Porphyrin Science by Women最新文献

{"title":"Towards microbe-targeted photosensitizers: Synthesis, characterization and in vitro photodynamic inactivation of the tuberculosis model pathogen M. smegmatis by porphyrin-peptide conjugates","authors":"E. Feese, H. Gracz, P. Boyle, R. Ghiladi","doi":"10.1142/s1088424619501505","DOIUrl":"https://doi.org/10.1142/s1088424619501505","url":null,"abstract":"Porphyrin-peptide conjugates have a breadth of potential applications, including use in photodynamic therapy, boron neutron capture therapy, as fluorescence imaging tags for tracking subcellular localization, as magnetic resonance imaging (MRI) positive-contrast reagents and as biomimetic catalysts. Here, we have explored three general routes to porphyrin-peptide conjugates using the Cu(I)-catalyzed Huisgen-Medal-Sharpless 1,3-dipolar cycloaddition of peptide-containing azides with a terminal alkyne-containing porphyrin, thereby generating porphyrin-peptide conjugates (PPCs) comprised of a cationic porphyrin coupled to short antimicrobial peptides. In addition to characterizing the PPCs using a variety of spectroscopic (UV-vis, [Formula: see text]H- and [Formula: see text]C-NMR) and mass spectrometric methods, we evaluated their efficacy as photosensitizers for the in vitro photodynamic inactivation of Mycobacterium smegmatis as a model for the pathogen Mycobacterium tuberculosis. Difficulties that needed to be overcome for the efficient synthesis of PPCs were the limited solubility of the quaternized pyridyl porphyrin in common solvents, undesired (de)metallation and transmetallation, and chromatographic purification. Photodynamic inactivation studies of a small library of PPCs against Mycobacterium smegmatis confirmed our hypothesis that the porphyrin-based photosensitizer maintains its ability to efficiently inactivate bacteria when conjugated to a small peptide by upwards of 5–6 log units (99.999[Formula: see text]%) using white light illumination (400–700 nm, 60 mW/cm[Formula: see text], 30 min). Further, hemolysis assays revealed the lack of toxicity of the PPCs against sheep blood at concentrations employed for in vitro photodynamic inactivation. Taken together, the results demonstrated the ability of PPCs to maintain their antimicrobial photodynamic inactivation efficacy when possessing a short cationic peptides for enabling the potential targeting of pathogens in vivo.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"71 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86586876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Peripherally carboxylic acid substituted asymmetric zinc(II) phthalocyanines: Synthesis and photophysicochemical properties","authors":"Gulenay Tunc, Mohamad Albakour, V. Ahsen, A. Gürek","doi":"10.1142/s1088424619501402","DOIUrl":"https://doi.org/10.1142/s1088424619501402","url":null,"abstract":"Four asymmetric Zn(II) phthalocyanines (Pc1–Pc4) bearing a carboxylic acid group in the peripheral position have been designed and synthesized to investigate the influence of the distance between COOH group and the phthalocyanine core on their photophysical and photochemical properties. The novel phthalocyanine complexes were characterized by [Formula: see text]H, [Formula: see text]C NMR, IR, and UV-vis spectroscopies, elemental analysis and matrix-assisted laser desorption ionization mass spectrometry (MALDI). The aggregation behavior, photophysical and photochemical properties such as fluorescence lifetime and quantum yields and singlet oxygen quantum yields of Pc1–Pc4 were explored in tetrahydrofuran (THF) to the determination of the potential use of these novel phthalocyanines as photosensitizers for different applications such as photovoltaic technologies and photodynamic therapy (PDT). Pc1–Pc4exhibited high singlet oxygen generation quantum yields (0.84, 0.66, 0.88 and 0.65, respectively). Fluorescence quantum yields could be obtained for Pc1, Pc2, Pc3 and Pc4 (0.13, 0.31, 0.10 and 0.25, respectively) in THF.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"15 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87414195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impedance spectroscopic study on hybrid phthalocyanine/lead sulphide nanocomposite film","authors":"Zahra Khozaee, I. Chambrier, L. Sosa Vargas, A. Cammidge, Asim K. Ray","doi":"10.1142/s1088424619502055","DOIUrl":"https://doi.org/10.1142/s1088424619502055","url":null,"abstract":"A unique organic/inorganic nanocomposite of non-aggregated lead sulphide (PbS) quantum dots (QDs) dispersed within a spun film of non-peripherally octakis(hexyl)-substituted metal-free phthalocyanine (C[Formula: see text]H[Formula: see text]Pc) has been prepared at room temperature by a simple and low-cost method. The frequency response of alternating current (AC) conduction in a 130 nm thick C[Formula: see text]H[Formula: see text]Pc /PbS film sandwiched between the indium-tin-oxide (ITO) and aluminum (Al) electrodes is found to obey the universal power-law. The cryogenic study of AC conduction reveals that the correlated barrier hopping (CBH) model closely fits to the experimental data at temperatures below 240 K. The parameters obtained by fitting the CBH model point out that the hopping process cannot take place directly between neighboring PbS QDs but involves the localized states within the matrix.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"17 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81673522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of PVP formulation on the in vitro photodynamic efficiency of a photosensitizing phthalocyanine","authors":"Eda Gazel Pehlivan, Yıldız Ek, D. Topkaya, U. Tazebay, F. Dumoulin","doi":"10.1142/s108842461950189x","DOIUrl":"https://doi.org/10.1142/s108842461950189x","url":null,"abstract":"The administration of photosensitizers and their biocompatibility is crucial to the success of photodynamic therapy treatment. Amongst the various strategies developed to administer photosensitizers of low water-solubility, the use of polyvinylpyrrolidone (PVP), an FDA-approved food additive, is emerging as extremely promising. Its effect on photodynamic outcome was compared to more classical formulation in DMSO and direct solubilization in water. The tetrakis (2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-Zn(II) phthalocyanine chosen as the model photosensitizer for this study proved to be a powerful photosensitizer. Even if slightly less efficient than DMSO formulation, PVP formulation proved to work very well, with submicromolar IC50 and IC90 values against MDA-MB-231 human cancer cells.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"21 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91488600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monocationic porphyrin dyads with fullerene as the electron-accepting material","authors":"Yuko Takao, K. Moriwaki, T. Mizuno, T. Ohno","doi":"10.1142/s1088424619501670","DOIUrl":"https://doi.org/10.1142/s1088424619501670","url":null,"abstract":"Dyad compounds in which a fullerene [Formula: see text] was covalently linked to a monocationic porphyrin at a N,N[Formula: see text]-bridge substituent, were synthesized by condensation reaction. The low solubility of a dyad containing tetraphenylporphyrin (TPP) derivative was improved by using octaethylporphyrin (OEP) derivatives and introduction of an alkyl substituent to the porphyrin derivatives. The energy levels of the frontier orbitals, estimated experimentally using potentiometric data and the optical energy band gaps obtained by the UV-vis spectra, were sufficiently low to be comparable to acceptor materials. They varied depending on the peripheral substituents on the porphyrin unit. DSC analysis of the drop-cast films of the P3HT/dyad blends showed that the film containing the OEP dyad, annealed at a higher temperature, had more amorphous fractions than the films containing the TPP dyad.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"58 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83953803","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3-Methylindole-substituted zinc phthalocyanines for photodynamic cancer therapy","authors":"Samia Ayari, Mehmet F. Sağlam, Elif Şenkuytu, Pelin Balcik Ercin, Y. Zorlu, İbrahim F. Sengul, B. Jamoussi, D. Atilla","doi":"10.1142/s1088424619501426","DOIUrl":"https://doi.org/10.1142/s1088424619501426","url":null,"abstract":"Novel peripherally and non-peripherally 3-methylindole-substituted zinc phthalocyanine derivatives were synthesized as photosensitizers for photodynamic therapy in cancer treatment. The photophysical, photochemical and photobiological properties of targeted phthalocyanines were also investigated. For this purpose, the fluorescence and singlet oxygen quantum yields, and fluorescence lifetime values of the final compounds were determined in DMF solutions. The phototoxicity and cytotoxicity of the phthalocyanine complexes were tested against the invasive human breast cancer cell line (MDA-MB-231) for determination of their photosensitizing ability in the area of photodynamic therapy. It was revealed that while peripherally 3-methylindole-substituted phthalocyanine was found to be toxic for cells in both dark and light conditions, its non-peripherally substituted phthalocyanine analogue significantly caused cell death following light irradiation. A preliminary assay suggested that the non-peripherally linked phthalocyanine could be a suitable candidate for cancer treatment via photodynamic therapy techniques.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"10 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89578621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"25 years of development of Mn porphyrins — from mimics of superoxide dismutase enzymes to thiol signaling to clinical trials: The story of our life in the USA","authors":"I. Batinic-Haberle, I. Spasojević","doi":"10.1142/s1088424619300283","DOIUrl":"https://doi.org/10.1142/s1088424619300283","url":null,"abstract":"We have developed Mn porphyrins (MnPs) initially as mimics of superoxide dismutase (SOD) enzymes based on structure–activity relationships. Several cationic Mn porphyrins, being substituted with cationic ortho [Formula: see text]-alkyl- or alkoxyalkylpyridyl groups in meso positions of the porphyrin ring, have been identified as potential therapeutics based on their high SOD-like activity and high bioavailability. Two of those [Mn(III) meso-tetrakis([Formula: see text]-ethylpyridinium-2-yl)porphyrin, MnTE-2-PyP[Formula: see text] (BMX-010, AEOL10113) and Mn(III) meso-tetrakis(Nn-butoxyethylpyridinium-2-yl)porphyrin, MnTnBuOE-2-PyP[Formula: see text] (BMX-001)] are now in five Phase II clinical trials. Studies of ours, and those of others, contributed to the understanding of the diverse activities of these compounds. With biologically compatible potentials and four biologically accessible oxidation states, Mn porphyrins interact with numerous reactive species, both as oxidants and reductants. Among those reactions, their abilities to (catalytically) oxidize [Formula: see text]-glutathionylate protein thiols may perhaps be their major in vivo mode of action. Via [Formula: see text]-glutathionylation, MnPs modulate actions of signaling proteins and, in turn, cellular apoptotic and proliferative pathways. During the major part of our stay in the USA, our lives have been dedicated to Mn porphyrins. Our families and especially our son and his three babies have been our inspiration not to give up on a life often burdened with hardship. It is thus our immense pleasure to see our compounds in clinical trials. Above all, we hope that our story will inspire future researchers to persevere — women in particular.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"56 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81488984","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A3B and ABAB aminophthalocyanines: Building blocks for dimeric and polymeric constructs","authors":"Safiye Bozkurt Ekren, F. Dumoulin, E. Musluoǧlu, V. Ahsen, Ö. Güngör","doi":"10.1142/s1088424619501499","DOIUrl":"https://doi.org/10.1142/s1088424619501499","url":null,"abstract":"Mono or diamino phthalocyanines with A3B or crosswise ABAB substitution patterns have been synthesized and used as building blocks for the preparation of dimeric and polymeric phthalocyanines. For this, 4,5-di(dodecylsulfanyl) phthalonitrile was converted into 1,3-diimino-6,7-di-([Formula: see text]-dodecylsulfanyl)-isoiminoindoline and then reacted with 6-nitro-1,3,3-trichloroisoindoline. The nitro functions on the resulting inseparable mixture of A3B and ABAB phthalocyanines were reduced into amines by Na2S and the phthalocyanines could be chromatographically separated. Dimeric phthalocyanine was synthesized by the reaction of the mono-amino AB3 with sebacoyldichloride, and a poorly soluble linear polymeric material was obtained by reaction of the ABAB di-amino phthalocyanine with sebacoyl dichloride.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"6 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86505364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unsymmetrical phthalocyanines containing azo moiety; Synthesis and photophysical properties","authors":"Ebru Özkan Garip, Mukaddes Özçeşmeci, R. Katırcı, İbrahim Özçeşmeci, E. Hamuryudan","doi":"10.1142/s1088424619501724","DOIUrl":"https://doi.org/10.1142/s1088424619501724","url":null,"abstract":"Unsymmetrical metal-free phthalocyanine was synthesized through cyclotetramerization of 4-[2,6-dimethyl-4-(4-tert-butyl-phenylazo)phenoxy]phthalonitrile and 4-(hexylthio)phthalonitrile in the presence of lithium in [Formula: see text]-pentanol, then metal-free phthalocyanine was obtained by acidification with acetic acid. Finally, metalation was achieved by refluxing metal-free phthalocyanine in [Formula: see text]-pentanol in the presence of zinc (II) salt. The structure of synthesized phthalocyanine derivatives were characterized by using proton nuclear magnetic resonance, mass spectrometry, ultraviolet–visible spectroscopy, and Fourier transform infrared spectroscopy. The HOMO–LUMO energies were computed using density functional theory. The HOMO–LUMO energy difference is 2.28 eV. The calculated results were consistent with the experimental data. In addition, aggregation behaviors and general trends for photophysical properties of these phthalocyanine derivatives were studied in tetrahydrofuran. The emission intensities of these phthalocyanine derivatives were strongly quenched by 1,4-benzoquinone in tetrahydrofuran.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"11 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91253370","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monitoring the encapsulation of chlorin e6 derivatives into polymer carriers by NMR spectroscopy","authors":"S. Pfister, L. Sauser, I. Gjuroski, J. Furrer, M. Vermathen","doi":"10.1142/s1088424619501815","DOIUrl":"https://doi.org/10.1142/s1088424619501815","url":null,"abstract":"The encapsulation of five derivatives of chlorin e6 with different hydrophobicity and aggregation properties into a series of five poloxamer-type triblock copolymer micelles (BCMs) with varying numbers of polyethylene and polypropylene glycol (PEG, PPG) units was monitored using 1H NMR spectroscopy. NMR chemical shift and line shape analysis, as well as dynamic methods including diffusion ordered spectroscopy (DOSY) and T1 and T2 relaxation time measurements of the chlorin and the polymer resonances, proved useful to assess the chlorin–BCM compatibility. The poloxamers had high capability to break up aggregates formed by chlorins up to intermediate hydrophobicity. Physically entrapped chlorins were always localized in the BCM core region. The loading capacity correlated with chlorin polarity for all poloxamers among which those with the lowest number of PPG units were most efficient. DOSY data revealed that relatively weakly aggregating chlorins partition between the aqueous bulk and micellar environment whereas more hydrophobic chlorins are well retained in the BCM core region, rendering these systems more stable. T1 and T2 relaxation time measurements indicated that motional freedom in the BCM core region contributes to encapsulation efficiency. The BCM corona dynamics were rather insensitive towards chlorin entrapment except for the poloxamers with short PEG chains. The presented data demonstrate that 1H NMR spectroscopy is a powerful complementary tool for probing the compatibility of porphyrinic compounds with polymeric carriers such as poloxamer BCMs, which is a prerequisite in the development of stable and highly efficient drug delivery systems suitable for medical applications like photodynamic therapy of tumors.","PeriodicalId":20283,"journal":{"name":"Porphyrin Science by Women","volume":"31 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2019-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82604307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}