One-step, synthesis of Hantzsch esters and polyhydroquinoline derivatives in fluoro alcohols

Hantzsch 1,4-dihydropyridine, polyhydroquinoline and 1,8-dioxodecahydroacridines derivatives were synthesized in excellent yields in trifluoroethanol (TFE). The solvent (TFE) can be readily separated from reaction products and recovered in excellent purity for direct reuse.     

Study of color centers produced in thulium doped YLF crystals irradiated by electron beam and femtosecond laser pulses

In this work, we report the influence of the presence of photochromic and color centers in the photobleaching of thulium ions blue emission in YLF (YLiF₄) crystals doped with 1 mol% Tm (3+). The samples were irradiated at room temperature both with electron beam and high intensity ultrashort pulses from a Ti:Sapphire CPA laser system. In both irradiations the production of photochromic and color centers was observed via the absorption bands in the UV and visible ranges. Pure LiF and pure and oxygen doped YLF crystals were used to identify the color centers produced and their optical properties. From a phenomenological model it was possible to study the interaction between color centers and thulium ions, and their effect in photobleaching and photodarkening behaviors. Finally, the blue up laser level population was computed using a rate equation analysis.     

Ionic liquid coated iron nanoparticles are promising peroxidase mimics for optical determination of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Ionic liquid coated nanoparticles (IL-NPs) consisting of zero-valent iron are shown to display intrinsic peroxidase-like activity with enhanced potential to catalyze the oxidation of the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. This results in the formation of a blue green colored product that can be detected with bare eyes and quantified by photometry at 652 nm. The IL-NPs were further doped with bismuth to enhance its catalytic properties. The Bi-doped IL-NPs were characterized by FTIR, X-ray diffraction and scanning electron microscopy. A colorimetric assay was worked out for hydrogen peroxide that is simple, sensitive and selective. Response is linear in the 30–300 μM H₂O₂ concentration range, and the detection limit is 0.15 μM.

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Graphical abstract Schematic of ionic liquid coated iron nanoparticles that display intrinsic peroxidase-like activity. They are capable of oxidizing the chromogenic substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide. This catalytic oxidation generated blue-green color can be measured by colorimetry. Response is linear in the range of 30–300 μM H₂O₂ concentration, and the detection limit is 0.15 μM.

     

Direct reductive amination and selective 1,2-reduction of α,β-unsaturated aldehydes and ketones by NaBH4 using H3PW12O40 as catalyst

A simple and convenient procedure for direct reductive amination of aldehydes and ketones with sodium borohydride is described. The reaction has been carried out in methanol in the presence of a catalytic amount of H₃PW₁₂O₄₀ (0.5 mol %). α,β-Unsaturated aldehydes and ketones can be easily converted into the corresponding allyl alcohols by reaction with H₃PW₁₂O₄₀ (0.5 mol %)/NaBH₄.     

Studies on Benzothiazolo‐asycyanino‐colorants Synthesis,Structural Correlation with UV Absorption Maxima and Bactericidal Potentiality

Fifteen new chromophoric chain β‐aryl substituted butadienyl‐benzothiazole asy‐cyanine colorants are synthesized by condensing substituted 3‐isopropylbenzothiazolium iodides and 4‐dimethylaminostyrylphenyl ketones using alkaline ethanolic DMF solution. The colorants show bathochromic shifts in comparison with unsubstituted analogues and styryl analogues but hypsochromic shifts when compared to 3‐methylbenzothiazolium analogues. The highly purified samples are screened in vitro against gram positive and gram negative microbes using Disc diffusion technique and found to be mildly active against some of them.     

One-pot three-component reaction for the synthesis of novel series of fully substituted 1,3,4-oxadiazole derivatives bearing pyridine moiety

(N-isocyanimino)triphenylphosphorane, 2-pyridinecarbaldehyde, and aromatic carboxylic acids (benzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 3-methoxybenzoic acid, 1-naphthoic acid, and 2-naphthoic acid) undergo a 1:1:1 addition reaction under mild conditions in a one-pot reaction to afford novel series of fully substituted 1,3,4-oxadiazole derivatives in good yields.     

Kinetic and Product Study of the S-oxidation vs HAT Chemoselectivity in Reactions Promoted by Nonheme Iron(IV)-oxo Complex/NHPI Mediator System

The chemoselectivity between S-oxidation and hydrogen atom transfer (HAT) from C−H bonds has been investigated in the oxidations of a series of aryl sulfides, alkyl aromatic compounds and benzylic alcohols promoted by the iron(IV)-oxo complex [(N4Py)Fe^IV(O)]²⁺ (N4Py: N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)-methylamine) either alone or in the presence of the N-hydroxyphthalimide (NHPI) mediator via kinetic and product studies. Kinetic analyses indicate a generally higher reactivity of [(N4Py)Fe^IV(O)]²⁺ for S-oxidation process while HAT is favored in the reactions promoted by phthalimide-N-oxyl radical (PINO) deriving from NHPI oxidation. Product analysis in intermolecular competitive oxidations confirms the kinetic results with sulfoxides obtained as major products in the oxidation promoted by [(N4Py)Fe^IV(O)]²⁺. Conversely, when NHPI is employed as a mediator, significant differences in terms of chemoselectivity are observed, and HAT-derived products are obtained in higher yields which translate into an inversion of selectivity in the case of the substrates containing activated C−H bonds like diphenylmethane, triphenylmethane and benzylic alcohols. A similar change of chemoselectivity is also observed in the oxidation of aromatic substrates containing both a sulfur atom and α to OH benzylic C−H bonds, with the sulfoxide product more abundant in the absence of NHPI and carbonyl products prevailing with the [(N4Py)Fe^IV(O)]²⁺/NHPI system.     

Exploring Gunnera tinctoria: From Nutritional and Anti-Tumoral Properties to Phytosome Development Following Structural Arrangement Based on Molecular Docking

Gunnera tinctoria, an underexplored invasive plant found in Azores, Portugal, was studied regarding its nutritional, antioxidant, and antitumoral properties. Higher antioxidant activity was found in baby leaves, followed by adult leaves and inflorescences. A phenolic fraction of the plant was enriched using adsorbent resin column chromatography (Diaion^TM HP20LX, and Relite EXA90). Antitumoral effects were observed with the enriched fractions in breast (MCF-7) and pancreatic (AsPC-1) cancer cell lines, being more pronounced in the latter. To improve protection and membrane absorption rates of phenolic compounds, nano-phytosomes and cholesterol-conjugated phytosomes coated with natural polymers were loaded with the enriched fraction. The particles were characterized, and their physiochemical properties were evaluated and compared. All samples presented anionic charge and nanometer size in relation to the inner layer and micrometer size regarding the external layers. In addition, the molecular arrangement of phenolics within both types of phytosomes were studied for the first time by molecular docking. Polarity and molecular size were key factors on the molecular arrangement of the lipid bilayer. In conclusion, G. tinctoria showed to be an interesting source of nutrients and phenolic compounds with anti-tumoral potential. Moreover, phytosome loading with these compounds can increase their stability and bioavailability having in view future applications.     

Hybrid Thermoelastic Stress Analysis of a Pinned Joint

Mechanical joints such as bolted or pinned connections are commonly used to fasten mechanical or structural members together. Inadequate knowledge of the stresses at the edge of the loaded holes can render it difficult to stress analyze such mechanical fasteners theoretically or numerically. Thermoelastic stress analysis (TSA) is utilized here to analyze a plane-stressed pin-loaded plate. The approach combines the recorded temperature information with an Airy stress function, plus imposes the traction-free conditions on the non-contacting edge of the hole and on the external boundaries of the plate. Individual components of stress are determined full-field as well as on the pin-plate interface. In addition to agreeing with the frequently assumed interface contact stresses in mechanical connections having zero clearance, the TSA results satisfy force equilibrium, are compatible with residual markings on the contacted surfaces of the pin and the hole, and correlate with FEM predictions. Significant advantages of TSA here include neither needing to know the elastic modulus nor to differentiate the recorded information.