Superhydrophilic Polystyrene Nanofiber Materials Generating O₂(¹Δ_g): Postprocessing Surface Modifications toward Efficient Antibacterial Effect

The surfaces of electrospun polystyrene (PS) nanofiber materials with encapsulated 1% w/w 5,10,15,20-tetraphenylporphyrin (TPP) photosensitizer were modified through sulfonation, radio frequency (RF) oxygen plasma treatment, and polydopamine coating. The nanofiber materials exhibited efficient photogeneration of singlet oxygen. The postprocessing modifications strongly increased the wettability of the pristine hydrophobic PS nanofibers without causing damage to the nanofibers, leakage of the photosensitizer, or any substantial change in the oxygen permeability of the inner bulk of the polymer nanofiber. The increase in the surface wettability yielded a significant increase in the photo-oxidation of external polar substrates and in the antibacterial activity of the nanofibers in aqueous surroundings. The results reveal the crucial role played by surface hydrophilicity/wettability in achieving the efficient photo-oxidation of a chemical substrate/biological target at the surface of a material generating O₂(¹Δ_g) with a short diffusion length

Expanding the Scope of Diamond Surface Chemistry: Stille and Sonogashira Cross-Coupling Reactions

Well-defined covalent surface functionalization of diamond is a crucial, yet nontrivial, matter because of diamond’s intrinsic chemical inertness and stability. Herein, we demonstrate a two-step functionalization approach for H-terminated boron-doped diamond thin films, which can lead to significant advances in the field of diamond hybrid photovoltaics. Primary diamond surface functionalization is performed via electrochemical diazonium grafting of <i>in situ</i> diazotized 4-iodoaniline. The freshly grafted iodophenyl functional moieties are then employed to couple a layer of thiophene molecules to the diamond surface via two well-established Pd-catalyzed cross-coupling reactions, i.e., Stille and Sonogashira. X-ray photoelectron spectroscopy analysis indicates a dense coverage and successful cross-coupling in both cases. However, we find that the Stille reaction is generally accompanied by severe surface contamination, in spite of process optimization and thorough rinsing. Sonogashira cross-coupling on the other hand provides a clean, high quality functionalization over a broad range of reaction conditions. The protocols employing Sonogashira reactions thus appear to be the method of choice toward future fabrication of high-performance dye-functionalized diamond electrodes for photovoltaic applications

Size and Purity Control of HPHT Nanodiamonds down to 1 nm

High-pressure high-temperature (HPHT) nanodiamonds originate from grinding of diamond microcrystals obtained by HPHT synthesis. Here we report on a simple two-step approach to obtain as small as 1.1 nm HPHT nanodiamonds of excellent purity and crystallinity, which are among the smallest artificially prepared nanodiamonds ever shown and characterized. Moreover we provide experimental evidence of diamond stability down to 1 nm. Controlled annealing at 450 °C in air leads to efficient purification from the nondiamond carbon (shells and dots), as evidenced by X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and scanning transmission electron microscopy. Annealing at 500 °C promotes, besides of purification, also size reduction of nanodiamonds down to ∼1 nm. Comparably short (1 h) centrifugation of the nanodiamonds aqueous colloidal solution ensures separation of the sub-10 nm fraction. Calculations show that an asymmetry of Raman diamond peak of sub-10 nm HPHT nanodiamonds can be well explained by modified phonon confinement model when the actual particle size distribution is taken into account. In contrast, larger Raman peak asymmetry commonly observed in Raman spectra of detonation nanodiamonds is mainly attributed to defects rather than to the phonon confinement. Thus, the obtained characteristics reflect high material quality including nanoscale effects in sub-10 nm HPHT nanodiamonds prepared by the presented method