Lewis Acid Promoted Dearomatization of Naphthols

Two-step dearomative functionalization of naphthols promoted by Lewis acids and copper(I) catalysis was developed. Initially, Lewis acid complexation inverted the electronic properties of the ring and established an equilibrium with the dearomatized counterpart. Subsequent trapping of the dearomatized intermediate with organometallics as well as organophosphines was demonstrated and provided the corresponding dearomatized products.     

Design and experimental validation of a nonlinear controller for underactuated surface vessels

Nonlinear Dynamics - This paper addresses the problem of trajectory tracking control of an underactuated surface vessel moving in a two-dimensional space in the presence of unknown disturbances. In...     

Metastable and stable pitting events at zinc passive layer in alkaline solutions

The electrochemical behavior of Zn in 0.5 M NaOH solutions containing various concentrations (0.01–0.1 M) of ClO₃ ^? or ClO₄ ^? anions was studied with potentiodynamic anodic polarization and chronoamperometry techniques. Microstructural and topographical characterization of the pitted surfaces was carried out by ex situ scanning electron microscopy and atomic force microscopy examinations. Addition of either ClO₃ ^? or ClO₄ ^? stimulated general corrosion and ruptured the passive layer (stable pitting), with ClO₃ ^? being more aggressive than ClO₄ ^?. Metastable pitting events appear as current oscillations (spikes) at potentials close to the pitting potential when Cl^? ions are produced by cathodic reduction of ClO₃ ^? and ClO₄ ^? before passive layer growth. Current–time measurements are performed at fixed potential after production of Cl^? ions and show that the rate of metastable pitting and the intensity of current spikes increase with the potential and the concentration of aggressive anions. Concepts of thin film growth are applied to the passive layer formation in order to explain those results. Metastable events are related to the presence of defects in the passive layer because their frequency and intensity are enhanced in conditions that favor defect formation and roughening in growing films, while stable pitting typically occurs at regions of high metal disorder.     

Electrochemical alcohol oxidation: a comparative study of the behavior of methanol,ethanol, propanol,and butanol on carbon-supported PtSn,PtCu, and Pt nanoparticles

Journal of Solid State Electrochemistry - Carbon-supported PtCu and PtSn (both with an atomic ratio of 3:1) nanoparticles were prepared by reducing Pt, Sn, and Cu precursors via refluxing in...     

Oxaliplatin preformulation studies for the development of innovative topical drug delivery systems

Journal of Thermal Analysis and Calorimetry - The objectives of this study were to verify the viability of the photoinitiating system using curcumin as a photoinitiator and glycerol as a...     

Discrete Orbits,Recurrence and Solvable Subgroups of $${{\mathrm{Diff}}\, ({{\mathbb {C}}}^2, 0)}$$

We discuss the local dynamics of a subgroup of \({{\mathrm{Diff}}\, ({{\mathbb {C}}}^2, 0)}\) possessing locally discrete orbits as well as the structure of the recurrent set for more general groups. It is proved, in particular, that a subgroup of \({{\mathrm{Diff}}\, ({{\mathbb {C}}}^2, 0)}\) possessing locally discrete orbits must be virtually solvable. These results are of considerable interest in problems concerning integrable systems.     

Catalytic Access to Chiral δ-Lactams via Nucleophilic Dearomatization of Pyridine Derivatives

Nitrogen-bearing rings are common features in the molecular structures of modern drugs, with chiral δ-lactams being an important subclass due to their known pharmacological properties. Catalytic dearomatization of preactivated pyridinium ion derivatives emerged as a powerful method for the rapid construction of chiral N-heterocycles. However, direct catalytic dearomatization of simple pyridine derivatives are scarce and methodologies yielding chiral δ-lactams are yet to be developed. Herein, we describe an enantioselective C4-dearomatization of methoxypyridine derivatives for the preparation of functionalised enantioenriched δ-lactams using chiral copper catalysis. Experimental ¹³C kinetic isotope effects and density functional theory calculations shed light on the reaction mechanism and the origin of enantioselectivity.     

Combined OX40 Agonist and PD-1 Inhibitor Immunotherapy Improves the Efficacy of Vascular Targeted Photodynamic Therapy in a Urothelial Tumor Model

Purpose: Vascular targeted photodynamic therapy (VTP) is a nonsurgical tumor ablation approach used to treat early-stage prostate cancer and may also be effective for upper tract urothelial cancer (UTUC) based on preclinical data. Toward increasing response rates to VTP, we evaluated its efficacy in combination with concurrent PD-1 inhibitor/OX40 agonist immunotherapy in a urothelial tumor-bearing model. Experimental design: In mice allografted with MB-49 UTUC cells, we compared the effects of combined VTP with PD-1 inhibitor/OX40 agonist with those of the component treatments on tumor growth, survival, lung metastasis, and antitumor immune responses. Results: The combination of VTP with both PD-1 inhibitor and OX40 agonist inhibited tumor growth and prolonged survival to a greater degree than VTP with either immunotherapeutic individually. These effects result from increased tumor infiltration and intratumoral proliferation of cytotoxic and helper T cells, depletion of Treg cells, and suppression of myeloid-derived suppressor cells. Conclusions: Our findings suggest that VTP synergizes with PD-1 blockade and OX40 agonist to promote strong antitumor immune responses, yielding therapeutic efficacy in an animal model of urothelial cancer.     

Optimal design of experiments applied to headspace solid phase microextraction for the quantification of vicinal diketones in beer through gas chromatography-mass spectrometric detection

Vicinal diketones, namely diacetyl (DC) and pentanedione (PN), are compounds naturally found in beer that play a key role in the definition of its aroma. In lager beer, they are responsible for off-flavors (buttery flavor) and therefore their presence and quantification is of paramount importance to beer producers. Aiming at developing an accurate quantitative monitoring scheme to follow these off-flavor compounds during beer production and in the final product, the head space solid-phase microextraction (HS-SPME) analytical procedure was tuned through experiments planned in an optimal way and the final settings were fully validated. Optimal design of experiments (O-DOE) is a computational, statistically-oriented approach for designing experiences that are most informative according to a well-defined criterion. This methodology was applied for HS-SPME optimization, leading to the following optimal extraction conditions for the quantification of VDK: use a CAR/PDMS fiber, 5 ml of samples in 20 ml vial, 5 min of pre-incubation time followed by 25 min of extraction at 30 °C, with agitation. The validation of the final analytical methodology was performed using a matrix-matched calibration, in order to minimize matrix effects. The following key features were obtained: linearity (R² > 0.999, both for diacetyl and 2,3-pentanedione), high sensitivity (LOD of 0.92 μg L⁻¹ and 2.80 μg L⁻¹, and LOQ of 3.30 μg L⁻¹ and 10.01 μg L⁻¹, for diacetyl and 2,3-pentanedione, respectively), recoveries of approximately 100% and suitable precision (repeatability and reproducibility lower than 3% and 7.5%, respectively). The applicability of the methodology was fully confirmed through an independent analysis of several beer samples, with analyte concentrations ranging from 4 to 200 g L⁻¹.