Helvetica Chimica Acta最新文献

Thermoresponsive polymers, which undergo phase transitions within physiologically tolerated temperatures, are key to developing drug delivery systems (DDS) with precise spatial and temporal control, potentially addressing challenges associated with the treatment of complex diseases. Inorganic nanoparticles with unique optical, electronic, and magnetic properties serve as efficient transducers, converting external stimuli into localized heat to trigger thermoresponsive nanocarriers. This review explores the design and application of thermoresponsive nanocarriers transduced by inorganic nanoparticles as DDS. Following a brief description of temperature-triggered phase transition of polymers and heat generation mechanisms by inorganic nanoparticles, strategies to integrate these components into hybrid systems are described. Examples demonstrating the utility of these hybrid systems as advanced DDS are discussed, highlighting their potential for precise drug release alongside theranostic capabilities by combining therapy with imaging. Despite the challenges in design, synthesis, and biological applications, thermoresponsive polymer-inorganic hybrids hold immense promise for transforming drug delivery and biomedical innovations.

α-Fluoroketones are versatile intermediates for the synthesis of fluorinated heterocycles and other fluorine-containing building blocks. We have recently disclosed a novel route to such an α-fluoroketone using the corresponding benzoic acid as a starting material. The reaction sequence started with the CDI-activation of the carboxylic acid and reaction with diethyl malonate, fluorination of the resulting acyl malonate with Selectfluor, and finally a double-decarboxylation to provide the desired α-fluoroketone in 73 % yield over three telescoped steps. We were interested in the generality of this approach to access α-fluoroketones from readily available carboxylic acids. In this article, we disclose the crucial modifications of the reaction conditions that were needed to make them broadly applicable to a diverse array of carboxylic acids. Under the optimized conditions, a wide range of α-fluoroketones were isolated in good to excellent yields and in high purity.

Supported nanoparticles (NPs) are an intense field of research in industry and academia due to their unique catalytic properties. Yet, establishing relationships between structure and activity is challenging due to multiple possible compositions, interfaces, and alloy formation. This is especially pronounced for bimetallic NPs used in the CO₂-hydrogenation-to-methanol, where the structure responds dynamically to the chemical potential of the reactants and products, resulting in distinct surface structures depending on the exact reaction conditions. These phenomena have been highlighted by combining ab initio Molecular Dynamics (AIMD) and Metadynamics (MTD) with in situ X-ray absorption spectroscopy, chemisorption, and CO-IR. Here, we aim to understand how particle size and simulation temperature influence the structure and dynamics of small Cu NPs using the diffusion coefficients and the radial distribution function/atomic pair density function as descriptors using AIMD simulations. We found that decreasing the particle size or increasing the simulation temperature results in increased atom mobility, highlighted by the increased metal diffusion and resulting in reduced particle crystallinity. We also find that alloying Cu with Ga significantly increases the diffusion of both elements in the particle compared to the monometallic ones. In contrast, such diffusion lies in between the individual elements composing the CuZn particles.

Despite their synthetic interest and potential attractive properties, the preparation of heteroleptic U(III) complexes containing monodentate ligands remains challenging. Here we report the synthesis, structure and magnetic properties of three heteroleptic U(III) complexes containing two siloxide donors in the coordination sphere. The bis-siloxide monoiodide complex [U(OSi(O^tBu)₃)₂I(thf)₃], 1 provides a very attractive precursor for accessing heteroleptic complexes and rationally modify the binding angle between the two strongly donating siloxide ligands. Here we reacted 1 with macrocyclic ligands to yield complexes [[U(OSi(O^tBu)₃)₂(crypt)]I, 3 and [[U(OSi(O^tBu)₃)₂(18c6)]I, 4. Magnetic studies of these compounds offer a snapshot on how the SMM properties depend on the local symmetry in the presence of siloxide ligands. The static and dynamic magnetic properties of these compounds reveal a weak dependence of their single-molecule magnet behavior on the local symmetry.

Amoxicillin is a frequently used beta-lactam antibiotic and at the same time a fragile analyte. Aim of this work was to investigate the sensitive properties of amoxicillin in biological samples and validate a quantification method for amoxicillin in soft tissue samples. Simple protein precipitation and 2D-High performance liquid chromatography coupled to tandem mass spectrometry was used for sample preparation and analysis. The formation of a covalent amoxicillin methanol-adduct could be observed in varying extents depending on matrix and sample preparation method. In-Source Products (ISPs) were investigated in plasma, soft tissue, and water and no differences could be observed. We successfully validated a method for amoxicillin determination in tissue samples using the sum of 2 ISPs of amoxicillin for quantification. 37 study samples of different deep-seated infections could be analyzed. Measured amoxicillin concentrations ranged from below 0.5 mg/kg up to 87 mg/kg. Concentrations in abscesses were lower than in other infections.

We report a study on the photoionization of the C₆H₆ isomer 3,4-dimethylenecyclobutene, DMCB. The molecule is an intermediate in the formation of benzene from the propargyl radical self-reaction, a suggested first step in the formation of polycyclic aromatic hydrocarbons and soot. From a threshold photoelectron spectrum we determine an adiabatic ionization energy of 8.75 eV. The geometry change upon ionization is associated with considerable vibrational activity, which is assigned to a symmetric in-plane bending mode of the =CH₂ groups. A breakdown diagram shows that the dissociative photoionization resembles the one observed for benzene. Computations reveal that DMCB cation isomerizes to the benzene cation and dissociates from there.