Electron Diffraction Tomography on Two-Phase Nanolamellae of Topochemically Synthesized Cu(Sb2S3)Cl.

The dark red semiconductor Cu(Sb2S3)Cl was obtained by leaching the layered precursor Cu(Sb2S3)[AlCl4] in a 0.1 M aqueous HCl solution. The selective extraction of AlCl3 yielded a mica-like lamellar product of poor crystallinity. Misalignment of lamellae down to the nanoscale prevented structure determination by conventional single-crystal X-ray diffraction, but a combination of transmission electron microscopy, selected area electron diffraction, and selected area electron precession diffraction tomography on a nanoscale spot with largely ordered crystalline lamellae revealed the crystal structures of two intergrown modifications. Orthorhombic o-Cu(Sb2S3)Cl and monoclinic m-Cu(Sb2S3)Cl have similar layers to the precursor and differ only in the stacking of the layers. These consist of uncharged Sb2S3 strands, whose sulfide ions, together with chloride ions, coordinate the copper(I) cations. Only one chloride ion remained from the [AlCl4]- group. DFT calculations confirm the structure solution for the orthorhombic form and suggest that the monoclinic structure is metastable against transformation to o-Cu(Sb2S3)Cl.

Processing Gray Selenium in Phosphonium-Based Ionic Liquids.

The dissolution of gray selenium in tetraalkylphosphonium acetate ionic liquids was investigated by UV-vis, NMR, and Raman spectroscopy as well as quantum chemical calculations and electrochemical methods. Acetate anions and tetraalkylphosphonium cations facilitate the formation and stabilization of oligoselenides Sen2- and cationic Se species in the ionic liquid phase. Chemical exchange of selenium atoms was demonstrated by variable-temperature 77Se NMR experiments. Additionally, uncharged cycloselenium molecules exist at high selenium concentrations. Upon dilution with ethanol, amorphous red selenium precipitates from the solution. Moreover, crystalline Se1-xTex solid solutions precipitate when elemental tellurium is added to the mixture as confirmed by powder X-ray diffraction and Raman spectroscopy.

Exploration of metal sulfide syntheses and the dissolution process of antimony sulfide in phosphonium-based ionic liquids.

Ionic liquids (ILs), especially task-specific ILs, are capable of dissolving various solids at moderate temperatures without the need for special reaction vessels. Direct synthesis of binary sulfides of B, Bi, Ge, Mo, Cu, Au, Sn, In, Ti, V, Fe, Co, Ga, Ni, Al, Zn, and Sb in [P66614]Cl was tested at 100 °C, i.e. below the melting point of sulfur. Under these conditions, substantial sulfide formation occurred only for nickel (Ni3S4, Ni3S2, NiS) and copper (Cu2S, CuS). Sb showed no formation of crystalline sulfide, but after addition of EtOH, an orange material precipitated which was identified as amorphous metastibnite. Subsequently, the dissolution of antimony sulfide (Sb2S3), the main source of antimony production, in the phosphonium-based ILs [P66614][OAc] and [P66614]Cl at 100 °C was studied in detail. The dissolution proceeds without H2S evolution, and amorphous Sb2S3 can be precipitated from these solutions. Heating Sb2S3 in the Lewis-acidic IL [BMIm]Cl·4.7AlCl3 led to the crystallization of [Sb13S16Cl2][AlCl4]5, which contains a new quadruple heterocubane cation.

Coexistence of Tellurium Cations and Anions in Phosphonium-Based Ionic Liquids.

Elemental tellurium readily dissolves in ionic liquids (ILs) based on tetraalkylphosphonium cations even at temperatures below 100 °C. In the case of ILs with acetate, decanoate, or dicyanamide anions, dark red to purple colored solutions form. A study combining NMR, UV-Vis and Raman spectroscopy revealed the formation of tellurium anions (Ten )2- with chain lengths up to at least n=5, which are in dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an ionic liquid reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. Although the spectroscopic detection of tellurium cations in these solutions is difficult, the coexistence of tellurium cations, such as (Te4 )2+ and (Te6 )4+ , and tellurium anions could be proven by cyclic voltammetry and electrodeposition experiments. DFT calculations indicate that electrostatic interactions with the ions of the ILs are sufficient to stabilize both types of tellurium ions in solution.

Low Temperature Activation of Tellurium and Resource-Efficient Synthesis of AuTe2 and Ag2 Te in Ionic Liquids.

The low temperature syntheses of AuTe2 and Ag2 Te starting from the elements were investigated in the ionic liquids (ILs) [BMIm]X and [P66614 ]Z ([BMIm]+ =1-butyl-3-methylimidazolium; X = Cl, [HSO4 ]- , [P66614 ]+ = trihexyltetradecylphosphonium; Z = Cl- , Br- , dicyanamide [DCA]- , bis(trifluoromethylsulfonyl)imide [NTf2 ]- , decanoate [dec]- , acetate [OAc]- , bis(2,4,4-trimethylpentyl)phosphinate [BTMP]- ). Powder X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy revealed that [P66614 ]Cl is the most promising candidate for the single phase synthesis of AuTe2 at 200 °C. Ag2 Te was obtained using the same ILs by reducing the temperature in the flask to 60 °C. Even at room temperature, quantitative yield was achieved by using either 2 mol % of [P66614 ]Cl in dichloromethane or a planetary ball mill. Diffusion experiments, 31 P and 125 Te-NMR, and mass spectroscopy revealed one of the reaction mechanisms at 60 °C. Catalytic amounts of alkylphosphanes in commercial [P66614 ]Cl activate tellurium and form soluble phosphane tellurides, which react on the metal surface to solid telluride and the initial phosphane. In addition, a convenient method for the purification of [P66614 ]Cl was developed.

The Genomic Basis of Rapid Adaptation to Antibiotic Combination Therapy in Pseudomonas aeruginosa.

Combination therapy is a common antibiotic treatment strategy that aims at minimizing the risk of resistance evolution in several infectious diseases. Nonetheless, evidence supporting its efficacy against the nosocomial opportunistic pathogen Pseudomonas aeruginosa remains elusive. Identification of the possible evolutionary paths to resistance in multidrug environments can help to explain treatment outcome. For this purpose, we here performed whole-genome sequencing of 127 previously evolved populations of P. aeruginosa adapted to sublethal doses of distinct antibiotic combinations and corresponding single-drug treatments, and experimentally characterized several of the identified variants. We found that alterations in the regulation of efflux pumps are the most favored mechanism of resistance, regardless of the environment. Unexpectedly, we repeatedly identified intergenic variants in the adapted populations, often with no additional mutations and usually associated with genes involved in efflux pump expression, possibly indicating a regulatory function of the intergenic regions. The experimental analysis of these variants demonstrated that the intergenic changes caused similar increases in resistance against single and multidrug treatments as those seen for efflux regulatory gene mutants. Surprisingly, we could find no substantial fitness costs for a majority of these variants, most likely enhancing their competitiveness toward sensitive cells, even in antibiotic-free environments. We conclude that the regulation of efflux is a central target of antibiotic-mediated selection in P. aeruginosa and that, importantly, changes in intergenic regions may represent a usually neglected alternative process underlying bacterial resistance evolution, which clearly deserves further attention in the future.

Radiation dose and fluoroscopy time of modern endovascular treatment techniques in patients with saccular unruptured intracranial aneurysms.

OBJECTIVES: Modern endovascular treatment of unruptured intracranial aneurysms (UIAs) demands for observance of diagnostic reference levels (DRLs). The national DRL (250 Gy cm2) is only defined for coiling. We provide dosimetric data for the following procedures: coiling, flow diverter (FD), Woven EndoBridge (WEB), combined techniques. METHODS: A retrospective single-centre study of saccular UIAs treated between 2015 and 2019. Regarding dosimetric analysis, the parameters dose area product (DAP) and fluoroscopy time were investigated for the following variables: endovascular technique, aneurysm location, DSA protocol, aneurysm size, and patient age. RESULTS: Eighty-seven patients (59 females, mean age 54 years) were included. Total mean and median DAP (Gy cm2) were 119 ± 73 (89-149) and 94 (73; 130) for coiling, 128 ± 53 (106-151) and 134 (80; 176) for FD, 128 ± 56 (102-153) and 118 (90; 176) for WEB, and 165 ± 102 (110-219) and 131 (98; 209) for combined techniques (p > .05). Regarding the aneurysm location, neither DAP nor fluoroscopy time was significantly different (p > .05). The lowest and highest fluoroscopy times were recorded for WEB and combined techniques, respectively (median 26 and 94 min; p < .001). A low-dose protocol yielded a 43% reduction of DAP (p < .001). Significantly positive correlations were found between DAP and both aneurysm size (r = .320, p = .003) and patient age (r = .214, p = .046). CONCLUSIONS: This UIA study establishes novel local DRLs for modern endovascular techniques such as FD and WEB. A low-dose protocol yielded a significant reduction of radiation dose. KEY POINTS: • This paper establishes local diagnostic reference levels for modern endovascular treatment techniques of unruptured intracranial aneurysms, including flow diverter stenting and Woven EndoBridge device. • Dose area product was not significantly different between endovascular techniques and aneurysm locations, but associated with aneurysm size and patient age. • A low-dose protocol yielded a significant reduction of dose area product and is particularly useful when applying materials with a high radiopacity (e.g. platinum coils).

Spontaneous Substitutions at Phosphorus Trihalides in Imidazolium Halide Ionic Liquids: Grotthuss Diffusion of Anions?

PX3 compounds (X=Cl, Br, I) in imidazolium halide ionic liquids combine with the anion Z (Z=Cl, Br, I) of the solvent to form [PX3 Z]- complex anions. These anions have a sawhorse shape in which the lone pair of the phosphorus atom fills the third equatorial position of the pseudotrigonal bipyramid. Theoretical results show that this association remains incomplete due to strong hydrogen bonding with the cations of the ionic liquid, which competes with the phosphorus trihalide for interaction with the Z- anion. Temperature-dependent 31 P NMR experiments indicated that the P-Z binding is weaker at higher temperature. Both theory and experiment evidence dynamic exchange of the halide anions at the phosphorus atom, together with continuous switching of the ligands at the phosphorus atom between equatorial and axial positions. Detailed knowledge of the mechanism of the spontaneous exchange of halogen atoms at phosphorus trihalides suggests a way to design novel, highly conducting ionic-liquid mixtures.

Controlled Synthesis of Polyions of Heavy Main-Group Elements in Ionic Liquids.

Ionic liquids (ILs) have been proven to be valuable reaction media for the synthesis of inorganic materials among an abundance of other applications in different fields of chemistry. Up to now, the syntheses have remained mostly "black boxes"; and researchers have to resort to trial-and-error in order to establish a new synthetic route to a specific compound. This review comprises decisive reaction parameters and techniques for the directed synthesis of polyions of heavy main-group elements (fourth period and beyond) in ILs. Several families of compounds are presented ranging from polyhalides over carbonyl complexes and selenidostannates to homo and heteropolycations.