- Convenient synthesis of porphine from β-tetra(tert-butyl)porphyrin
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β-Tetra(tert-butyl)porphyrin was prepared from 2-dimethylaminomethyl- 4-tert-butylpyrrole and converted into porphine, the mother compound of porphyrins, in 64% yield. The dealkylation smoothly proceeded in aqueous sulfuric acid over 15 min at 190°C under
- Neya, Saburo,Quan, Jingshun,Hoshino, Tyuji,Hata, Masayuki,Funasaki, Noriaki
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- Protonation salt derivative with heavy-atom effect on phthalocyanine for enhanced in vitro photodynamic therapy
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In order to improve water-solubility and photodynamic activity of 2(3), 9(10), 16(17), 23(24)-tetra-((amino)methyl)phenoxy)phthalocyaninato-zinc (ZnPc) simultaneously, here, we present the first attempt to introduce heavy atoms (Br and I) to ZnPc though a simple method by synthesizing the hydrobromide and hydriodate protonation salt derivatives of ZnPc. Researches indicated that these protonation salt derivatives of ZnPc can stably disperse in aqueous system for a long time. Furthermore, the internal heavy atom effect from hydriodate in the ZnPc molecules enhances the intersystem crossing (ISC) efficiency of ZnPc during its photo-exciting process. Therefore, the generation of reactive oxygen species (ROSs), especially singlet oxygen (1O2), is significantly improved, which leads to an improved in vitro photodynamic therapy (PDT).
- Chen, Xianglan,Li, Yejing,Wang, Ao,Zhou, Lin,Lu, Shan,Zhou, Jiahong,Lin, Yun,Wei, Shaohua
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- Inducing Open-Shell Character in Porphyrins through Surface-Assisted Phenalenyl π-Extension
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Organic open-shell compounds are extraordinarily attractive materials for their use in molecular spintronics thanks to their long spin-relaxation times and structural flexibility. Porphyrins (Pors) have widely been used as molecular platforms to craft persistent open-shell structures through solution-based redox chemistry. However, very few examples of inherently open-shell Pors have been reported, which are typically obtained through the fusion of non-Kekulé polyaromatic hydrocarbon moieties to the Por core. The inherent instability and low solubility of these radical species, however, requires the use of bulky substituents and multistep synthetic approaches. On-surface synthesis has emerged as a powerful tool to overcome such limitations, giving access to structures that cannot be obtained through classical methods. Herein, we present a simple and straightforward method for the on-surface synthesis of phenalenyl-fused Pors using readily available molecular precursors. In a systematic study, we examine the structural and electronic properties of three surface-supported Pors, bearing zero, two (PorA2), and four (PorA4) meso-fused phenalenyl moieties. Through atomically resolved real-space imaging by scanning probe microscopy and high-resolution scanning tunneling spectroscopy combined with density functional theory calculations, we unambiguously demonstrate a triplet ground state for PorA2 and a charge-transfer-induced open-shell character for the intrinsically closed-shell PorA4.
- Bottari, Giovanni,Fasel, Roman,Lorente, Nicolas,Mateo, Luis M.,Robles, Roberto,Ruffieux, Pascal,Sun, Qiang,Torres, Tomás
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- meso-tetra(tert-butyl)porphyrin as a precursor of porphine
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Treatment of meso-tetra(tert-butyl)porphyrin with sulfuric acid/1-butanol at 90°C over 15 min afforded porphine in an isolated yield of 74%. De-tert-butylation of the substituted porphyrin provides a rational access to porphine.
- Neya, Saburo,Funasaki, Noriaki
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- Direct synthesis of magnesium porphine via 1-formyldipyrromethane
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(Chemical Equation Presented) The reaction of 1-formyldipyrromethane (100 mM) in toluene at 115°C containing DBU (10 mol equiv) and MgBr2 (3 mol equiv) in the presence of air affords the magnesium chelate Mg(II) porphine in 30-40% yield. The advantages of the new method include simplicity, high concentration, chromatography-free purification, gram-scale synthesis, and avoidance of the poorly soluble free base porphine. Mg(II) porphine exhibits good solubility in common organic solvents and is a valuable core scaffold for derivatization.
- Dogutan, Dilek Kiper,Ptaszek, Marcin,Lindsey, Jonathan S.
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- A facile route to tripyrrane from 2,5-bis(hydroxymethyl)pyrrole and the improved synthesis of porphine by the '3+1' approach
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The treatment of 2,5-bis(hydroxymethyl)pyrrole with pyrrole in the presence of hydrochloric acid gave tripyrrane in 61% yield, which afforded porphine in an improved 31% yield by the '3+1' approach.
- Taniguchi, Shozo,Hasegawa, Hikaru,Nishimura, Masato,Takahashi, Masahiko
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- Porphine and pyrrole-substituted porphyrin from cyclocondensation of tripyrrane with mono-substituted pyrroles
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The condensation of non-substituted tripyrrane with mono-substituted pyrroles did not lead to corrole, but to porphine and 5-pyrrolyl-porphyrin. Both compounds were fully characterized by a combination of spectroscopic methods and X-ray crystallography.
- Saltsman, Irena,Goldberg, Israel,Balasz, Yael,Gross, Zeev
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- A novel and efficient synthesis of porphine
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meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.
- Neya, Saburo,Quan, Jingshun,Hata, Masayuki,Hoshino, Tyuji,Funasaki, Noriaki
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- The facile synthesis of 5-formylporphyrin
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A facile synthetic route of 5-formylporphyrin (2) has been developed. Using pyrrole and pivaldehyde as the starting materials, 2 was obtained through several facile reactions. The synthetic route is easy to perform and can be scaled up, which gives the compound a better application perspective.
- Liu, Peng Peng,Feng, Ya Qing,Gu, Cheng Zhi,Meng, Shu Xian,Zhang, Bao
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- High-Resolution Solid-State 13C NMR Spectra of Porphine and 5,10,15,20-Tetraalkylporphyrins: Implications for the N-H Tautomerization Process
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The solid-state high-resolution 13C nuclear magnetic resonance spectra of porphine and of 5,10,15,20-tetraalkylporphyrins were recorded with use of the CP/MAS technique.The solution kinetics of the hydogen migration between the two tautomers of porphine, meso-tetrapropyl- and meso-tetrahexylporphyrins, were also studied, and the activation parameters were found to be similar to those reported in the literature for tetraarylporphyrins.Porphine showed the same dynamical behavior in the solid state as in solution, while in the solid state the tetraalkylporphyrins showed doubling of the pyrrole carbon resonances at room temperature.The results obtained with the tetraalkylporphyrins can be explained assuming either a proton-transfer reaction slow on the NMR time scale or a fast exchange between two unequally populated tautomers.Three hypotheses are discussed with regard to the kinetic solid-state effects involved: (a) a quenching of the tunneling contribution to the proton-migration process; (b) a fixed geometry adopted by the four nitrogen atoms in the crystal that controls the migration; (c) a coupling between the proton-exchange process and the deformation of the porphyrin skeleton, the latter being hindered by neighboring molecules.
- Frydman, Lucio,Olivieri, Alejandro C.,Diaz, Luis E.,Frydman, Benjamin,Morin, Frederick G.,et al.
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- Concerning the Crystal Structure of Porphine: A Proton Pulsed and 13C CPMAS NMR Study
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Solid-state NMR techniques were employed in order to study the structure and the dynamics of prophine.The changes observed in the line width of the 1H NMR signal between 173 and 443 K suggest that the porphine macrocycles rotate in the crystals.This was confirmed by recording the 13C CPMAS NMR spectra at different temperatures which showed, in addition to expected coalescence of signals due to the central hydrogens tautomerism, a broadening of the resonances due to overall molecular rotation.These studies, coupled to measurements at different temperatures and fieldsof the relaxation times of the 1H magnetization in the rotating frame, allowed us to obtain activation parametres for the motion which are, within experimental error, equal to those made available by CPMAS NMR for the tautomerism of the central hydrogens.These results suggest an explanation for what seems to be a contradiction between the structure of phorphine observed by X-ray, according to which the central hydrogens are localized in opposite pairs of nitrogens, and the structure observed by CPMAS in which the hydrogen migrate between the four central nitrogens.If it is assumed that the migration of the central hydrogens is coupled to a 90 deg rotation of the molecules, the translational symmetry of the crystal will not be changed by the tautomerism, and an X-ray analysis would always detect a single tautomer.
- Frydman, Lucio,Olivieri, Alejandro C.,Diaz, Luis E.,Frydman, Benjamin,Kustanovich, Irina,Vega, Shimon
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- The influence of protonation on the structure and spectral properties of porphine: UV-vis, 1H NMR and: Ab initio studies
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In this study, protonation of porphine (H2P) with a range of weak and strong acids was investigated. The dication of H2P was water soluble and therefore UV-vis and 1H NMR studies were performed in water and D2O as well as in dichloromethane and dimethylformamide. In contrast to the dication of other porphyrins, protonated species of H2P were completely decomposed upon evaporation of solvent at room temperature and therefore were studied in solution. Also, high level ab initio calculations were used to predict the structure, frontier molecular orbitals and transition energies of H2P dication. The Soret band of H2P was only slightly shifted to longer or shorter wavelengths in reaction with weak and strong acids, respectively. The results show that the presence of aryl or at least alkyl substituents at the meso positions of porphyrin macrocycle is necessary for the observation of significant red shifts of the Soret band. In the case of the Q(0,0) band, large blue shifts of the band were observed for the dications that correlate with the absence of any π electron-donating group at the meso position. In 1H NMR spectra, signals for both the β and meso protons were shifted downfield, which shows the negligible decrease in the porphine ring current caused by the out-of-plane distortion of the macrocycle. While ab initio calculations show a saddle shaped conformation for [H4P]2+, H4P(CF3COO)2 was found to adopt an unusual wave conformation that clearly differs from that of previously characterized dications of meso-tetra(aryl)- and meso-tetra(alkyl)porphyrins. Also, the calculations on monoprotonated species show that [H3P]+ and H3P(CF3COO) adopt a nearly saddle type and dome shaped conformation, respectively. On the other hand, the energies of absorption bands of H4P(CF3COO)2 calculated at the TD-B3LYP/cc-pVDZ level of theory predicted the red shift of the Soret band and the blue shift of the Q(0,0) bands that are in accord with the results of UV-vis studies. The results revealed the role played by the acid molecules on the blue shift of the Q(0,0) band of the diprotonated species. Furthermore, the calculated changes in the bond lengths and bond angles show that the involvement of in-plane nuclear reorganization (IPNR) in the observed red shifts of the Soret and Q(0,0) bands cannot be excluded.
- Zakavi, Saeed,Omidyan, Reza,Talebzadeh, Sadegh
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p. 82219 - 82226
(2016/09/09)
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- Synthesis and evaluation of analgesic, anti-inflammatory and anti-bacterial activity of synthetic porphyrin derivatives
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In this work porphyrins compounds (N1-N4) were synthesized from monohydroxy tetraphenylporphyrin, and then characterized on the basis of their chemical properties and spectral data. They were further tested for their potential analgesic and anti-inflammatory activities in acetic acid induced writhing test in mice and carrageenan induced paw edema in rats. The compounds were also evaluated for antibacterial activity in disc diffusion method. Compounds N1, N2 and N4 showed significant analgesic and anti-inflammatory activity at 10 and 30 mg/kg (b.w), comparable to the standard reference drugs. Furthermore, all the tested compounds possessed significant anti-bacterial activity against both gram positive and gram negative bacteria. The analgesic, anti-inflammatory and anti-bacterial activities of the tested compounds were found comparable to reference drugs. These compounds can serve as precursors for the development of clinically useful analgesics, anti-inflammatory and anti-bacterial agents.
- Naveed Umar, Muhammad,Ur. Rashid, Haroon,Gul Sayed, Mian,Karim, Nasiara,Ghaffar, Rukhsana,Antonio Utrera Martines, Marco,Shoaib, Mohammad
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p. 861 - 866
(2015/11/24)
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- Soluble porphyrin polymers
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Porphyrin polymers of Structure 1, where n is an integer (e.g., 1, 2, 3, 4, 5, or greater) are synthesized by the method shown in FIGS. 2A and 2B. The porphyrin polymers of Structure 1 are soluble in organic solvents such as 2-MeTHF and the like, and can be synthesized in bulk (i.e., in processes other than electropolymerization). These porphyrin polymers have long excited state lifetimes, making the material suitable as an organic semiconductor for organic electronic devices including transistors and memories, as well as solar cells, sensors, light-emitting devices, and other opto-electronic devices.
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(2015/07/15)
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- ORGANIC COMPOUND, CHARGE-TRANSPORTING MATERIAL, AND ORGANIC ELECTROLUMINESCENT ELEMENT
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There are provided an organic having both excellent hole transporting property and satisfactory electron transporting and showing excellent durability against electric oxidation/reduction and a high triplet excitation level, and a charge transporting material and an organic electroluminescent device each using the organic compound. The organic compound is represented by following Formula (I): wherein Cz 1 and Cz 2 each represent a carbazolyl group; Z represents a direct bond or an arbitrary linkage group enabling the conjugation of nitrogen atoms in the carbazole rings of Cz 1 and Cz 2 with each other; and Q represents a direct bond connecting to "G" in following Formula (II): wherein Ring B 1 represents a six-membered aromatic heterocyclic ring having "n" nitrogen atom(s) as hetero atom(s); "n" represents an integer of from 1 to 3; G represents a direct bond or an arbitrary linkage group connecting to Q when G connects to Q; Gs connect to carbon atoms at the ortho-position and the para-position with respect to nitrogen atom(s) in Ring B 1 ; G represents an aromatic hydrocarbon group when G does not connect to Q; and "m" represents an integer of from 3 to 5.
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- Synthesis of functionalized, sterically congested calix[4]phyrin macrocycles using donor-acceptor-substituted cyclopropanes-first example of a mono-meso-spirolactone incorporated into a calix[4]phyrin
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Calix[4]phyrins are an important class of hybrid macrocyclic systems at the interface between porphyrins and calixpyrroles (porphyrinogens). A new stepwise synthesis of oxidation-resistant meso-hydrogenated calix[4]phyrins is reported, which allows variable substitution in the residues of their sp 2-meso-centers without the need for a porphyrin intermediate. It relies on the acid-catalyzed condensation of a sterically hindered donor-acceptor-substituted cyclopropane precursor with pyrrole to form a sterically congested dipyrromethane. This was subsequently condensed with a wide range of alkyl and aryl aldehydes bearing electron-donating or electron-withdrawing substituents followed by an oxidation step to form stable calix[4]phyrin(1.1.1.1)s with bridging meso-CH hydrogen atoms through an acid-promoted dehydrative condensation. The methodology avoids any need for premetallation of the macrocycle and/or the use of organometallic catalysts or reagents and allows the incorporation of the bulky cyclopropane-derived substituents specifically into the 5,15-meso-like positions. The resulting regioisomerically pure products display conformational features that reflect their mixed nature between porphyrins and calixpyrroles and they were assessed by X-ray diffraction analysis, NMR techniques and UV/Vis spectroscopy. The possibility to introduce key functional groups enables subsequent modification of these calix[4]phyrins and allows their connection to other groups such as biologically active moieties. Of special interest is an unprecedented example of an acid-driven lactonization that results in the incorporation of a mono-meso-spirolactone into a calix[4]phyrin(1.1.1.1). Moreover, it is demonstrated that this approach to calix[4]phyrins is also applicable to other sterically congested dipyrromethanes.
- Beyzavi, M. Hassan,Lentz, Dieter,Reissig, Hans-Ulrich,Wiehe, Arno
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supporting information
p. 269 - 282
(2013/03/13)
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- Recoverable polymer-bound homogeneous catalysts for catalytic chain transfer process
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Disclosed herein are novel polymer-tethered ligands, metal complexes comprising these ligands, and the use of these complexes as chain transfer catalysts to control the molecular weight of oligomeric and polymeric materials produced in a radical polymerization process. The materials made by the processes disclosed herein have significantly reduced color, making them suitable for a wide range of color-critical end-uses, including automotive coatings.
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- METHODS AND COMPOSITIONS COMPRISING MACROCYCLES
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The present invention relates generally to methods and compositions comprising macrocycles. In some embodiments, the present invention provides methods for modifying macrocycles comprising a pendant group. In some cases, the pendent group comprises a hydrolyzable group. The present invention also provides methods for metallating a macrocycle using microwave energy, in some embodiments.
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(2011/06/26)
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- Efficient synthesis of hangman porphyrins
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Chemical equation presented A two-step synthetic method has been designed to furnish hangman porphyrins In good yields from easily available starting materials. The use of the microwave Irradiation technique has been found to be valuable for delivering the car boxy lie acid hanging group in a much simplified and less time-consuming basic ester hydrolysis (4 h vs 7 days under harsh acidic conditions). The new route facilitates the synthesis of various hangman porphyrins that previously had limited or no access.
- Dogutan, Dilek K.,Kwabena Bediako,Teets, Thomas S.,Schwalbe, Matthias,Nocera, Daniel G.
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supporting information; experimental part
p. 1036 - 1039
(2010/06/15)
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- METHOD OF MAKING PORPHYRINS
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A method of making a compound of Formula I: is carried out by condensing a pair of compounds of Formula II (which pair may be the same or different), or by condensing a compound of Formula III with a compound Formula IV, to produce a compound of Formula I. The condensing step may be carried out with a metal salt under basic conditions.
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(2008/12/08)
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- Rational or statistical routes from 1-acyldipyrromethanes to meso-substituted porphyrins. Distinct patterns, multiple pyridyl substituents, and amphipathic architectures
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(Figure Presented) New methodology is described for the synthesis of porphyrins bearing four (A4, cis-A2B2, cis-ABC2, trans-A2B2) or fewer (A, cis-AB, cis-A2, trans-A)2 meso substituents. The method entails condensation of two 1-acyldipyrromethanes in the presence of a metal salt (MgBr2, 3 mol equiv) and a noncoordinating base (DBU, 10 mol equiv) in a noncoordinating solvent (toluene) with heating (conventional or microwave irradiation) and exposure to air. The rational synthesis of trans-A 2B2- or trans-A2-porphyrins was achieved via condensation of two identical 1-acyldipyrromethanes. The statistical synthesis of various meso-substituted porphyrins was achieved via condensation of two nonidentical 1-acyldipyrromethanes. Both routes possess attractive features including (1) no scrambling, (2) good yield (up to 60%) at high concentration (100 mM) for the macrocycle-forming step, (3) reasonable scope (aryl, heteroaryl, alkyl, or no substituent), (4) short reaction time (~2 h) via microwave irradiation, (5) magnesium porphyrins as the products, which easily undergo demetalation, and (6) facile chromatographic purification. A key advantage of the statistical route is to obtain a cis-substituted porphyrin without the corresponding trans isomer. For example, reaction of an A/B-substituted 1-acyldipyrromethane and the fully unsubstituted 1-formyldipyrromethane gave the magnesium chelates of three porphyrins: the trans-A2B2-porphyrin, the "hybrid" cis-AB-porphyrin, and porphine (no trans-AB-porphyrin can form), which were readily demetalated and separated as the free base species. Altogether 26 1-acyldipyrromethanes and 26 target porphyrins have been prepared, including many with two different pyridyl substituents. One set of amphipathic porphyrins includes cis-A2B2- or cis-A2BC-porphyrins wherein A = pentyl and B/C = pyridyl (o-, m-, p-). Taken together, the rational and statistical routes enable facile conversion of readily available 1-acyldipyrromethanes to diverse porphyrins bearing 1-4 meso substituents for which access is limited via other methods.
- Dogutan, Dilek Kiper,Ptaszek, Marcin,Lindsey, Jonathan S.
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p. 6187 - 6201
(2008/12/22)
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- Element having porphyrin polymer fixed on a substrate and method of preparing the same
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A photo-functional molecule element having, on a substrate, a porphyrin polymer containing covalently-fixed porphyrin units, and the method of preparing the same. The photo-functional molecule element may be used as a photoelectric conversion element such as an organic solar cell or a three-dimensional, non-linear organic material.
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- Multypodal tethers for high-density attachment of redox-active moieties to substrates
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This invention provides redox-active molecules attached to polypodal (e.g., bipodal, tripodal, quadrapodal, pentapodal, etc.) tethers that can be used for attachment of the redox-active molecules to a substrate (e.g., an electrode). The tethered redox-active molecules are useful for the fabrication of memory devices.
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- COMPOUND, CHARGE TRANSPORT MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE
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An object of the invention is to provide a charge transporting material having an excellent heat resistance, excellent filming properties, an excellent charge transporting ability, and excellent light-emitting characteristics and, also, to provide an organic electroluminescent element providing a high luminance and a highly luminous efficiency and having a long life. The invention relates to a charge transporting material comprising a compound having within the molecule two or more pyridine rings substituted at 2-, 4- and 6-positions thereof, which rings do not substantially conjugate each other (provided that the 3- and 5-positions of the pyridine rings may be substituted) and an organic electroluminescent element using the charge transporting material.
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- Chiral porphyrins, chiral metalloporphyrins, and methods for synthesis of the same
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Novel methods of synthesizing heteroatom-containing chiral porphyrins and chiral metalloporphyrins and the novel chiral porphyrins and chiral metalloporphyrins themselves are disclosed. Metal complexes of the chiral porphyrins are prepared in high yields and shown to be active catalysts for highly enantioselective and diastereoselective cyclopropanation, aziridination, and epoxidation of alkenes under a practical one-pot protocol.
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- Boron complexation strategy for use in manipulating 1-acyldipyrromethanes
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A method of making a metal complex comprises combining a 1-monoacyldipyrromethane with a compound of the formula R1R2MX, wherein M is boron, R1 and R2 are each independently organic substituents; and X is an anion leaving group; to produce a metal complex of the formula DMR1R2 wherein DH is a 1-monoacyldipyrromethane. The methods and complexes are useful for the purification and synthesis of dipyrromethanes and porphyrins.
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- Chelation of charged and uncharged molecules with porphyrin-based compounds
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Porphyrins containing one or more neutral or negatively-charged, closo- or nido-carborane substituents are useful as chelators. The carbon-carbon bonds linking the boron-containing groups to the porphyrin ring make the compounds highly resistant to hydrolysis. These compounds have potential for use in selective binding to specific ligands. These compounds are highly stable, soluble in water and organic solvents, and have low toxicity.
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- Treating and preventing viral infections with porphyrin-based compounds
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Porphyrins containing one or more negatively-charged, amphiphilic nido-carborane substituents have antiviral or virucidal activity. The most active compounds tested to date are negatively charged, amphiphilic, and water-soluble. The negative charges lie primarily in the boron clusters. The carbon-carbon bonds linking the boron-containing groups to the porphyrin ring make the compounds highly resistant to hydrolysis. These compounds have strong potential for use as antiviral and virucidal drugs, as they are highly stable, water-soluble, negatively-charged, amphiphilic, and have low toxicity to normal mammalian cells. Preliminary tests in vitro have shown high activity against HIV.
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- Substituted porphyrins
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The present invention relates, in general, to a method of modulating physiological and pathological processes and, in particular, to a method of modulating cellular levels of oxidants and thereby processes in which such oxidants are a participant. The invention also relates to compounds and compositions suitable for use in such methods.
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- Metallotetrapyrrolic photosensitizing agents for use in photodynamic therapy
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Metallotetrapyrrolic compounds having photherapeutic properties useful in photodetection and phototherapy of target issues, particularly porphyrins and azaporphyrins that including gallium in the central pyrrolic core. Also disclosed are methods of using metallotetrapyrrolic compounds for the treatment or detection of cardiovascular disease.
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- Methods of making porphyrins and related compounds with Lewis acids
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The present invention provides methods of making porphyrins and related compounds such as chlorins by condensing suitable starting materials (e.g., a dipyrromethane-dicarbinol plus dipyrromethane) in a polar solvent in the presence of a Lewis acid. The reactions are preferably carried out in a manner that minimizes rearrangement of the reaction product.
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- Substituted porphyrin and azaporphyrin derivatives and their use in photodynamic therapy, radioimaging and MRI diagnosis
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Substituted porphyrin and azaporphyrin deviations with various substitutents in the 12- and 17-positions of the porphyrin skeleton as pharmaceutical agents for use in photodynamic therapy, MRI diagnosis, and radiodiagnostics.
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- Porphyrin array having imidazolyl porphyrin metal complex as structural unit thereof and method of producing the same
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A porphyrin array represented by the following general formula (1-1) or (1-2): wherein R1 represents an alkyl group or a substituted or unsubstituted aryl group; M1 represents a metal ion; R2 and R3 independently represent an electron acceptor or an electron donor; Im represents Im1 or Im2 set forth below: wherein R4 represents a hydrogen atom or a methyl group; and n represents an integer in the range of 1 to 100.
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- Convergent synthesis of multiporphyrin light-harvesting rods
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The present invention provides a convergent method for the synthesis of light harvesting rods. The rods are oligomers of the formula A1(Ab+1)b, wherein b is at least 1, A1through Ab+1are covalently coupled rod segments, and each rod segment A1through A1+bcomprises a compound of the formula X1(Xm+1)mwherein m is at least 1 and X1through Xm+1are covalently coupled porphyrinic macrocycles. Light harvesting arrays and solar cells containing such light harvesting rods are also described, along with intermediates useful in such methods and rods produced by such methods.
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- Porphyrin derivatives for photodynamic therapy
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The invention relates to porphyrin compounds used to destroy or impair the functioning of a target biological material in photodynamic therapy, in particular against virus, tumoral cells, bacteria, tumorous tissues. The invention also relates to compositions containing such compounds and to a method in vitro to photosensitize, destroy or impair the functioning such target biological material.
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- Substituted porphyrins
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The present invention relates, in general, to a method of modulating physiological and pathological processes and, in particular, to a method of modulating cellular levels of oxidants and thereby processes in which such oxidants are a participant. The invention also relates to compounds and compositions suitable for use in such methods. Compounds of the invention include those of Formula I.
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- NITROIMIDAZOLE SUBSTITUTED PORPHYRIN COMPLEX
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The present invention provides the porphyrin compound having nitroimidazole in the molecule, which is used for diagnosis and/or treatment of cancer in magnetic resonance imaging (MRI) and/or radiotherapy as well as for DDS therapy. The porphyrin compound of the present invention shows no phototoxicity, and represented by the following formula: 1[wherein, R1 and R2 are —CH=CH2 or —CH(CH3)—OH, —CH(CH3)—O—(CH2)n—NH—Ra; R3 is hydrogen atom or —CO—(CH2)m—COOH; and M is transition metal of Mn, Fe, Co or Cu], (in which, Ra is hydrogen atom or the group represented by the following formula: 2n and m are the integer 2 or 3), or a pharmaceutically acceptable salt thereof.
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- Hybrid phthalocyanine derivatives and their uses
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Water soluble hybrid phthalocyanine derivatives useful in competitive and noncompetitive assays immunoassays, nucleic acid and assays are disclosed and claimed having (1) at least one donor subunit with a desired excitation peak; and (2) at least one acceptor subunit with a desired emission peak, wherein said derivative(s) is/are capable of intramolecular energy transfer from said donor subunit to said acceptor subunit. Such derivatives also may contain an electron transfer subunit. Axial ligands may be covalently bound to the metals contained in the water soluble hybrid phthalocyanine derivatives. Ligands, ligand analogues, polypeptides, proteins and nucleic acids can be linked to the axial ligands of the dyes to form dye conjugates useful in immunoassays and nucleic acid assays.
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- Process for synthesis of a porphyrin compound using a molecular sieve catalyst under microwave irradiation
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The present invention provides an improved process for synthesis of porphyrin compounds of the general formula 1 from pyrrole and aromatic aldehyde over zeolite molecular sieve catalysts using microwave heating, (solvent free) to provide an eco-friendly, economical, faster and selective heterogeneous method.
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- Porphyrin compounds as telomerase inhibitors
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The present invention has identified compounds with extended aromatic chromophores that bind the G-quadruplex formed by the folding of single-stranded human telomeric DNA. These compounds have been shown to be effective telomerase inhibitors and are contemplated to be useful in developing cancer treatments. A model of cationic porphyrin interaction with quadruplex DNA by intercalation has been established and in combination with structure activity relations has provided novel porphyrin compounds that exhibit discrimination between binding duplex and quadruplex DNA and show improved activity against telomerase.
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- PORPHYRIN LABELING OF POLYNUCLEOTIDES
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The invention provides various porphyrin labeled compounds and reagents for labeling molecules with porphyrins. The porphyrin labeled compounds include porphyrin labeled nucleosides, nucleotides, polynucleotides and the like. The porphyrin labeled compounds of the invention are designed so that the porphyrin moiety on the labeled compound may be detected on the basis of a reaction product produced by the porphyrin catalyzed oxidation of a porphyrin detection reagent. The oxidation of the porphyrin detection reagent may result in the formation of light, i.e., a chemiluminescent reaction, or a colored compound, i.e., a colorimetric reaction. The compounds of the invention contain the general structure of: porphyrin-linker-base-sugar-(phos)n-OH. Another aspect of the invention is to provide methods of labeling and detecting polynucleotides by incorporating a porphyrin-labeled nucleotide into a polynucleotide.
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- Method for the demethoxycarbonylation of porphyrinic compounds such as pheophorbides
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An improved method for the demethoxycarbonylation of porphyrinic compounds such as pheophorbides involving reacting the starting porphyrinic compound with a high boiling point solvent to which a selected amount of water has been added.
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- Porphyrins and porphyrin synthesis techniques
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Strapped porphyrins and electron-deficient porphyrins are provided, as well as processes and intermediates for their preparation. In certain embodiments, such compounds are prepared by nucleophilic displacement of leaving groups from methylpyrroles. In other embodiments, such compounds are prepared by condensing pyrrole derivatives and removing water thus formed from the resulting reaction mixture.
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- Use of synthetic metalloporphyrins for preparation and prediction of drug metabolites
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A method for the systematic and efficient synthetic preparation and identification of metabolites of a pharmaceutical product in order to study possible toxic and/or otherwise biologically-active metabolites of such pharmaceutical products as early and conveniently as possible in the very expensive drug development process, comprising adding samples of the pharmaceutical product to a series of combinations of a synthetic metalloporphyrin (SMP) with a synthetic metalloporphyrin-co-oxidizing reagent in the presence of a suitable solvent, under specified conditions, in a manner such that each sample of pharmaceutical product is reacted with a different combination of synthetic metalloporphyrin, SMP-co-oxidizing reagent and solvent, followed by separation and isolation of the resulting oxidative products, then confirmation of the identity of metabolites from the pre-identified oxidative products by appropriate animal model studies, and subjecting the actual metabolites prepared in larger quantities by the above method to toxicologic, pathologic, histopathologic, mechanistic or genotoxic testing in order to identify toxic and/or otherwise metabolically-active beneficial or detrimental individual metabolites.
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- Pyrrolic compounds
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Novel methylpyrroles are provided, as well as processes for their preparation.
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- Photoactivatable compositions and to methods for the diagnosis and treating medical conditions
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A broad class of photosensitive compounds having enhanced in vivo target tissue selectivity and versatility in photodynamic therapy. Many furocoumarin compounds, such as psoralens, exhibit cytostatic activity when photoactivated but exhibit little in vivo specificity for selectively accumulating in any particular target tissue such as atheromatous plaques. Reactive Oxygen Producing Photosensitizers ("ROPPs") are photoactivatable compounds having an affinity for hyperproliferating cells (such as atheromatous plaque cells), which when photoactivated, produce cytotoxic reaction products. The photoactivity of a ROPP, such as a porphyrin, may be reduced by metalating the porphyrin while the selective affinity of the metalized ROPP for hyperproliferating tissue remains substantially unchanged. By linking a furocoumarin compound to a ROPP to form a F-ROPP, the cytostatic properties of the furocoumarin portion of the F-ROPP can be exploited while the selective affinity of the ROPP portion of the compound for hyperproliferating cells such as atheromatous plaque provides enhanced tissue selectivity without cytotoxicity. In vivo, certain F-ROPPs may be forced to selectively accumulate in a target tissue by illuminating only the target tissue with light having a wavelength operable for photoactivating the F portion of the F-ROPP thereby causing the F-ROPP to either form a monoadduct with or crosslink the cellular DNA in the target tissue. Light of a second wavelength can then be delivered to the target tissue to photoactivate the ROPP portion causing further interference with cellular activity.
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- Hybrid phthalocyanine derivatives and their uses
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Water soluble hybrid phthalocyanine derivatives useful in competitive and noncompetitive assays immunoassays, nucleic acid and assays are disclosed and claimed having (1) at least one donor subunit with a desired excitation peak; and (2) at least one acceptor subunit with a desired emission peak, wherein said derivative(s) is/are capable of intramolecular energy transfer from said donor subunit to said acceptor subunit. Such derivatives also may contain an electron transfer subunit. Axial ligands may be covalently bound to the metals contained in the water soluble hybrid phthalocyanine derivatives. Ligands, ligand analogs, polypeptides, proteins and nucleic acids can be linked to the axial ligands of the dyes to form dye conjugates useful in immunoassays and nucleic acid assays.
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- D4 -symmetric porphyrin-based catalysts, processes for preparing same, and processes for using same
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The present invention provides novel D4 -symmetric chiral porphyrins derived from 1R-(+)-nopinone. The simplicity and flexibility of this synthetic protocol provides an attractive route to this novel class of porphyrins starting from cyclic ketones. For example, the chloromanganese (III) derivatives of the new macrocycles have utility as catalysts for the asymmetric epoxidation of aromatic alkenes.
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- Diels alder adducts of vinyl porphyrins
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Families of Diels Alder adducts and of metal complexes of Diels Alder adducts, which are useful as particularly active compounds for use in photodynamic therapy, are disclosed. The Diels Alder adducts and a preferred family of metal complexes have the structures of Formulas 1, 2, 3 and 4, below: STR1 where R1, R2, R3 and R4 can be the same or different, and each is methyl, ethyl or an amino acid moiety which is a part of an amide produced by reaction between an amine function of a naturally occurring amino acid and a carbonyl function of the adduct, R5, R6 and R7 can be the same or different, and each is ethyl or an amino acid moiety which is a part of an amide produced by reaction between an amine function of a naturally occurring amino acid and a carbonyl function of the adduct, M comprises a metal cation, e.g., Sn or Zn, that is complexed with two of the nitrogens of the adduct, and R8 is an alkyl group other than t-butyl having from one to four carbon atoms. The use of the adducts and complexes in PHD is also disclosed.
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- Production and use of diels alder adducts of vinyl porphyrins, of metal complexes thereof, and of compositions containing such adducts and complexes
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Families of Diels Alder adducts and of metal complexes of Diels Alder adducts, which are useful as particularly active compounds for use in photodynamic therapy, are disclosed. The Diels Alder adducts and a preferred family of metal complexes have the structures of Formulas 1, 2, 3 and 4, below: STR1 where R1, R2, R3 and R4 can be the same or different, and each is methyl, ethyl or an amino acid moiety which is a part of an amide produced by reaction between an amine function of a naturally occurring amino acid and a carbonyl function of the adduct, R5, R6 and R7 can be the same or different, and each is ethyl or an amino acid moiety which is a part of an amide produced by reaction between an amine function of a naturally occurring amino acid and a carbonyl function of the adduct.
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- Porphyrin synthesis in surfactant solution: Multicomponent assembly in micelles
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A synthesis of meso-substituted porphyrins in anionic sodium dodecyl sulfate micelles has been developed. Polar, functionalized aromatic aldehydes condense reversibly with pyrrole in the micellar phase. Oxidation of the porphyrinogen then provides functionalized porphyrins in yields of 10-48%. Hydrophobic aldehydes condense irreversibly to give low yields at practical substrate concentrations. Synthesis in D2O solution results in per-β-deuterated porphyrins. A two-phase model is used to rationalize the dependence of porphyrin yield on reactant and surfactant concentration. Micelles are viewed as potential wells which promote porphyrinogen assembly by binding products more tightly than reactants.
- Bonar-Law, Richard P.
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p. 3623 - 3634
(2007/10/03)
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- Tetraphenylporphyrin compounds and method
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The invention includes a water-soluble oxygen carrier. The oxygen carrier includes a meso-α,α,α,α-tetrakis(o-propanoylamino)phenylporphyrin, in which the 3-carbons of the propanoyl groups are each covalently bound to an amine nitrogen, and iron or cobalt is bound to the pyrrole nitrogens of the porphyrin. The oxygen carrier also includes a ligand L for protecting the open face of the porphyrin from μ-oxo dimer formation.
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