- Surface supramolecular organization of a terbium(III) double-decker complex on graphite and its single molecule magnet behavior
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The two-dimensional self-assembly of a terbium(III) double-decker phthalocyanine on highly oriented pyrolitic graphite (HOPG) was studied by atomic force microscopy (AFM), and it was shown that it forms highly regular rectangular two-dimensional nanocryst
- Gonidec, Mathieu,Biagi, Roberto,Corradini, Valdis,Moro, Fabrizio,De Renzi, Valentina,Del Pennino, Umberto,Summa, Domenico,Muccioli, Luca,Zannoni, Claudio,Amabilino, David B.,Veciana, Jaume
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Read Online
- Helical self-assembly and nonlinear optical properties of optically active phthalocyanine derivatives bearing eight optically active diethyleneglycol mono-(S)-2-methylbutyl ether moieties on the β-position of the phthalocyanine ring
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Two phthalocyanine derivatives with eight peripheral chiral diethyleneglycol mono-(S)-2-methylbutyl ether moieties on the β-position of the phthalocyanine ring were prepared from the tetramerization of corresponding phthalonitriles, promoted by organic ba
- Tian, Jing,Jing, Lu,Ji, Lisha,Zhang, Congcong,Liu, Qingyun,Zhang, Xiaomei
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Read Online
- Revisiting the Ullman's Radical Chemistry for Phthalocyanine Derivatives
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Phthalocyanine derivatives do not cease to gain attention due to their numerous properties and applications (e.g., sensor, PDT). This makes them a unique scaffold for the design of new material. In this context, we were interested to develop the synthesis of an imino nitroxide-substituted phthalocyanine by Ullman's procedure; a challenge due to the intrinsic low solubility of most phthalocyanine derivative in much solvents. To overcome this solubility problem, we designed a phthalocyanine with bulky neopentyl substituents in peripheral positions as counterpart to the imino nitroxide moieties. The imino nitroxide-substituted phthalocyanine was obtained by condensation of a monoformyl-substituted phthalocyanine with 2,3-bis(hydroxylamino)-2,3-dimethylbutane in refluxing THF–MeOH (2:1) mixture in the presence of p-toluenesulfonic acid monohydrate, follow by oxidation with PbO2. Characterization was performed by electrochemistry, UV/Vis and EPR spectroscopy in solution as well as SQUID in solid state.
- Fidan, Ismail,Luneau, Dominique,Ahsen, Vefa,Hirel, Catherine
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supporting information
p. 5359 - 5365
(2018/02/09)
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- Synthesis of phenylethynylbenzenes
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A method of: reacting a dihydroxybenzene with bromine to form a bromodihydroxybenzene; reacting the bromodihydroxybenzene with trifluoromethanesulfonyl chloride or trifluoromethanesulfonic anhydride to form a bromotrifluoromethanesulfonatobenzene; and reacting the bromotrifluoromethanesulfonatobenzene with phenylacetylene to form a phenylethynylbenzene.
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Page/Page column 11
(2018/06/08)
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- Co-delivery system of photo-responsive chemotherapeutic drug and preparation method thereof
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The invention discloses a co-delivery system of a photo-responsive chemotherapeutic drug and a preparation method thereof. A prodrug is prepared through covalent linkage of a double branched type photosensitive carrier with o-nitrobenzyl as a structural u
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Paragraph 0050; 0052; 0055
(2017/09/01)
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- Predominant effect of connecting atom and position of substituents on azomethine nitrogens' basicity in phthalocyanines
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The basicity of azomethine nitrogens was studied on a series of phthalocyanines (Pcs) that differed in a position of substituent, i.e. peripherally (β-series) and non-peripherally substituted Pcs (a-series), and in a type of substituent (alkylsulfanyl, alkyloxy or alkyl). Appropriate 3,6-or 4,5-disubstituted phthalonitriles were prepared either by nucleophilic substitution or by Negishi coupling. Target zinc Pcs were synthesized by Linstead method. The basicity was studied by the mean of absorption and 1H NMR spectroscopies in chloroform upon titration with trifluoroacetic acid. Equilibrium constants (log K) indicated significant difference within the series. Basicity decreased as follows: α-alkyloxy > α-alkylsulfanyl > β-alkyloxy > β-alkyl > β-alkylsulfanyl ~ α-alkyl with log K higher than 7 down to 2.6 M-1. Increased basicity of a-alkyloxy and a-alkylsulfanyl Pcs is caused by the stabilization of trapped hydrogen at azomethine nitrogen via hydrogen bonding and van der Waals interactions, respectively. The basicity of b-series clearly correlated with the electronic effects of substituents. 1H NMR studies confirmed the possibility of the weak bonding interactions in a-alkyloxy and α-alkylsulfanyl Pcs, however, the position of the 1H NMR signal of azomethine-NH proton was even more influenced by the electronic effects of present substituents than by the weak interactions.
- Cidlina, Antonin,Svec, Jan,Ludvová, Lucie,Kune?, Ji?í,Zimcik, Petr,Novakova, Veronika
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p. 1122 - 1133
(2016/12/16)
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- A double branched photosensitive prodrug: Synthesis and characterization of light triggered drug release
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A novel oNB based, double branched photosensitive prodrug 1, and a biphenyl counterpart 2 were designed and synthesized. Their photo-triggered drug release properties were studied by HPLC and UV-vis spectra. The isobestic points in UV-vis spectra of prodr
- Liu, Wei,Liang, Li,Lo, Pik Kwan,Gou, Xiao Jun,Sun, Xiao Hua
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p. 959 - 963
(2016/02/05)
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- THERAPEUTIC CATECHOLS
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The invention provides compounds of formula I: and salts thereof wherein R1-R4 have any of the meanings defined in the specification, as well as pharmaceutical compositions comprising the compounds or salts, and methods for their use
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Paragraph 0086; 0087; 0088
(2015/11/30)
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- Pd-catalyzed direct arylation approach to the 6H-dibenzo[c,h]chromenes: Total synthesis of arnottin I
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An efficient synthesis of 6H-dibenzo[c,h]chromenes has been achieved from 2-bromobenzyl-α-naphthyl ethers via a Pd-catalyzed Intramolecular direct-arylation using easily available Pd(PPh3)4 or Pd(OAc)2/PPh3 at elevated temperature. The reaction affords biaryl-coupling products in good to excellent yields in 6-9 h (up to 94% yields). A tentative mechanism has been proposed to understand the reaction pathway. Applying the methodology, a straightforward and concise total synthesis of arnottin I has been demonstrated by converting the biaryl-coupling products to the 6H-benzo[d]naphtho[1,2-b]pyran-6-one using pyridinium chlorochromate (PCC) mediated oxidation.
- De, Subhadip,Chaudhuri, Saikat,Mishra, Sourabh,Mamtani, Himanshu,Bisai, Alakesh
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p. 1871 - 1884
(2014/01/17)
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- Regioselective and high-yielding bromination of phenols and anilins using N-bromosaccharin and amberlyst-15
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A regioselective and facile conversion method for bromination of anilines and phenols using N-bromosaccharine in the presence of a catalytic amount of Amberlyst-15 lead to enhancement of the reaction rate and yielded brominated products in good to excellent yields and short reaction times.
- Baharfar,Alinezhad,Azimi,Salehian
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experimental part
p. 863 - 865
(2012/04/23)
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- The synthesis and characterization of a side-by-side iron phthalocyanine dimer
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The QCA paradigm is one of the approaches to decrease the size scale of computing devices. When molecules are used as QCA cells, they may be able to perform computing at room temperature. This paper describes a novel molecular QCA cell candidate which is
- He, Wei,Lieberman, Marya
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experimental part
p. 277 - 292
(2012/06/01)
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- Efficient synthesis of benzo fused tetrathia[7]helicenes
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An efficient route toward the synthesis of symmetrical and unsymmetrical benzo fused tetrathia[7]helicenes substituted with electron donor (ED) and electron acceptor (EA) groups is reported. A common, readily available precursor 1,2- bis-(2-thienyl)benzen
- Waghray, Deepali,Nulens, Wienand,Dehaen, Wim
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body text
p. 5516 - 5519
(2011/12/22)
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- Concise enantioselective total syntheses of (+)-homochelidonine, (+)-chelamidine, (+)-chelidonine, (+)-chelamine and (+)-norchelidonine by a PdII-catalyzed ring-opening strategy
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New enantioselective syntheses of the B/C hexahydrobenzo[c]phenanthridine alkaloids (+)-homochelidonine, (+)-chelamidine, (+)-chelidonine, (+)-chelamine, and (+)-norchelidonine are described. Our rapid and convergent route to this class of natural products involved the development and application of a Pd II-catalyzed asymmetric ring-opening reaction of a mesoazabicyclic alkene with an aryl boronic acid as the key step. By screening a variety of functionalized ortho-substituted aryl boronic acids, chiral ligands and reaction conditions we were able to prepare the requisite cis-1-amino-2- aryldihydronaphthalenes in high yield and in up to 90% ee. Early attempts to complete the synthesis of (+)-homochelidonine using an N-Boc azabicyclic alkene are described in full. The successful route required a protecting group alteration followed by B ring for-mation and then stereoselective installation of the C-11 syn-hydroxy group by regioselective epoxide ring-opening using a hydride source. Ring-opening of the same epoxide intermediate with water ultimately led to the synthesis of (+)-chelamidine. The same strategy was then used to synthesize the other structurally similar B/C hexahydrobenzo[c] phenanthridine alkaloids, (+)-chelidonine, (+)-chelamidine, and (+)norchelidonine.
- Fleming, Matthew J.,McManus, Helen A.,Rudolph, Alena,Chan, Walter H.,Ruiz, Jeremy,Dockendorff, Chris,Lautens, Mark
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experimental part
p. 2112 - 2124
(2009/04/06)
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- Enantioselective total synthesis of (+)-homochelidonine by a Pd II-catalyzed asymmetric ring-opening reaction of a meso-azabicyclic alkene with an aryl boronic acid
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(Chemical Equation Presented) An efficient and highly convergent enantioselective synthesis of (+)-homochelidonine has been achieved (see scheme; Cbz = benzyloxycarbonyl, MOM = methoxymethyl) and relied on a new and powerful desymmetrizing ring-opening reaction of a meso-azabicycle with an aryl boronic acid. The route should allow access to other hexahydrobenzo[c]phenanthridine alkaloids.
- McManus, Helen A.,Fleming, Matthew J.,Lautens, Mark
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p. 433 - 436
(2008/02/02)
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- Peripheral and axial substitution of phthalocyanines with solketal groups: Synthesis and in vitro evaluation for photodynamic therapy
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Phthalocyanines (Pcs) are a class of photosensitizers (PSs) with a strong tendency to aggregate in aqueous environment, which has a negative influence on their photosensitizing ability in photodynamic therapy. Pcs with either peripheral or axial solketal substituents, that is, ZnPc(sol)8 and Si(sol)2Pc, respectively, were synthesized and their tendency to aggregate as well as their photodynamic properties in 14C and B16F10 cell lines were evaluated. The results were compared to more hydrophilic silicon Pcs, that is, Si(PEG750)2Pc and Pc4. The order of cellular uptake was Pc4 > ZnPc(sol)8 > Si(PEG750)2Pc > Si(sol2)Pc. In contrast, Si(sol2)Pc showed the highest photocytotoxicity, while ZnPc(sol)8 did not show any photocytotoxicity up to a concentration of 10 μM in both cell types. UV/vis spectroscopy showed that Si(sol) 2Pc is less prone to aggregation than ZnPc(sol)8, which can explain the lack of photoactivity of the latter. Si(sol)2Pc was predominantly located in lipid droplets, whereas Si(PEG750)2Pc was homogeneously distributed in the cytosol, which is probably the main cause of their difference in photoactivity. The very high photodynamic efficacy of Si(sol)2Pc makes this PS an interesting candidate for future studies.
- Hofman, Jan-Willem,Van Zeeland, Femke,Turker, Selcan,Talsma, Herre,Lambrechts, Saskia A. G.,Sakharov, Dmitri V.,Hennink, Wim E.,Van Nostrum, Cornelus F.
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p. 1485 - 1494
(2008/02/01)
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- Hexadecapropyloxy-substituted diphthalocyanine complexes of rare-earth elements: Synthesis, spectroscopic and electrochemical studies
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Hexadecapropyloxy-substituted diphthalocyanine complexes of rare-earth elements (REE = Lu, Tm, Sm) were synthesized. The new symmetrically substituted diphthalocyanine complexes prepared starting from 4,5- dipropyloxyphthalodinitrile (phthalogen) are char
- Kalashnikova,Zhukov,Tomilova,Zefirov
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p. 1709 - 1714
(2007/10/03)
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- Beta-cyclodextrin dimers and phthalocyanines and uses thereof
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The invention provides β-cyclodextrin dimers and phthalocyanines which can be used in photodynamic therapy of cancer.
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- Synthesis and structure/property correlation of fully functionalized photorefractive polymers
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This paper describes the synthesis and physical study of several new photorefractive polymers. The Heck reaction was successfully applied in the synthesis of these multifunctional polymers. These polymers are conjugated poly(phenylenevinylene)s copolymerized with a small amount of macrocyclic zinc complexes as the photosensitizers. Nonlinear optical chromophores were incorporated as the pendant groups. Both electron-rich and electron-deficient PPV backbones were synthesized. Experimental results showed that when an electron-rich photosensitizer is used, the electron-deficient component for charge transport (CN-PPV) enhances photorefractive performance and reduces the response time.
- You, Wei,Wang, Liming,Wang, Qing,Yu, Luping
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p. 4636 - 4645
(2007/10/03)
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- Synthesis and properties of optically active 6,6′-didodecyl-1,1′-binaphthyl-phthalocyanine linked through crown ether units
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A novel optically active 6,6′-didodecyl-1,1′-binaphthyl-metallophthalocyanine linked through crown ether units ((S)-Pc) has been synthesized. A stable monolayer of (S)-Pc that is able to bind metal ions can be formed at the air-water interface. Nonlinear
- Liu, Hongwei,Liu, Yaohu,Liu, Minghua,Chen, Chuanfu,Xi, Fu
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p. 7083 - 7086
(2007/10/03)
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- Cyclodextrin dimers as cleavable carriers of photodynamic sensitizers
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Several phthalocyanines carrying hydrophobic components have been synthesized and shown to bind to a group of cyclodextrin dimers with a carbon - carbon double bond in the linker. The complexes are soluble in water. On irradiation in the presence of oxygen, the singlet oxygen produced cleaves the olefinic linkers in the complexes, resulting in precipitation of the sensitizers. This process concentrates the sensitizers in the light beam, a process that has useful potential in photodynamic therapy.
- Baugh,Yang,Leung,Wilson,Breslow
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p. 12488 - 12494
(2007/10/03)
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- Methyl- and methoxy-substituted di[1,4]benzodithiio[2,3-b:2,3-e]-pyridines as new electron donor compounds: Synthesis, molecular structure, electrochemical properties, and EPR studies
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Two new derivatives of di[1,4]benzodithiino[2,3-b:2,3-e]pyridine (5) tetrasubstituted with methyl (7) and methoxy (8) groups at the 2,3,9 and 10 positions have been prepared from 2,3,5,6-tetrachloropyridine, by cyclization reaction with the bidentate nucleophiles, 4,5-dimethyl-and 4,5-dimethoxy-benzene-1,2-dithiol. Cyclic voltammograms for the oxidation of both polyheterocyclic compounds 7 and 8 in CH2Cl2 exhibit two consecutive redox couples. The first pairs are due to the equilibria between the initial compounds and their radical cations, while in the second couples, the electrogenerated radical cations are in equilibrium with the corresponding dications. Radical cations of these molecules have been generated in fluid solution, by oxidation of the parent compounds with thallium(III) trifluoroacetate in trifluoroacetic acid in the case of 7, and by irradiation of a CH2Cl2 solution containing trifluoroacetic acid (10%) in the case of 8. Both species were analyzed by electron paramagnetic resonance (EPR). X-Ray analysis of the molecular structures of both 7 and 8 shows a stable chair-shaped conformation with interplanar angles between the phenyl rings and the pyridine ring of 139.9 and 141.4° for 7 and 133.7° for 8.
- Bueno,Esteve,Irurre,Brillas,Torrelles,Rius,Alvarez-Larena,Piniella,Aleman,Julia
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p. 1503 - 1512
(2007/10/03)
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- Hydroxyphthalocyanines as potential photodynamic agents for cancer therapy
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A series of benzyl-substituted phthalonitriles, substituted at the 3-, 4-, and 4,5-positions, underwent varied condensations with phthalonitrile to give a series of protected (monohydroxy- and polyhydroxyphthalocyaninato)zinc(II) derivatives which were readily cleaved to give several hydroxyphthalocyanines (ZnPc) (phthalocyanine phenol analogues). Their efficacy as sensitizers for the photodynamic therapy (PDT) of cancer was evaluated on the EMT-6 mammary tumor cell line. In vitro, the 2-hydroxy ZnPc (32) was the most active, followed by the 2,3- and 2,9- dihydroxy ZnPc (39 and 45), with the 2,9,16-trihydroxy ZnPc (33) exhibiting the least activity. In vivo, the monohydroxy derivative 32 and the 2,3- dihydroxy derivative 39 were both efficient in inducing tumor necrosis at 1 μmol kg-1, but complete tumor regression was poor, even at 2 μmol/kg. In contrast, the 2,9-dihydroxy isomer 45, at 2 μmol kg-1, induced tumor necrosis in all animals treated, with 75% complete regression. These results underline the importance of the position of the substituents on the Pc macrocycle to optimize tumor response and confirm the PDT potential of the unsymmetrical Pcs bearing functional groups on adjacent benzene rings.
- Hu, Mougang,Brasseur, Nicole,Zeki Yildiz,Van Lier, Johan E.,Leznoff, Clifford C.
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p. 1789 - 1802
(2007/10/03)
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- Synthesis and supramolecular chemistry of novel liquid crystalline crown ether-substituted phthalocyanines: Toward molecular wires and molecular ionoelectronics
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The synthesis of the metal-free and the dihydroxysilicon derivatives of tetrakis[4′,5′-bis(decoxy)benzo-18-crown-6]phthalocyanine is described. The metal-free phthalocyanine is liquid crystalline and exhibits a crystalline phase to mesophase transition at
- Van Nostrum, Cornelus F.,Picken, Stephen J.,Schouten, Arend-Jan,Nolte, Roeland J. M.
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p. 9957 - 9965
(2007/10/03)
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- THE ESR SPECTRA, STRUCTURE, AND REACTIVITY OF AROMATIC RADICAL-CATIONS IN SUPERACIDS
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The oxidation of aromatic compounds by lead dioxide in superacids based on fluorosulfonic acid at -75 deg C takes place by a one-electron mechanism and leads in many cases to relatively stable radical-cations.The ESR spectra, the isotropic hyperfine coupling constants, data on the reactivity of the radical-cations, and the structures of the final products from their transformations under "long-life" conditions are presented.
- Rudenko, A. P.
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p. 1946 - 1980
(2007/10/03)
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- 13C and 17O NMR Study of Methoxy Groups in Chlorinated Di- and Trimethoxybenzenes
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13C and 17O NMR data for the methoxy groups in isomeric 1,2-, 1,3- and 1,4-dimethoxybenzenes, 1,2,3-trimethoxybenzenes and most of their chlorinated derivatives and some related brominated compounds were measured for CDCl3 solutions.The 17O NMR chemical shifts show up to 60 ppm dispersion.Comparison between the compounds with and without adjacent chlorine atoms (2,6-di- and 2,4,6-trisubstitution) also showed a clear methoxy carbon chemical shift change.The number and position of the chlorine atoms in the aromatic ring give small but observable effects on the 17O NMR chemical shifts of the methoxy group if it is coplanar with the aromatic plane.Similarly, the degree and nature of the substitution have a minor effect (about 1 Hz) on the 1J(CH) direct coupling values.
- Knuutinen, J.,Kolehmainen, E.
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p. 315 - 317
(2007/10/02)
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- Control of the Discotic to Isotropic Transition in Alkoxy-Substituted Silicondihydroxo-Phthalocyanines by Axial Substituents
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The synthesis of a homologous series of octaalkoxy-substituted silicondihydroxo-phthalocyanines is described.The mesomorphic properties of these new materials were studied by DSC, optical microscopy and X-ray investigations.Compounds with n >/= 4 (n is the number of carbon atoms in a single alkoxy side chain) show a discotic mesophase transition.A transition to the isotropic state is only observed when n >/= 8.X-ray diffraction patterns of the mesophases confirm that all compounds form a hexagonal columnar mesophase of the type Dhd.
- Sauer, Thomas,Wegner, Gerhard
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- Synthesis and Morphology of New Discogenic Phthalocyanine Derivatives
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New discogens based on the octasubstituted phthalocyanines (Pc) were synthesized: 2,3,9,10,16,17,23,24-octakis-phthalocyanine (1a), 2,3,9,10,16,17,23,24-octakis-phthalocyanine (1b), 2,3,9,10,16,17,23,24-o
- Cho, Iwhan,Lim, Youngsoo
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