Analytical Chemistry
DOI: 10.1021/acs.analchem.3c03691
[ASAP] Enhancing Point-of-Care Diagnosis of African Swine Fever Virus (ASFV) DNA with the CRISPR-Cas12a-Assisted Triplex Amplified Assay
Analytical Chemistry
DOI: 10.1021/acs.analchem.3c05364
New Schiff’s base derivative and their nano‐sized Cr (III), Fe (III), Ru (III), and Ir (III) complexes: Preparation, DFT, characterization, bio‐catalytic, DNA interactions, cytotoxicity, and docking studies
Nano-sized trivalent metal complexes were synthesized and characterized. The interaction of nano-sized metal (III) complexes with CT-DNA using absorption measurements signifies that nano-sized metal (III) complexes bind via an intercalation with intrinsic binding constant, and the present report discusses the synthesis, characterization, and biological activity.
Nano-sized trivalent metal complexes of Cr (III), Fe (III), Ru (III), and Ir (III) were synthesized and characterized of the form [M (FMAVIEP)Cl2] where FMAVIEP = ligand (C14H11N2O2) and M = Cr (III), Fe (III), Ru (III), and Ir (III). Several spectral techniques studies were used to assess our trivalent metal complexes. The trivalent metal complexes' XRD results revealed sharp and intense diffraction peaks, signifying their crystalline properties at nanoscale particle size. Further evidence was obtained from images captured through techniques such as SEM, TEM, energy-dispersive X-ray, and AFM. These images confirmed the homogeneous distribution of the trivalent metal complexes over the surface of the complex. DFT studies were used to study the nano-sized metal (III) complexes via the DFT\B3LYP computational approach, employing a 6–311G* correlation consistent basis set. The energy gap of synthesized complexes was inspected. The obtained data exhibited a strong correlation with the experimental ones, implying the bio-efficiency of the Ru (III) complex. The absorption measurements for the nano-sized complexes' interaction with CT-DNA signify that nano-sized metal (III) complexes bind through an intercalation mechanism. This conclusion is supported by the observed intrinsic binding constant (Kb) 3.33 × 105–5.84 × 105 M−1.
Microkinetic Modeling to Decode Catalytic Reactions and Empower Catalytic Design
Kinetic model development is integral for designing, redesigning, monitoring, and optimizing chemical processes. Of the various approaches used within this field, microkinetic modeling is a crucial tool that focuses on surface events to analyze overall and preferential reaction pathways. This work covers noticeable features of microkinetic modeling for three critical case studies: (i) ammonia to hydrogen, (ii) oxidative coupling of methane to chemicals, and (iii) carbon dioxide hydrogenation for methanol synthesis. We analyze how microkinetic modeling enables predicting and optimizing complex reaction networks, allowing the design of efficient and tailored catalysts with enhanced activity and selectivity.
Key Role of Water in Copper‐ and Base‐free Sonogashira Coupling in Ethanol with [{Pd(µ‐OH)Cl(IPr)}2] as a Highly Effective Precatalyst
Aryl bromides and 4-chlorotoluene as an example aryl chloride in the presence of N-heterocyclic carbene (NHC) palladium hydroxo dimers of the type [{Pd(µ-OH)Cl(NHC)}2] (where NHC = IPr, SIPr, IMes, SIMes) undergo an efficient and selective Sonogashira cross-coupling with (hetero)arylacetylenes. The procedure allows the high-throughput and selective synthesis of a broad spectrum of 1,2-diarylacetylenes using 10 ppm of [{Pd(OH)Cl(IPr)}2] as precatalyst. For the coupling of 4-chlorotoluene with phenylacetylene, TON = 560000 was achieved. Hydrogen chloride was observed as a product of the Sonogashira cross-coupling reaction. The formation of the active Pd(0) from the Pd(II) complex was found to proceed via ethanol oxidation. Mechanistic studies showed that water plays a key role in the reaction.
Co3O4‐Based Catalysts for the Low‐Temperature Catalytic Oxidation of VOCs
Catalytic oxidation is an efficient method for VOCs elimination. Co3O4-based catalysts have been widely studied due to cost-effectiveness and superior low-temperature activity. The construction strategies and structure-activity relationship of Co3O4-based catalysts in VOCs oxidation were illustrated in detail, including monometallic Co3O4 and multimetallic cobalt-based catalysts. This work provides a theoretical foundation to guide the catalyst construction for low-temperature VOCs oxidation.
Abstract
Volatile organic compounds (VOCs) are a significant source of environmental pollution, posing threats to human safety. With growing concerns about environmental degradation, catalytic oxidation technology emerges as a paramount and widely adopted approach for VOC elimination, renowned for its operational simplicity, energy efficiency, and environmental friendliness. As a representative transition metal catalyst, cobalt-based catalysts have garnered widespread use in VOC catalytic oxidation due to their cost-effectiveness, versatility, and distinctive physicochemical properties. This paper provides a detailed exposition of the construction strategies and structure-activity relationship of Co3O4-based catalysts in VOCs oxidation reaction, encompassing both monometallic Co3O4 and multimetallic cobalt-based catalysts. Furthermore, it offers a comprehensive summary and discussion of the latest research progress concerning Co3O4-based catalysts in practical applications. Concluding with a meticulous analysis, the paper addresses the technical challenges inherent in developing Co3O4-based catalysts for VOCs degradation. Additionally, it proposes research directions aimed at overcoming these challenges, contributing to the ongoing discourse on environmental sustainability.
Light‐Activatable Photocaged UNC2025 for Triggering TAM Kinase Inhibition in Bladder Cancer
Photopharmacology: three photoactivatable small molecules based on the UNC2025 scaffold were developed for controlling TAM kinase activity in vitro and in cellulo assays. The dicaged compound 3 proved to be the most striking with a complete loss of inhibition while recovering full activity upon light irradiation.
Abstract
Photopharmacology is an emerging field that utilizes photo-responsive molecules to enable control over the activity of a drug using light. The aim is to limit the therapeutic action of a drug at the level of diseased tissues and organs. Considering the well-known implications of protein kinases in cancer and the therapeutic issues associated with protein kinase inhibitors, the photopharmacology is seen as an innovative and alternative solution with great potential in oncology. In this context, we developed the first photocaged TAM kinase inhibitors based on UNC2025, a first-in-class small molecule kinase inhibitor. These prodrugs showed good stability in biologically relevant buffer and rapid photorelease of the photoremovable protecting group upon UV-light irradiation (<10 min.). These light-activatable prodrugs led to a 16-fold decrease to a complete loss of kinase inhibition, depending on the protein and the position at which the coumarin-type phototrigger was introduced. The most promising candidate was the N,O-dicaged compound, showing the superiority of having two photolabile protecting groups on UNC2025 for being entirely inactive on TAM kinases. Under UV-light irradiation, the N,O-dicaged compound recovered its inhibitory potency in enzymatic assays and displayed excellent antiproliferative activity in RT112 cell lines.
Palladium‐Catalyzed C−H Alkenylation of α‐Aryl Alkyl Nitriles
The direct α-alkenylation of nitrile was realized with palladium catalyst for the first time. Both cyano group and alkenyl group in the product can be functionalized, rendering this method a powerful protocol to synthesis a series of useful compounds.
Abstract
A direct α-alkenylation of nitrile compounds was realized with a palladium complex. This method exhibited excellent tolerance toward a variety of α-aryl alkyl nitriles and vinyl bromides, leading to the formation of a series of α-quaternary nitriles containing vinyl groups. Further manipulations of the obtained products were demonstrated, highlighting the potential synthetic utility of this method.
Design, Synthesis, and Characterization of Novel Styryl Dyes as Fluorescent Probes for Tau Aggregate Detection in Vitro and in Cells
Chanat Aonbangkhen et al. made new indolium and quinolinium styryl compounds as fluorescent dyes to study how they interact with and bind to tau aggregates, which are a hallmark of Alzheimer′s disease, both in cells and in vitro. Due to restricted methine bridge rotation in their core structures, these dyes fluoresced more in viscous solutions. When attached to tau aggregates, Dye 4 (the cover structure) with a quinolinium part and two positively charged residues made the red fluorescence 28 times brighter. This dye-stained live cell tau aggregates. The non-toxic fluorescent probes introduced in this study may be useful for early AD detection.
Mechanism and Kinetics Guided Design of Catalysts for Functionalized Nitroarenes Hydrogenation
This review describes the overview of mechanistic and kinetics insights for guiding the design of catalysts for selective hydrogenation of functionalized nitroarenes to produce anilines, and summarizes the strategies developed for controlling the selectivity to target product, including isolating active sites, constructing synergistic active sites and regulating local environments of active sites.
Abstract
Selective hydrogenation of functionalized nitroarenes to anilines employed with heterogeneous catalysts is a significant process and widely applied in chemical industry. However, designing high-performance catalysts for these processes remains challenging. Recently, notable advancements have been achieved in synthesis methodologies, characterization techniques, and theoretical calculations, offering opportunities to gain insights into mechanisms. This review summarizes the recent progress in understanding the mechanistic aspects of selective hydrogenation catalysis for functionalized nitroarenes. We initiate by delving into the structure-performance relationship, with the aim of providing a comprehensive understanding of mechanistic and kinetic details in the selective hydrogenation of functionalized nitroarenes. Subsequently, we introduce various strategies for designing high-performance catalysts, categorizing them into three key aspects: isolating active sites, synergizing active sites and regulating local environments of active sites. Finally, we conclude with a concise overview of the current state of this field and provide a forward-looking perspective for future studies, emphasizing the high-performance design and manipulation of catalysts to achieve precise control over selectivity towards target products.