Mass spectrometric studies of competitive binding of C60 and C70 to mesosubstituted porphyrins

( Sunghan Jung ),( Seung Koo Shin ) 한국질량분석학회 2011 Mass spectrometry letters Vol.2 No.2

Competitive binding of C60 and C70 to meso-substituted porphyrins was studied by mass spectrometry (MS). Electrospray ionization MS was employed to acquire the mass spectra of 1 : 1 porphyrin.fullerene complexes formed in a mixture of mesosubstituted porphyrin and fullerite to determine the ratio of complexes between C60 and C70. Matrix-free laser desorption ionization MS was used to obtain the mass spectra of fullerite to measure the mole fraction of C60 and C70. The binding constant ratio (K70/K60) was determined from the mass spectral data. The difference in standard Gibbs free energy change, .(.Go)70.60, for the competitive binding of C60 and C70 was calculated from K70/K60. Of the five porphyrins, tetraphenyl, tetra(4-pyridyl), tetra(4-carboxyphenyl), tetra(3,5-di-tert-butylphenyl), and tetra(pentafluorophenyl) porphyrins, the first three non-bulky porphyrins yield negative values of .(.Go)70.60, whereas the other two bulky porphyrins result in positive values of .(.Go)70.60. This result indicates that C70 binding to porphyrin is thermodynamically favored over C60 binding in non-bulky porphyrins, but disfavored in bulky ones. It also suggests that the binding mode of C70 is different between non-bulky and bulky porphyrins, which is in line with previous experimental findings of the “side-on” binding to non-bulky porphyrins and the C60-like “end-on” binding to bulky porphyrins.

Mass spectrometric studies of competitive binding of C₆₀ and C₇₀ to mesosubstituted porphyrins

Jung, Sung-Han,Shin, Seung-Koo Korean Society for Mass Spectrometry 2011 Mass spectrometry letters Vol.2 No.2

Competitive binding of $C_{60}$ and $C_{70}$ to meso-substituted porphyrins was studied by mass spectrometry (MS). Electrospray ionization MS was employed to acquire the mass spectra of 1 : 1 porphyrin-fullerene complexes formed in a mixture of mesosubstituted porphyrin and fullerite to determine the ratio of complexes between $C_{60}$ and $C_{70}$. Matrix-free laser desorption ionization MS was used to obtain the mass spectra of fullerite to measure the mole fraction of $C_{60}$ and $C_{70}$. The binding constant ratio ($K_{70}$/$K_{60}$) was determined from the mass spectral data. The difference in standard Gibbs free energy change, ${\Delta}({\Delta}G^o)_{70-60}$, for the competitive binding of $C_{60}$ and $C_{70}$ was calculated from $K_{70}$/$K_{60}$. Of the five porphyrins, tetraphenyl, tetra(4-pyridyl), tetra(4-carboxyphenyl), tetra(3,5-di-tert-butylphenyl), and tetra(pentafluorophenyl) porphyrins, the first three non-bulky porphyrins yield negative values of ${\Delta}({\Delta}G^o)_{70-60}$, whereas the other two bulky porphyrins result in positive values of ${\Delta}({\Delta}G^o)_{70-60}$. This result indicates that $C_{70}$ binding to porphyrin is thermodynamically favored over $C_{60}$ binding in non-bulky porphyrins, but disfavored in bulky ones. It also suggests that the binding mode of $C_{70}$is different between non-bulky and bulky porphyrins, which is in line with previous experimental findings of the "side-on" binding to non-bulky porphyrins and the $C_{60}$-like "end-on" binding to bulky porphyrins.

Exploratory synthesis and photovoltaic performance comparison of D–π–A structured Zn-porphyrins for dye-sensitized solar cells

Kang, Sung Ho,Jung, Seung Young,Kim, Yeon Wook,Eom, Yu Kyung,Kim, Hwan Kyu Elsevier 2018 Dyes and pigments Vol.149 No.-

<P><B>Abstract</B></P> <P>The design and synthesis of D–π–A structured Zn(II)–porphyrin sensitizers with extended π-conjugation, coded as <B>SGT-012, SGT-016, SGT-052</B> and <B>SGT-053</B>, were explored. The key schematic concept for the molecular design and synthesis of porphyrin sensitizers, with the target of modulation of donor groups by embedding an electron donor into the skeleton of two typical D‐π‐A porphyrin models, such as D–porphyrin-A sensitizers (<B>SGT-012</B> and <B>SGT-016</B>) and D-triple bond-porphyrin-triple bond-<B>BTD</B>-acceptor sensitizers (<B>SGT-052</B> and <B>SGT-053</B>), was proposed investigate the influence of the donor ability and the bulk of donor groups on the photophysical properties and cell performance of dye-sensitized solar cells (DSSCs). Also, based on the photophysical properties and cell performances, the co-sensitisation strategy was conducted to further enhance the cell performances. <B>SGT-012</B> and <B>SGT-052</B> porphyrins, containing a strong donor unit, exhibited similar S-band absorption and a slightly red-shifted Q-band absorption compared to <B>SGT-016</B> and <B>SGT-053</B> porphyrins containing a weak bulky donor unit, respectively. To further extend the π-conjugation and absorption to a longer wavelength range, the triple bond at two <I>meso</I>-positions of the porphyrin core and a benzothiadiazole (<B>BTD</B>) strong electron acceptor was introduced to yield <B>SGT-052</B> and <B>SGT-053</B>, resulting in a red-shift and broad visible region absorption ability. It was indicated that these modifications lead to the formation of a stronger intramolecular charge transfer complex, which is favourable for harvesting sunlight, than those of <B>SGT-012</B> and <B>SGT-016</B> porphyrins. To prevent undesirably reduced <I>V</I> <SUB>oc</SUB> caused by charge recombination processes and dye aggregation from porphyrin-sensitized solar cells, <B>HC-Al</B> of co-adsorbent was adopted to fabricate <B>SGT-052-</B> and <B>SGT-053</B>-based solar cells. The DSSCs with <B>SGT-052</B> and <B>SGT-053</B> exhibit better light harvesting ability than the DSSCs with <B>SGT-012</B> and <B>SGT-016</B> porphyrins, due to the formation of the stronger intramolecular charge transfer complex. Thus, the incident photon-to-current conversion efficiency (<B>IPCE</B>) of <B>SGT-052</B> and <B>SGT-053</B>-based DSSCs was extremely red-shifted to a wavelength of 800 nm, resulting in higher <I>J</I> <SUB>sc</SUB> values of 15.3 and 14.6 mA cm<SUP>−2</SUP>, respectively. The DSSC utilising <B>SGT-052</B> and <B>HC-A1</B> exhibited a higher photovoltaic performance (<I>η</I> <SUB> <I>eff</I> </SUB> ∼9.6%) than did other sensitizers. On the basis of <B>SGT-052</B>-based DSSC, its DSSCs co-sensitized with <B>SGT-012</B> were prepared to improve the <I>J</I> <SUB>sc</SUB>, <I>V</I> <SUB>oc</SUB> and power conversion efficiency (10.2%).</P> <P><B>Highlights</B></P> <P> <UL> <LI> The influence of donor ability and bulkiness on the photophysical properties and cell performance of DSSCs was investigated. </LI> <LI> The triple bond at the porphyrin core and electron acceptor was introduced to extend the π-conjugation lengths. </LI> <LI> The co-sensitization strategy was conducted to further enhance the cell performances. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Patterning of porphyrin molecules and their acid-vapor sensing properties

강귀운,안희준 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

Porphyrin and its derivatives are attractive due to advantageous properties that include chemical and thermal stability, rigidity, optical and electronic properties and anisotropy. Owing to these properties, they are finding potential applications in photosensitization, photodynamic therapy (PDT), photovoltaics, and optical sensing. In particular, porphyrins have been widely used as active materials in gas and pH sensors because of their high sensitivity, broad selectivity, and fast response. Porphyrin-containing sensor systems are generally based on electrochemical, optical, or surface plasmon resonance measurements. The optical technique is particularly appealing because porphyrins possess extremely rich UV-vis absorption spectra due to their highly conjugated π-electron system. While there are numerous reports of sensors based on porphyrin films, to the best of our knowledge there are no reports related to patterned porphyrin sensor devices. In this research, we demonstrate a simple and straightforward method to pattern porphyrin molecules using Langmuir-Blodgett (LB) deposition and micro-contact printing (μ-CP). The general procedure consists of the following steps. First, a surface-patterned PDMS mold is replicated from a photoresistpatterned silicon substrate. Secondly, LB films of the porphyrins are deposited on the surface of the patterned PDMS. Lastly, the porphyrin LB films are selectively transferred onto quartz substrates using the μ -CP technique. The combination of LB deposition and μ-CP can conveniently fabricate micron and submicron-sized patterns of well-ordered and densely-packed porphyrin molecules. This methodology is suitable for molecules which cannot be obtained by conventional film fabrication methods suchas spin-coating or thermal evaporation. Therefore, we believe this method can expand the limits of molecules which are suitable for sensor devices.

Design and applications of molecular probes containing porphyrin derivatives

Lee, Hosoowi,Hong, Kyeong-Im,Jang, Woo-Dong Elsevier 2018 Coordination chemistry reviews Vol.354 No.-

<P><B>Abstract</B></P> <P>Porphyrins are heterocyclic macrocycle organic compounds, composed of four modified pyrrole subunits interconnected at their α carbon atoms via methine bridges. Because of their unique properties, synthetic porphyrin derivatives are powerful tools for molecular recognition. The optical or electronic monitoring of porphyrin derivatives permits the detection of the binding of transition metals. The binding of the metal ion to the porphyrin center provides additional axial ligand binding sites, which can be utilized for molecular recognition and sensing. Because of the large extinction coefficient and emission property, porphyrin derivatives can be utilized as fluorescent chromophores for the detection of various chemicals. In this paper, important development in terms of porphyrin-based chemical probes will be reviewed. This review is divided into nine sections focusing on porphyrin-based probes for (i) cations, (ii) anions, (iii) ion pairs, (iv) volatile organic chemicals, (v) nitroaromatic compounds, (vi) gases, (vii), reactive oxygen species, (viii) chiral discrimination, and (ix) environmental change detection, respectively.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Porphyrin derivatives serve as fluorescent chromophores to detect chemicals. </LI> <LI> The coordination of metal ions to the porphyrin center provides Lewis acid sites. </LI> <LI> Porphyrin derivatives act as signaling units for emission or absorption changes. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Poster Presentation : 1P-179 ;Fabrication of dicyanopyrazine-Linked porphyrin Langmuir-blodgett films

박창용,황정욱,안수현,안희준 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

We have fabricated dicyanopyrazine-linked porphyrin mono and multilayer films on polycrystalline gold and quartz substrates using the Langmuir-Blodgett (LB) technique. Two different porphyrins were studied, one with two and the other with four positions of the porphyrin ring substituted with the dicyanopyrazine containing moiety (desig nated 2-DCPP and 4-DCPP, respectively). XPS indicates that the atomic ratios of C, N, and O for the LB films are similar to the theoretical ratios for the dicyanopyrazine-linked porphyrins. AFM reveals that the surface roughness of LB multilayers are higher than that of the LB monolayers due to aggregation of the porphyrin molecules in the multilayer films. The 11-multilayer LB films are only 6 and 4.6 times thicker than the monolayer LB films. This result is consistent with the surface roughness data showing aggregation of dicyanopyrazine-linked porphyrin in multilayer LB films. UV-vis spectroscopy indicates a blue shift of the Q band of the LB films compared with the dicyanopyrazine-linked porphyrin solution due to interaction between stacked porphyrin rings.

Porphyrin-4`-bromoacetophenone Conjugates의 설계, 합성 및 DNA 절단 활성

김효진,전라옥 숙명여자대학교 약학연구소 2010 약학논문집-숙명여자대학교 Vol.25 No.-

Photodynamic therapy, in which light activates a photosensitizing drug, is a type of cancer therapy based on the selective uptake and retention of photosensitizers such as porphyrins in tumor tissues. These compounds display cytotoxic effects when activated by light of particular wavelength. Porphyrin sensitizers have been a subject of intense research in the past decades because of their unique photophysical and pharmacokinetic properties. In order to increase the biological effectiveness and reduce toxicity of porphyrin as a sensitizer, their conjugation to various molecules, such as peptides, oligonucleotides, proteins, monoclonal antibodies, and small DNA cleaver have been investigated in recent years. With the aim to develop efficient photoinducible cytotoxic agent, porphyrin-4'-bromoacetophenone conjugates were designed as new photoinducible DNA cleavers. (Tri-p-tolyl)-(4-hydroxyphenyl) porphyrin and tetrakis( 4-hydroxyphenyl) porphyrin were synthesized and conjugated to 4'-bromoacetophenone, which can generate active carbon radicals upon irradiation and cleave DNA strand, through the appropriate linker. We describe the photolytic behavior of 4'-bromoacetophenone. The effect of the irradiation time of the compound on the photolysis was examined in order to optimize photoreaction condition. The photo cleaving activity of porphyrin-4'-bromoacetophenone conjugates were evaluated using the supercoiled plasmid pBR322 in the presence and absence of light.

β-Functionalized Push-Pull Porphyrin Sensitizers in Dye-Sensitized Solar Cells: Effect of π-Conjugated Spacers.

Ishida, Masatoshi,Hwang, Daesub,Zhang, Zhan,Choi, Yung Ji,Oh, Juwon,Lynch, Vincent M,Kim, Dong Young,Sessler, Jonanthan L,Kim, Dongho Wiley-VCH 2015 ChemSusChem Vol.8 No.17

<P>A series of new beta-functionalized push-pull-structured porphyrin dyes were synthesized so as to investigate the effect of the p-conjugated spacer on the performance of dye-sensitized solar cells (DSSCs). Suzuki-and Heck-type palladium-catalyzed coupling methodologies were used to obtain various beta-functionalized porphyrins and beta-benzoic acid (ZnPHn) and beta-vinylbenzoic acid (ZnPVn) derivatives from beta-borylated porphyrin precursors. Photophysical studies of the resulting porphyrins revealed a clear dependence on the nature of the beta linker. In particular, it was found that a beta-vinylene linkage perturbs the electronic structure of the porphyrin core; this is less true for a beta-phenyl linkage. Theoretical analyses provided support for the intrinsic intramolecular charge-transfer character of the beta-functionalized, push-pull porphyrins of this study. The extent of charge transfer depends on the nature of the beta-conjugated linkage. The photovoltaic performances of the cells sensitized with beta-phenylenevinylene ZnPVn exhibited higher power conversion efficiency values than those bearing beta-phenyl linkages (ZnPHn). This was ascribed to differences in light-harvesting efficiency. Furthermore, compared to the use of a standard iodine-based electrolyte, the DSSC performance of cells made from the present porphyrins was improved by more than 1% upon using a cobalt(II/III)-based electrolyte. Under standard AM 1.5 illumination, the highest efficiency, 8.2 %, was obtained by using cells made from the doubly beta-butadiene-linked porphyrin.</P>

An Isothermal Titration Microcalorimetric Study on the Interaction of Three Water-Soluble Porphyrins with Histone H₂B

Bordbar, A.K.,Ghaderi, A.R.,Safaei, E.,Tangestaninejad, S.,Eslami, A.,Saboury, A.A.,Moosavi Movahedi, A.A. Korean Chemical Society 2003 Bulletin of the Korean Chemical Society Vol.24 No.5

In the present work, the interaction of three water soluble porphyrins, tetra(p-trimethyle) ammonium phenyl porphyrin iodide (TAPP) as a cationic porphyrin, tetra sodium meso-tetrakis (p-sulphonato phenyle) porphyrin (TSPP) as an anionic porphyrin and manganese tetrakis (p-sulphonato phenyl) porphinato acetate (MnTSPP) as a metal porphyrin, with histone H₂B have been studied by isothermal titration microcalorimetry at 8 mM phosphate buffer, pH 6.8 and 27 °C. The values of binding constant, entropy, enthalpy and Gibbs free energy changes for binding of the first MnTSPP, and first and second TSPP and TAPP molecules were estimated from microcalorimetric data analysis. The results represent that the process is both entropy and enthalpy driven and histone induces self-aggregation of the porphyrins. The results indicate that both columbic and hydrophobic interactions act as self-aggregation driving forces for the formation of aggregates around histone.

Spectroscopic, Redox and Biological Studies of Push-Pull Porphyrins and Their Metal Complexes

K. Rajesh,A. Kalilur Rahiman,K. Shanmuga Bharathi,S. Sreedaran,V. Gangadevi,V. Narayanan 대한화학회 2010 Bulletin of the Korean Chemical Society Vol.31 No.9

We have synthesized a series of push-pull porphyrins containing both donor and acceptor substituents at the mesopositions and have examined their spectral and biological properties. The push-pull porphyrins containing both strong donor NH2 and acceptor NO2 at meso-positions, in which donor group condensed with the ligand, (2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formlyphenol (L) to form imine linkages with porphyrin. The Schiff base ligand 5-[4-(2,6-bis(4-methylpiperazine-1-yl-methyl)-4-iminomethylphenol)phenyl]-10,15,20-tris(4-nitrophenyl) porphyrin [an3(TPP)L] can be synthesized from 2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formylphenol (L) and 5-(4-aminophenyl)-10, 15,20-tris(4-nitrophenyl)porphyrin. The push-pull porphyrin [an3(TPP)L] was metallated to get copper,nickel and zinc complexes. The spectral, electrochemical, antibacterial, antifungal and cytotoxicity properties of all the donor- acceptor push-pull porphyrins and their complexes were characterized and studied.