We present a general thermodynamic top-down analysis of the effects of oxidants and pH on dopamine oxidation and cyclization, supplemented with UV–vis and electrochemical studies. The model is applicable to other catecholamines and various experimental conditions. The results show that the decisive physicochemical parameters in autoxidation are the pK values of the semiquinone and the amino group in the oxidized quinone. Addition of Ce(IV) or Fe(III) enhances dopamine oxidation in acidic media in aerobic and anaerobic conditions by the direct oxidation of dopamine and, in the presence of oxygen, also by the autoxidation of the formed semiquinone. At pH 4.5, the enhancement of the one-electron oxidation of dopamine explains the overall reaction enhancement, but at a lower pH, cyclization becomes rate-determining. Oxidation by Cu(II) at reasonable rates requires the presence of oxygen or chloride ions.

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Deep eutectic solvents (DESs) formed by hydrogen bond donors and acceptors are a promising new class of solvents. Both hydrophilic and hydrophobic binary DESs readily absorb water, making them ternary mixtures, and a small water content is always inevitable under ambient conditions. We present a thorough study of a typical hydrophobic DES formed by a 1:2 mole ratio of tetrabutyl ammonium chloride and decanoic acid, focusing on the effects of a low water content caused by absorbed water vapor, using multinuclear NMR techniques, molecular modeling, and several other physicochemical techniques. Already very low water contents cause dynamic nanoscale phase segregation, reduce solvent viscosity and fragility, increase self-diffusion coefficients and conductivity, and enhance local dynamics. Water interferes with the hydrogen-bonding network between the chloride ions and carboxylic acid groups by solvating them, which enhances carboxylic acid self-correlation and ion pair formation between tetrabutyl ammonium and chloride. Simulations show that the component molar ratio can be varied, with an effect on the internal structure. The water-induced changes in the physical properties are beneficial for most prospective applications but water creates an acidic aqueous nanophase with a high halide ion concentration, which may have chemically adverse effects.

Autoxidation of dopamine to polydopamine by dissolved oxygen is a slow process that requires highly alkaline conditions. Polydopamine can be formed rapidly also in mildly acidic and neutral solutions by using redox-active transition-metal ions. We present a comparative study of polydopamine nanoparticles formed by autoxidation and aerobic or anaerobic oxidation in the presence of Ce(IV), Fe(III), Cu(II), and Mn(VII). The UV–vis spectra of the purified nanoparticles are similar, and dopaminechrome is an early intermediate species. At low pH, Cu(II) requires the presence of oxygen and chloride ions to produce polydopamine at a reasonable rate. The changes in dispersibility and surface charge take place at around pH 4, which indicates the presence of ionizable groups, especially carboxylic acids, on their surface. X-ray photoelectron spectroscopy shows the presence of three different classes of carbons, and the carbonyl/carboxylate carbons amount to 5–15 atom %. The N 1s spectra show the presence of protonated free amino groups, suggesting that these groups may interact with the π-electrons of the intact aromatic dihydroxyindole moieties, especially in the metal-induced samples. The autoxidized and Mn(VII)-induced samples do not contain metals, but the metal content is 1–2 atom % in samples prepared with Ce(IV) or Cu(II), and ca. 20 atom % in polydopamine prepared in the presence of Fe(III). These differences in the metal content can be explained by the oxidation and complexation properties of the metals using the general model developed. In addition, the nitrogen content is lower in the metal-induced samples. All of the metal oxidants studied can be used to rapidly prepare polydopamine at room temperature, but the possible influence of the metal content and nitrogen loss should be taken into account.

The regioselective syntheses of 3-alkyl(aryl)-2-(anthracen-9'-ylimino)-1,3-thiazolidin-4-ones (2) and 2-alkyl(aryl)imino-3-(anthracen-9'-yl)-1,3-thiazolidin-4-ones (3) from N-(anthracen-9-yl)-N'-alkyl(aryl)thioureas were accomplished effectively using methyl bromoacetate and bromoacetyl bromide, respectively. Detailed structural characteristics were confirmed mainly by NMR techniques. The mass spectrometric behavior of the resulting sets of compounds of known structures was shown to be characteristic for each set. Some interesting fragmentation pathways involving the transfer and rearrangements of various moieties were also revealed, as well as regioisomerization for particular substituent-specific fragmentations.