Formation of polydopamine nanofibers with the aid of folic acid.

Polydopamine (PDA) generated by the oxidative self-polymerization of dopamine shows great potential for surface modification. Observed PDA nanostructures are nanoparticles and thin films. The formation mechanism of PDA is still unclear; thus, the manipulation of PDA nanostructures is a big challenge. In this study, we first demonstrated that folic acid shows a dramatic effect on the PDA nanostructure: New aggregated nanostructures of PDA, nanobelts and nanofibers, were generated in a dopamine/folic acid system. We hypothesized that folic acid may be involved in the stacking of protomolecules of PDA by π-π interactions and hydrogen bonding. Herein we describe the first experimental strategy to manipulate the aggregation of PDA by using small molecules. This study not only provides a new method for generating PDA nanofibers, which are proposed bioorganic electronic materials, but also a possible way to understand the formation mechanism of PDA and its analogues in nature, melanins.

[1]  S. Apte,et al.  Melanin Aggregation and Polymerization: Possible Implications in Age-Related Macular Degeneration , 2005, Ophthalmic Research.

[2]  T. Sarna,et al.  Chemical and structural diversity in eumelanins: unexplored bio-optoelectronic materials. , 2009, Angewandte Chemie.

[3]  Mark R Pederson,et al.  Towards structure-property-function relationships for eumelanin. , 2005, Soft matter.

[4]  G. Prota,et al.  Melanins and melanogenesis , 1992 .

[5]  K. Schallreuter,et al.  Regulation of melanogenesis – controversies and new concepts , 2008, Experimental dermatology.

[6]  Xiwen He,et al.  A self-assembled polydopamine film on the surface of magnetic nanoparticles for specific capture of protein. , 2012, Nanoscale.

[7]  J. Simon,et al.  Ultrastructural organization of eumelanin from Sepia officinalis measured by atomic force microscopy. , 2001, Biochemistry.

[8]  M. Buehler,et al.  Self-Assembly of Tetramers of 5,6-Dihydroxyindole Explains the Primary Physical Properties of Eumelanin: Experiment, Simulation, and Design ARTICLE , 2022 .

[9]  F. Caruso,et al.  Immobilization and intracellular delivery of an anticancer drug using mussel-inspired polydopamine capsules. , 2012, Biomacromolecules.

[10]  J. Simon,et al.  The effect of preparation procedures on the morphology of melanin from the ink sac of Sepia officinalis. , 2003, Pigment cell research.

[11]  Heungsoo Shin,et al.  Mussel-inspired immobilization of vascular endothelial growth factor (VEGF) for enhanced endothelialization of vascular grafts. , 2012, Biomacromolecules.

[12]  Graeme R. Hanson,et al.  Role of semiconductivity and ion transport in the electrical conduction of melanin , 2012, Proceedings of the National Academy of Sciences.

[13]  Marco d'Ischia,et al.  Chemische und strukturelle Vielfalt der Eumelanine – ein kaum erforschtes optoelektronisches Biopolymer , 2009 .

[14]  R. Heenan,et al.  Eumelanin buildup on the nanoscale: aggregate growth/assembly and visible absorption development in biomimetic 5,6-dihydroxyindole polymerization. , 2012, Biomacromolecules.

[15]  Lei Tao,et al.  Biocompatible polydopamine fluorescent organic nanoparticles: facile preparation and cell imaging. , 2012, Nanoscale.

[16]  Y. Y. He,et al.  Complexation of anthracene with folic acid studied by FTIR and UV spectroscopies. , 2009, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[17]  G. Zajac,et al.  Spectroscopic Study and Simulation from Recent Structural Models for Eumelanin: II. Oligomers , 2003 .

[18]  Radosław Mrówczyński,et al.  Structure of polydopamine: a never-ending story? , 2013, Langmuir : the ACS journal of surfaces and colloids.

[19]  Paul Meredith,et al.  The physical and chemical properties of eumelanin. , 2006, Pigment cell research.

[20]  Myung-Hyun Ryou,et al.  Mussel‐Inspired Polydopamine‐Treated Polyethylene Separators for High‐Power Li‐Ion Batteries , 2011, Advanced materials.

[21]  Henrik Birkedal,et al.  pH-induced metal-ligand cross-links inspired by mussel yield self-healing polymer networks with near-covalent elastic moduli , 2011, Proceedings of the National Academy of Sciences.

[22]  Jacques P. Bothma,et al.  Device‐Quality Electrically Conducting Melanin Thin Films , 2008 .

[23]  Haeshin Lee,et al.  Facile Conjugation of Biomolecules onto Surfaces via Mussel Adhesive Protein Inspired Coatings , 2009, Advanced materials.

[24]  T. McIntire,et al.  Effect of stacking and redox state on optical absorption spectra of melanins -- comparison of theoretical and experimental results. , 2005, The journal of physical chemistry. B.

[25]  G. Gottarelli,et al.  Lyomesophases formed by the dinucleoside phosphate d(GpG) , 1988 .

[26]  S. Centeno,et al.  Surface enhanced Raman scattering (SERS) and FTIR characterization of the sepia melanin pigment used in works of art , 2008 .

[27]  K. Littrell,et al.  Structural Studies of Bleached Melanin by Synchrotron Small-angle X-ray Scattering¶ , 2003 .

[28]  J. Gardella,et al.  Solid-state analysis of eumelanin biopolymers by electron spectroscopy for chemical analysis , 1990 .

[29]  Jin Kim,et al.  Polydopamine-mediated surface modification of scaffold materials for human neural stem cell engineering. , 2012, Biomaterials.

[30]  F. Ciuchi,et al.  Self-Recognition and Self-Assembly of Folic Acid Salts: Columnar Liquid Crystalline Polymorphism and the Column Growth Process , 1994 .

[31]  Haeshin Lee,et al.  Mussel-Inspired Surface Chemistry for Multifunctional Coatings , 2007, Science.

[32]  Jin-Kyu Lee,et al.  Bioinspired polymerization of dopamine to generate melanin-like nanoparticles having an excellent free-radical-scavenging property. , 2011, Biomacromolecules.

[33]  R. Wrzalik,et al.  AFM investigations of self-assembled DOPA–melanin nano-aggregates , 2010 .

[34]  Feng Zhou,et al.  Bioinspired catecholic chemistry for surface modification. , 2011, Chemical Society reviews.

[35]  Rambabu Atluri,et al.  Self-assembly mechanism of folate-templated mesoporous silica. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[36]  José G Rivera,et al.  Polydopamine-enabled surface functionalization of gold nanorods for cancer cell-targeted imaging and photothermal therapy. , 2013, Nanomedicine.

[37]  Efthimios Kaxiras,et al.  Theoretical models of eumelanin protomolecules and their optical properties. , 2008, Biophysical journal.

[38]  G. Prota.  Melanins, melanogenesis and melanocytes: looking at their functional significance from the chemist's viewpoint. , 2000, Pigment cell research.

[39]  F. Bechstedt,et al.  Large bandwidths in synthetic one-dimensional stacks of biological molecules , 2012 .

[40]  Rambabu Atluri,et al.  Nonsurfactant supramolecular synthesis of ordered mesoporous silica. , 2009, Journal of the American Chemical Society.

[41]  Kiyoshi Kanie,et al.  Self-assembly of thermotropic liquid-crystalline folic acid derivatives: hydrogen-bonded complexes forming layers and columns , 2001 .

[42]  Kisuk Yang,et al.  Polydopamine-assisted osteoinductive peptide immobilization of polymer scaffolds for enhanced bone regeneration by human adipose-derived stem cells. , 2013, Biomacromolecules.

[43]  Dayang Wang,et al.  Electrostatic repulsion-controlled formation of polydopamine-gold Janus particles. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[44]  P. Mariani,et al.  Four-stranded aggregates of oligodeoxyguanylates forming lyotropic liquid crystals: a study by circular dichroism, optical microscopy, and x-ray diffraction , 1991 .

[45]  Zhaoxia Jin,et al.  Characterization of carbonized polydopamine nanoparticles suggests ordered supramolecular structure of polydopamine. , 2014, Langmuir.

[46]  Andrés H. Thomas,et al.  Study of the photolysis of folic acid and 6-formylpterin in acid aqueous solutions , 2000 .

[47]  N. Jablonski,et al.  Human skin pigmentation as an adaptation to UV radiation , 2010, Proceedings of the National Academy of Sciences.

[48]  Efthimios Kaxiras,et al.  Structural model of eumelanin. , 2006, Physical review letters.

[49]  R. Mezzenga,et al.  Self-assembly and fibrillization of a Fmoc-functionalized polyphenolic amino acid , 2013 .

[50]  P. Traldi,et al.  Identification of Partially Degraded Oligomers of 5,6-Dihydroxyindole-2-carboxylic Acid inSepia Melanin by Matrix-assisted Laser Desorption/Ionization Mass Spectrometry , 1997 .

[51]  Sung Min Kang,et al.  One‐Step Multipurpose Surface Functionalization by Adhesive Catecholamine , 2012, Advanced functional materials.

[52]  Michael J. Tarlov,et al.  Characterization of polydopamine thin films deposited at short times by autoxidation of dopamine. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[53]  P. Schaaf,et al.  Characterization of Dopamine−Melanin Growth on Silicon Oxide , 2009 .

[54]  M. Alfè,et al.  Building‐Block Diversity in Polydopamine Underpins a Multifunctional Eumelanin‐Type Platform Tunable Through a Quinone Control Point , 2013 .

[55]  Chun Xing Li,et al.  Optically active supramolecular complexes of water-soluble achiral polythiophenes and folic acid: spectroscopic studies and sensing applications. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[56]  Almar Postma,et al.  Polydopamine--a nature-inspired polymer coating for biomedical science. , 2011, Nanoscale.

[57]  G. Zajac,et al.  The fundamental unit of synthetic melanin: a verification by tunneling microscopy of X-ray scattering results. , 1994, Biochimica et biophysica acta.

[58]  K. Neoh,et al.  The effect of VEGF functionalization of titanium on endothelial cells in vitro. , 2010, Biomaterials.

[59]  D. Birch,et al.  Eumelanin kinetics and sheet structure , 2012 .

[60]  P. Mariani,et al.  A study of the structure of the lyomesophases formed by the dinucleoside phosphate d(GpG). An approach by X-ray diffraction and optical microscopy , 1989 .

[61]  E. Land,et al.  Early steps in the free radical polymerisation of 3,4-dihydroxyphenylalanine (dopa) into malanin , 1984 .

[62]  Jian Ji,et al.  Mussel-inspired polydopamine: a biocompatible and ultrastable coating for nanoparticles in vivo. , 2013, ACS nano.