Flavin-Helicene Amphiphilic Hybrids: Synthesis, Characterization, and Preparation of Surface-Supported Films.

This work reports on the preparation and structural characterization of flavo[7]helicene 1 (flavin-[7]helicene conjugate), which was subsequently characterized at the molecular level in either an aqueous environment or an organic phase, at the supramolecular level in the form of polymeric layers, and also embedded in a lipidic mesophase environment to study the resulting properties of such a hybrid relative to its parent molecules. The flavin benzo[g]pteridin-2,4-dione (isoalloxazine) was selected for conjugation because of its photoactivity and reversible redox behavior. Compound 1 was prepared from 2-nitroso[6]helicene and 6-methylamino-3-methyluracil, and characterized using common structural and spectroscopic tools: circular dichroism (CD), circularly polarized luminescence (CPL) spectroscopy, cyclic voltammetry (CV), and DFT quantum calculations. In addition, a methodology that allows the loading of 1 enantiomers into an internally nanostructured lipid (1-monoolein) matrix was developed.

[1]  J. Storch,et al.  Recent advances in functionalizations of helicene backbone. , 2020, The Journal of organic chemistry.

[2]  J. Vacek,et al.  Chiral Electrochemistry: Anodic Deposition of Enantiopure Helical Molecules. , 2020, ChemPlusChem.

[3]  J. Sýkora,et al.  Photochemical Oxidation Specific to Distorted Aromatic Amines Providing ortho-Diketones. , 2020, Organic letters.

[4]  J. Crassous.  Circularly Polarized Luminescence in Helicene and Helicenoid Derivatives , 2020 .

[5]  L. Fekete,et al.  Redox and optically active carbohelicene layers prepared by potentiodynamic polymerization , 2020 .

[6]  J. Crassous,et al.  Enantioenriched Helicenes and Helicenoids Containing Main-Group Elements (B, Si, N, P). , 2019, Chemical reviews.

[7]  J. Sýkora,et al.  2-Bromo[6]helicene as a Key Intermediate for [6]Helicene Functionalization. , 2018, The Journal of organic chemistry.

[8]  J. Vacek,et al.  Lipidic liquid crystalline cubic phases for preparation of ATP-hydrolysing enzyme electrodes. , 2018, Biosensors & bioelectronics.

[9]  E. Landau,et al.  Charged additives modify drug release rates from lipidic cubic phase carriers by modulating electrostatic interactions , 2017, Journal of Electroanalytical Chemistry.

[10]  J. Vacek,et al.  Development of separation methods for the chiral resolution of hexahelicenes. , 2016, Journal of chromatography. A.

[11]  M. Tokeshi,et al.  Microfluidic Approaches for Protein Crystal Structure Analysis , 2016, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[12]  M. B. Braiek,et al.  Synthesis and characterization of new helically chiral heptacyclic systems , 2015 .

[13]  E. Landau,et al.  Lyotropic Cubic Phases for Drug Delivery: Diffusion and Sustained Release from the Mesophase Evaluated by Electrochemical Methods. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[14]  J. Vacek,et al.  Synthesis and characterization of a helicene-based imidazolium salt and its application in organic molecular electronics. , 2015, Chemistry.

[15]  R. Cibulka.  Artificial Flavin Systems for Chemoselective and Stereoselective Oxidations (Eur. J. Org. Chem. 5/2015) , 2015 .

[16]  Alasdair J. Campbell,et al.  Circularly polarized light detection by a chiral organic semiconductor transistor , 2013, Nature Photonics.

[17]  K. Akagi,et al.  Hierarchically self-assembled helical aromatic conjugated polymers , 2013 .

[18]  Masaharu Nakamura,et al.  Azaboradibenzo[6]helicene: carrier inversion induced by helical homochirality. , 2012, Journal of the American Chemical Society.

[19]  Y. Qiu,et al.  Synthesis, structure, properties, and application of a carbazole-based diaza[7]helicene in a deep-blue-emitting OLED. , 2012, Chemistry.

[20]  Andrew J. P. White,et al.  An unusual oxidative rearrangement of [7]-helicene , 2012 .

[21]  M. Caffrey,et al.  Lipid cubic phase as a membrane mimetic for integral membrane protein enzymes , 2011, Proceedings of the National Academy of Sciences.

[22]  H. Fukuoka,et al.  Mechanofluorochromism of heteropolycyclic donor–π-acceptor type fluorescent dyes , 2010 .

[23]  A. Cohen,et al.  Limits on fluorescence detected circular dichroism of single helicene molecules. , 2009, The journal of physical chemistry. A.

[24]  G. Lindblom,et al.  Cubic phases in biosensing systems , 2008, Analytical and bioanalytical chemistry.

[25]  Masood Parvez,et al.  7:8,9:10-dibenzo-1,2,3,4-tetrafluoro- triphenylene: synthesis, structure, and photophysical properties of a novel [5]helicene. , 2005, The Journal of organic chemistry.

[26]  V. Rotello,et al.  Model systems for flavoenzyme activity: relationships between cofactor structure, binding and redox properties. , 2003, Journal of the American Chemical Society.

[27]  J. E. Field,et al.  Circularly polarized luminescence from bridged triarylamine helicenes. , 2003, Journal of the American Chemical Society.

[28]  B. Stoltz,et al.  The palladium-catalyzed oxidative kinetic resolution of secondary alcohols with molecular oxygen. , 2001, Journal of the American Chemical Society.

[29]  V. Massey.  The chemical and biological versatility of riboflavin. , 2000, Biochemical Society transactions.

[30]  C. Rizzo,et al.  Linear Free Energy Substituent Effect on Flavin Redox Chemistry , 1998 .

[31]  J. Rosenbusch,et al.  Lipidic cubic phases: a novel concept for the crystallization of membrane proteins. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[32]  F. Diederich,et al.  Redox-dependent binding ability of a flavin cyclophane in aqueous solution: hydrophobic stacking versus cavity-inclusion complexation , 1990 .

[33]  Marcel Knossow,et al.  Lamellar Twinning Explains the Nearly Racemic Composition of Chiral, Single Crystals of Hexahelicene , 1981, Science.

[34]  D. Cremer,et al.  General definition of ring puckering coordinates , 1975 .

[35]  V. Cherezov,et al.  Crystallizing membrane proteins using lipidic mesophases , 2009, Nature Protocols.