On the Structure of Intermediates in Enyne Gold(I)-Catalyzed Cyclizations: Formation of trans-Fused Bicyclo[5.1.0]octanes as a Case Study

The nature of cyclopropyl gold(I) carbene-type intermediates has been reexamined as part of a mechanistic study on the formation of cis- or trans-fused bicyclo[5.1.0]octanes in a gold(I)-catalyzed cascade reaction. Benchmark of DFT methods together with QTAIM theory and NBO analysis confirms the formation of distinct intermediates with carbenic or carbocationic structures in the cycloisomerizations of enynes.     

Structure of a Reactive Gold Carbenoid

A formal gold‐for‐chromium transmetalation allowed the gold carbenoid species [Cy₃PAuCAr₂]NTf₂ ( 11 ) (Ar=pMeOC₆H₄‐) to be obtained in crystalline form. The structure in the solid state suggests that there is only little back donation of electron density from gold to the carbene center of 11 and hence very modest Au? C double‐bond character; rather, it is the organic ligand framework that is responsible for stabilizing this species by resonance delocalization of the accumulated positive charge. Because 11 is capable of cyclopropanating p‐methoxystyrene even at low temperature, the discussion of its structure is deemed relevant for a better understanding of the mechanisms of π‐acid catalysis in general.     

Advanced Sensing of Antibiotics with Magnetic Gold Nanocomposite: Electrochemical Detection of Chloramphenicol

The sensing and accurate determination of antibiotics in various environments represents a big challenge, mainly owing to their widespread use in medicine, veterinary practice, and other fields. Therefore, a new, simple electrochemical sensor for the detection of antibiotic chloramphenicol (CAP) has been developed in this work. The amplification strategy of the sensor is based on the application of magnetite nanostructures stabilized with carboxymethyl cellulose (Fe₃O₄‐CMC) and decorated with nanometer‐sized Au nanoparticles (NPs) (Fe₃O₄‐CMC@Au). In this case, CMC serves as a stabilizing agent, preventing the aggregation of Fe₃O₄ NPs, and hence, enabling the kinetic barrier for electron transport to be overcome, and the Au NPs serve as an electron‐conducting tunnel for better electron transport. As a proof of concept, the developed nanosensor is used for the detection of CAP in human urine samples, giving a recovery value of around 97 %, which indicates the high accuracy of the as‐prepared nanosensor.     

How the Physicochemical Properties of the Bulk Material Affect the Ablation Crater Profile,Mass Balance,and Bubble Dynamics During Single-Pulse,Nanosecond Laser Ablation in Water

Understanding the key steps that drive the laser-based synthesis of colloids is a prerequisite for learning how to optimize the ablation process in terms of nanoparticle output and functional design of the nanomaterials. Even though many studies focus on cavitation bubble formation using single-pulse ablation conditions, the ablation efficiency and nanoparticle properties are typically investigated under prolonged ablation conditions with repetition rate lasers. Linking single-pulse and multiple-pulse ablation is difficult due to limitations induced by gas formation cross-effects, which occur on longer timescales and depend on the target materials’ oxidation-sensitivity. Therefore, this study investigates the ablation and cavitation bubble dynamics under nanosecond, single laser pulse conditions for six different bulk materials (Au, Ag, Cu, Fe, Ti, and Al). Also, the effective threshold fluences, ablation volumes, and penetration depths are quantified for these materials. The thermal and chemical properties of the corresponding bulk materials not only favor the formation of larger spot sizes but also lead to the highest molar ablation efficiencies for low melting materials such as aluminum. Furthermore, the concept of the cavitation bubble growth linked with the oxidation sensitivity of the ablated material is discussed. With this, evidence is provided that intensive chemical reactions occurring during the very early timescale of ablation are significantly enhanced by the bubble collapse.     

Die aktivierungsanalytische Bestimmung von Verunreinigungen in Platin

Ein Bericht über die aktivierungsanalytische Bestimmung des Cu, Au, Ir, Os und Ru in Platin durch radiochemische Trennung und gammaspektrometrische Strahlungsmessung. Aufbau eines radiochemischen Trenungsganges durch Verflüchtigung der Tetroxide des Os und Ru, Beseitigung der Matrixaktivität durch Adsorption am Anionenaustauscher, Extraktion des Au, Cu u. a. Elemente als Chloro-, DDTC- und BPHA-Komplexe. Diskussion der Möglichkeiten für den Einsatz des Trennungsganges in der Aktivierungsanalyse. Wiedergabe der Arbeitsvorschrift und der Ergebnisse der Analyse einiger Platinproben mit Verunreinigungen im Bereich von 0,05…400 ppm.