Search Results (632)

A plasma-assisted electrochemical deposition (PAECD) technology was introduced to coat a cast iron brake disc for the possible reduction of brake wear and brake wear particle (BWP) emission. The majority of the coating consisted of alumina (Al₂O₃), determined by energy dispersive X-ray (EDX) analysis and X-ray diffraction (XRD) analysis. To validate the above strategy of the coating technology for automotive brake corners, one brake stock rotor was replaced by a PAECD-coated rotor for a vehicle road test. After the road test, weight loss of the brake components (rotors and pads) was measured, showing that the alumina coating can reduce the brake wear by more than 70%. BWPs were also collected from wheel barrels, spokes, and brake friction rings of the coated and uncoated rotors during the road test. A morphology and chemical composition analysis of the collected BWPs indicated that the coating could reduce BWP generation from the original sources and avoid a metal pick-up (MPU) issue, leading to less metallic content in BWPs. This alumina coating may provide the auto sector with a sustainable approach to overcome the brake dust emission problem, evidenced by less wear of the brake pads, minimal wear of the coated brake rotor, less MPUs, and a clean wheel rim on the coated brake corner. Full article

Proline is considered the model organocatalytic amino acid. However, other naturally occurring amino acids remain a potent and perhaps overlooked source of organocatalytic potential. In this work, we investigated the capacity of various natural amino acids to promote enantioselectivity in a synthesis of warfarin. We have identified L- and d-arginine as enantioselective catalysts for this reaction and have developed a recrystallization method to isolate the enantiomers of warfarin with high enantiopurity. In addition, we used methylated derivatives of arginine to provide insight into the reaction mechanism. Full article

This study presents a comprehensive analysis of the chemical composition and bioactive properties of six newly cultivated varieties of pigmented and non-pigmented rice: Neunkeunheukchal (NKH), Neunkeunssal, Heukjagwang 709 (H709), Heukjagwang 1601, Hongjinju, and Hongchapssal (HCS). This study aims to characterize the chemical information and the industrial potential of lesser-known rice varieties. Significant differences were observed in the levels of phenolic compounds, flavonoids, γ-oryzanol, and free amino acids among these varieties, correlating with their antioxidant capacities. Among these varieties, NKH consistently exhibited the highest total phenolic, flavonoid, and γ-oryzanol contents, along with the strongest radical-scavenging activities, indicating its potential as a valuable functional food ingredient. Additionally, H709 and HCS demonstrated significant antioxidant activities, highlighting their potential roles in health-promoting applications. These findings highlight the potential of these varieties for functional food and nutraceutical applications. Future research should investigate the effects of cultivation conditions and processing methods on bioactive compound levels while conducting clinical trials to validate these health benefits in human models. The findings suggest that NKH, given its rich bioactive profile, may be particularly effective in managing oxidative stress and associated chronic diseases. Furthermore, the γ-oryzanol contents, the highest in NKH, highlight its potential for metabolic health benefits. This study lays the groundwork for future investigations into the development of functional foods and nutraceuticals derived from the unique characteristics of pigmented and non-pigmented rice varieties. Full article

The complexation behavior of lanthanide(III) ions with terephthalic acid (1,4-benzene-dicarboxylic acid) in 0.01 M KNO₃ aqueous solutions was studied across a broad pH range and at two metal-to-ligand ratios using potentiometric titration combined with photoluminescence spectroscopy. Chemometric analysis of titration curves enabled the determination of relative molar fractions, stability constants, and probable stoichiometry of the formed complexes. In solutions with a 1:2 metal-to-ligand ratio, bis-complexes (two terephthalate ligands per lanthanide ion) predominated, while ligand-rich conditions favored the formation of tetra-complexes (four ligands per metal ion). In alkaline media, bis-complexes transform into mixed hydroxy-terephthalate species. Meanwhile, for the tetra-complexes, the addition of NaOH results in the formation of lanthanide ion hydroxo complexes without organic ligands. The structural diversity of these complexes, driven by the terephthalate ligand’s tendency to maximize denticity, suggested dimeric or oligomeric configurations. The stability constants and structural features of complexes in solution were found to align with those of known solid-state lanthanide–terephthalate polymers, highlighting their potential as models for polymeric structures. Full article

The electronic and phonon bands of Skaergaardite are investigated using density functional theory (DFT) as implemented in Quantum ESPRESSO. Skaergaardite is a copper palladium mineral (CuPd) found in the Skaergaard intrusion with a CsCl-type (B2) structure. Due to its porous structure, it presents a large surface area available for interactions, which makes it a promising catalyst. The PBE-GGA functional with a Hubbard-like localized term (DFT+U) is combined with ultrasoft and norm-conserving pseudopotentials, and a conventional approach with a dense Monkhorst–Pack grid of k-points 12 × 12 × 12 is applied. The electronic valence bands are mainly constituted by 3d orbitals of Cu and 4d orbitals of Pd and a pseudo-gap can be recognized. With respect to DFT, DFT+U causes a general downward shift in the valence band. The acoustic and optical phonon branches are separated by a few cm⁻¹ gap at about 150 cm⁻¹ and show a density of state curve typical of ordered materials. These results highlight the reliability of DFT+U in studying bimetallic systems with scarce experimental benchmarks, offering insights into the behavior of Skaergaardite and its potential applications in material science such as reduction reactions and hydrogen storage. Full article

Carbon-based materials have garnered significant attention for electrocatalysis applications in fuel cells due to their unique structural and electronic properties, but rapid oxygen reduction reaction (ORR) at the cathode of fuel cells is challenging. Dopants are typically used as active sites for ORR, and increasing the number of active sites for carbon-based catalysts remains a challenge. Here, we carried out first-principles calculations for the electrocatalytic ORR performance of the recently reported monolayer superconductors of carbon-rich selenides. Remarkably, the abundant C atoms serve as the active centers instead of the foreign atoms (Se). All the free energy changes during the ORR process are downhill, suggesting that these carbon-rich selenides hold promise as metal-free electrocatalysts for ORR. Note that the promising electrocatalytic performance of carbon-rich selenides is theoretically predicted; validation is encouraged for experimental efforts. Full article

Microbiologically influenced corrosion (MIC) is one of the key causes of material failure in marine engineering, and sulfate-reducing bacteria (SRB) and iron-oxidizing bacteria (IOB) are typical representatives of anaerobic and aerobic microorganisms, respectively. These microorganisms are widely present in marine environments and can form synergistic communities on the surface of metal materials, posing a corrosion threat to them. At the same time, the presence of mixed bacteria may have an effect on cathodic protection, so this study investigates the growth metabolism of mixed SRB and IOB under different cathodic protection potentials in an impressed current cathodic protection (ICCP) system in a marine environment containing SRB and IOB. It also examines the attachment of these microorganisms to the anode and cathode, and the impact on cathodic protection efficiency. The results indicate that in a marine environment containing IOB and SRB, the cathodic protection efficiency of the ICCP system increases with the negative shift of the protection potential. A more positive cathodic protection potential promotes the adhesion of mixed bacteria on the electrode surface and the formation of a biofilm, which reduces cathodic protection efficiency. In contrast, at a cathodic protection potential of −1.05 V (SCE), bacterial growth is inhibited, and a dense crystalline corrosion film primarily composed of Fe₂O₃ and Fe(OH)₃ forms on the cathode surface. This film effectively protects the cathodic metal, significantly mitigating MIC. Full article

The present work represented results from a comprehensive study of free radicals and the antioxidant properties of irradiated walnuts. The effects of gamma irradiation on free radical generation and their stability, as well as on the antioxidant activity in walnuts, were investigated by Electron Paramagnetic Resonance (EPR) spectroscopy, Oxygen Radical Absorbance Capacity (ORAC), and Hydroxyl Radical Antioxidant Capacity (HORAC) assays. Walnut samples were irradiated using ⁶⁰Co at two different doses: 10 and 25 kGy. As a marker for the identification of high-energy radiation treatment, characteristic cellulose radical signals were detected after irradiation and remained observable for over eight months. A significant increase in antioxidant activity was observed at higher irradiation doses, as measured by DPPH free radical scavenging activity, ORAC and HORAC assays. Full article

As examples of “Click Chemistry”, the reaction of 1-(oxiran-2-ylmethyl)piperidine with several 1,2,4-triazoles derivatives was studied. As a result, the reaction shows that the oxirane ring opens regiospecifically, according to Krasusky’s rule, without using a catalyst. The basic nitrogen present in 1-(oxiran-2-ylmethyl)piperidine has a catalytic (anchimer) effect. Full article

Multiple reduced π-conjugated hydrocarbons exhibit π-electron conjugation modes different from neutral species due to the distinct number of electrons. Herein, we report the generation of a 32 π-electron tetraanion of a derivative of a doubly cyclic π-conjugated system with 28 π-electrons, tetracyclopentatetraphenylene (TCPTP), through an exhaustive reduction with potassium. Although aggregation causes some complications, based on spectroscopic and theoretical investigations, it is revealed that negative charges are located at the outer and inner peripheries, suggesting that the tetraanion adopts a globally delocalized double annulenoid (annulene-within-an-annulene, AWA) mode, with 22 π-electron outer and 10 π-electron inner aromatic perimeters. On the other hand, excess charges of the outer perimeter are mainly located at the apical position of the pentagonal rings, indicating a significant contribution of the cyclopentadienide form. The theoretical analysis of magnetically induced ring current tropicities reveals counter-rotating ring currents at the outer and inner rings, supporting the predominant contribution of the cyclopentadienide form. Full article

Benzimidazolinones exhibit unique biological activities and serve as building blocks in synthesizing pharmaceutical compounds. Although multiple synthetic approaches involving intermolecular cyclization reactions have been reported, intramolecular cyclization reactions are scarce, and more rational synthetic methods are required. Hypervalent iodine-catalyzed oxidative C–N coupling is a potentially effective approach for synthesizing benzimidazolinones under metal-free conditions. In this study, we present a method utilizing hypervalent iodine catalysis for the oxidative cyclization of N’-aryl urea compounds, resulting in the first metal-free synthesis of various benzimidazolinones. Full article

Crystalline lanthanide terephthalates, Ln₂bdc₃‧nH₂O (Ln = La–Lu, excluding Pm), were synthesized using a surfactant-free, ultrasound-assisted method. This approach yielded microcrystals with diverse shapes and sizes ranging from 2 to 10 μm. Notably, under these conditions, lutetium terephthalate uniquely crystallized as Lu₂(1,4-bdc)₃·2.5H₂O, while the remaining lanthanides formed tetrahydrate terephthalates, Ln₂bdc₃‧4H₂O (Ln = La–Nd, Sm–Yb). Full article

Considering the importance of organic functionalization of MOFs, we here report a simple, tunable and efficient one-step post-modification procedure for introducing amino and carboxylic groups into the mesoporous metal–organic framework Al- and Cr-MIL-101-NH₂ based on its reaction with alkyl bromides. This procedure allows also access to polyfunctionalized MIL-101 decorated with both carboxylic and primary amino groups. Other chemical functions, such as alcohols and alkynes, were also successfully introduced by this method. Full article

In this work, we have considered the family of indenofluorene (IF) and its longitudinally elongated variants fluorenofluorene and diindenoanthracene and investigated their low-lying excited states and optical properties via quantum-chemical studies at the density functional theory (DFT) level. Singlet ground-state diradicals exhibit distinct optical properties due to the presence of a low-lying state dominated by a doubly excited configuration (DE state), often below the lowest allowed singly excited state (SE state). IFs and their elongated derivatives, with tunable diradical character and both symmetric and nonsymmetric structures, provide an ideal platform for exploring DE state energy modulation and spectroscopic behavior. The study shows that absorption spectra simulated using time-dependent (TD) calculations based on unrestricted broken-symmetry antiparallel-spin reference configuration (TDUDFT) closely match the available experimental data. Additionally, it reveals distinct spectral behavior for symmetric and nonsymmetric derivatives, highlighting the role of lowest-lying weakly allowed excited states potentially promoting non-radiative deactivation pathways. Full article

In this work, we present fully $\pi$-conjugated diradical(oid)s and tetraradical(oid)s with five-membered non-alternant cyclopentadienyl and quasi-alternant thiophene rings, the latter of which is used as a source of aromatic stabilization. By controlling the topology of the $\pi$-systems, we can restrict the lower-bound number of unpaired electrons. Aromaticity and/or antiaromaticity in the different configurations of the compounds can be used to design conjugated compounds with high open-shell characters. We also designed the diradical(oid) based only on the five-membered rings, without any terminal radical groups. This work exemplifies the application of our theory of rational design of polyradicals to heteroatomic and non/quasi-alternant organic systems. The ability to create polyradicals with different classes of organic compounds establishes the possibility of creating multifunctional organic materials with tunable magnetic properties. Full article