Rational Development of Guanidinate and Amidinate Based Cerium and Ytterbium Complexes as Atomic Layer Deposition Precursors: Synthesis,Modeling, and Application

Owing to the limited availability of suitable precursors for vapor phase deposition of rare-earth containing thin-film materials, new or improved precursors are sought after. In this study, we explored new precursors for atomic layer deposition (ALD) of cerium (Ce) and ytterbium (Yb) containing thin films. A series of homoleptic tris-guanidinate and tris-amidinate complexes of cerium (Ce) and ytterbium (Yb) were synthesized and thoroughly characterized. The C-substituents on the N-C-N backbone (Me, NMe₂, NEt₂, where Me=methyl, Et=ethyl) and the N-substituents from symmetrical iso-propyl (iPr) to asymmetrical tertiary-butyl (tBu) and Et were systematically varied to study the influence of the substituents on the physicochemical properties of the resulting compounds. Single crystal structures of [Ce(dpdmg)₃] 1 and [Yb(dpdmg)₃] 6 (dpdmg=N,N'-diisopropyl-2-dimethylamido-guanidinate) highlight a monomeric nature in the solid-state with a distorted trigonal prismatic geometry. The thermogravimetric analysis shows that the complexes are volatile and emphasize that increasing asymmetry in the complexes lowers their melting points while reducing their thermal stability. Density functional theory (DFT) was used to study the reactivity of amidinates and guanidinates of Ce and Yb complexes towards oxygen (O₂) and water (H₂O). Signified by the DFT calculations, the guanidinates show an increased reactivity toward water compared to the amidinate complexes. Furthermore, the Ce complexes are more reactive compared to the Yb complexes, indicating even a reactivity towards oxygen potentially exploitable for ALD purposes. As a representative precursor, the highly reactive [Ce(dpdmg)₃] 1 was used for proof-of-principle ALD depositions of CeO₂ thin films using water as co-reactant. The self-limited ALD growth process could be confirmed at 160 °C with polycrystalline cubic CeO₂ films formed on Si(100) substrates. This study confirms that moving towards nitrogen-coordinated rare-earth complexes bearing the guanidinate and amidinate ligands can indeed be very appealing in terms of new precursors for ALD of rare earth based materials.     

Formulation of Piperine–Chitosan-Coated Liposomes: Characterization and In Vitro Cytotoxic Evaluation

The present research work is designed to prepare and evaluate piperine liposomes and piperine–chitosan-coated liposomes for oral delivery. Piperine (PPN) is a water-insoluble bioactive compound used for different diseases. The prepared formulations were evaluated for physicochemical study, mucoadhesive study, permeation study and in vitro cytotoxic study using the MCF7 breast cancer cell line. Piperine-loaded liposomes (PLF) were prepared by the thin-film evaporation method. The selected liposomes were coated with chitosan (PLFC) by electrostatic deposition to enhance the mucoadhesive property and in vitro therapeutic efficacy. Based on the findings of the study, the prepared PPN liposomes (PLF3) and chitosan coated PPN liposomes (PLF3C1) showed a nanometric size range of 165.7 ± 7.4 to 243.4 ± 7.5, a narrow polydispersity index (>0.3) and zeta potential (−7.1 to 29.8 mV). The average encapsulation efficiency was found to be between 60 and 80% for all prepared formulations. The drug release and permeation study profile showed biphasic release behavior and enhanced PPN permeation. The in vitro antioxidant study results showed a comparable antioxidant activity with pure PPN. The anticancer study depicted that the cell viability assay of tested PLF3C2 has significantly (p < 0.001)) reduced the IC₅₀ when compared with pure PPN. The study revealed that oral chitosan-coated liposomes are a promising delivery system for the PPN and can increase the therapeutic efficacy against the breast cancer cell line.     

Enhanced Sensitive Electrochemical Sensor for Simultaneous Catechol and Hydroquinone Detection by Using Ultrasmall Ternary Pt-based Nanomaterial

The simple and effective method for the novel synthesis of Pt-based nanoparticle was presented with high efficiency. The sensitive catalyst for the simultaneous detection of catechol and hydroquinone was prepared by depositing ternary metal complex on fluorine-doped tin-oxide (FTO). The composition and morphology of nanomaterials were characterized by TEM, HRTEM, XRD, XPS, and EDS (energy dispersive spectroscopy). The size of the Pt-based nanomaterial was about 5±1 nm. The electrochemical performance of the modified catalyst was studied by CV, DPV, and EIS. The modified PtNiCu@FTO catalyst possessed good electro-oxidation activity for hydroquinone and catechol and used for simultaneous detection of catechol and hydroquinone at scan rate of 20 mV s⁻¹ (vs. Ag/AgCl). Detection responses were found in the ranges of 5–2900 μM for hydroquinone and 5–3000 μM for catechol. The detection limits (LOD) for HQ and CC were observed as 0.35 and 0.29 μM, respectively. The sensitivity of HQ and CC were 1515.55 and 1485 μA mM⁻¹ cm⁻², respectively. The prepared nanomaterial were effectively applied for the determination of CC and HQ in real samples.     

Monitoring Imidazoline Derivatives via Functionalized Nano-Potentiometric Platforms in Aqueous Humor and Dosage Forms

The determination of two imidazoline derivatives [oxymetazoline HCl (OXY) and xylometazoline HCl (XYLO)] was described using different potentiometric platforms. The first electrode type was constructed using tetraphenyl borate (TPB) as anionic exchanger with β-cyclodextrins (β-CD) as ionophore forming oxymetazoline-tetraphenyl borate (OXY-TPB) and xylometazoline-tetraphenyl borate (XYLO-TPB), respectively. The second electrode type was prepared by modification of the first type by conjugation with magnetic iron oxide nanoparticles (MNP) forming (OXY-MNP) and (XYLO-MNP). The synthesized electrodes were fully characterized. The effect of magnetic nano-sized particles as a highly dispersible material with β-CDs on the electrode characteristics was investigated and compared against the classical electrodes. The response time, working pH range and selectivity coefficients were studied. The functionalized nano-electrodes (OXY-MNP and (XYLO-MNP) were found to be more sensitive than the classical electrodes with linearity ranges (1×10⁻⁶–1×10⁻² M). The functionalized nano-electrodes were successfully applied for the in-line analysis of OXY and XYLO in pharmaceutical dosage forms and spiked rabbit aqueous humor samples with no prior extraction of treatment. This suggests the future use of these electrodes in clinical studies of both drugs of interest.     

Convergent synthesis of carbonic anhydrase inhibiting bi-heterocyclic benzamides: Structure–activity relationship and mechanistic explorations through enzyme inhibition,kinetics, and computational studies

By using a convergent methodology, a novel series of N-arylated 4-yl-benzamides containing a bi-heterocyclic thiazole–triazole core was synthesized, and the structures of these hybrid molecules, 9a–k , were corroborated through spectral analyses. The in vitro studies of these multifunctional molecules demonstrated their potent carbonic anhydrase inhibition relative to the standard used. The kinetics mechanism was exposed by Lineweaver–Burk plots, which revealed that 9j inhibited carbonic anhydrase non-competitively by forming an enzyme-inhibitor complex. The inhibition constants K_i calculated from Dixon plots for this compound was 1.2 μM. The computational study was also persuasive with the experimental results, and these molecules disclosed good results of all scoring functions and interactions, which suggested a good binding to carbonic anhydrase. So, it was predicted from the inferred results that these molecules might be considered as promising medicinal scaffolds for various diseases related to the uncontrolled production of this enzyme.     

Synthesis,Antibacterial, and Antioxidant Evaluation of Novel Series of Condensed Thiazoloquinazoline with Pyrido,Pyrano, and Benzol Moieties as Five- and Six-Membered Heterocycle Derivatives

A novel synthesis of thiazolo[2,3-b]quinazolines 4(a–e), pyrido[2′,3′:4,5]thiazolo[2,3-b]quinazolines {5(a–e), 6(a–e), and 7(a–e)}, pyrano[2′,3′:4,5]thiazolo[2,3-b]quinazolines 8(a–e), and benzo[4,5]thiazolo[2,3-b]quinazoloine9(a–e) derivatives starting from 2-(Bis-methylsulfanyl-methylene)-5,5-dimethyl-cyclohexane-1,3-dione 2 as efficient α,α dioxoketen dithioacetal is reported and the synthetic approaches of these types of compounds will provide an innovative molecular framework to the designing of new active heterocyclic compounds. In our study, we also present optimization of the synthetic method along with a biological evaluation of these newly synthesized compounds as antioxidants and antibacterial agents against the bacterial strains, like S. aureus, E. coli, and P. aeruginosa. Among all the evaluated compounds, it was found that some showed significant antioxidant activity at 10 μg/mL while the others exhibited better antibacterial activity at 100 μg/mL. The results of this study showed that compound 6(c) possessed remarkable antibacterial activity, whereas compound 9(c) exhibited the highest efficacy as an antioxidant. The structures of the new synthetic compounds were elucidated by elemental analysis, IR, ¹H-NMR, and ¹³C-NMR.     

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.     

Selenium Alleviates the Adverse Effect of Drought in Oilseed Crops Camelina (Camelina sativa L.) and Canola (Brassica napus L.)

Drought poses a serious threat to oilseed crops by lowering yield and crop failures under prolonged spells. A multi-year field investigation was conducted to enhance the drought tolerance in four genotypes of Camelina and canola by selenium (Se) application. The principal aim of the research was to optimize the crop yield by eliciting the physio-biochemical attributes by alleviating the adverse effects of drought stress. Both crops were cultivated under control (normal irrigation) and drought stress (skipping irrigation at stages i.e., vegetative and reproductive) conditions. Four different treatments of Se viz., seed priming with Se (75 μM), foliar application of Se (7.06 μM), foliar application of Se + Seed priming with Se (7.06 μM and 75 μM, respectively) and control (without Se), were implemented at the vegetative and reproductive stages of both crops. Sodium selenite (Na₂SeO₃), an inorganic compound was used as Se sources for both seed priming and foliar application. Data regarding physiochemical, antioxidants, and yield components were recorded as response variables at crop maturity. Results indicated that WP, OP, TP, proline, TSS, TFAA, TPr, TS, total chlorophyll contents, osmoprotectant (GB, anthocyanin, TPC, and flavonoids), antioxidants (APX, SOD, POD, and CAT), and yield components (number of branches per plant, thousand seed weight, seed, and biological yields were significantly improved by foliar Se + priming Se in both crops under drought stress. Moreover, this treatment was also helpful in boosting yield attributes under irrigated (non-stress) conditions. Camelina genotypes responded better to Se application as seed priming and foliar spray than canola for both years. It has concluded that Se application (either foliar or priming) can potentially alleviate adverse effects of drought stress in camelina and canola by eliciting various physio-biochemicals attributes under drought stress. Furthermore, Se application was also helpful for crop health under irrigated condition.     

Bimetallic Iron–Palladium Catalyst System as a Lewis-Acid for the Synthesis of Novel Pharmacophores Based Indole Scaffold as Anticancer Agents

The Friedel–Crafts reaction between substituted indoles as nucleophiles with chalcones-based benzofuran and benzothiophene scaffolds was carried out by employing a highly efficient bimetallic iron–palladium catalyst system. This catalytic approach produced the desired bis-heteroaryl products with low catalyst loading, a simple procedure, and with acceptable yield. All synthesized indole scaffolds 3a–3s were initially evaluated for their cytotoxic effect against human fibroblast BJ cell lines and appeared to be non-cytotoxic. All non-cytotoxic compounds 3a–3s were then evaluated for their anticancer activities against cervical cancer HeLa, prostate cancer PC3, and breast cancer MCF-7 cell lines, in comparison to standard drug doxorubicin, with IC₅₀ values 1.9 ± 0.4 µM, 0.9 ± 0.14 µM and 0.79 ± 0.05 µM, respectively, and appeared to be moderate to weak anticancer agents. Fluoro-substituted chalcone moiety-containing compounds, 3b appeared to be the most active member of the series against cervical HeLa (IC₅₀ = 8.2 ± 0.2 µM) and breast MCF-7 cancer cell line (IC₅₀ = 12.3 ± 0.04 µM), whereas 6-fluroindol-4-bromophenyl chalcone-containing compound 3e (IC₅₀ = 7.8 ± 0.4 µM) appeared to be more active against PC3 prostate cancer cell line.