Bulletin of the Korean Chemical Society最新文献

Plasmonic nanoparticles exhibit dramatic changes in optical properties depending on their spatial organization. Therefore, the ability to precisely control their assembly structure is important for both fundamental understanding and practical applications. In this personal account, we describe a templated surfactant-assisted seed-growth method to synthesize core–shell-type gold nanoparticle assemblies with controllable surface morphologies and optical properties. This approach provides a simple procedure for simultaneous growth and assembly of metal nanoparticles on polymer templates, producing well-defined nanostructures such as spiky nanoshells and raspberry-like metamolecules with useful and interesting optical properties, such as strong and uniform surface-enhanced Raman scattering and metamaterial properties. We discuss the factors that control the morphology and collective properties, describe the design rules acquired from the system, and suggest future directions of this research area.

The tumor-suppressing phosphorylation cascade is primarily regulated by transcriptional enhanced associate domain (TEAD) transcription factors, and the overexpression of these factors is associated with tumorigenesis and cancer progression. The central pocket of TEAD protein can be targeted by noncovalent inhibitors, and therefore, investigating the interaction patterns for TEAD and its available inhibitors seems essential. In this regard, molecular dynamics simulations were conducted to identify the most potent TEAD3 noncovalent inhibitors and to study TEAD3–inhibitor interaction patterns. We developed a 3D-quantitative structure–activity relationship model to investigate the structure–activity correlation for the available TEAD3 inhibitors. Our results indicated the role of Tyr230, Val317, Thr333, Met367, Cys368, Met371, Phe394, Ile396, Gln398, and Phe416 residues in TEAD3–inhibitor interactions. Dihydropyrazolo pyrimidines and compound 2 were identified as the most potent TEAD3 noncovalent inhibitors. The Comparative Molecular Field Analysis model analysis identified the hydrophobic-favored regions around the pyrazolo[1,5-a]pyrimidin-7(4H)-one ring and the unfavored steric regions around cyclohexane and phenyl groups of dihydropyrazolo pyrimidines.

The cover picture illustrates metal-organic frameworks (MOFs) being used as fluorescent probes to detect biomarkers in human urine. MOF-based fluorescent probes facilitate the diagnosis of diseases, including pheochromocytoma, toluene exposure, vitamin deficiencies, gout, hyperuricemia, cancers, various body disorders, and teratogenic effects, with low detection limits. Unlike conventional disease diagnosis methods such as biopsies or blood collection, detecting pathogenic biomarkers in human urine is non-invasive and carries less risk. More details are available in the article by Seyeon Jeong and Hoi Ri Moon.

Atomically precise metal nanoclusters (NCs) have emerged as a new frontier in electrocatalysis, enabling the study of electrocatalytic reactions on well-defined stable surfaces and rational electrocatalyst design based on atomic-level tailoring. In this review, we focus on the recent applications of these NCs to energy conversion reactions, including those involved in water splitting (hydrogen and oxygen evolution reactions), fuel cell operation (oxygen reduction and hydrogen oxidation reactions), and electrochemical CO₂ reduction. Emblematic examples are used to highlight the roles of different NC parts, for example, core metal and surrounding ligands, and the significance of the electrode substrate. Finally, we discuss the perspectives of the future development and implementation of NC-based energy conversion systems.

The conduction band edge (E_CB) energy levels of a mesoporous TiO₂ film were investigated in aprotic dimethylformamide (DMF) and aqueous media to explore the influence of various proton additives and electron donors. Spectroelectrolysis (SE) technique was employed to measure the E_CB in non-aqueous solvents, revealing a significantly negative E_CB in dry non-aqueous solvents compared to values obtained in aqueous solvents. In non-aqueous DMF, the E_CB of TiO₂ was found to be highly dependent on the proton-donating additive due to the establishment of a proton adsorption–desorption equilibrium, reaching –(1.42–1.94) V versus SCE. The introduction of a well-known electron donor, 1,3-dimethyl-2-phenyl-1,3-dihydrobenzimidazole (BIH) led to a slight positive shift in the TiO₂ E_CB, indicating that the electron donor contributes to the to the CB energetics of the mesoporous TiO₂ films. Under aqueous conditions and in the presence of various electron donors (TEA, TEOA, ascorbic acid, EDTA•2Na, and sodium ascorbate), the proton-donating/accepting capacity of the additive significantly influenced the pH of the aqueous solvent, causing changes in the TiO₂ E_CB across the electrolyte solution. This study emphasizes the crucial role of proton additives and electron donors in influencing the CB energetics of mesoporous TiO₂ electrodes and aims to determine the extent to which the E_CB of TiO₂ can shift as a result of the adsorption and intercalation of protons on its surface. The findings obtained herein contribute to the understanding of the energy efficiency of TiO₂-mediated photocatalytic systems in various solvent environments.

Biomolecular phase separation is a vital mechanism for orchestrating biomolecules within living cells. This crucial role has spurred an intense pursuit to comprehend the molecular underpinnings governing and regulating these processes. Computational methodologies offer a unique perspective, augmenting experimental techniques by providing detailed information that cannot be obtained otherwise. In this review, we briefly overview the theoretical and computational approaches to investigate biomolecular phase separation. As a short primer, we explain the factors driving and affecting phase separation of biomolecules, and then we delve into analytical and simulation methods used to study phase separation. We explain how analytical methods like the Flory–Huggins theory, random phase approximation, and graph-based methods have been used to study phase behaviors of various proteins. We also discuss principles and applications of all-atom simulations, coarse-grained simulations, and field-theoretical approaches. Additionally, we explore the recent advances in machine learning approach to predict phase separation of biomolecules.

Transition metal dichalcogenide quantum dots (TMDs QDs) have garnered significant attention for a variety of applications due to their unique electronic structures and exceptional photonic and catalytic characteristics. This paper provides a succinct overview of various synthesis methods, properties, applications, and current bottlenecks of TMDs QDs. More details are available in the article by Lee et al. More details are available in the article Hoon Ju Lee, Weiguang Yang, Hyeon Suk Shin

This study focuses on derivatizing 1-(dicyanomethylene)indan as a viscosity sensor. The indan was extended with various functionalized naphthaldehydes under a push–pull design strategy. Among synthesized derivatives, salt-capped derivatives exhibited an excellent linearity between fluorescent intensity and viscosity (R² = 0.99), and further investigation underscores the reversible nature of fluorescence intensity changes at two temperatures as an important trait of viscosity sensors.

The theoretical study on the fixation and release of nitric oxide (NO) by N-heterocyclic carbenes (NHCs) is explored by utilizing a multivariate linear regression approach. We utilized data-driven tools to establish correlations between molecular descriptors of NHC and reaction outputs of the formation and NO release of NHC nitric oxide radicals (NHCNOs). A key electronic parameter, the singlet-triplet energy gap (ΔE_ST), plays a pivotal role in the thermodynamics of NHCNO formation (ΔG_f) and NO release (ΔG_r). The activation energy models highlight HOMO energy level (E_HOMO), C–N bond length (d_C–N), and NBO charge on N atom (q^NBO_N) as crucial factors for the formation of NHCNO (ΔG^‡_f), while the activation energy for the NO release (ΔG^‡_r) significantly correlates with free energy difference (ΔG_r), resulting a strong ΔE_ST dependency. This study provides valuable insights into the thermodynamics and kinetics of NHCNO processes, offering predictive capabilities to design NHCs tailored for NO release.

Oxazolo[5,4-d]pyrimidine derivatives have been reported to exhibit interesting biological activities. Herein, we described a solid-phase synthetic method to produce N-alkyl-7-alkylamino-2-aryloxazolo[5,4-d]pyrimidine-5-carboxamide derivatives. The strategy consists of loading the template compounds (i.e., 2-aryl-6,7-dihydrooxazolo[5,4-d]pyrimidin-7-one-5-carboxylic acids) onto aminated acid-sensitive methoxybenzaldehyde (AMEBA) resins, the subsequent benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP)-mediated direct amination with primary/secondary amines, and the final cleavage from the solid support to afford the target compounds. The template 2-aryl-6,7-dihydrooxazolo[5,4-d]pyrimidin-7-one-5-carboxylic acids were prepared using a five-step solution-phase synthetic route from ethyl 2-cyano-2-(hydroxyimino)acetate. BOP-mediated direct amination conditions were optimized by a solution-phase model study. The solid-phase synthetic method provided the 17 target compounds in 16%–92% five-step overall isolated yields from the Merrified resin for selected template compounds and primary/secondary amines.