- Synthetic study and structure of cage-type cyclophane C36H36S6
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A cage compound was synthesized in order to investigate the structure and cation-π interactions of the metal ion complex. The multi-step synthesis was achieved starting from trimesic acid triethyl ester. In solution, a completely symmetrical structure that was anticipated by the molecular design was observed by 1H and 13C NMR spectroscopy. However, in the solid state, X-ray crystallographic analysis revealed that the compound had a collapsed structure.
- Takemura, Hiroyuki,Nagaoka, Maiko,Kawasaki, Chihiro,Tokumoto, Kasumi,Tobita, Noriko,Takano, Yuki,Iwanaga, Tetsuo
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p. 1066 - 1070
(2017/03/31)
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- Anionic hexadeca-carboxylate tetrapyrazinoporphyrazine: Synthesis and in vitro photodynamic studies of a water-soluble, non-aggregating photosensitizer
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A sodium salt of zinc tetrapyrazinoporphyrazine bearing eight 3,5-dicarboxylatophenyl substituents (1) was synthesized. The presence of sixteen negative charges in a rigid arrangement on the periphery of the macrocycle inhibited its aggregation in water or buffers at pH > 5.8. Strong aggregation was, however, observed in buffers at pH 50 = 5.7 ± 1.1 μM) was found to be influenced by both pH and interactions with serum proteins. This was demonstrated with a detailed in vitro study based on the inhibition of vacuolar H+-ATPase using bafilomycin A1, which increased the intracellular fluorescence of 1. Compound 1 also formed interactions with serum proteins that partially quenched its excited states; however, they also protected the compound from self-aggregation at low pH.
- MacHacek, Miloslav,Kollár, Jan,Miletin, Miroslav,Ku?era, Radim,Kubát, Pavel,Simunek, Tomas,Novakova, Veronika,Zimcik, Petr
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p. 10064 - 10077
(2016/02/05)
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- Viologen-based benzylic dendrimers: selective synthesis of 3,5-bis(hydroxymethyl)benzylbromide and conformational analysis of the corresponding viologen dendrimer subunit
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Convergent and divergent strategies for the synthesis of viologen dendrimers with 1,3,5-tri-methylene-branching units are discussed. The title compound is easily transformed into 1-[3,5-bis(hydroxymethyl)benzyl]-4-(pyridin-4-yl)pyridinium hexafluorophosphate, which is used in sequential growth and activation steps as a CB2 compound in the cascade-type dendrimer synthesis (B = -OH, activation = -OH → Br). Analysis of the dendrimer structure reveals that three torsional angles, that is, τ1 between the two pyridinium units, τ2 between the methylene and pyridinium and τ3 between the methylene and phenyl, determine the conformational space of the dendrimers. We report here the crystal structure of 1-[3,5-bis(hydroxymethyl)benzyl]-4-(pyridin-4-yl)pyridinium as PF6- salt which represents the smallest subunit of the dendrimer that shows the same three torsional angles. The crystal structure together with the results from PM3 calculations opens an avenue to judge the structure of benzylic viologen-based dendrimers.
- Kathiresan, Murugavel,Walder, Lorenz,Ye, Fei,Reuter, Hans
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supporting information; experimental part
p. 2188 - 2192
(2010/06/19)
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- Synthesis and supramolecular properties of a novel octaphosphonate porphyrin
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Two complementary routes were developed for preparing novel octaphosphonate porphyrins. The use of protected/deprotected phosphonate-substituted precursors in the rational synthesis gave an overall yield 16%. A more streamlined synthetic path gave 21 % overall yield, of the target molecule. Octaphosphonate porphyrin possesses promising properties in supramolecular aggregate formation with cyclam. Cofacial reversible self-assembly of a meso-substituted octaphosphonate porphyrin with cyclam yields micrometer-long nanowires with a height of about 1-1.5 nm. The resulting wires were characterized by UV/Vis absorption, emission and atomic force microscopy and transmission electron microscopy. ( Wiley-VCH Verlag GmbH & Co. KGaA.
- Bhosale, Sheshanath V.,Kalyankar, Mohan B.,Langibrd, Steven J.,Bhosale, Sidhanath V.,Oliver, Ruth F.
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experimental part
p. 4128 - 4134
(2009/12/26)
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- Isophthalate ester-terminated dendrimers: Versatile nanoscopic building blocks with readily modifiable surface functionalities
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The preparation and modification of highly functionalized polyether dendrimers containing a versatile diethyl isophthalate terminal group is presented. The convergent synthesis consists of the construction of diester-terminated dendrons containing benzylic bromide functions at the focal point and their subsequent attachment to 4,4'-biphenol cores. Dendrons up to the third generation can be prepared using recrystallization alone as the primary means of purification, allowing the synthesis to be performed on the scale of tens to hundreds of grams. The third and fourth generation bidendron dendrimers (with 32 and 64 terminal ester functionalities, respectively) have been subjected to a variety of surface modification reactions including hydrolysis, ester interchange, and amide-ester interchange, many of which proceed with complete conversion of the functional groups and in high isolated yield. The addition of alcohols such as benzyl alcohol or a first generation 3,5-di(benzyloxy)benzyl alcohol dendron to the dendrimer surface serves to increase the generation number of the dendrimers by one or two in what amounts to a 'double convergent growth' approach. The analysis of these structurally precise dendrimers by matrix-assisted laser desorption ionization time of flight is described.
- Leon, Jeffrey W.,Kawa, Manabu,Fréchet, Jean M. J.
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p. 8847 - 8859
(2007/10/03)
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