Synthesis of morpholin-2-ones by chemoselective intramolecular rhodium-catalyzed reductive ring expansion of oxazolidines

The rhodium-catalyzed reductive intramolecular ring expansion of N-(ethoxycarboxymethyl)oxazolidines was carried out under an atmosphere of carbon monoxide and hydrogen to afford N-methylmorpholin-2-ones in good to excellent yields.     

The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room-Temperature Luminescent Members

Low-dimensional ns²-metal halide compounds have received immense attention for applications in solid-state lighting, optical thermometry and thermography, and scintillation. However, these are based primarily on the combination of organic cations with toxic Pb²⁺ or unstable Sn²⁺, and a stable inorganic luminescent material has yet to be found. Here, the zero-dimensional Rb₇Sb₃Cl₁₆ phase, comprised of isolated [SbCl₆]³⁻ octahedra and edge-sharing [Sb₂Cl₁₀]⁴⁻ dimers, shows room-temperature photoluminescence (RT PL) centered at 560 nm with a quantum yield of 3.8±0.2 % at 296 K (99.4 % at 77 K). The temperature-dependent PL lifetime rivals that of previous low-dimensional materials with a specific temperature sensitivity above 0.06 K⁻¹ at RT, making it an excellent thermometric material. Utilizing both DFT and chemical substitution with Bi³⁺ in the Rb₇Bi_3−3xSb_3xCl₁₆ (x≤1) family, we present the edge-shared [Sb₂Cl₁₀]⁴⁻ dimer as a design principle for Sb-based luminescent materials.     

Pressure-assisted strategy for the synthesis of vinyl pyrrolidone-based macro-star photoiniferters. A route to star block copolymers

Star-shaped 1-vinyl-2-pyrrolidone (VP)-based polymers having four pendant arms were produced via high-pressure RAFT using the trithiocarbonate-functionalized core. The use of compression (p = 250 MPa) significantly reduced or eliminated star-star/star-chain coupling side reactions and termination process characteristics the for “core-first” R-type approach, still allowing for a “pseudo-living” reaction course up to very high monomer conversion (>98%). Consequently, tailored and highly living star-shaped poly(1-vinyl-2-pyrrolidone)s (PVP) in a wide range of molecular weights M _n = 2.0–175.6 kg/mol (Đ = 1.18–1.80) have been obtained. The chain extension of the produced polymer was carried out with methyl methacrylate (MMA) via photo-induced RAFT (λ = 365 nm) in the presence of tertiary amine catalyst, yielding well-defined amphiphilic star-shaped block copolymers. DSC measurements showed that synthesized star-shaped PVP homopolymers revealed much lower glass transition temperature values compared to their commercially supplied linear analogs.     

Guest induced reversible on–off switching of elastic frustration in a 3D spin crossover coordination polymer with room temperature hysteretic behaviour

A binary reversible switch between low-temperature multi-step spin crossover (SCO), through the evolution of the population γ_HS(T) with high-spin (HS)-low-spin (LS) sequence: HS₁LS₀ (state 1) ↔ HS_2/3LS_1/3 (state 2) ↔ HS_1/2LS_1/2 (state 3) ↔ HS_1/3LS_2/3 (state 4) ↔ HS₀LS₁ (state 5), and complete one step hysteretic spin transition featuring 20 K wide thermal hysteresis centred at 290 K occurs in the three-dimensional (3D) Hofmann-type porous coordination polymer {Fe^II(3,8phen)[Au(CN)₂]₂}·xPhNO₂ (3,8phen = 3,8-phenanthroline, PhNO₂ = nitrobenzene), made up of two identical interpenetrated pcu-type frameworks. The included PhNO₂ guest (x = 1, 1·PhNO₂) acts as a molecular wedge between the interpenetrated 3D frameworks via PhNO₂-3,8phen intermolecular recognition and is the source of the strong elastic frustration responsible for the multi-step regime. Detailed X-ray single crystal analysis reflects competition between spatial periodicities of structurally inequivalent HS and LS SCO centres featuring: (i) symmetry breaking (state 3) with ⋯HS–LS⋯ ordering with γ_HS = 1/2; and (ii) occurrence of spatial modulation of the structure providing evidence for stabilization of local or aperiodic ordered mixed spin states for states 2 and 4 (with γ_HS ≈ 2/3) and 4 (with γ_HS ≈ 1/3), respectively. Below c.a. 20 K, structural and magnetic analyses show the photogeneration of a metastable HS*, state 6. The room-temperature single-step hysteretic regime appears with release of the guest (x = 0, 1) and the elastic frustration, and reversibly switches back to the original four-step behaviour upon guest re-adsorption. Both uncommon relevant SCO events meeting in the same material represent a rare opportunity to compare them in the frame of antiferro- and ferro-elastic transitions.

Reversible switch between a robust bistable two-state room temperature spin crossover (SCO) and its transformation in a four-stepped elastically frustrated SCO due to guest inclusion in a metal–organic Hofmann framework.     

Reversible pH-Controlled Catenation of a Benzobisimidazole-Based Tetranuclear Rectangle

The development of methodologies to control on demand and reversibly supramolecular transformations from self-assembled metalla-structures requires the rational design of architectures able to answer to an applied stimulus. While solvent or concentration changes, light exposure or addition of a chemical have been largely explored to provide these transformations, the case of pH sensitive materials is less described. Herein, we report the first example of a pH-triggered dissociation of a coordination-driven self-assembled interlocked molecular link. It incorporates a pH sensitive benzobisimidazole-based ligand that can be selectively protonated on its bisimidazole moieties. This generates intermolecular electrostatic repulsions that reduces drastically the stability of the interlocked structure, leading to its dissociation without any sign of protonation of the pyridine moieties involved in the coordination bonds. Importantly, the dissociation process is reversible through addition of a base.     

Bioactivity Performance of Pure Mg after Plasma Electrolytic Oxidation in Silicate-Based Solutions

The biodegradable metals, including magnesium (Mg), are a convenient alternative to permanent metals but fast uncontrolled corrosion limited wide clinical application. Formation of a barrier coating on Mg alloys could be a successful strategy for the production of a stable external layer that prevents fast corrosion. Our research was aimed to develop an Mg stable oxide coating using plasma electrolytic oxidation (PEO) in silicate-based solutions. 99.9% pure Mg alloy was anodized in electrolytes contained mixtures of sodium silicate and sodium fluoride, calcium hydroxide and sodium hydroxide. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), contact angle (CA), Photoluminescence analysis and immersion tests were performed to assess structural and long-term corrosion properties of the new coating. Biocompatibility and antibacterial potential of the new coating were evaluated using U2OS cell culture and the gram-positive Staphylococcus aureus (S. aureus, strain B 918). PEO provided the formation of a porous oxide layer with relatively high roughness. It was shown that Ca(OH)₂ was a crucial compound for oxidation and surface modification of Mg implants, treated with the PEO method. The addition of Ca²⁺ ions resulted in more intense oxidation of the Mg surface and growth of the oxide layer with a higher active surface area. Cell culture experiments demonstrated appropriate cell adhesion to all investigated coatings with a significantly better proliferation rate for the samples treated in Ca(OH)₂-containing electrolyte. In contrast, NaOH-based electrolyte provided more relevant antibacterial effects but did not support cell proliferation. In conclusion, it should be noted that PEO of Mg alloy in silicate baths containing Ca(OH)₂ provided the formation of stable biocompatible oxide coatings that could be used in the development of commercial degradable implants.     

A Promiscuous Halogenase for the Derivatization of Flavonoids

Halogenation often improves the bioactive properties of natural products and is used in pharmaceutical research for the generation of new potential drug leads. High regio- and stereospecificity, simple reaction conditions and straightforward downstream processing are the main advantages of halogenation using enzymatic biocatalysts compared to chemical synthetic approaches. The identification of new promiscuous halogenases for the modification of various natural products is of great interest in modern drug discovery. In this paper, we report the identification of a new promiscuous FAD-dependent halogenase, DklH, from Frankia alni ACN14a. The identified halogenase readily modifies various flavonoid compounds, including those with well-studied biological activities. This halogenase has been demonstrated to modify not only flavones and isoflavones, but also flavonols, flavanones and flavanonols. The structural requirements for DklH substrate recognition were determined using a feeding approach. The homology model of DklH and the mechanism of substrate recognition are also proposed in this paper.     

Impact of Electrospinning Parameters and Post-Treatment Method on Antibacterial and Antibiofilm Activity of Chitosan Nanofibers

Chitosan, a natural biopolymer, is an ideal candidate to prepare biomaterials capable of preventing microbial infections due to its antibacterial properties. Electrospinning is a versatile method ideally suited to process biopolymers with minimal impact on their physicochemical properties. However, fabrication parameters and post-processing routine can affect biological activity and, therefore, must be well adjusted. In this study, nanofibrous membranes were prepared using trifluoroacetic acid and dichloromethane and evaluated for physiochemical and antimicrobial properties. The use of such biomaterials as potential antibacterial agents was extensively studied in vitro using Staphylococcus aureus and Escherichia coli as test organisms. The antibacterial assay showed inhibition of bacterial growth and eradication of the planktonic cells of both E. coli and S. aureus in the liquid medium for up to 6 hrs. The quantitative assay showed a significant reduction in bacteria cell viability by nanofibers depending on the method of fabrication. The antibacterial properties of these biomaterials can be attributed to the structural modifications provided by co-solvent formulation and application of post-treatment procedure. Consequently, the proposed antimicrobial surface modification method is a promising technique to prepare biomaterials designed to induce antimicrobial resistance via antiadhesive capability and the biocide-releasing mechanism.