Synthesis and Characterization of Na4Si2Se6-tP24 and Na4Si2Se6-oP48, Two Polymorphs with Different Anionic Structures.

Two different polymorphs of the new selenosilicate Na4Si2Se6 were synthesized by solid-state reactions. The high-temperature polymorph Na4Si2Se6-tP24 crystallizes in the tetragonal space group P42/mcm (No. 132) with lattice parameters a = 7.2793(2) Å, c = 12.4960(4) Å, and V = 662.14(3) Å3. The main structural motifs are isolated Si2Se6 units of two edge-sharing SiSe4 tetrahedra. The high-pressure/low-temperature polymorph Na4Si2Se6-oP48 crystallizes in the orthorhombic space group Pbca (No. 61) with lattice parameters a = 12.9276(1) Å, b = 15.9324(1) Å, c = 6.0349(1) Å, and V = 1243.00(2) Å3 showing zweier single chains ∞1[Si2Se6]4-. The lattice parameters of Na4Si2Se6-tP24 were determined by single-crystal X-ray diffraction, whereas those of Na4Si2Se6-oP48 were investigated by powder X-ray diffraction. Both modifications crystallize in new structure types. An energetic comparison of the two polymorphs and further hypothetical structure types was carried out by density functional theory modeling. Calculations reveal that the polymorphs are very close in energy (ΔE = 3.4 kJ mol-1). Impedance spectroscopic measurements show ionic conductivity (σspec = 1.4 × 10-8 S cm-1 at 50 °C and 6.8 × 10-6 S cm-1 at 200 °C) with an activation energy of EA = 0.54(2) eV for Na4Si2Se6-oP48.

Investigating nanocatalyst-embedding laser-induced carbon nanofibers for non-enzymatic electrochemical sensing of hydrogen peroxide.

In this present study, we explored the catalytic behaviors of the in situ generated metal nanoparticles, i.e., Pt/Ni, embedded in laser-induced carbon nanofibers (LCNFs) and their potential for H2O2 detection under physiological conditions. Furthermore, we demonstrate current limitations of laser-generated nanocatalyst embedded within LCNFs as electrochemical detectors and possible strategies to overcome the issues. Cyclic voltammetry revealed the distinctive electrocatalytic behaviors of carbon nanofibers embedding Pt and Ni in various ratios. With chronoamperometry at +0.5 V, it was found that modulation of Pt and Ni content affected only current related to H2O2 but not other interfering electroactive substances, i.e., ascorbic acid (AA), uric acid (UA), dopamine (DA), and glucose. This implies that the interferences react to the carbon nanofibers regardless of the presence of metal nanocatalysts. Carbon nanofibers loaded only with Pt and without Ni performed best in H2O2 detection in phosphate-buffered solution with a limit of detection (LOD) of 1.4 µM, a limit of quantification (LOQ) of 5.7 µM, a linear range from 5 to 500 µM, and a sensitivity of 15 µA mM-1 cm-2. By increasing Pt loading, the interfering signals from UA and DA could be minimized. Furthermore, we found that modification of electrodes with nylon improves the recovery of H2O2 spiked in diluted and undiluted human serum. The study is paving the way for the efficient utilization of laser-generated nanocatalyst-embedding carbon nanomaterials for non-enzymatic sensors, which ultimately will lead to inexpensive point-of-need devices with favorable analytical performance.

Twelve-month efficacy of second-generation cryoballoon ablation for atrial fibrillation performed at community hospitals: results of the German register on cryoballoon ablation in local hospitals (regional).

BACKGROUND: The 12-month follow-up (F/U) efficacy of CBA PVI performed at community hospitals for treatment of symptomatic paroxysmal and persistent atrial fibrillation (AF) is unknown. This study determined the 12-month efficacy of pulmonary vein isolation (PVI) using cryoballoon ablation (CBA) performed at community hospitals with limited annual case numbers. METHODS: This registry study included 983 consecutive patients (pts) from 19 hospitals, each with an annual procedural volume of < 100 PVI procedures/year. Pts underwent CBA PVI for paroxysmal AF (n = 520), persistent AF (n = 423), or redo PVI (n = 40). The primary endpoint was frequency of documented recurrent AF, the occurrence of atrial flutter or tachycardia following a 90-day period after the index ablation and up to 12 months. The frequency of repeat ablation was determined. RESULTS: Isolation of all PVs was documented in 98% of pts at the end of the procedure. Twelve-month F/U data could be obtained in 916 pts. A 24-h ECG registration was performed in 641 pts (70.0%); in 107 pts (16.7%) of them, recurrent AF was documented. The primary endpoint was met in 193 F/U pts (21.1%). It occurred in 80/486 F/U pts with paroxysmal AF (16.4%), and in 107/390 F/U pts with persistent AF (27.4%). Redo PVI was performed in 71 pts (7.8%), and atrial flutter ablation was performed in 12 pts (1.4%). CONCLUSIONS: CBA PVI for paroxysmal or persistent AF can be performed at community hospitals with adequate rates of 12-month symptom freedom and arrhythmia recurrence. The study was registered at the German register of clinical studies (DRKS00016504).

Safety and acute efficacy of cryoballoon ablation for atrial fibrillation at community hospitals.

AIMS: Pulmonary vein isolation (PVI) using cryoballoon ablation (CBA) is an established procedure for treating symptomatic paroxysmal and persistent atrial fibrillation (AF). The safety and efficacy of PVI performed at community hospitals are unknown. We aimed to determine the safety and acute efficacy of PVI using CBA performed at community hospitals with limited annual case numbers. METHODS AND RESULTS: This registry study included 1004 consecutive patients who had PVI performed for symptomatic paroxysmal (n = 563) or persistent AF (n = 441) from January 2019 to September 2020 at 20 hospitals. Each hospital performed fewer than 100 CBA-PVI procedures/year according to local standards. Procedural data, efficacy, and complication rates were determined. The mean number of CBA procedures performed/year at each centre was 59 ± 25. The average procedure time was 90.1 ± 31.6 min and the average fluoroscopy time was 19.2 ± 11.4 min. Isolation of all pulmonary veins was documented in 97.9% of patients. The most frequent reason for not achieving complete isolation was development of phrenic nerve palsy. No hospital deaths were observed. Two patients (0.2%) suffered a clinical stroke. Pericardial effusion occurred in six patients (0.6%), two of whom (0.2%) required pericardial drainage. Vascular complications occurred in 24 patients (2.4%), two of whom (0.2%) required vascular surgery. Phrenic nerve palsy occurred in 48 patients (4.8%) and persisted up to hospital discharge in six patients (0.6%). CONCLUSION: Pulmonary vein isolation procedures for paroxysmal or persistent AF using CBA can be performed at community hospitals with high acute efficacy and low complication rates.

Printable 3D Carbon Nanofiber Networks with Embedded Metal Nanocatalysts.

Carbon nanofiber (CNF) nanocatalyst hybrids hold great promise in fields such as energy storage, synthetic chemistry, and sensors. Current strategies to generate such hybrids are laborious and utterly incompatible with miniaturization and large-scale production. Instead, this work demonstrates that Ni nanoparticles embedded in three-dimensional (3D) CNFs of any shape and design can be easily prepared using electrospinning, followed by laser carbonization under ambient conditions. Specifically, a solution of nickel acetylacetonate /polyimide is electrospun and subsequently a design is printed via CO2 laser (Ni-laser-induced carbon nanofiber (LCNFs)). This creates uniformly distributed small Ni nanoparticles (∼8 nm) very tightly adhered to the CNF network. Morphological and performance characteristics can be directly influenced by metal content and lasing power and hence adapted for the desired application. Here, Ni-LCNFs are optimized for nonenzymatic electrochemical sensing of glucose with great sensitivity of 2092 µA mM-1 cm-2 and a detection limit down to 0.3 µM. Its selectivity for glucose vs interfering species (ascorbic and uric acid) is essentially governed by the Ni content. Most importantly, this strategy can be adapted to a whole range of metal precursors and hence provide opportunities for such 3D CNF-nanocatalyst hybrids in point-of-care applications where high-performance but also sustainable and low-cost fabrications are of utmost importance.

Synthesis and Characterization of Cs4 Ga6 Q11 (Q=S, Se): Chalcogenometalates with Exotic Polymeric Anions.

Two new chalcogenogallates Cs4 Ga6 Q11 (Q=S, Se) were obtained by a controlled thermal treatment of CsN3 in the presence of stoichiometric amounts of Ga2 Q3 and the elemental chalcogens at elevates temperatures. Both isotypic compounds crystallize in the space group P 1 ‾ (no. 2). The most prominent structural feature in these chalcogenogallates are the complex anionic Dreier double chains 1 ∞ [Ga6 Q11 4- ] formed by condensed GaQ4 tetrahedra. The semiconductors Cs4 Ga6 S11 (Eg =3.14 eV) and Cs4 Ga6 Se11 (Eg =2.41 eV) were further studied by using UV/Vis, 133 Cs and 71 Ga solid-state NMR spectroscopy, and complementary DFT calculations. The 133 Cs MAS NMR spectra are characteristic for cationic cesium and vibrational spectra show two distinct regions, attributed to the Ga-Q valence and deformation vibrations, respectively. High-temperature studies revealed incongruent melting of both solids, which is also depicted in updated binary phase-diagrams Cs2 Q-Ga2 Q3 (Q=S, Se).

In Situ X-ray Diffraction Study of the Thermal Decomposition of Selenogallates Cs2[Ga2(Se2)2- xSe2+ x] ( x = 0, 1, 2).

The selenogallates CsGaSe3 and Cs2Ga2Se5 release gaseous selenium upon heating. An in situ high-temperature X-ray powder diffraction analysis revealed a two-step degradation process from CsGaSe3 to Cs2Ga2Se5 and finally to CsGaSe2. During each step, one Se22- unit of the anionic chains in Cs2[Ga2(Se2)2- xSe2+ x] ( x = 0, 1, 2) decomposes, and one equivalent of selenium is released. This thermal decomposition can be reverted by simple addition of elemental selenium and subsequent annealing of the samples below the decomposition temperature. The influence of the diselenide units in the anionic selenogallate chains on the optical properties and electronic structures was further studied by UV/vis diffuse reflectance spectroscopy and relativistic density functional theory calculations, revealing increasing optical band gaps with decreasing Se22- content.

Preparation of Magnesium, Cobalt and Nickel Ferrite Nanoparticles from Metal Oxides using Deep Eutectic Solvents.

Natural deep eutectic solvents (DESs) dissolve simple metal oxides and are used as a reaction medium to synthesize spinel-type ferrite nanoparticles MFe2 O4 (M=Mg, Zn, Co, Ni). The best results for phase-pure spinel ferrites are obtained with the DES consisting of choline chloride (ChCl) and maleic acid. By employing DESs, the reactions proceed at much lower temperatures than usual for the respective solid-phase reactions of the metal oxides and at the same temperatures as synthesis with comparable calcination processes using metal salts. The method therefore reduces the overall required energy for the nanoparticle synthesis. Thermogravimetric analysis shows that the thermolysis process of the eutectic melts in air occurs in one major step. The phase-pure spinel-type ferrite particles are thoroughly characterized by X-ray diffraction, diffuse-reflectance UV/Vis spectroscopy, and scanning electron microscopy. The properties of the obtained nanoparticles are shown to be comparable to those obtained by other methods, illustrating the potential of natural DESs for processing metal oxides.

Synthesis, structural characterization, and physical properties of Cs2Ga2S5, and redetermination of the crystal structure of Cs2S6.

The reaction of CsN3 with GaS and S at elevated temperatures results in Cs2Ga2S5. Its crystal structure was determined from single-crystal X-ray diffraction data. The colorless solid crystallizes in space group C2/c (no. 15) with V = 1073.3(4) Å(3) and Z = 4. Cs2Ga2S5 is the first compound that features one-dimensional chains ∞(1)([Ga2S3(S2)(2-)] of edge- and corner-sharing GaS4 tetrahedra. The vibrational band of the S2(2-) units at 493 cm(-1) was revealed by Raman spectroscopy. Cs2Ga2S5 has a wide bandgap of about 3.26 eV. The thermal decomposition of CsN3 yields elemental Cs, which reacts with sulfur to provide Cs2S6 as an intermediate product. The crystal structure of Cs2S6 was redetermined from selected single crystals. The red compound crystallizes in space group P1 with V = 488.99(8) Å(3) and Z = 2. Cs2S6 consists of S6(2-) polysulfide chains and two Cs positions with coordination numbers of 10 and 11, respectively. Results of DFT calculations on Cs2Ga2S5 are in good agreement with the experimental crystal structure and Raman data. The analysis of the chemical bonding behavior revealed completely ionic bonds for Cs, whereas Ga-S and S-S form polarized and fully covalent bonds, respectively. HOMO and LUMO are centered at the S2 units.

Cap for copper(I) ions! Metallosupramolecular solid and solution state structures on the basis of the dynamic tetrahedral [Cu(phenAr2)(py)2]+ motif.

The tetrahedral [Cu(phenAr(2))(py)(2)](+) coordination motif (phen = 1,10-phenanthroline; py = pyridine) conceived on the basis of the HETPYP concept (heteroleptic pyridyl and phenanthroline metal complexes) is a versatile dynamic unit for constructing various heteroleptic metallosupramolecular pseudo-1D, 2D, and 3D structures, both in solution and the solid state. The 2,9-diaryl substituted phenanthroline (phenAr(2)) serves as a capping ligand for copper(I) ions, as its bulky nature prevents formation of the homoleptic complex [Cu(phenAr(2))(2)](+). Combination of the dynamic and concave metal ligand building block [Cu(phenAr(2))](+) with various pyridine (py) ligands, such as bi-, tri-, and tetra-pyridines, opened the way to infinite 1D helicates, 2D networks, and discrete 3D hexanuclear cages, whereas spatial integration of both phenAr(2) and py units into a single ligand resulted in the formation of a Borromean-ring-type hexanuclear cage.

Synthesis of 6-amino-3,4-dihydroisoquinolinium derivatives by ring-opening reactions of acridizinium ions.

The reaction of the 9-fluoroacridizinium (9-fluorobenzo[b]quinolizinium) or the 9-aminoacridizinium (9-aminobenzo[b]quinolizinium) ion with primary alkyl amines gives with high diastereoselectivity 6-amino-3,4-dihydroisoquinolinium derivatives as main products, which exhibit pronounced absorption and fluorescence properties. It is proposed that the reaction proceeds via a nucleophilic ring-opening followed by an aza Diels-Alder reaction.

Cyclic Se6 and helical infinity1[Sex] as neutral ligands in the new compounds PdBr2Se6 and PdCl2Se8.

PdBr2Se6 and PdCl2Se8 are two new compounds with cyclic Se6 coordinated to PdBr2 molecules and one-dimensional helical Sex chains coordinated to PdCl2 molecules. PdBr2Se6 is a black solid with a crystal structure similar, but not equal, to PdCl2Se6. It crystallizes in the space group P1 with the lattice constants a = 4.3946(8) A, b = 7.605(1) A, c = 7.992(2) A, alpha = 66.15(2) degrees , beta = 86.44(2) degrees , gamma = 80.90(2) degrees , and Z = 1 and can be handled in air like the deep red PdCl2Se8 which crystallizes in the orthorhombic space group Pbca with the lattice constants a = 9.609(2) A, b = 8.958(2) A, c = 13.799(3) A, and Z = 4. In PdBr2Se6, two cyclic Se6 molecules (chair conformation) are directly coordinated to Pd atoms, forming Pd(Se6)2Br2 groups. These are connected to one-dimensional chains via trans-standing Se atoms. In PdCl2Se8, the selenium substructure consists of helical chains with every fifth Se atom directly coordinated to the Pd atom of a PdCl2 group. Each PdCl2 group on the other hand connects two neighboring Sex helices. The type of Sex helix found for this compound is unique and differs from all other ones reported up to now including elemental alpha-Se. A reproducible twinning observed for PdBr2Se6 crystals in the course of the X-ray single-crystal investigations is checked by transmission electron microscopy in connection with details of the atomic arrangement. The Raman spectra of PdBr2Se6 and PdCl2Se8 are compared to Raman data of elemental Se modifications and give significant support for the Se6 and helical Sex to be neutral molecules. A discussion of the results of thermal analyses gives clear evidence that cyclic Se6 and helical Sex are considerably stabilized by bonding to the PdX2 molecules because the melting temperatures of the composite materials are significantly higher than the ones of the respective elemental modifications.