Sabina Abbrent

Urea groups appear in many biomolecules and polymers. They have a significant impact on the properties of the materials because of their inherent strength and for their ability to participate in hydrogen bonds. Typically, in classical urea-based polymer materials, the urea groups occur in their N,N′-disubstituted state. Recently, bis-aspartates have been introduced as a novel type of hindered amine resins providing, upon crosslinking with (poly)isocyanates, the polyurea–polyaspartate thermosets (PU-ASPE) for coatings, sealants, polyelectrolytes, and other applications. These materials contain N,N′N′-trisubstituted urea linkages in their structures. However, the infrared (IR) characterization of trisubstituted urea groups has not been documented in sufficient detail. Consequently, studies on the structure of aspartate-based polyurea materials often rely on data from N,N′-disubstituted ureas, which can lead to inaccurate conclusions. This study presents a detailed evaluation of the possible urea H-bonding states, focusing on the difference between the di- and trisubstituted species. Particularly, the attributions of the IR spectra to urea-based hydrogen bonding states are presented both in neat materials and their solutions. To systematize this study, we initially focus on a simple trisubstituted urea model system, tributyl urea (3BUA), and compare its spectral response with disubstituted N-butyl-N′-cyclohexyl urea (1B1CHUA) and trisubstituted N-butyl-N′,N′-dicyclohexyl urea (1B2CHUA), to elucidate their hydrogen-bonding fingerprints. This research provides a thorough understanding of the IR response of the di- and trisubstituted urea species and their structural characteristics in urea-containing materials.

Lead‐free halide double perovskite (HDP) Cs ₂ AgBiBr ₆ has set a benchmark for research in HDP photoelectric applications due to its attractive optoelectronic properties. However, its narrow absorption range is a key limitation of this material. Herein, a novel dopant, palladium (Pd), is doped into Cs ₂ AgBiBr ₆ and significantly extends the absorption to ≈1400 nm. Pd ²⁺ ions are partially doped in the host lattice, most probably replacing Ag atoms and introducing a sub‐bandgap state within the host bandgap, as indicated by the combination of spectroscopical measurements and theoretical calculations. Importantly, this sub‐bandgap state extends the photoresponse of Cs ₂ AgBiBr ₆ up to the NIR‐II region of 1300 nm, setting a new record for HDPs. This work demonstrates a novel and efficient dopant for HDPs and highlights the effectiveness of employing a sub‐bandgap to broaden the absorption of HDPs, shedding new light on tailoring large bandgap HDPs for NIR optoelectronic applications.

A new generation biomass-based filler for natural rubber, ‘hydrochar’ (HC), was obtained by hydrothermal carbonization of hardwood waste (sawdust). It was intended as a potential partial replacement for the traditional carbon black (CB) filler. The HC particles were found (TEM) to be much larger (and less regular) than CB: 0.5–3 µm vs. 30–60 nm, but the specific surface areas were relatively close to each other (HC: 21.4 m²/g vs. CB: 77.8 m²/g), indicating a considerable porosity of HC. The carbon content of HC was 71%, up from 46% in sawdust feed. FTIR and ¹³C-NMR analyses indicated that HC preserved its organic character, but it strongly differs from both lignin and cellulose. Experimental rubber nanocomposites were prepared, in which the content of the combined fillers was set at 50 phr (31 wt.%), while the HC/CB ratios were varied between 40/10 and 0/50. Morphology investigations proved a fairly even distribution of HC and CB, as well as the disappearance of bubbles after vulcanization. Vulcanization rheology tests demonstrated that the HC filler does not hinder the process, but it significantly influences vulcanization chemistry, canceling scorch time on one hand and slowing down the reaction on the other. Generally, the results suggest that rubber composites in which 10–20 phr of CB are replaced by HC might be promising materials. The use of HC in the rubber industry would represent a high-tonnage application for hardwood waste.

Light absorption enhancement was achieved through structure modulation of the Cs₃Bi₂Br₉ perovskite crystal via Cu-alloying. The Cs₃Bi₂Br₉ perovskite retains its matrix structure with homogeneously distributed Cs₂CuBr₄ large domains.

Spikelets NMR spectra are very popular as they enable the shortening of experimental time and give the possibility to obtain required NMR parameters for nuclei with ultrawide NMR patterns. Unfortunately, these resulted ssNMR spectra cannot be fitted directly in common software. For this reason, we developed UWNMRSpectralShape (USS) software which transforms spikelets NMR patterns into single continuous lines. Subsequently, these reconstructed spectral envelopes of the (Q)CPMG spikelets patterns can be loaded into common NMR software and automatically fitted, independently of experimental settings. This allows the quadrupole and chemical shift parameters to be accurately determined. Moreover, it makes fitting of spikelets NMR spectra exact, fast and straightforward.