6164-53-0Relevant academic research and scientific papers
Development of the sensitizer for generating higher-energy photons under diluted condition via the triplet-triplet annihilation-supported upconversion
Tanaka, Kazuo,Ohashi, Wataru,Inafuku, Kenichi,Shiotsu, Shohei,Chujo, Yoshiki
, (2019/08/26)
It was previously reported that photon upconversion can occur in the solution containing anthracene and the Pt complex of octaethylporphyrin (PtOEP) via the triplet-triplet annihilation process. In this study, by employing the modified Pt complex of the dual anthracene-tethered porphyrin, DA-PtP as a sensitizer, it is demonstrated that shorter-wavelength light can be generated under diluted condition. We synthesized DA-PtP and compared upconversion properties by changing the type of sensitizers. Accordingly, it was shown that the photon upconversion proceeded with the xenon lamp (540 nm) in the presence of DA-PtP. Furthermore, it was found that the emission band in the shorter wavelength light in the near UV region was observed from the solution containing DA-PtP even under diluted condition. From the mechanistic investigation, it was proposed that the anthracene moieties in DA-PtP might inhibit to form agglomeration with the free anthracene. As a result, reabsorption of the higher-energy light generated from upconversion could be suppressed.
Albumin aggregation promoted by protoporphyrin in vitro
Gubarev, Yury A.,Kiselev, Aleksey N.,Lebedeva, Natalya Sh.,Syrbu, Sergey A.,Yurina, Elena S.
, p. 211 - 213 (2020/05/25)
Protoporphyrin upon its binding with serum albumin changes its secondary structure due to the conversion of part of α helices into β-folding. This process results in the association of albumin globules in vitro.
Functionalization of Deutero- and Protoporphyrin IX Dimethyl Esters via Palladium-Catalyzed Coupling Reactions
O'Brien, Jessica M.,Sitte, Elisabeth,Flanagan, Keith J.,Kühner, Hannes,Hallen, Lukas J.,Gibbons, Dáire,Senge, Mathias O.
, p. 6158 - 6173 (2019/05/15)
Herein, we report the functionalization of the β-positions of deutero- and protoporphyrin IX dimethyl esters. Initial halogenations were carried out on both deutero- and protoporphyrin IX dimethyl esters. Although previously reported, vastly optimized yields with respect to deuteroporphyrin halogenation were obtained. Methods were developed for the bromination of the vinyl groups of protoporphyin IX dimethyl ester. Subsequent palladium-catalyzed coupling reactions were utilized to modify the periphery of these naturally occurring porphyrin derivatives with a variety of functionalities. The described Suzuki, Sonogashira, and "Click" reactions demonstrate the ease at which these porphyrins may be manipulated and even interchangeable, as will be discussed for one example. X-ray crystallographic analysis successfully determined the structure of two derivatives synthesized. Results identified a unique head-to-tail stacking pattern for 3,8-diphenyldeuteroporphyrin IX dimethyl ester, most likely due to the presence of additional aromatic moieties on the periphery of the porphyrin.
Preparation method of protoporphyrin disodium
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Paragraph 0063-0082, (2018/11/22)
The invention provides a preparation method of protoporphyrin disodium, and belongs to the field of synthesis of organic compounds. The method comprises the following steps: ensuring that protoporphyrin, absolute methanol and concentrated sulfuric acid are subjected to alcohol acid reaction in an ultrasound condition, so as to obtain protoporphyrin diester; ensuring that the protoporphyrin diester, a NaOH methanol solution and methylbenzene are subjected to saponification reaction in an ultrasound condition, so as to obtain the protoporphyrin disodium. The method has the advantages that assistance of ultrasonic wave is adopted to replace high-temperature reflux, so as to form the protoporphyrin disodium, hydrogen chloride gas is not required to be prepared during preparation, the adoptionof strong-toxicity reagents, such as chloroform, is further avoided, a high-temperature condition is not required to be use, the technology is simplified, and the whole process is easy to operate.
Facile iodination of the vinyl groups in protoporphyrin IX dimethyl ester and subsequent transformation of the iodinated moieties
Miyata, Kota,Yasuda, Satoru,Masuya, Takuto,Ito, Satoshi,Kinoshita, Yusuke,Tamiaki, Hitoshi,Oba, Toru
supporting information, p. 3707 - 3711 (2018/05/28)
Iodination of protoporphyrin IX dimethyl ester using phenyliodine bis(trifluoroacetate) (PIFA) and I2 was studied. Iodine added to both the C3- and C8-vinyl groups equally to afford the iodohydrin or iodoether in the presence of water or alcohol, respectively. Any meso-hydrogen atom was not substituted by an iodine atom under these conditions, although both the vinyl group and one of the meso positions of methyl pyropheophorbide-a bearing a chlorin π-system, a chlorophyll-a derivative, was modified with PIFA and I2. The reaction intermediates derived from the porphyrin were more reactive than those from the chlorin and liable to form intermolecular linkages. The obtained 2-iodo-1-hydroxyethyl group was transformed into a formyl group by a mild treatment. The corresponding iodoether moiety was readily converted into the acetyl group under basic conditions. These transformations were also applicable to smaller olefins such as styrene.
Chlorin derivatives sterically-prevented from self-aggregation with high antitumor activity for photodynamic therapy
Linares, Irwin A.P.,de Oliveira, Kleber T.,Perussi, Janice Rodrigues
, p. 518 - 527 (2017/06/29)
In this study two new chlorin derivatives sterically prevented from aggregation were synthesised by the Diels-Alder reaction between protoporphyrin IX dimethyl ester and 1-(2-hydroxyethyl)maleimide. The compounds were fully characterised by 1H NMR, 13C NMR, UV-Vis and high-resolution mass spectroscopy (HRMS) and their photochemical properties such as singlet oxygen quantum yield (?0), fluorescence quantum yield (?f) and photodegradation were also evaluated. Furthermore, the partition coefficient (log P) revealed that these compounds present amphiphilic properties. Studies of the photodynamic action in tumour cells (HEp-2 and HeLa) and non-tumour cells (Vero) were also performed in order to confirm the photodynamic therapy (PDT) activity that was indicated by the preliminary photophysical studies. Those phototoxicity results were 55–77% higher than the results obtained with the commercial photosensitiser verteporfin. Finally, cytotoxic assays were performed with the new photosensitiser candidates and cell death was determined using fluorescence microscopy, which provided information about the mechanisms of cell death. In general, we have obtained improved and accessible compounds for PDT studies, as highlighted by the research presented here.
Light harvesting in silicon(111) surfaces using covalently attached protoporphyrin IX dyes
Alderman, Nicholas,Danos, Lefteris,Fang, Liping,Grossel, Martin C.,Markvart, Tom
, p. 12120 - 12123 (2017/11/14)
We report the photosensitization of crystalline silicon via energy transfer using covalently attached protoporphyrin IX (PpIX) derivative molecules at different distances via changing the diol linker to the surface. The diol linker molecule chain length was varied from 2 carbon to 10 carbon lengths in order to change the distance of PpIX to the Si(111) surface between 6 ? and 18 ?. Fluorescence quenching as a function of the PpIX-Si surface distance showed a decrease in the fluorescence lifetime by almost two orders of magnitude at the closest separation. The experimental fluorescence lifetimes are explained theoretically by a classical Chance-Prock-Silbey model. At a separation below 2 nm, we observe for the first time, a F?rster-like dipole-dipole energy transfer with a characteristic distance of R0 = 2.7 nm.
Photophysical properties of porphyrin derivatives: Influence of the alkyl chains in homogeneous and micro-heterogeneous systems
Santos, Sandra Cruz Dos,Moreira, Leonardo Marmo,Novo, Diogo La Rosa,Santin, Luiza Rosimeri Romano,Bianchini, Daniela,Bonacin, Juliano Alves,Romani, Ana Paula,Fernandes, Adjaci Uchoa,Baptista, Mauricio S.,De Oliveira, Hueder Paulo Moises
, p. 920 - 933 (2015/09/02)
This work is focused on the evaluation of the photophysical properties of protoporphyrin-IX derivatives with different alkyl chains. The goal of this work is to understand the physicochemical properties and select prototypes of photosensitizers for photodynamic therapy. Solvents with different dielectric constants were used to obtain relevant data on different physical and chemical processes, such as fluorescence quantum yield and emission level of aggregation in nonpolar media. In addition, studies were conducted in micro-heterogeneous systems through the interaction of porphyrin derivatives with different surfactants, such as cetyltrimethylammonium bromide, sodium dodecyl sulfate and octyl phenol ethoxylate. The compounds were characterized by electronic absorption spectroscopy in the ultraviolet-visible region and fluorescence emission spectroscopy. The comparative study between the different chemical environments evaluated in the present study represents a relevant contribution to the comprehension of the properties acquired by the porphyrins in different micro-heterogeneous systems, which allows us to understand various interactions that these compounds are subject in biological medium, such as the influence of the polarity of the medium in the reactivity of porphyrins with nonpolar substituents. These results show the decisive physicochemical influence of the alkyl chains on the properties of the tetraazomacrocycle porphyrin.
Protonation-deprotonation equilibria in tetrapyrroles Part 4: Mono- and diprotonations of deutero-, hemato-, meso-, and protoporphyrin IX dimethyl esters in methanolic hydrochloric acid
Hynninen, Paavo H.
, p. 385 - 395 (2015/05/20)
The N-protonations in the deutero, hemato, meso and protoporphyrin IX dimethyl esters (DME) were investigated by spectrophotometric titrations using HCl as the acid and methanol as the solvent. Two spectroscopically different protonated species were observed for each porphyrin DME in addition to the neutral form. These were assigned to the N-protonated monocation and dication. There were no difficulties encountered in observing the monocation formation in the HCl-MeOH system. Very sharp isosbestic points were characteristic of each protonation stage. The pK3 values for the porphyrins in the above order were 3.23, 4.70, 2.93 and 3.37; the pK4 values were 2.48, 2.62, 2.41 and 2.64, respectively. For all porphyrins studied, no further spectral changes were observed after the dication was completely formed. This was interpreted as indicating that the formation of more highly protonated species is not possible in fullydelocalized porphyrins possessing the 18 π-electron [18]diazaannulene delocalization pathway. When the titration was performed on the free dicarboxylic acid porphyrins, aggregation obscured the first protonation step and no clear monocation spectrum could be distinguished. However, also in that case the titration ended up to a UVvis spectrum typical of the dication and the effect of aggregation on the pK4 values was negligible. The UVvis spectrometric parameters are given for the neutral forms and for the protonated species of the porphyrin DMEs. The results are discussed in terms of the NH tautomerization connected to the π-electron delocalization pathway (aromaticity), which tends to hinder outofplane distortions in the porphyrin plane, and in terms of solvation and counterion stabilization of the protonated forms.
Synthesis of protoporphyrin-lipids and biological evaluation of micelles and liposomes
Tachikawa, Shoji,El-Zaria, Mohamed E.,Inomata, Ryu,Sato, Shinichi,Nakamura, Hiroyuki
, p. 4745 - 4751 (2014/12/09)
Protoporphyrin IX (PPIX) lipids were synthesized by introducing a long alkyl chain, such as C13, C15, and C17, at each vinyl group on PPIX via hydrobromination. The PPIX lipids exhibited a water-soluble property by forming their micelles in water and the PPIX-lipid micelles showed relatively low cytotoxicity toward HeLa cells (IC50 = 151.7-379.9 μM) without light irradiation. PL-C17 liposomes (post-inserted liposomes) were readily prepared by adding PL-C17 micelle solution to the liposome solution. The IC 50 values of PPIX, PL-C17 micelles, and PL-C17 liposomes toward HeLa cells were 0.53, 5.65, and 12.9 μM, respectively, after irradiation with a xenon lamp in the 400-800 nm range for 2 min. PL-C17 liposomes were selectively accumulated in the Golgi apparatus in cells.
