Despite the great interest in nanoconfined materials nowadays, nanocompartmentalized poly(ionic liquid)s (PILs) have been rarely investigated so far. Herein, we report on the successful alkylation of poly(1-vinylimidazole) with methyl iodide in bicontinuous nanophasic poly(1-vinylimidazole)-l-poly(tetrahydrofuran) (PVIm-l-PTHF) amphiphilic conetworks (APCNs) to obtain nanoconfined methylated PVImMe-l-PTHF poly(ionic liquid) conetworks (PIL-CNs). A high extent of alkylation (~95%) was achieved via a simple alkylation process with MeI at room temperature. This does not destroy the bicontinuous nanophasic morphology as proved by SAXS and AFM, and PIL-CNs with 15–20 nm d-spacing and poly(3-methyl-1-vinylimidazolium iodide) PIL nanophases with average domain sizes of 8.2–8.4 nm are formed. Unexpectedly, while the swelling capacity of the PIL-CN dramatically increases in aprotic polar solvents, such as DMF, NMP, and DMSO, reaching higher than 1000% superabsorbent swelling degrees, the equilibrium swelling degrees decrease in even highly polar protic (hydrophilic) solvents, like water and methanol. An unprecedented Gaussian-type relationship was found between the ratios of the swelling degrees versus the polarity index, indicating increased swelling for the nanoconfined PVImMe-l-PTHF PIL-CNs in solvents with a polarity index between ~6 and 9.5. In addition to the nanoconfined structural features, the unique selective superabsorbent swelling behavior of the PIL-CNs can also be utilized in various application fields.

We have developed an easy route to prepare (nano-ZrO₂,nano-ZrC_x)@C composites with varying ZrO₂/ZrC_x content. The process consists of preparing a zirconium-loaded, iminodiacetate-functionalized styrene-divinylbenzene (STY-DVB) copolymer, and its subsequent carbonization in a tube furnace and/or a thermal plasma reactor. Depending on the zirconium salt used (zirconyl chloride, zirconyl nitrate or zirconium (IV) sulfate) in the Zr loading, the Zr-loaded resins resulted in ZrO₂@C pre-pyrolizates with C to Zr molar ratios of 5.8, 6.8 and 6.60. This carbon surplus is sufficient for the partial or even complete reduction of ZrO₂ into ZrC_0.58 at 1400 °C. The reaction products also contain 5 to 55 mass% residual free carbon. The plasma processing of the ZrO₂@C composite formed at 1000 °C in a tube furnace led to ZrC_0.94@C composites. The transformation of amorphous carbon content during the plasma treatment strongly depended on the atmosphere (He or H₂) in the reactor and the anion type of the Zr salt. In the presence of He, amorphous carbon could be completely transformed into graphite. In the presence of H₂, amorphous carbon and graphite were found at roughly the same ratio. No ZrO₂ could be detected in the plasma-treated samples, whilst different ZrO₂ polymorphs were found in the samples prepared in the tube furnace, depending on the synthesis conditions.

Delivering of hydrophobic drugs by polymeric nanoparticles is an intensively investigated research and development field worldwide due to the insufficient solubility of many existing and potential new drugs in aqueous media. Among polymeric nanoparticles, micelles of biocompatible amphiphilic block copolymers are among the most promising candidates for solubilization, encapsulation, and delivery of hydrophobic drugs to improve the water solubility and thus the bioavailability of such drugs. In this study, amphiphilic ABA triblock copolymers containing biocompatible hydrophilic hyperbranched (dendritic) polyglycerol (HbPG) outer and hydrophobic poly(tetrahydrofuran) (PTHF) inner segments were synthesized using amine-telechelic PTHF as a macroinitiator for glycidol polymerization. These hyperbranched–linear–hyperbranched block copolymers form nanosized micelles with 15–20 nm diameter above the critical micelle concentration. Coagulation experiments proved high colloidal stability of the aqueous micellar solutions of these block copolymers against temperature changes. The applicability of block copolymers as drug delivery systems was investigated using curcumin, a highly hydrophobic, water-insoluble, natural anti-cancer agent. High and efficient drug solubilization up to more than 3 orders of magnitude to that of the water solubility of curcumin (>1500-fold) is achieved with the HbPG-PTHF-HbPG block copolymer nanomicelles, locating the drug in amorphous form in the inner PTHF core. Outstanding stability of and sustained curcumin release from the drug-loaded block copolymer micelles were observed. The in vitro bioactivity of the curcumin-loaded nanomicelles was investigated on U-87 glioblastoma cell line, and an optimal triblock copolymer composition was found, which showed highly effective cellular uptake and no toxicity. These findings indicate that the HbPG-PTHF-HbPG triblock copolymers are promising candidates for advanced drug solubilization and delivery systems.

A tremendous number of solvents, either as liquids or vapors, contaminate the environment on a daily basis worldwide. Olefin metathesis, which has been widely used as high-yielding protocols for ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), and isomerization reactions, is typically performed in toxic and volatile solvents such as dichloromethane. In this study, the results of our systematic experiments with the Grubbs G1, G2, and Hoveyda-Grubbs HG2 catalysts proved that benzotrifluoride (BTF) can replace dichloromethane (DCM) in these reactions, providing high yields and similar or even higher reaction rates in certain cases. The ROMP of norbornene resulted not only in high yields but also in polynorbornenes with a high molecular weight at low catalyst loadings. Ring-closing metathesis (RCM) experiments proved that, with the exception of the G1 catalyst, RCM occurs with similar high efficiencies in BTF as in DCM. It was found that isomerization of (Z)-but-2-ene-1,4-diyl diacetate with the G2 and HG2 catalysts proceeds at significantly higher initial rates in BTF than in DCM, leading to rapid isomerization with high yields in a short time. Overall, BTF is a suitable solvent for olefin metathesis, such as polymer syntheses by ROMP and the ring-closing and isomerization reactions.

The emergence of a peculiar molecular phenomenon, the single-centered, but multiple Lewis acidity, is uncovered among Lewis acidic boranes with appropriate steric crowding and symmetry design.

In a systematic study combining experimental and theoretical approaches we investigated the effect of electron withdrawing (EW) and donating (ED) substituents at the axial 4' position on both ground and excited state properties of the [Fe(terpy)2]2+ complex. While these modifications have negligible impact on the ground-state geometries of the complexes, DFT calculations predict systematic changes in the electron density along the molecular axis (Fe and the two axial N atoms) upon substitution, and this is confirmed experimentally by 15N NMR and 57Fe Mössbauer spectroscopy. The predicted variations in the electron density and molecular orbital energies are further corroborated by UV-Vis spectroscopy and cyclic voltammetry measurements. DFT calculations of the excited-state properties relevant for photoswitching applications revealed that the singlet--quintet energy gap is highly sensitive to the ED/EW character of the substituents, whereas the triplet energies are much less affected. Comparison with the quintet lifetimes determined by transient optical absorption spectroscopy (TOAS) experiments show that conventional energy barrier-based theoretical models yield unsatisfactory results for strong substituents. However, inclusion of tunnelling processes between the quintet and singlet states leads to excellent agreement with experiment. The results presented demonstrate the potential of efficient computational screening to guide ligand design for tunable photoactive molecular switches based on abundant 3d transition metals.