14609-54-2Relevant articles and documents
Efficient electrocatalytic hydrogen gas evolution by a cobalt-porphyrin-based crystalline polymer
Wu, Yanyu,Veleta, José M.,Tang, Diya,Price, Alex D.,Botez, Cristian E.,Villagrán, Dino
, p. 8801 - 8806 (2018)
Herein, we report a crystalline CoTcPP-based [TcPP = the anion of meso-tetra(4-carboxyphenyl)porphyrin] polymeric system, 1, as a hydrogen evolution reaction (HER) electrocatalyst in acidic aqueous media. The material was characterized by powder X-ray diffraction (p-XRD), Fourier transform infrared (FT-IR) spectroscopy, and energy dispersive X-ray (EDX) analysis and its morphology was probed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polymer 1 shows a surface area of 441.74 m3 g-1, while the discrete CoTcPP molecule (2) shows a surface area of 3.44 m3 g-1. The HER catalytic performance was evaluated by means of linear sweep voltammetry in the presence of 0.5 M H2SO4 aqueous solution. To achieve 10 mA cm-2 cathodic current density, 1 and 2 respectively require an overpotential of 0.475 V and 0.666 V, providing strong evidence that the extended network of cobalt-based porphyrin leads to enhanced HER efficiency. The polymer also shows great tolerance for HER electrolysis in the presence of an acid remaining active over 10 hours.
Control of Listeria innocua biofilms by biocompatible photodynamic antifouling chitosan based materials
Castro, Kelly A.D.F.,Moura, Nuno M.M.,Fernandes, Ana,Faustino, Maria A.F.,Sim?es, Mário M.Q.,Cavaleiro, José A.S.,Nakagaki, Shirley,Almeida, Adelaide,Cunha, ?ngela,Silvestre, Armando J.D.,Freire, Carmem S.R.,Pinto, Ricardo J.B.,Neves, Maria da Gra?a P.M.S.
, p. 265 - 276 (2017)
New materials obtained through the incorporation of meso-tetraarylporphyrins, bearing phenyl or pentafluorophenyl groups at the meso positions with or without acid groups, in chitosan films have been prepared and characterized in detail. The efficiency of these porphyrinic-chitosan films (PS-CF) to prevent Listeria innocua attachment and subsequent biofilm formation was evaluated under different irradiation protocols (dark, light, light + dark, dark + light). All tested porphyrinic-chitosan films were photostable and effective in reducing Listeria innocua attachment during a period of 24 h exposure to white light. Biofilm development was nearly completely inhibited in two of the PS-CF films (one containing the 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin and the other one of the thio-carboxylate porphyrins) after being exposed to white light for 24 h followed by incubation in the dark for 48 h. Experiments with the non-immobilized porphyrins against cell suspensions of the same Listeria innocua strain showed that, the photodynamic inactivation efficiency was dependent on porphyrin. The demonstrated antimicrobial activity of PS-CF films, associated with the easy recovery of these films, make them promising photodynamic antifouling materials.
A zinc sulfide-supported iron tetrakis (4-carboxyl phenyl) porphyrin catalyst for aerobic oxidation of cyclohexane
Jiang, Yue-Xiu,Su, Tong-Ming,Qin, Zu-Zeng,Huang, Guan
, p. 24788 - 24794 (2015)
Zinc sulfide-supported iron tetrakis (4-carboxyl phenyl) porphyrin (Fe TCPP/ZnS) was prepared and used for aerobic cyclohexane oxidation. X-ray diffraction, ultraviolet-visible spectroscopy and Fourier-transform infrared spectroscopy were carried out. The effects of oxygen pressure, reaction temperature, amount of iron tetrakis (4-carboxyl phenyl) porphyrin (Fe TCPP) and reaction time on the Fe TCPP/ZnS-catalyzed cyclohexane oxidation process were investigated. Fe TCPP/ZnS exhibited excellent activity for aerobic cyclohexane oxidation. Under optimal reaction conditions, the turnover number, cyclohexane conversion, cyclohexanone and cyclohexanol yields were 8.6 × 105, 64.9% and 24.4%, respectively. The stability of Fe TCPP was improved after immobilization on zinc sulfide (ZnS), and the catalyst maintained nearly original levels of activity after several reaction cycles.
Facile synthesis, photophysical and electrochemical redox properties of octa- and tetracarboxamidophenylporphyrins and the first example of amido-imidol tautomerism in porphyrins
Yadav, Pinky,Sankar, Muniappan
, p. 651 - 657 (2017)
5,10,15,20-tetrakis(4′-carboxamidophenyl)porphyrin (1) and 5,10,15,20-tetrakis(3′,5′-dicarboxamidophenyl)porphyrin (2) have been synthesized in excellent yields and characterized by various spectroscopic techniques and cyclic voltammetric studies. Notably, 1 and 2 exhibited amido-imidol tautomerism in DMSO-d6. The imido tautomer ([sbnd]C(OH)[dbnd]NH) was stabilised in DMSO-d6 at 293?K while the same was converted into amido form ([sbnd]CONH2) at high temperature (418?K). This is a first example of amido-imidol tautomerism in porphyrins. The moderate electron withdrawing nature of imidol groups at meso-phenyl rings lead to 80–95?mV anodic shift in their first ring reduction potential whereas 50–110?mV anodic shift in first ring oxidation potential as compared to that of H2TPP.
N-confused porphyrin possessing glucamine-appendants: Aggregation and acid/base properties in aqueous media
Ikawa, Yoshiya,Ogawa, Hiroaki,Harada, Hiroyuki,Furuta, Hiroyuki
, p. 6394 - 6397 (2008)
A water-soluble derivative of N-confused porphyrin (NCP: 5,10,15,20-tetraaryl-2-aza-21-carbaporphyrin) was synthesized by introducing glucamine groups at the para-position of meso-aryl groups. The tetraglucamine-appended NCP (TG-NCP) exists as monocation in aqueous solution containing 6 mM sodium dodecyl sulfate (SDS) but exists as freebase to form aggregates in pure water. These properties are distinct from those of corresponding regular porphyrin, which exists as freebase in the micellar solution and practically insoluble in water.
In situ self-assembly of zirconium metal-organic frameworks onto ultrathin carbon nitride for enhanced visible light-driven conversion of CO2 to CO
Guo, Haiwei,Wan, Shipeng,Wang, Yanan,Zeng, Yiqing,Zhang, Shule,Zhen, Wenlong,Zhong, Qin
, p. 6034 - 6040 (2020)
A series of Zr-porphyrin metal-organic framework (Zr-PMOF)/ultrathin g-C3N4 (UCN) (ZPUCN) heterostructure photocatalysts, as stable and efficient catalysts for the photoreduction of CO2, have been fabricated via a facile in situ hydrothermal self-assembly method. An interfacial interaction is formed due to hollow Zr-PMOF nanotubes being surrounded by 3D ultrathin g-C3N4 (UCN) and benefiting from the ultrathin and conjugated π-structure of UCN, the unsaturated metal atoms and organic ligands of Zr-PMOFs can covalently link to organic g-C3N4. The interaction provides a platform for UCN as a conductor to transfer e- or as a donor to transfer e- to Zr-O cluster active sites to catalyze CO2, substantially achieving the spatial separation of charge carriers and suppressing the photogenerated electron-hole (e--h+) pair recombination rate. Benefitting from the cooperative effects of the well-designed nanostructure and chemical grafting, in the absence of triethanolamine, cocatalysts and photosensitizers, the optimized ZPUCN hybrid not only exhibits a better CO evolution yield (5.05 μmol g-1 h-1), which is 2.2 times and 3.2 times higher than those of pure Zr-PMOFs and UCN, respectively, but also displays excellent stability after 96 h photocatalysis. Information about the mechanism is also elucidated from selected characterizations.
Extra Unsaturated Metal Centers of Zirconium-Based MOFs: a Facile Approach towards Increasing CO2 Uptake Capacity at Low Pressure
Li, Zhong,Li, Xue,Chen, Chong,Zhou, Lijin,Guo, Qirui,Yuan, Dashui,Wan, Hui,Ding, Jing,Guan, Guofeng
, p. 194 - 202 (2018)
Developing adsorption materials to capture CO2 at low pressure has attracted great attention due to the low CO2 partial pressure in fuel gases. Herein, zirconium-based metal–organic frameworks (PCN-X) are successfully synthesized and open metal sites (Fe3+ and Al3+) are incorporated into the PCN-X MOFs. The results indicate that the CO2 adsorption capability is enhanced through the strong interaction between extra open metal centers and CO2 molecules at low pressure. Meanwhile, the CO2 adsorption capacity of PCN-X with incorporated Al3+ is higher than with incorporated Fe3+, which can be attributed to the higher isosteric heat of CO2 adsorption. The adsorption kinetics further indicate the faster CO2 transmission on PCN-X with extra Al3+ than with extra Fe3+. Besides, modified PCN-X, treated by some inorganic acids, exhibits favorable chemical stability, which is suitable for CO2 capture from acidic fuel gases.
From Metal–Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media
Jiao, Long,Wan, Gang,Zhang, Rui,Zhou, Hua,Yu, Shu-Hong,Jiang, Hai-Long
, p. 8525 - 8529 (2018)
It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized based on a novel mixed-ligand strategy to afford high-content (1.76 wt %) single-atom (SA) iron-implanted N-doped porous carbon (FeSA-N-C) via pyrolysis. Thanks to the single-atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized FeSA-N-C exhibits excellent oxygen reduction activity and stability, surpassing almost all non-noble-metal catalysts and state-of-the-art Pt/C, in both alkaline and more challenging acidic media. More far-reaching, this MOF-based mixed-ligand strategy opens a novel avenue to the precise fabrication of efficient single-atom catalysts.
Metalloporphyrins as chemical shift reagents: the unambiguous NMR characterization of the cis- and trans-isomers of meso-(bis)-4′-pyridyl-(bis)-4′-carboxymethylphenylporphyrins
Gianferrara, Teresa,Giust, Davide,Bratsos, Ioannis,Alessio, Enzo
, p. 5006 - 5013 (2007)
The condensation of pyrrole with 4-pyridylcarboxyaldehyde and methyl 4-formyl benzoate under Adler-Longo conditions yielded the series of meso-(4′-pyridyl)/(4′-carboxymethylphenyl)porphyrins as a mixture. Careful column chromatography afforded each isomer in pure form. In this paper we focus on the two bis-substituted isomeric meso-porphyrins, 5,10-bis(4′-pyridyl)-15,20-bis(4′-carboxymethylphenyl)porphyrin and 5,15-bis(4′-pyridyl)-10,20-bis(4′-carboxymethylphenyl)porphyrin, respectively, 4′-cis and 4′-transDPyDMeP. The assignment of the geometry of the two isomers was performed by 1H NMR spectroscopy on the trinuclear adducts [(4′-cisDPyDMeP){Ru(TPP)(CO)}2] and [(4′-transDPyDMeP){Ru(TPP)(CO)}2], obtained by selective coordination of [Ru(TPP)(CO)(EtOH)] (TPP=tetraphenylporphyrin) to the peripheral nitrogen atoms. The axially bound ruthenium porphyrins act as chemical shift reagents on the central porphyrin, allowing a clear distinction of the pyrrole proton resonances and consequent unambiguous assignment of the geometry of each isomer based upon symmetry considerations.
Nanoscale Synthesis of Two Porphyrin-Based MOFs with Gallium and Indium
Rhauderwiek, Timo,Waitschat, Steve,Wuttke, Stefan,Reinsch, Helge,Bein, Thomas,Stock, Norbert
, p. 5312 - 5319 (2016)
Two porphyrin-based metal-organic frameworks (MOFs) containing gallium or indium, [Ga2(OH)2(H2TCPP)]·3DMF·3H2O (Ga-PMOF) and [In2(OH)2(H2TCPP)]·3DMF·4H2O (In-PMOF) (H6TCPP = 4-tetracarboxyphenylporphyrin), were discovered using high-throughput methods. The structure was refined by the Rietveld-method starting from the structure model of Al-PMOF, [Al2(OH)2(H2TCPP)]. The new PMOFs exhibit BET surface areas between 1150 and 1400 m2 g-1 and are also porous toward CO2 (Ga-PMOF, 15.2 wt %; In-PMOF, 12.9 wt %). They are thermally stable in air up to 330 °C, but show limited chemical stabilities toward acids and bases. In order to achieve size control, different synthesis routes were investigated, i.e., batch synthesis at different temperatures (yield: In-PMOF-bs-th 96%, Ga-PMOF-bs-th 87%), ultrasound-assisted synthesis (yield: In-PMOF-bs-us 85%), and continuous-flow synthesis (yield: Ga-PMOF-cf 71%). By using these different methods we could control the nucleation rate and the crystal size. The crystal sizes were found to vary about 60 to 160 nm and 70 to 130 nm for Ga- and In-PMOF, respectively, which was proven by dynamic light scattering (DLS), powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements.
Porphyrinic Metal-Organic Framework Catalyzed Heck-Reaction: Fluorescence "turn-On" Sensing of Cu(II) Ion
Chen, Yu-Zhen,Jiang, Hai-Long
, p. 6698 - 6704 (2016)
It is of great importance for the highly selective, rapid, and sensitive detection of Cu(II) ion, as copper is an essential element in the environment and the human body, and exposure to high concentrations of Cu(II) will potentially cause health issues. In this work, we have developed a novel catalytic Heck reaction system based on Pd(II)-porphyrinic metal-organic framework (MOF), PCN-222-Pd(II), to generate highly fluorescent product in the presence of Cu(II). In this system, the achieved signal enlargement toward Cu(II) with high sensitivity not only takes advantage of a stronger binding affinity of Cu(II) over Pd(II) to the nitrogen atoms in the porphyrin, but also a rapid Pd(0)-catalyzed Heck-reaction triggered by the addition of Cu(II) ion. Compared with the previous detection methods, the current fluorescence "turn-on" approach not only realizes highly selective and sensitive detection of Cu(II) in aqueous solution, but also is able to separate the Cu(II) from the system. This work would open up a new door for MOF applications in the detection of metal ions in complex environments.
MOF/PEDOT/HPMo-based polycomponent hierarchical hollow micro-vesicles for high performance flexible supercapacitors
Wang, Bing,Liu, Shuo,Liu, Lin,Song, Wen-Wei,Zhang, Yue,Wang, Shi-Ming,Han, Zheng-Bo
, p. 2948 - 2958 (2021)
Metal-organic frameworks (MOFs) are promising electrode materials for supercapacitors; however, their electrochemical performances are limited by their low electrical conductivities. To address this problem, “conductive ink” poly(3,4-ethylenedioxythiophene) (PEDOT) was used to enhance the conductivity, while “electron sponge” polyoxometalate [PMo12O40]3?(PMo12) with large electronic transfer capability was used as the capacitance contributor. Finally, MOFs (PCN-224) acted as the host of this composite that provided the electrical double-layer capacitor and a PCN-224@PEDOT/PMo12-CC-II hierarchical hollow micro-vesicle nanostructure was obtainedviaa simple one-step electro-codeposition. The microvesicle nanocomposite was interspersed in MOF hosts. Benefiting from the novel structure and the synergistic effect of three components, the optimal areal capacitance of the PCN-224@PEDOT/PMo12-CC-II electrode was 4077.8 mF cm?2at 5 mA cm?2(the concentration ratio of EDOT?:?PMo12is 1?:?0.75), which is 32.9 times more than that of pristine PCN-224 (123.6 mF cm?2). Furthermore, a symmetric supercapacitor device was constructed by the PCN-224@PEDOT/PMo12-CC-II nanocomposite, which possessed an excellent energy density of 0.297-0.0192 mW h cm?2(at a power density of 0.324-5.128 W cm?2) and a good long-term cycle ability (84.59% for 10?000 cycles at 5 mA cm?2). This study presented a one-step electro-deposition synthetic strategy for the design and fabrication of the high-capacitance MOF-based electrode material, which showed great promise in the future design of high-performance materials for advanced energy production.
Metal–Organic Frameworks for the Exploitation of Distance between Active Sites in Efficient Photocatalysis
Deng, Hexiang,Gong, Xuan,Jiang, Zhuo,Lu, Lingxiang,Shu, Yufei,Wang, Chao,Xu, Xiaohui
, p. 5326 - 5331 (2020)
Discoveries of the accurate spatial arrangement of active sites in biological systems and cooperation between them for high catalytic efficiency are two major events in biology. However, precise tuning of these aspects is largely missing in the design of artificial catalysts. Here, a series of metal–organic frameworks (MOFs) were used, not only to overcome the limit of distance between active sites in bio-systems, but also to unveil the critical role of this distance for efficient catalysis. A linear correlation was established between photocatalytic activity and the reciprocal of inter active-site distance; a smaller distance led to higher activity. Vacancies created at selected crystallographic positions of MOFs promoted their photocatalytic efficiency. MOF-525-J33 with 15.6 ? inter active-site distance and 33 % vacancies exhibited unprecedented high turnover frequency of 29.5 h?1 in visible-light-driven acceptorless dehydrogenation of tetrahydroquinoline at room temperature.
Metal–Organic Framework-Derived FeCo-N-Doped Hollow Porous Carbon Nanocubes for Electrocatalysis in Acidic and Alkaline Media
Fang, Xinzuo,Jiao, Long,Yu, Shu-Hong,Jiang, Hai-Long
, p. 3019 - 3024 (2017)
Metal–organic frameworks (MOFs) are ideal precursors/ templates for porous carbons with homogeneous doping of active components for energy storage and conversion applications. Herein, metalloporphyrinic MOFs, PCN-224-FeCo, with adjustable molar ratio of FeII/CoII alternatively residing inside the porphyrin center, were employed as precursors to afford FeCo-N-doped porous carbon (denoted as FeCo-NPC) by pyrolysis. Thanks to the hollow porous structure, the synergetic effect between highly dispersed FeNx and CoNx active sites accompanied with a high degree of graphitization, the optimized FeCo2-NPC-900 obtained by pyrolysis at 900 °C exhibits more positive half-wave potential, higher diffusion-limited current density, and better stability than the state-of-the-art Pt/C, under both alkaline and acidic media. More importantly, the current synthetic approach based on MOFs offers a rational strategy to structure- and composition-controlled porous carbons for efficient electrocatalysis.
Enhanced Photodynamic Therapy by Reduced Levels of Intracellular Glutathione Obtained By Employing a Nano-MOF with CuII as the Active Center
Zhang, Wei,Lu, Jun,Gao, Xiaonan,Li, Ping,Zhang, Wen,Ma, Yu,Wang, Hui,Tang, Bo
, p. 4891 - 4896 (2018)
In photodynamic therapy (PDT), the level of reactive oxygen species (ROS) produced in the cell directly determines the therapeutic effect. Improvement in ROS concentration can be realized by reducing the glutathione (GSH) level or increasing the amount of photosensitizer. However, excessive amounts photosensitizer may cause side effects. Therefore, the development of photosensitizers that reduce GSH levels through synergistically improving ROS concentration in order to strengthen the efficacy of PDT for tumor is important. We report a nano-metal–organic framework (CuII-metalated nano-MOF {CuL-[AlOH]2}n (MOF-2, H6L=mesotetrakis(4-carboxylphenyl)porphyrin)) based on CuII as the active center for PDT. This MOF-2 is readily taken up by breast cancer cells, and high levels of ROS are generated under light irradiation. Meanwhile, intracellular GSH is considerably decreased owing to absorption on MOF-2; this synergistically increases ROS concentration and accelerates apoptosis, thereby enhancing the effect of PDT. Notably, based on the direct adsorption of GSH, MOF-2 showed a comparable effect with the commercial antitumor drug camptothecin in a mouse breast cancer model. This work provides strong evidence for MOF-2 as a promising new PDT candidate and anticancer drug.
Neutral Porphyrin Derivative Exerts Anticancer Activity by Targeting Cellular Topoisomerase i (Top1) and Promotes Apoptotic Cell Death without Stabilizing Top1-DNA Cleavage Complexes
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)
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.
Porphyrin derivatives as potent and selective blockers of neuronal Kv1 channels
Daly,Al-Sabi,Kinsella,Nolan,Dolly
, p. 1066 - 1069 (2015)
Selective inhibitors of voltage-activated K+ channels are needed for the treatment of multiple sclerosis. In this work it was discovered that porphyrins bearing 2-4 carbon alkyl ammonium side chains predominantly blocked the Kv1.1 current whilst Kv1.2 was susceptible to a porphyrin bearing polyamine side chains.
Synthesis of magnetite-porphyrin nanocomposite and its application as a novel magnetic adsorbent for removing heavy cations
Bakhshayesh, Sara,Dehghani, Hossein
, p. 2614 - 2624 (2013)
Magnetite-porphyrin nanocomposite (MPNC) was synthesized as a novel magnetic adsorbent for removing heavy cations. Firstly, we prepared nano-sized magnetite using a simple hydrothermal route. The synthesis of nanoscaled magnetite was carried out through reaction between iron source and various amines. In this paper, we studied effective parameters in controlling shape and size of nanoscaled magnetite. These parameters were presence of alkaline, reaction time, kind of amine and iron salt. Morphology, particle size and magnetic properties of the nanoscaled magnetite were obtained by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier transform infrared (FT-IR), diffuse reflectance spectra (DRS) and vibrating sample magnetometer (VSM). Our study showed that the synthesized magnetite from reaction between FeSO4 and hydrazinum hydrate has spherical shape. The synthesized magnetite was a nanosized compound and used for preparation of magnetite-porphyrin nanocomposite. The synthesized magnetite-porphyrin hybrid material had magnetic property and was used as magnetic adsorbent for removing heavy cations of water. Satisfactory separation from solutions in the order of Pb2+ > Cd2+ > Hg 2+ was obtained.
A spectroscopic and molecular docking study of interactions of tetracarboxyphenyl porphyrin and chlorin e6 with bovine serum albumin
Vicente-Escobar, Jonathan Osiris,García-Sánchez, Miguel A.,González,Cipagauta-Díaz,Estrella González
, p. 4501 - 4515 (2021)
Abstract: In order to use tetrapyrrolic macrocyclic species in medical applications, the interactions of bovine serum albumin (BSA) with tetrakis-para-carboxyphenyl-porphyrin (H2T(p-COOH) PP or TCPP) and Chlorin e6 (Ce6), under different conditions, were investigated by fluorescence spectroscopy and UV–VIS absorption spectroscopy and contrasted with molecular docking study. The binding constant (Kb) values at three different temperatures were calculated using the modified Stern–Volmer equation. The enthalpy change (ΔH) and entropy change (ΔS) were determined based on the van’t Hoff equation. The results of fluorescence spectroscopy indicate that static quenching is the dominant process resulting from the BSA-TCPP complex formation. In the case of the BSA-Ce6 complex, static quenching was confirmed too. Thermodynamic analysis indicated that hydrogen bonds and van der Waals interactions were the predominant intermolecular forces in the binding process to stabilize the BSA-TCPP and BSA-Ce6 complexes. Molecular docking suggests that the probable binding site of the two macrocyclic species at BSA occurs in the vicinity of the Trp-134 residue. Molecular modeling study further confirmed interactions in the binding mode obtained experimentally. Graphic abstract: [Figure not available: see fulltext.]
Photocatalytic activity of nanohybrid Co-TCPP@TiO2/WO3 in aerobic oxidation of alcohols under visible light
Safaei, Elham,Mohebbi, Sajjad
, p. 3933 - 3946 (2016)
Here the photocatalytic performance activity of a novel Co-TCPP@TiO2/WO3 nanohybrid toward selective alcohol oxidation is reported. The Co-TCPP@TiO2/WO3 nanohybrid was prepared in three major steps. After the synthesis of nano-disk WO3 by a new green chemical method using natural pomegranate juice, a TiO2/WO3 nanocomposite was obtained via a sonochemical assisted hydrothermal method, followed by anchoring of cobalt(ii)-meso-tetra(4-carboxyphenyl)porphyrin (Co-TCPP) on TiO2/WO3. All intermediate nanomaterials and the final nanohybrid compound were characterized by FE-SEM, EDAX, XRD, DRS and FT-IR spectroscopy. The photocatalytic behavior of the TiO2/WO3 nanocomposite and Co-TCPP@TiO2/WO3 nanohybrid were investigated in oxidation of primary alcohols under visible light irradiation in the presence of air as the oxygen source. The progress of the catalytic reactions was monitored using a TLC technique. Remarkably, the photocatalytic performance of the TiO2/WO3 nanocomposite was enhanced from 70 to 95% by anchoring the TCPP on the composite. This nanohybrid catalyst was reused and recovered ten times without losing photocatalytic activity. In fact, nanohybrid Co-TCPP@TiO2/WO3 shows an extremely higher efficiency and shorter reaction time (1 h) than the TiO2/WO3 nanocomposite. So, this nanohybrid compound has the potential to be used as a high performance heterogeneous photocatalyst under visible light irradiation for oxidation reactions, with advantages of high activity, high selectivity, reusability and easy separation.
Conjugates of platinum nanoparticles with gallium tetra - (4-Carboxyphenyl) porphyrin and their use in photodynamic antimicrobial chemotherapy when in solution or embedded in electrospun fiber
Managa, Muthumuni,Antunes, Edith,Nyokong, Tebello
, p. 94 - 101 (2014)
The conjugation of Pt nanoparticles with ClGa(III) 5,10,15,20-tetrakis-(4- carboxyphenyl) porphyrin (ClGaTCPP) showed greater antimicrobial activity against a gram positive and drug resistant bacteria Staphylococcus aureus, than when the porphyrin was used alone. ClGaTCPP and its conjugate with platinum nanoparticle was successfully electrospun into a polystyrene polymer where the diameter ranged from 10 to 22 μm. The conjugates within the fiber still showed activity towards S. aureus.
DNA photocleavage by porphyrin-polyamine conjugates
Garcia, Guillaume,Sarrazy, Vincent,Sol, Vincent,Morvan, Caroline Le,Granet, Robert,Alves, Sandra,Krausz, Pierre
, p. 767 - 776 (2009)
A series of polyamine-porphyrin conjugates bearing two (cis or trans position) or four units of spermidine or spermine was synthesized. We studied the binding of these cationic porphyrins to calf thymus DNA by the means of UV-vis spectroscopy and we investigated their ability to cleave plasmid DNA in the presence of light. DNA binding and DNA photocleavage abilities were found to depend on structural characteristics as (a) the relative positions of the side chains on the porphyrin ring and (b) the nature of the attached side chains (spermidine or spermine). DNA cleavage was also studied in the presence of a singlet oxygen quencher (NaN3) and in the presence of a hydroxyl radical scavenger (mannitol). Singlet oxygen was the major species responsible for the cleavage of DNA previously observed. Collectively, these data show that polyamine-porphyrin conjugates could be promising phototherapeutic agents.
Visible light superoxide radical anion generation by tetra(4-carboxyphenyl) porphyrin/TiO2: EPR characterization
Diaz-Uribe, Carlos E.,Daza, Martha C.,Martínez, Fernando,Páez-Mozo, Edgar A.,Guedes, Carmen L.B.,Di Mauro, Eduardo
, p. 172 - 178 (2010)
The generation of superoxide radical anion O2- from tetra(4-carboxyphenyl)porphyrin (TCPP) adsorbed on TiO2 in DMSO and irradiated by visible light was studied using EPR spectroscopy and 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as spin trap. A chemical filter was used to remove light with wave lengths 2- and the second to the so-called nitroxide-like radical. Hyperfine coupling constants determined for the DMPO-O2 - adduct are: aN = 14.1 G, aHβ = 10.8 G and aHγ = 1.4 G, and for the nitroxide-like radical adduct aN = 14 G. An increased intensity of the EPR lines corresponding to the nitroxide-like radical adduct was observed under irradiation without chemical filter, which suggests a possible DMPO-O 2- decomposition. No singlet oxygen could be detected by EPR spectroscopy using 2,2,6,6-tetramethyl-4-piperidone (TEMP) as spin trap and by chemical trapping using anthracene as the trap.
Porphyrin supramolecular arrays formed by weakly interacting meso-functional groups on Au(111)
Sánchez-Mu?oz, Esteban,Gárate-Morales, José L.,Sandoval-Lira, Jacinto,Hernández-Pérez, Julio M.,Aguilar-Sánchez, Rocío
, (2019)
The formation of a binary porphyrinic self-assembled system between meso-tetrakis(4-carboxyphenyl) porphyrin (TCPP) and meso-tetrakis(4-dimethyl amino) porphyrin (TDAP) was easily designed through non-covalent interactions in solution and adsorbed on a gold substrate. It was found that non-covalent interactions and geometrical conformations between porphyrins allow their self-assembly into a well-defined arrangement, which was confirmed by UV-Vis spectroscopy, electrochemistry, atomic force microscopy and density functional theory (DFT) studies.
A large π-conjugated tetrakis (4-carboxyphenyl) porphyrin anode enables high specific capacity and superior cycling stability in lithium-ion batteries
Cui, Guanglei,Du, Xiaofan,Liu, Hao,Luo, Ting,Wu, Han,Xu, Hai,Yang, Jinfeng,Zhang, Jianjun,Zhang, Jinning,Zhang, Min
, p. 11370 - 11373 (2019)
We demonstrated a novel single molecule-tetrakis(4-carboxyphenyl) porphyrin (TCPP) with a large π-conjugated system as a high-performance organic anode of lithium batteries. It was found that this TCPP displayed relatively low solubility (-1) in a 1 M LiDFOB/PC electrolyte, high reversible specific capacity (ca. 1200 mA h g-1 at 358 mA g-1), excellent rate capability (548.4 mA h g-1 at 8 A g-1) and superior cycling performance (capacity retention of 89percent after 2500 cycles at 6 A g-1).
Fabrication and application of copper metal–organic frameworks as nanocarriers for pH-responsive anticancer drug delivery
Gharehdaghi, Zahra,Molaabasi, Fatemeh,Naghib, Seyed Morteza,Rahimi, Rahmatollah
, (2022/01/11)
Copper-based metal?organic frameworks (Cu-MOFs) have been extensively used in delivery of several therapeutics because of their cytocompatibility, favorable degradation and structural flexibility. In this work, we investigated two types of Cu-MOF-based nanocomposites including GO/Cu-TCPP and Fe3O4@Cu3(BTC)2 for loading of doxorubicin (DOX) and pH-sensitive release of the drug in vitro. The Fe3O4@Cu3(BTC)2 is an octahedron network structure, while the GO/Cu-TCPP nanocomposite consists of copper (II)-porphyrin metal–organic framework (Cu-TCPP) crystals embedded between exfoliated graphene oxide (GO) layers. Our studies show that GO/Cu-TCPP has adsorbed more doxorubicin (DOX) (45.7?wt.%) compared to Fe3O4@Cu3(BTC)2 (40.5?wt.%). More drug loading for Cu3(BTC)2 was also obtained than that of Cu-TCPP. For GO/Cu-TCPP at pH 5, 98.9% of DOX released for 60?h and 33.5% of DOX released after 60?h at pH 7.4, while the released amount of DOX from Fe3O4@Cu3(BTC)2 at pH 5 reached 85.5% and 33.5% at pH 7.4 afterward 60?h. The difference between the amount of drug released in two nanocomposites related to drug loading capacity demonstrating the impact nanocomposite structure on the smart MOF construction for pH-responsive behavior in vitro. Based on the results, the GO/Cu-TCPP and Fe3O4@Cu3(BTC)2 nanocomposites possess low toxicity and good biocompatibility, but DOX-loaded GO/Cu-TCPP generate better toxicity to cancer cells compared with Fe3O4@Cu3(BTC)2-DOX. Graphical abstract: [Figure not available: see fulltext.]
A chromatography-free synthesis of meso-Tetrakis(4-formylphenyl) porphyrin and meso-Tetrakis(3-formylphenyl) porphyrin: Versatile synthons in supramolecular and macromolecular chemistry
De Bruin, Bas,Mathew, Simon,Meeus, Eva J.,Mouarrawis, Valentinos,Reek, Joost
, (2021/05/25)
A facile synthetic strategy was developed for the synthesis of meso-Tetrakis(4-formyl-phenyl)porphyrin and meso-Tetrakis(3-formylphenyl)porphyrin from commercially available starting materials. This method gives facile access to practical amounts of these synthons in high purity and good overall yield, without employing laborious chromatographic separations. The reduction of the respective carboxylic acid-functionalized porphyrins by LiAlH4 afforded the tetra(benzylalcohol)porphyrin intermediates, subsequently utilized in a Parikh-Doering oxidation to selectively afford the desired tetraformylated products. The inherent ease of synthesis of these porphyrin building blocks provides a convenient pathway for the synthesis of various macromolecular and supramolecular architectures for applied chemical technologies.
