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We performed high-level ab initio quantum chemical calculations, incorporating higher-order excitations, spin–orbit coupling (SOC), and the Gaunt interaction, to calculate the electron affinities (EAs) of alkaline earth (AE) metal atoms (Ca, Sr, Ba, and Ra), which are notably small. The coupled-cluster singles and doubles with perturbative triples [CCSD(T)] method is insufficient to accurately calculate the EAs of AE metal atoms. Higher-order excitations proved crucial, with the coupled-cluster singles, doubles, and triples with perturbative quadruples [CCSDT(2)Q] method effectively capturing dynamic electron correlation effects. The contributions of SOC (ΔESOs) to the EAs calculated using the multireference configuration interaction method with the Davidson correction, including SOC, positively enhance the EAs; however, these contributions are overestimated. The Dirac–Hartree–Fock (DHF)-CCSD(T) method addresses this overestimation and provides reasonable values for ΔESO (ΔESO−D). Employing additional sets of diffuse and core–valence correlation basis sets is critical for accurately calculating the EAs of AE metal atoms. The contributions of the Gaunt interaction (ΔEGaunt) to the EAs of AE metal atoms are negligible. Notably, the CCSDT(2)Q with the complete basis set limit + ΔESO−D + ΔEGaunt produced EA values for Ca, Sr, and Ba that closely aligned with experimental data and achieved accuracy exceeding the chemical accuracy. Based on our findings, the accurately proposed EA for Ra is 9.88 kJ/mol. [ABSTRACT FROM AUTHOR]

Glucose, an abundant and renewable form of biomass, has garnered significant attention in research for its conversion into high‐value chemicals such as gluconic acid. Traditional methods for biomass transformation typically involve high energy input, elevated temperature, pressure, and costly systems. In contrast, photocatalysis emerges as a promising approach to produce organic molecules under mild conditions, harnessing energy from natural sunlight or lamps. This study presents the nitrogen‐enriched graphene with zeolite second Mobil–5 (NenG/ZSM‐5) photocatalyst, evaluated for generating high‐value chemicals (gluconic acid and leucodopaminechrome) under solar light irradiation. The NenG/ZSM‐5 photocatalyst, synthesized from nitrogen‐doped graphene and ZSM‐5, successfully converted dopamine into leucodopaminechrome (71.54 %) — a critical step in dopamine regeneration and transformed glucose into gluconic acid (85 %). The addition of ZSM‐5 to NenG provided stability and enhanced product selectivity. The outstanding performance of the NenG/ZSM‐5 photocatalyst can be attributed to its heightened solar light harvesting potential, appropriate energy band gap, and uniformly arranged π‐electron channels. This research focuses on solar conversion of glucose to gluconic acid and dopamine regeneration, with potential for further exploration in the research domain. [ABSTRACT FROM AUTHOR]

Nicotinamide Adenine Dinucleotide Phosphate (NAD(P)H) plays an important role in numerous biologically significant redox reactions. The photochemical restoration of its oxidized form (NAD(P)+) under physiological conditions is intriguing in the context of integrated photo and catalysis. Herein, we report the functionalized graphitic carbon‐based solar light active photocatalyst by doping boron and fluorine in the native graphitic carbon nitride (GCN) (nonfunctionalized) for the regeneration of enzymatically visible light active coenzyme and in photo‐acetalization reactions. The metal‐free functionalized photocatalyst systems such as BFGCN‐x leads to higher yield NADH and NADPH regeneration. They are also capable of catalyzing acetal reactions in the absence of any Lewis and Bronsted acids. The current research endeavor provides the advancement and the application of functionalized GCN‐based photocatalysts for NADH (61.89%), NADPH (59.84%) regeneration, and photo‐acetalization reactions. [ABSTRACT FROM AUTHOR]

Carbon dioxide reduction together with aerobic oxidative cyclization using eosin Y-based light-harvesting photocatalysts remains a key challenge. In this study, we present the first-ever synthesis of unique in situ Se-infused eosin Y (Sein–EY) flexible photocatalysts through a simple one-pot method. The as-synthesized Sein–EY flexible film photocatalyst exhibits outstanding performance for the production of formic acid (204 μM in 2 h) and aerobic oxidative cyclization of thioamides via the formation of C–N/C–S bonds with outstanding yields (98.6%) when exposed to solar light. The presence of infused Se significantly extends the solar light absorption capacity of the Sein–EY photocatalyst, reaching up to 580 nm. This study opens up a new pathway for the rational design and synthesis of potentially effective Se-infused-EY photocatalysts through a simple and scalable method, enabling both solar chemical production and efficient one-pot three-component reactions. [ABSTRACT FROM AUTHOR]

Elevated global pollution level is the prime reason that contributes to the onset of various harmful health diseases. The products of Biginelli reaction are enormously used in the pharmaceutical industry as they have antiviral, antibacterial, and calcium channel modulation abilities. This work reports a novel eosin Y sensitized boron graphitic carbon nitride (EY‐Ben‐g‐C3N4) as a photocatalyst that efficiently produced 3,4‐dihydropyrimidine‐2‐(1H)‐one by the Biginelli reaction of benzaldehyde, urea, and methyl acetoacetate. The photocatalyst EY‐Ben‐g‐C3N4 showed a successful generation of 3,4‐dihydropyrimidine‐2‐(1H)‐one (Biginelli product) in good yield via photocatalysis which is an eco‐friendly method and has facile operational process. In addition to the production of Biginelli products, the photocatalyst also showed a remarkable NADH regeneration of 81.18%. The incorporation of g‐C3N4 with boron helps increase the surface area and the incorporation of eosin Y which is an inexpensive and non‐toxic dye, and in Ben‐g‐C3N4, enhanced the light‐harvesting capacity of the photocatalyst. The production of 3,4‐dihydropyrimidine‐2‐(1H)‐one and NADH by the EY‐Ben‐g‐C3N4 photocatalyst is attributed to the requisite band gap, high molar absorbance, low rate of charge recombination, and increased capacity of the photocatalyst to harvest solar light energy. [ABSTRACT FROM AUTHOR]

A schematic strategy is presented to overcome the problem of low photocatalytic performance of graphene. Herein, we synthesized nitrogen-doped graphene (NDG)-coupled acid fuchsin (AF) photocatalyst, i.e.; NDGCAF photocatalyst. The NDGCAF photocatalyst has excellent solar light harvesting ability, band gap suitability, and high molar extinction coefficient than the NDG photocatalyst. Due to these properties, the NDGCAF photocatalyst has the ability to oxidize aryl-vinyl into aryl-vinyl-aldehyde under the irradiation of visible light. In this context, it exhibited the utmost conversion efficiency of aryl-vinyl to aryl-vinyl-aldehyde with a good yield of 98.15%. Current research highlights the significant application of NDGCAF light-harvesting photocatalysts in the research field of organic transformations. [ABSTRACT FROM AUTHOR]

The generation of a low HOMO-LUMO energy gap makes organic polymer-based composites an important class of materials with outstanding catalytic efficiency. The present work describes the simple and direct synthesis of an excellent photocatalyst, PC (C26H16NO7S)n via doping of erythrosine-B dye on sulfone infused poly(2-amino thiophenol) assembly (PA, (C6H4NO2S)n). The O 1 s spectrum displays peaks at 531.8 eV and 533.3 eV, representing the O=C and O–C groups of the in-situ generated fluorescein loaded on PA surface. Through absorption study (Tauc's plot), the optical band gap (Eg) for polymer PA (2.9 eV) and photocatalyst PC (2.1 eV) has been calculated. Further, due to the efficient absorbance in the range of 400–600 nm with a low optical band gap, the applicability of the catalyst, PC has been checked in photocatalytic C–H activation in thiophene, and the generation of C–C bond with p-nitro aryldiazonium salt. [ABSTRACT FROM AUTHOR]

The combination of excellent electronic properties and thermal stability positions orange‐derived graphene quantum dots (GQDs) as promising materials for solar light‐based applications. Researchers are actively exploring their potential in fields such as photovoltaics, photocatalysis, optoelectronics, and energy storage. Their abundance, cost‐effectiveness, and eco‐friendly nature further contribute to their growing relevance in cutting‐edge scientific research. Furthermore, only GQDs are not much more effective in the UV‐visible region, therefore, required band gap engineering in GQDs material. In this context, we designed GQDs‐based light harvesting materials, which is active in UV‐visible region. Herein we synthesized GQDs coupled with 2,6‐diaminoanthrquninone (AQ), that is, GQDs@AQ light harvesting photocatalyst the first time for the oxidation of sulfide to sulfoxide under visible light. For the integrating reactions of sulfide in aerobic conditions under visible light by GQDs@AQ photocatalyst exhibit utmost higher photocatalytic activity than simple GQDs due to low molar extinction coefficient and slow recombination charges. The use of GQDs@AQ light harvesting photocatalyst, showed the excellent organic transformation efficiency of sulfide to sulfoxide with excellent yield (94%). The high efficiency and excellent yield of 94% indicate the effectiveness of GQDs@AQ as a photocatalyst for these specific organic transformations. [ABSTRACT FROM AUTHOR]

Fluorinated and enzymatic chemicals are widely used in society due to their chemical, physical, and biological qualities. Nevertheless, despite their vital importance, present approaches to adding fluorine to molecules and regenerating enzyme cofactors have serious flaws. For instance, numerous approaches are photocatalytic and employ stoichiometric counterparts of heavy metals. Prevailing photocatalytic approaches, on the other hand, show very poor activity, and selectivity has not been attained by heterogeneous photocatalysis, despite the several benefits such a method would provide. Here, we show how heterogeneous photocatalysis may be used to selectively create C(sp3)‐F bonds and 1,4‐NADH regeneration cofactor. Employing NiS‐NiO/S‐g‐C3N4 nanocomposite photocatalyst as a photocatalyst, NAD+ and Selectfluor as an acceptor and mild fluorine donor, effective 1,4‐NADH regeneration, and decarboxylative fluorination of carboxylic acids can be attained in very short reaction times. Furthermore, NiS‐NiO/S‐g‐C3N4 nanocomposite photocatalyst exhibits outstanding levels of robustness and photo‐catching capacity. These aspects, attached to the mild environment of the reaction scheme, exhibit a breakthrough toward the sustainable cofactor of 1,4‐NADH regeneration and synthesis of fluorinated compounds. [ABSTRACT FROM AUTHOR]

Topological insulators, a class of materials possessing bulk bandgap and metallic surface states with a topological nontrivial symmetry, are considered promising candidates for emerging quantum and optoelectronic applications. However, achieving scalable growth and control over the parameters including thickness, carrier density, bulk bandgap, and defect density remains a challenge in realizing such applications. In this work, we show the scalable growth of topological insulator alloys Bi2Se(3−x)Sx and demonstrate composition-tunable bandgap, using chemical vapor deposition (CVD). A bandgap increase of up to ∼40% at a sulfur concentration of ∼15% is demonstrated. Correspondingly, the real part (n) of the refractive index is reduced in the alloy by ∼25% relative to that of Bi2Se3. Additionally, electronic transport measurements indicate a bulk p-type doping and field-effect tunable metallic surface states of the alloy. This work paves the way for the controlled growth of topological insulators, free from surface-state pinning, suitable for quantum optoelectronics and spintronics applications. [ABSTRACT FROM AUTHOR]

Aloe vera‐derived graphene (ADG) coupled system photocatalyst, mimicking natural photosynthesis, is one of the most promising ways for converting solar energy into ammonia (NH3) and nicotinamide adenine dinucleotide (NADH) that have been widely used to make the numerous chemicals such as fertilizer and fuel. In this study, we report the synthesis of the aloe vera‐derived graphene‐coupled phenosafranin (ADGCP) acting as a highly efficient photocatalyst for the generation of NH3 and regeneration of NADH from nitrogen (N2) and oxidized form of nicotinamide adenine dinucleotide (NAD+). The results show a benchmark instance for mimicking natural photosynthesis activity as well as the practical applications for the solar‐driven selective formation of NH3 and the regeneration of NADH by using the newly designed photocatalyst. [ABSTRACT FROM AUTHOR]

Melanoma and nonmelanoma skin cancers are among the most prevalent and most lethal forms of skin cancers. To identify new lead compounds with potential anticancer properties for further optimization, in vitro assays combined with in‐silico target fishing and docking have been used to identify and further map out the antiproliferative and potential mode of action of molecules from a small library of compounds previously prepared in our laboratory. From screening these compounds in vitro against A375, SK‐MEL‐28, A431, and SCC‐12 skin cancer cell lines, 35 displayed antiproliferative activities at the micromolar level, with the majority being primarily potent against the A431 and SCC‐12 squamous carcinoma cell lines. The most active compounds 11 (A431: IC50 = 5.0 μM, SCC‐12: IC50 = 2.9 μM, SKMEL‐28: IC50 = 4.9 μM, A375: IC50 = 6.7 μM) and 13 (A431: IC50 = 5.0 μM, SCC‐12: IC50 = 3.3 μM, SKMEL‐28: IC50 = 13.8 μM, A375: IC50 = 17.1 μM), significantly and dose‐dependently induced apoptosis of SCC‐12 and SK‐MEL‐28 cells, as evidenced by the suppression of Bcl‐2 and upregulation of Bax, cleaved caspase‐3, caspase‐9, and PARP protein expression levels. Both agents significantly reduced scratch wound healing, colony formation, and expression levels of deregulated cancer molecular targets including RSK/Akt/ERK1/2 and S6K1. In silico target prediction and docking studies using the SwissTargetPrediction web‐based tool suggested that CDK8, CLK4, nuclear receptor ROR, tyrosine protein‐kinase Fyn/LCK, ROCK1/2, and PARP, all of which are dysregulated in skin cancers, might be prospective targets for the two most active compounds. Further validation of these targets by western blot analyses, revealed that ROCK/Fyn and its associated Hedgehog (Hh) pathways were downregulated or modulated by the two lead compounds. In aggregate, these results provide a strong framework for further validation of the observed activities and the development of a more comprehensive structure–activity relationship through the preparation and biological evaluation of analogs. [ABSTRACT FROM AUTHOR]

The need for sunlight chemical renewal and contemporary organic transformation has fostered the advancement of environmentally friendly photocatalytic techniques. For the first time, we report on the novel crafting of a bright future with selenium-infused Eosin-B (Se in -E-B) nanocomposite photocatalysts in this work. The Se in -E-B nanocomposite materials were created using a hydrothermal process for solar chemical regeneration and organic transformation under visible light. The synthesized samples were subjected to UV-DRS-visible spectroscopy, FT-IR, SEM, EDX, EIS and XRD analysis. The energy band gap of the Se in -E-B nanocomposite photocatalyst was measured using UV-DRS, and the result was around 2.06 eV. to investigate the generated Se in -E-B catalytic activity as a nanocomposite for 1,4-NADH/NADPH re-formation and C-N bond activation. This novel photocatalyst offers a promising alternative for the regeneration of solar chemicals and C-N bond creation between pyrrole and aryl halides., (© 2024 Wiley-VHCA AG, Zurich, Switzerland.)