Folic acid-polydopamine nanofibers show enhanced ordered-stacking via π-π interactions.

Recent research has indicated that polydopamine and synthetic eumelanins are optoelectronic biomaterials in which one-dimensional aggregates composed of ordered-stacking oligomers have been proposed as unique organic semiconductors. However, improving the ordered-stacking of oligomers in polydopamine nanostructures is a big challenge. Herein, we first demonstrate how folic acid molecules influence the morphology and nanostructure of polydopamine via tuning the π-π interactions of oligomers. MALDI-TOF mass spectrometry reveals that porphyrin-like tetramers are characteristic of folic acid-polydopamine (FA-PDA) nanofibers. X-ray diffraction combined with simulation studies indicate that these oligomers favour aggregation into graphite-like ordered nanostructures via strong π-π interactions. High-resolution TEM characterization of carbonized FA-PDA hybrids show that in FA-PDA nanofibers the size of the graphite-like domains is over 100 nm. The addition of folic acid in polydopamine enhances the ordered stacking of oligomers in its nanostructure. Our study steps forward to discover the mystery of the structure-property relationship of FA-PDA hybrids. It paves a way to optimize the properties of PDA through the design and selection of oligomer structures.

[1]  M. Peter,et al.  Detection of melanochromes by MALDI-TOF mass spectrometry , 1996 .

[2]  Julio Daniel Carvalho Maia,et al.  GPU Linear Algebra Libraries and GPGPU Programming for Accelerating MOPAC Semiempirical Quantum Chemistry Calculations. , 2012, Journal of chemical theory and computation.

[3]  Bruce P. Lee,et al.  A reversible wet/dry adhesive inspired by mussels and geckos , 2007, Nature.

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

[5]  P. Low,et al.  Folate-targeted therapies for cancer. , 2010, Journal of medicinal chemistry.

[6]  J. Simon.  Spectroscopic and dynamic studies of the epidermal chromophores trans-urocanic acid and eumelanin. , 2000, Accounts of chemical research.

[7]  Liping Zhu,et al.  A facile method of surface modification for hydrophobic polymer membranes based on the adhesive behavior of poly(DOPA) and poly(dopamine) , 2009 .

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

[9]  Danke Xu,et al.  Bioinspired polydopamine nanospheres: a superquencher for fluorescence sensing of biomolecules , 2014 .

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

[11]  K. Wakamatsu,et al.  Degree of polymerization of 5,6‐dihydroxyindole‐derived eumelanin from chemical degradation study , 2014, Pigment cell & melanoma research.

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

[13]  G. Vitiello,et al.  Tris buffer modulates polydopamine growth, aggregation, and paramagnetic properties. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[14]  Joon-Seok Lee,et al.  Spatial control of cell adhesion and patterning through mussel-inspired surface modification by polydopamine. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[15]  Bruce P. Lee,et al.  Mussel-Inspired Adhesives and Coatings. , 2011, Annual review of materials research.

[16]  G. Hervieu,et al.  Melanin-concentrating hormone functions in the nervous system: food intake and stress , 2003, Expert opinion on therapeutic targets.

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

[18]  K. J. Jeong,et al.  Polydopamine coatings enhance biointegration of a model polymeric implant , 2011 .

[19]  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 .

[20]  Bong Hoon Kim,et al.  Mussel‐Inspired Block Copolymer Lithography for Low Surface Energy Materials of Teflon, Graphene, and Gold , 2011, Advanced materials.

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

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

[23]  M. Buehler,et al.  Polydopamine and eumelanin: from structure-property relationships to a unified tailoring strategy. , 2014, Accounts of chemical research.

[24]  B. Freeman,et al.  Elucidating the structure of poly(dopamine). , 2012, Langmuir : the ACS journal of surfaces and colloids.

[25]  B. Freeman,et al.  Perspectives on poly(dopamine) , 2013 .

[26]  J. Herbert Waite,et al.  Hydrophobic enhancement of Dopa-mediated adhesion in a mussel foot protein. , 2013, Journal of the American Chemical Society.

[27]  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.

[28]  J. Riesz,et al.  The spectroscopic properties of melanin , 2007 .

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

[30]  Norbert F Scherer,et al.  Single-molecule mechanics of mussel adhesion , 2006, Proceedings of the National Academy of Sciences.

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

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

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

[34]  Lehui Lu,et al.  Dopamine‐Melanin Colloidal Nanospheres: An Efficient Near‐Infrared Photothermal Therapeutic Agent for In Vivo Cancer Therapy , 2013, Advanced materials.

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

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

[37]  P. Traldi,et al.  Structural Analysis of Synthetic Melanins from 5,6‐Dihydroxyindole by Matrix‐assisted Laser Desorption/Ionization Mass Spectrometry , 1996 .

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

[39]  Zhaoxia Jin,et al.  Formation of polydopamine nanofibers with the aid of folic acid. , 2014, Angewandte Chemie.

[40]  Admir Masic,et al.  Adhesion of mussel foot protein-3 to TiO2 surfaces: the effect of pH. , 2013, Biomacromolecules.

[41]  J. Gracio,et al.  Dopamine-melanin film deposition depends on the used oxidant and buffer solution. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[42]  N. Voelcker,et al.  Polydopamine Nanoparticles as a New and Highly Selective Biosorbent for the Removal of Copper (II) Ions from Aqueous Solutions , 2012, Water, Air, & Soil Pollution.

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

[44]  J. Waite,et al.  Polyphenolic Substance of Mytilus edulis: Novel Adhesive Containing L-Dopa and Hydroxyproline. , 1981, Science.

[45]  M. d’Ischia,et al.  Exploring the frontiers of synthetic eumelanin polymers by high-resolution matrix-assisted laser/desorption ionization mass spectrometry. , 2012, Journal of mass spectrometry : JMS.

[46]  R. Tang,et al.  Antigenically shielded universal red blood cells by polydopamine-based cell surface engineering , 2014 .

[47]  R. Reiter,et al.  Chemical and physical properties and potential mechanisms: melatonin as a broad spectrum antioxidant and free radical scavenger. , 2002, Current topics in medicinal chemistry.

[48]  S. Grosse,et al.  Folic acid supplementation and neural tube defect recurrence prevention. , 2007, Birth defects research. Part A, Clinical and molecular teratology.

[49]  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 .

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

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