Radosław Mrówczyński

Structure of Polydopamine: A Never-Ending Story?

Polydopamine (PDA) formed by the oxidation of dopamine is an important polymer, in particular, for coating various surfaces. It is composed of dihydroxyindole, indoledione, and dopamine units, which are assumed to be covalently linked. Although PDA has been applied in a manifold way, its structure is still under discussion. Similarities have been observed in melanins/eumelanins as naturally occurring, deeply colored polymer pigments derived from L-DOPA. Recently, an alternative structure was proposed for PDA wherein dihydroxyindoline, indolinedione, and eventually dopamine units are not covalently linked to each other but are held together by hydrogen bonding between oxygen atoms or π stacking. In this study, we show that this structural proposal is very unlikely to occur taking into account unambiguous results obtained by different analytical methods, among them (13)C CPPI MAS NMR (cross-polarization polarization-inversion magic angle spinning NMR), (1)H MAS NMR (magic angle spinning NMR), and ES-HRMS (electrospray ionization high-resolution mass spectrometry) for the first time in addition to XPS (X-ray photoelectron spectroscopy) and FTIR spectroscopy. The results give rise to a verified structural assignment of PDA wherein dihydroxyindole and indoledione units with different degrees of (un)saturation are covalently linked by C-C bonds between their benzene rings. Furthermore, proof of open-chain (dopamine) monomer units in PDA is provided. Advanced DFT calculations imply the arrangements of several PDA chains preferably by quinone-hydroquinone-type interactions in a parallel or antiparallel manner. From all of these results, a number of hypotheses published before could be experimentally supported or were found to be contradictory, thus leading to a better understanding of the PDA structure.

Magnetic nanoparticle-supported organocatalysts – an efficient way of recycling and reuse

Recycling of organocatalysts is an important aspect in green chemistry. Several techniques have been applied to address this issue ranging from traditional separation techniques (extraction, chromatography) to immobilization on solid supports. Magnetic separation, i.e. attraction of the catalyst by an external magnet and decantation of the supernatant appeared as a new way for separation of organocatalysts omitting problems connected to filtration when solid supported catalysts are used. In this publication, the state of the art of magnetic nanoparticle-supported organocatalysts is reviewed demonstrating a wide range of applications but at the same time hitherto unaddressed fields awaiting future exploration are discussed.

Polydopamine—An Organocatalyst Rather than an Innocent Polymer

Polydopamine (PDA) is easily available by oxidation of dopamine and is widely used for persistent coatings of various materials. It is hitherto considered to be inert in many interesting biomedical and other applications. Results presented here, reveal an unexpected behavior of polydopamine as an organocatalyst in direct aldol reactions under mild conditions. Evidence was found for dual catalysis making use of amino and phenolic hydroxy groups found in PDA. Thus scientists must be aware that PDA is not an innocent polymer and can cause unwanted side effects in important applications, such as in biomedicine or as supports in catalysis.

Assessment of polydopamine coated magnetic nanoparticles in doxorubicin delivery

Magnetic nanoparticles (MNP) coated with bioinspired polydopamine (PDA) were obtained via a co-precipitation method and oxidative polymerization of dopamine. Nanoparticles were investigated by FTIR, TEM and SQUID. Loading capacity of anticancer drug doxorubicin was determined by UV-Vis spectroscopy. The nanocomposites exhibit a high drug loading capacity of 0.46 mg mg−1. Anticancer activity of the nanocomposites was proved in profound in vitro tests on HeLa cells. Cytotoxicity and internalization of nanoparticles were checked using various method, i.e. proliferation assay (WST-1), a two-colour fluorescence cell viability assay, and fluorescent and confocal microscopy.

Electron Paramagnetic Resonance Imaging and Spectroscopy of Polydopamine Radicals

A thorough investigation of biomimetic polydopamine (PDA) by Electron Paramagnetic Resonance (EPR) is shown. In addition, temperature dependent spectroscopic EPR data are presented in the range 3.8-300 K. Small discrepancies in magnetic susceptibility behavior are observed between previously reported melanin samples. These variations were attributed to thermally acitivated processes. More importantly, EPR spatial-spatial 2D imaging of polydopamine radicals on a phantom is presented for the first time. In consequence, a new possible application of polydopamine as EPR imagining marker is addressed.

Diazo transfer at polydopamine – a new way to functionalization

The possibility of introducing azido functions onto polydopamine by diazo transfer making use of existing aminoethyl moieties was verified at polydopamine-coated magnetite nanoparticles. The resulting azido-functionalized Fe3O4@polydopamine nanoparticles serve as a magnetic nano-platform for the introduction of interesting applicatory functions by click-chemistry (CuAAC) as exemplified by linking biotin, tetraacetylglucose, dansyl and proline.

Polydopamine-Based Multifunctional (Nano)materials for Cancer Therapy

Since Lee published a pioneering paper about polydopamine (PDA), application of that polymer in a number of areas has grown enormously in the last 10 years and is still growing. PDAs spectacular success can be attributed to its unique features, i.e., simple preparation protocol, strong adhesive properties, easy and straightforward functionalization, and biocompatibility. Therefore, this polymer has attracted the attention of a vast group of scientists, including those working in the field of nanomedicine. In consequence, polydopamine has been merged with various nanostructures that differ in size and nature, which has resulted in novel types of multifunctional nanomaterials that have recently been extensively exploited in nanomedicine and particularly in cancer therapy. The aim of this article is to offer insight into the latest achievements (up until the end of 2016) in the field of synthesis and application of nanomaterials based on polydopamine and their application in cancer therapy. The conclusions regarding the application of polydopamine-based nanoplatforms in this area and future prospects are given at the end.

Melanin-like polydopa amides – synthesis and application in functionalization of magnetic nanoparticles

Polydopa amides are obtained by oxidative polymerization of amides of L-dopa. These products are analogues of naturally occurring melanins and of polydopamine. They can be used as shells for magnetic core shell nanoparticles. The materials are characterized by FTIR-spectroscopy, 13C ss-NMR spectroscopy, magnetic measurements, TEM and TGA. Comparison with the structures of melanins or polydopamine shows similarities, i.e. cyclized indole monomer units and non-cyclized dopa amide moieties. The majority of the amide groups is maintained during the oxidative polymerization. The functional groups linked to the amide N-atoms open a way of connecting functions to the organic shell that have interesting applicatory potential, e.g. in biomedicine.

In vitro genotoxicity and cytotoxicity of polydopamine-coated magnetic nanostructures

Synthesis of magnetic nanoparticles and magnetic nanoclusters was performed by the co-precipitation method or solvothermal synthesis, respectively, followed by oxidative polymerization of dopamine, resulting in a polydopamine (PDA) shell. The nanomaterials obtained were described using TEM, FTIR and magnetic measurements. For the first time, cyto- and genotoxicity studies of polydopamine-coated nanostructures were performed on cancer and normal cell lines, providing in-depth insight into the toxicity of such materials. The tests conducted, e.g. ROS, apoptosis and DNA double-break of the nanomaterials obtained revealed the low toxicity of these structures. Thus, these results prove the biocompatibility and low genotoxicity of these materials and provide new data on the toxicity of PDA-coated materials, which is of great importance for their biomedical application.

One-step ligand exchange reaction as an efficient way for functionalization of magnetic nanoparticles

Novel magnetic Fe3O4 nanoparticles (NPs) covered by one layer of functionalized fatty acids, bearing entities (Hayashi catalyst, biotin, quinine, proline, and galactose) of high interest for practical application in nanomedicine or organocatalysis, were synthesized. The functionalized fatty acids were obtained by Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) of azido fatty acids with alkynes. All the magnetic NPs show superparamagnetic behavior with high values of magnetization and high colloidal stability in DCM solution.