dong,Gao, Hong,Yang, Zhou,Xing, Yan,Cao, Hui,He, Wanli,Wang, Huihui,Gu, Jianming,Hu, Huiying
, p. 155 - 163 (2016)
The novel kind of charge-transfer porphyrin complexes with symmetrical and asymmetrical side groups were synthesized by the high-yielding [2?+?2] click chemistry reaction involved a two-step procedure. Both electrochemical and UV–vis studies were characterized and proved that the side groups of the porphyrin complexes played an important role on optical properties and energy gaps. The novel series did show the narrower band gap and broader absorption in the visible and near infrared region. As the side groups, the click moieties also affected the third-order nonlinear optical responses, and all the compounds exhibited the expected nonlinear optical properties which were affected by the chemical structures. The optical-limiting performance had also been studied, which was in agreement with the result of Z-scan experiments.
Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening
Haldar, Ritesh,Batra, Kamal,Marschner, Stefan Michael,Kuc, Agnieszka B.,Zahn, Stefan,Fischer, Roland A.,Br?se, Stefan,Heine, Thomas,W?ll, Christof
, p. 7847 - 7851 (2019)
In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.
The effect of pyridyl substituents on the thermodynamics of porphyrin binding to G-quadruplex DNA
Rowland, Gerald B.,Barnett, Kerry,Dupont, Jesse I.,Akurathi, Gopalakrishna,Le, Vu H.,Lewis, Edwin A.
, p. 7515 - 7522 (2013)
Most of the G-quadruplex interactive molecules reported to date contain extended aromatic flat ring systems and are believed to bind principally by π-π stacking on the end G-tetrads of the quadruplex structure. One such molecule, TMPyP4, (5,10,15,20-tetra(N-methyl-4-pyridyl)porphyrin), exhibits high affinity and some selectivity for G-quadruplex DNA over duplex DNA. Although not a realistic drug candidate, TMPyP4 is used in many nucleic acid research laboratories as a model ligand for the study of small molecule G-quadruplex interactions. Here we report on the synthesis and G-quadruplex interactions of four new cationic porphyrin ligands having only 1, 2, or 3 (N-methyl-4-pyridyl) substituents. The four new ligands are: P(5) (5-(N-methyl-4-pyridyl)porphyrin), P(5,10) (5,10-di(N-methyl-4-pyridyl)porphyrin), P(5,15) (5,15-di(N-methyl-4- pyridyl)porphyrin), and P(5,10,15) (5,10,15-tri(N-methyl-4-pyridyl)porphyrin). Even though these compounds have been previously synthesized, we report alternative synthetic routes that are more efficient and that result in higher yields. We have used ITC, CD, and ESI-MS to explore the effects of the number of N-methyl-4-pyridyl substituents and the substituent position on the porphyrin on the G-quadruplex binding energetics. The relative affinities for binding these ligands to the WT Bcl-2 promoter sequence G-quadruplex are: K TMPyP4 ≈ KP(5,15) > KP(5,10,15) >>> KP(5,10), KP(5). The saturation stoichiometry is 2:1 for both P(5,15) and P(5,10,15), while neither P(5) nor P(5,10) exhibit significant complex formation with the WT Bcl-2 promoter sequence G-quadruplex. Additionally, binding of P(5,15) appears to interact by an 'intercalation mode' while P(5,10,15) appears to interact by an 'end-stacking mode'.
A New Potent Antimicrobial Metalloporphyrin
Jiang, Lu,Chee, Pei Lin,Gao, Jian,Gan, Ching Ruey Raymond,Owh, Cally,Lakshminarayanan, Rajamani,Jiang, Shan,Hor, T. S. Andy,Loh, Xian Jun
, p. 1007 - 1015 (2021/03/30)
A series of bis-acryl functionalized porphyrins and their corresponding metalloporphyrins (M=Co, Mn) were synthesized and investigated for their antimicrobial properties through MIC screening and bacteria time-kill kinetic studies. The Mn(III) 4-(bis)methylphenyl-substituted-porphyrins showed superior batericidal activities even in the dark with low hemotoxicity and good cytotoxicity profile.
A Synthetic Strategy for Cofacial Porphyrin-Based Homo- and Heterobimetallic Complexes
Schissler, Christoph,Schneider, Erik K.,Felker, Benjamin,Weis, Patrick,Nieger, Martin,Kappes, Manfred M.,Br?se, Stefan
supporting information, p. 3047 - 3054 (2021/01/20)
We present a straightforward and generally applicable synthesis route for cofacially linked homo- and heterobimetallic porphyrin complexes. The protocol allows the synthesis of unsymmetrical aryl-based meso-meso as well as β-meso-linked porphyrins. Our method significantly increases the overall yield for the published compound known as o-phenylene-bisporphyrin (OBBP) by a factor of 6.8. Besides the synthesis of 16 novel homobimetallic complexes containing MnIII, FeIII, NiII, CuII, ZnII, and PdII, we achieved the first single-crystal X-ray structure of an unsymmetrical cofacial benzene-linked porphyrin dimer containing both planar-chiral enantiomers of a NiII2 complex. Additionally, this new methodology allows access to heterobimetallic complexes such as the FeIII-NiII containing carbon monoxide dehydrogenase active site analogue. The isolated species were investigated by various techniques, including ion mobility spectrometry, DFT calculations, and UV/Vis spectroscopy. This allowed us to probe the influence of interplane distance on Soret band splitting.
