Nanoweb Surface-Mounted Metal–Organic Framework Films with Tunable Amounts of Acid Sites as Tailored Catalysts

Metal–organic frameworks (MOFs) are a promising class of materials for many applications, due to their high chemical tunability and superb porosity. By growing MOFs as (thin-)films, additional properties and potential applications become available. Here, copper (II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal–organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in “nanowebs”, that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm ) was determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varying the rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that rotation speeds ≥2000 rpm (with precursors in a water/ethanol solution) generate the catena-triaqua-μ-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H₂O)₃ coordination polymer. X-ray photoelectron spectroscopy (XPS) highlighted the strong decrease in number of (defective) Cu⁺ sites, as the nanowebs mainly consist of coordinated Cu²⁺ Lewis acid sites (LAS) and organic linker–linker, for example, hydrogen-bonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of α-pinene oxide. The higher number of LAS (≥3000 rpm), result in higher campholenic aldehyde selectivity reaching up to 87.7 %. Furthermore, the strength of a combined micro- and spectroscopic approach in understanding the nature of MOF thin-films in a spatially resolved manner is highlighted.     

On the use of AES data analysis to determine local enrichments of conversion coating elements at intermetallic particles on rolled Al

In this paper, the behaviour of the industrial applied Ti/Zr conversion coating (CC) pretreatment on rolled automotive aluminium samples (AA5182) is analysed. Due to its nanometre lateral and depth resolution, Auger electron spectroscopy (AES) is used to analyse the CC distribution at surface cathodic intermetallic particles. As a result of its high surface sensitivity, the AES technique is very susceptible to differences in the top contamination layer thickness. It is demonstrated that AES point measurements performed on aluminium model samples coated with 1.5 and 3 nm of Ti (oxide) layer cannot differentiate the two-layer thicknesses if a difference in the top contamination thickness is not taken into account. A data analysis methodology is introduced, based on the ratio of normalized peak areas (enrichment ratios), to eliminate the effect of the contamination layer thickness. The experimental validation of the methodology is performed on the model samples, demonstrating errors of 2% on the enrichment ratios on similar samples with different contamination layer thicknesses, while the conventional spectra quantification results in errors of 49%. The methodology is also theoretically substantiated within certain constraints. By the use of the AES methodology, an enriched Ti and Zr deposition is confirmed at the cathodic intermetallic particles at the surface of the industrial no-rinse CC sprayed automotive aluminium sheet samples.     

Non-Pincer-Type Manganese Complexes as Efficient Catalysts for the Hydrogenation of Esters

Catalytic hydrogenation of carboxylic acid esters is essential for the green production of pharmaceuticals, fragrances, and fine chemicals. Herein, we report the efficient hydrogenation of esters with manganese catalysts based on simple bidentate aminophosphine ligands. Monoligated Mn PN complexes are particularly active for the conversion of esters into the corresponding alcohols at Mn concentrations as low as 0.2 mol % in the presence of sub-stoichiometric amounts of KO^tBu base.     

Cyanide Binding to [FeFe]-Hydrogenase Stabilizes the Alternative Configuration of the Proton Transfer Pathway

Hydrogenases are H₂ converting enzymes that harbor catalytic cofactors in which iron (Fe) ions are coordinated by biologically unusual carbon monoxide (CO) and cyanide (CN⁻) ligands. Extrinsic CO and CN⁻, however, inhibit hydrogenases. The mechanism by which CN⁻ binds to [FeFe]-hydrogenases is not known. Here, we obtained crystal structures of the CN⁻-treated [FeFe]-hydrogenase CpI from Clostridium pasteurianum. The high resolution of 1.39 Å allowed us to distinguish intrinsic CN⁻ and CO ligands and to show that extrinsic CN⁻ binds to the open coordination site of the cofactor where CO is known to bind. In contrast to other inhibitors, CN⁻ treated crystals show conformational changes of conserved residues within the proton transfer pathway which could allow a direct proton transfer between E279 and S319. This configuration has been proposed to be vital for efficient proton transfer, but has never been observed structurally.     

Azobioisosteres of Curcumin with Pronounced Activity against Amyloid Aggregation,Intracellular Oxidative Stress,and Neuroinflammation

Many (poly-)phenolic natural products, for example, curcumin and taxifolin, have been studied for their activity against specific hallmarks of neurodegeneration, such as amyloid-β 42 (Aβ42) aggregation and neuroinflammation. Due to their drawbacks, arising from poor pharmacokinetics, rapid metabolism, and even instability in aqueous medium, the biological activity of azobenzene compounds carrying a pharmacophoric catechol group, which have been designed as bioisoteres of curcumin has been examined. Molecular simulations reveal the ability of these compounds to form a hydrophobic cluster with Aβ42, which adopts different folds, affecting the propensity to populate fibril-like conformations. Furthermore, the curcumin bioisosteres exceeded the parent compound in activity against Aβ42 aggregation inhibition, glutamate-induced intracellular oxidative stress in HT22 cells, and neuroinflammation in microglial BV-2 cells. The most active compound prevented apoptosis of HT22 cells at a concentration of 2.5 μm (83 % cell survival), whereas curcumin only showed very low protection at 10 μm (21 % cell survival).     

GC-MS Studies on Derivatization of Creatinine and Creatine by BSTFA and Their Measurement in Human Urine

In consideration of its relatively constant urinary excretion rate, creatinine (2-amino-1-methyl-5H-imidazol-4-one, MW 113.1) in urine is a useful endogenous biochemical parameter to correct the urinary excretion rate of numerous endogenous and exogenous substances. Reliable measurement of creatinine by gas chromatography (GC)-based methods requires derivatization of its amine and keto groups. Creatinine exists in equilibrium with its open form creatine (methylguanidoacetic acid, MW 131.1), which has a guanidine and a carboxylic group. Trimethylsilylation and trifluoroacetylation of creatinine and creatine are the oldest reported derivatization methods for their GC-mass spectrometry (MS) analysis in human serum using flame- or electron-ionization. We performed GC-MS studies on the derivatization of creatinine (d₀-creatinine), [methylo-²H₃]creatinine (d₃-creatinine, internal standard) and creatine (d₀-creatine) with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) using standard derivatization conditions (60 min, 60 °C), yet in the absence of any base. Reaction products were characterized both in the negative-ion chemical ionization (NICI) and in the positive-ion chemical ionization (PICI) mode. Creatinine and creatine reacted with BSTFA to form several derivatives. Their early eluting N,N,O-tris(trimethylsilyl) derivatives (8.9 min) were found to be useful for the precise and accurate measurement of the sum of creatinine and creatine in human urine (10 µL, up to 20 mM) by selected-ion monitoring (SIM) of m/z 271 (d₀-creatinine/d₀-creatine) and m/z 274 (d₃-creatinine) in the NICI mode. In the PICI mode, SIM of m/z 256, m/z 259, m/z 272 and m/z 275 was performed. BSTFA derivatization of d₀-creatine from a freshly prepared solution in distilled water resulted in formation of two lMate-eluting derivatives (14.08 min, 14.72 min), presumably creatinyl-creatinine, with the creatininyl residue existing in its enol form (14.08 min) and keto form (14.72 min). Our results suggest that BSTFA derivatization does not allow specific analysis of creatine and creatinine by GC-MS. Preliminary analyses suggest that pentafluoropropionic anhydride (PFPA) is also not useful for the measurement of creatinine in the presence of creatine. Both BSTFA and PFPA facilitate the conversion of creatine to creatinine. Specific measurement of creatinine in urine is possible by using pentafluorobenzyl bromide in aqueous acetone.