Palladium-catalyzed α-arylation of ketones on solid support: scope and limitations

The palladium-catalyzed α-arylation of ketones on solid support is described. Using modified Buchwald-Hartwig reaction conditions, the coupling of immobilized 4-bromobenzamide with various aromatic, heteroaromatic, and aliphatic ketones was investigated. Subsequent cleavage from the resin provided the desired α-aryl ketones almost in moderate to high yields and good to excellent purities. The scope and limitations of this protocol will be discussed.     

Quantitative Depth Profiling Using Online-Laser Ablation of Solid Samples in Liquid (LASIL) to Investigate the Oxidation Behavior of Transition Metal Borides

The increased demand for sustainability requires, among others, the development of new materials with enhanced corrosion resistance. Transition metal diborides are exceptional candidates, as they exhibit fascinating mechanical and thermal properties. However, at elevated temperatures and oxidizing atmospheres, their use is limited due to the fact of their inadequate oxidation resistance. Recently, it was found that chromium diboride doped with silicon can overcome this limitation. Further improvement of this protective coating requires detailed knowledge regarding the composition of the forming oxide layer and the change in the composition of the remaining thin film. In this work, an analytical method for the quantitative measurement of depth profiles without using matrix-matched reference materials was developed. Using this approach, based on the recently introduced online-LASIL technique, it was possible to achieve a depth resolution of 240 nm. A further decrease in the ablation rate is possible but demands a more sensitive detection of silicon. Two chromium diboride samples with different Si contents suffering an oxidation treatment were used to demonstrate the capabilities of this technique. The concentration profiles resembled the pathway of the formed oxidation layers as monitored with transmission electron microscopy. The stoichiometry of the oxidation layers differed strongly between the samples, suggesting different processes were taking place. The validity of the LASIL results was cross-checked with several other analytical techniques.     

Tetrahydrofuranylmethylamines: An efficient and simple one‐step synthesis and biological activities

Various tetrahydrofuran‐2‐ylmethylamines have been prepared in good yields by an efficient one‐step synthesis utilizing the reaction of tetrahydrofurfurylchloride with different secondary cyclic amines without any catalyst. The compounds were tested for their in vitro affinity for the (α4)₂(β2)₃ and α7* nicotinic acetylcholine receptor (nAChR) subtypes. Pyrrolidine, piperidine and azepane containing analogs ( 1a, 1b, 1c ) showed K_i values in the lower micromolar range for these neuronal nAChR subtypes in rat brain.     

Recent developments in assessment of bio-accessible trace metal fractions in airborne particulate matter: A review

In the last years a great deal of research has been focused on the determination of harmful trace metals such as Cd, Co, Cr, Cu, Ni or Pb in airborne particulate matter (APM). However, the commonly applied determination of total element concentrations in APM provides only an upper-end estimate of potential metal toxicity. For improved risk assessment it is important to determine bio-accessible concentrations instead of total metal contents. The present review gives an overview of analytical procedures reported for measurement of bio-accessible trace metal fractions in APM. The different approaches developed for extraction of soluble trace metals in APM are summarized. Furthermore the analytical techniques applied for accurate determination of dissolved trace metals in the presence of complex sample matrix are presented. Finally a compilation of published results for bio-accessible trace metals in APM is included.     

Bioaccessibility of selected trace metals in urban PM<Subscript>2.5</Subscript> and PM<Subscript>10</Subscript> samples: a model study

Bioaccessibility of trace metals originating from urban particulate matter was assessed in a worst case scenario to evaluate the uptake and thus the hazardous potential of these metals via gastric juice. Sampling was performed over a period of about two months at the Getreidemarkt in downtown Vienna. Concentrations of the assayed trace metals (Ti, Cr, Mn, Co, Ni, Cu, Zn, Mo, Ag, Cd, Sn, Sb, Tl and Pb) were determined in PM_2.5 and PM₁₀ samples by ICP-MS. The metal concentrations in sampled air were in the low picogram to high nanogram per cubic metre range. The concentrations in PM_2.5 samples were generally lower than those in PM₁₀ samples. The average daily intake of these metals by inhalation for a healthy adult was estimated to be in the range of <1 ng (Tl) to >1,000 ng (Zn). To estimate the accessibility of the inhaled and subsequently ingested metals (i.e. after lung clearance had taken place) in the size range from 2.5- to 10-μm aerodynamic equivalent diameter, a batch-extraction with synthetic gastric juice was performed. The data were used to calculate the bioaccessibility of the investigated trace metals. Extractable fractions ranged from 2.10% (Ti in PM_2.5) to 91.0% (Cd in PM_2.5), thus yielding bioaccessible fractions (PM_2.5–10) from 0.16 ng (Ag) to 178 ng (Cu).     

Microwave-assisted UV-digestion procedure for the accurate determination of Pd in natural waters

A procedure was developed for the selective determination of Pd in environmental aquatic solutions. The method is based on a preliminary microwave-assisted UV-digestion for the degradation of dissolved organic material, and the subsequent determination of Pd using a recently presented enrichment procedure with ETAAS detection. Due to the simultaneous use of microwave and UV irradiation only extremely small quantities of hydrogen peroxide were necessary to yield a quantitative degradation of interfering organic ligands. Thus the on-line pre-concentration of Pd in the digested samples using the complexing agent N,N-diethyl-N′-benzoylthiourea was possible without any further sample pre-treatment. Using a sample volume of 1.57 ml for FI-ETAAS analysis a limit of detection of 15 ng l⁻¹ was obtained for the combined procedure, with a relative standard deviation being not more than 4.9%. The method was applied to quantify the water-soluble fraction of Pd in urban road dust. Extractions with a rain sample of pH 5.9 revealed that an average of 2.2% (n = 8) of the total Pd present in urban road dust was water soluble.     

Determination of water soluble trace metals in airborne particulate matter using a dynamic extraction procedure with on-line inductively coupled plasma optical emission spectrometric detection

A novel continuous-flow system for the dynamic extraction of water soluble metal fractions in airborne particulate matter (APM) with subsequent inductively coupled plasma optical emission spectrometric (ICP-OES) analysis of derived extracts is presented. The fully automated extraction system with on-line multi-element detection offers enhanced sensitivity when compared to batch-wise counterparts; additionally it provides information about the extraction process. With the developed procedure detection limits in the order of 1.5 (Ba) to 8.0 (Ni) ng extractable mass per investigated sample could be achieved, which translates to method detection limits for soluble metal concentrations in APM ranging from 0.2 ng m⁻³ (Ba) to 0.9 ng m⁻³ (Fe). Reproducibility of analysis was determined by replicate measurement (n = 6) of an APM sample with an aerodynamic diameter ≤10 μm (PM10), derived results varied between 3.5% (Mn) and 12.1% (Ni) relative standard deviation. Method validation was accomplished by comparison of extracted soluble and remaining non-soluble fractions with the total metal contents of the investigated PM10 samples, showing an excellent mass balance for all elements. Application of the developed procedure for the analysis of water soluble metal fractions in PM10 samples (n = 16) from Linz (Austria) indicated a high variability of extractable fractions ranging from 11.7 ± 7.2% (Fe) to 48.8 ± 15.4% (Mn) of the total metal contents.