ChemPlusChem最新文献

Tamsulosin is an α1A blocker used to manage lower urinary tract symptoms in prostate hyperplasia patients. Research has shown a marked variation in patients' response to the drug, which may require continuous therapeutic drug monitoring (TDM) to aid in dose manipulations for better treatment outcomes. Electrochemical sensors are the least explored for tamsulosin. Here, we report the first exploration of a facile synthesis and electrochemical study of a ternary nanocomposite of cobalt oxide nanoparticles, cadmium sulfide nanorods, and multiwalled carbon nanotubes (Co3O4@CdS/MWCNT/SPE) and its application for the detection of tamsulosin in serum. A precipitation oxidation and hydrothermal method were used to synthesise Co3O4 nanoparticles and CdS/MWCNT, respectively. Co3O4 and CdS/MWCNT masses were dispersed in deionised water and sonicated to obtain Co3O4@CdS/MWCNT. The fabricated sensor recorded the lowest-ever detection limits of 2.06×10-9 and 3.89×10-9 for CV and SWV. The sensor showed remarkable selectivity in the presence of multiple interfering agents and average recovery was 96.4, with an RSD of 1.38%. This study is the first to report a composite of Co3O4, CdS and MWCNT and the first disposable tamsulosin sensor. As a disposable sensor, the current sensor offers portability and miniaturisation for point-of-care applications.

The open-shell organic and carbon-based systems, with either a doublet, triplet or higher spin-states, play a key role in contemporary research, opening potential applicability for several crucial fields. Among those derivatives, specific attention has been given to p-phenylene-based systems derived from the original Thiele hydrocarbon. These systems stabilize an open-shell diradicaloid resonance structure with a thermally accessible triplet state and are derived from a quinone-benzene (Clar's sextet) equilibrium. In our discussion, we very carefully choose examples which focus on fundamental derivatives that merge diatropic subunits, ready to stabilize two unpaired electrons via a dynamic modulation of geometry. This process provides an additional factor to the resonance energy of aromatics, mostly responsible for stabilization of two unpaired electrons.

Platinum(IV) complexes are being studied as potential alternatives to traditional platinum(II)-based chemotherapy drugs. They promise reduced side effects and potential for oral administration. In fact, a preliminary reduction in the cellular medium is recognized as a crucial step for activation. However, a deeper understanding of the protonation sites and substitution behavior of Pt(IV) complexes is needed, considering that ligand hydrolysis may compete with reduction-mediated activation, particularly in acidic environments such as the stomach. In this study, we investigated protonated Pt(IV) complexes with equatorial ligands common to widely used Pt(II) drugs containing square planar geometry, such as cisplatin and carboplatin,. The additional axial substituents in the octahedral coordination sphere of Pt(IV) include different combinations of hydroxido and acetato ligands. Mass spectrometry-based methods, including collision-induced dissociation (CID) and infrared multiple photon dissociation (IRMPD) spectroscopy, supported by density functional theory (DFT) calculations, were employed. Structural characterization revealed that protonation preferences are influenced by the type and position of the ligands. Notably, protonation is generally favored on the carboxylato ligands; however, the carboplatin-derived complex exhibited a mixed population of protomers, highlighting the significance of both axial and equatorial ligand configurations in shaping the prototropic equilibria happening in solution.

The cover feature shows the interaction of hybrid methanofullerenes with β-amyloid peptide (Aβ) aggregates. The combination of three privileged structures, fullerenes, selenosugars, and steroids, makes these hybrid molecules potential inhibitors of Aβ peptide aggregation, as theoretical calculations suggest. More details can be found in the Research Article by Margarita Suárez, Silvana Pedatella, and co-workers (DOI: 10.1002/cplu.202400404).

The cover feature shows AFM detection of exfoliation agent residue removal on perovskite nanosheet-based nanofilms after UV exposure. AFM measurements, performed using a silicon probe, reveal how surface properties evolve with UV exposure duration, influencing nanosheet homogeneity and adhesion. The findings highlight the need to optimize UV exposure duration for effective residue removal while preserving surface quality. More details can be found in the Research Article by Fatma Pinar Gordesli-Duatepe, Özge Sağlam, and Begümnur Küçükcan (DOI: 10.1002/cplu.202400678).

Adapting high-throughput (HT) synthetic methods to the modification of drugs and to testing of their bioactivity should expedite drug discovery. Here, we demonstrate the applicability of HT desorption electrospray ionization mass spectrometry (DESI MS) to achieve late-stage functionalization (LSF) and so to rapidly generate a modified opioid library. Specifically, aza-Michael addition and sulfur (VI) fluoride exchange (SuFEx) reactions were used for functionalization. The modified drugs are both synthesized and characterized using an automated HT-DESI MS platform, with the reaction occurring during the droplet flight. Analysis by MS characterizes reaction products at a throughput of ˃ 1 reaction per second. With this platform, multiple nor-opioid scaffolds and functionalization reagents were screened and a selection of the hits obtained was subjected to HT label-free bioassays using the same DESI-MS platform. This combination of accelerated LSF reactions to rapidly create a diverse library of functionalized drugs with direct bioassays of the crude reaction mixtures for SAR evaluation, both using the same platform, is anticipated to help expedite the early drug discovery process.

The front cover showcases Au single-atoms and clusters stabilized on nanoparticulate edge-faces-rich Mg-Al layered double hydroxides (LDHs), supported on SiO₂ or CeO₂. The catalysts demonstrate impressive activity for aerobic oxidation of alcohols and selective hydrogenation of 4-nitrostyrene. In-situ XAFS and HRTEM reveal the well-dispersed Au(0) single atoms with 1.0 wt% Au loading. The surface OH of LDH NPs effectively stabilize Au and enhances catalytic activity by basic sites of LDH. More details can be found in the Research Article by Tamao Ishida and co-workers (DOI: 10.1002/cplu.202400465).

In this study, two new BOPHY-based derivatives were efficiently synthesized with high yields and characterized by using spectroscopic, electrochemical, and spectroelectrochemical techniques. The introduction of non-conjugated (carbazole (CBZ)) and conjugated (triphenylamine (TPA)) donor groups into the BOPHY macrocycle imparted different electrochemical and spectroscopic properties. Oxidation of BP-2CBZ led to the formation of unstable CBZ radical cations, which further reacted to generate dicarbazole (DCBZ) units, allowing the formation of a polymeric film during anodic cycling. In contrast, BP-2TPA exhibited a reversible oxidation process, generating stable BOPHY and TPA radical cations which inhibited the polymerization process. Spectroscopic differences were also observed, with BP-2CBZ displaying a high fluorescence quantum yield (Ff), while BP-2TPA emission was nearly quenched, exhibiting solvent-dependent fluorescence with a large Stokes shift (~160 nm). BP-2TPA also demonstrated aggregation-induced emission (AIE) properties, showing an increase in fluorescence intensity of around 12 times when the water content changes from 0 to 90%. These experimental findings were further corroborated by DFT and TDDFT calculations. The BP-2CBZ polymer presented electrochromic properties, showing color changes upon oxidation. This work represents the first report of a BOPHY-based polymer synthesized through electrochemical methods.

The present work investigates the impact of the external electric field (EEF) on the oxidizing power of N 2 O, by employing kinetics and quantum chemical calculations. We have taken the oxidation of olefin (Ethene and cyclohexene) by N 2 O as a prototype to demonstrate the effectiveness of EEF. The investigation suggests that the reaction barrier is significantly reduced by choosing an electric field in an appropriate direction. Quantitatively, we found that the rate of EEF catalyzed reaction can be as high as ∼ 13 orders of magnitude compared to the bare reaction.

Electrochemiluminescence (ECL) combines electrochemical redox processes with photochemical light emission, offering exceptional sensitivity, spatial control, and stability. Widely applied in biosensing, medical diagnostics, and environmental monitoring, its efficiency often depends on advanced catalytic materials. Single-atom catalysts (SACs), featuring isolated metal atoms dispersed on a support, have emerged as promising candidates due to their unique electronic structures, high atom utilization, and tunable catalytic properties. These features enable SACs to improve reaction kinetics, enhance light-emitting efficiency, and provide precise control over the generation of excited-state species essential for ECL. This review highlights recent advancements in SACs-boosted ECL systems, with a focus on their reaction mechanisms, design strategies, and roles in improving electrocatalytic and luminescent performance. Additionally, it summarizes the applications of SACs-boosted ECL in bioanalysis, environmental monitoring, and single-particle imaging. By highlighting the synergies between single-atom catalysis and ECL, this work aims to provide a comprehensive overview of the field and a roadmap for future research, paving the way for innovative applications in analytical and sensing technologies.