Synthesis and Biological Evaluation of New N-Acyl-α-amino Ketones and 1,3-Oxazoles Derivatives

In order to develop novel bioactive substances with potent activities, some new valine-derived compounds incorporating a 4-(phenylsulfonyl)phenyl fragment, namely, acyclic precursors from N-acyl-α-amino acids and N-acyl-α-amino ketones classes, and heterocycles from the large family of 1,3-oxazole-based compounds, were synthesized. The structures of the new compounds were established using elemental analysis and spectral (UV-Vis, FT-IR, MS, NMR) data, and their purity was checked by reversed-phase HPLC. The newly synthesized compounds were evaluated for their antimicrobial and antibiofilm activities, for toxicity on D. magna, and by in silico studies regarding their potential mechanism of action and toxicity. The 2-aza-3-isopropyl-1-[4-(phenylsulfonyl)phenyl]-1,4-butanedione 4b bearing a p-tolyl group in 4-position exhibited the best antibacterial activity against the planktonic growth of both Gram-positive and Gram-negative strains, while the N-acyl-α-amino acid 2 and 1,3-oxazol-5(4H)-one 3 inhibited the Enterococcus faecium biofilms. Despite not all newly synthesized compounds showing significant biological activity, the general scaffold allows several future optimizations for obtaining better novel antimicrobial agents by the introduction of various substituents on the phenyl moiety at position 5 of the 1,3-oxazole nucleus.     

New Organophosphorus Proligands and Amide Precursors: Crystal and Molecular Structures of Ph2P(X)NH(C6H3Pri 2-2,6) (X = O,S) and (OPPh2)(O2SMe)N(C6H3Pri 2-2,6)

The new organophosphorus proligand (OPPh₂)(O₂SMe)NR (R = C₆H₃Prⁱ ₂–2,6) (3) was prepared as a white crystalline solid by reacting the lithiated compound Li[Ph₂P(O)NR] with MeSO₂Cl in a 1:1 molar ratio. The precursor Ph₂P(O)NHR (1), as well as its thio analogue Ph₂P(S)NHR (2), were obtained in the reaction between the lithiated amine RNHLi and the corresponding organophosphorus chloride. All compounds were characterized by multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy. The molecular structures of 1–3 were established by single-crystal X-ray diffraction. A zigzag polymeric chain is formed in the crystals of 1 and 2 by hydrogen N–H···X (X = O, S) bonding, while the crystal of 3 contains discrete monomeric units with a syn–syn conformation of the O?P(C)₂–N–S(C)(?O)₂ skeleton.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Two-stage latexes of polystyrene acrylates

ABSTRACT

The modification of decomposition rate of the potassium persulfate initiator during the synthesis of “two-stage latexes” polystyrene-ethyl acrylate (EtA) of butyl acrylale (BuA) and of 2-ethylhexyl acrylate (EHA) is studied. This rate is minimum for BuA and maximum for EHA, in good agreement with the value of solubility parameters. The appearance of poryacrvlaf.es determines the existence of water bonded to the polar polymer. The amount of water bonded increases in the sequence PEtA?PBuA?PEHA, function of the modification of the diameters of the particles resulted from the latexes obtained.     

Phenylmercury(II) derivatives of tetraorganodichalcogenoimidodiphosphorus acids. Crystal and molecular structure of [PhHg{(OPR2)(SPPh2)N}]2 (R=Me, Ph)

The reactions between PhHgCl or PhHgAc and M[(XPR₂)(YPR′₂)N] (M=Na, K; X, Y=O, S; R, R′=Me, Ph, OEt), in 1:1 molar ratio, have been investigated. PhHg[(XPR₂)(YPR′₂)N] derivatives were isolated as microcrystalline powders and were characterised using IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and mass spectrometry. The molecular structure of PhHg[(OPR₂)(SPPh₂)N] [R=Me (1), Ph (2)] was investigated by X-ray diffraction. In the monomeric unit, PhHg[(OPR₂)(SPPh₂)N], the mercury atom forms the primary bonds with the carbon of the phenyl group and the sulfur atom of the phosphorus ligand [Hg(1)-S(1) 2.405(1) Å for 1, 2.398(2) Å for 2]. These primary bonds are significantly deviated from the expected linear arrangement [C(1)-Hg(1)-S(1) 166.4(2)° for 1, 165.0(2)° for 2]. Both compounds exhibit dimeric associations in the crystal through S,O-bridging organophosphorus ligands [Hg(1)-O(1) 2.556(4) Å for 1, 2.588(4) Å for 2], thus resulting in a distorted T-shaped arrangement of the CHgSO coordination core.. The formation of a 12-membered Hg₂O₂S₂P₄N₂ ring with different conformation in 1 and 2, respectively, results in different additional chalcogen atoms being in the proximity of the metal atom. Weak transannular Hg?O [2.753(4) Å] are also established in 1, leading to a tricyclic ladder structure with a planar central Hg₂O₂ ring.     

Photochemical Bromination of 2,5-Dimethylbenzoic Acid as Key Step of an Improved Alkyne-Functionalized Blue Box Synthesis**

Cyclobis(paraquat-p-phenylene), also known as “blue box”, is a highly electron-deficient macrocycle, widely used as a molecular receptor for small electron-rich molecules. Inserting a reactive functional group onto the molecular structure of this cyclophane is paramount for its inclusion into complex architectures. To this aim, including an alkyne moiety would be ideal, because it can participate in click reactions. However, the synthesis of such alkyne-functionalized cyclophane suffers from several drawbacks: the use of toxic and expensive CCl₄, the need for high-pressure reactors, and overall low yield. We have revised the existing synthesis of this cyclophane derivative bearing an alkyne moiety, to overcome all these limitations. In particular, photochemical radical bromination is adopted to obtain a sensitive intermediate. We demonstrated that the synthesized host molecule can be functionalized via click reactions and take part in radical-radical interactions. Our work makes a key functionalized paraquat macrocycle more accessible, facilitating the development of novel redox-responsive systems.     

Elucidating the N−N and C−N Bond-breaking Mechanism in the Photoinduced Formation of Nitrile Imine

In this study, we revealed the significance of chemical bonding for the photochemically induced mechanism of 2-phenyl tetrazole derivatives generating nitrile imines. The correlated electron localization function shows that the formation of imine nitrile involves two key bond events: (i) the heterolytic C−N breakage taking place in the T₁ state and (ii) the homolytic N−N rupture occurring in the T₂ excited state. In particular, a cation-radical specie results from the C−N cleavage, whereas the N−N rupture creates a biradical resonant form of imine nitrile. Additionally, we noticed that the substantial pair delocalization of the C−C-N bonded structure could play a significant role in the conversion of the biradical imine nitrile into both the propargylic and allenic forms via the T₁→S₀ deactivation.     

Homogenization heat treatment and segregation analysis of equiaxed CMSX-4 superalloy for gas turbine components

Journal of Thermal Analysis and Calorimetry - Two new zinc(II) coordination compounds have been synthesized by the reaction of diazine-ring containing Schiff bases di(2-pyridyl) ketone...     

Characterization of the complexing agents’ influence on bioscouring cotton fabrics by FT-IR and TG/DTG/DTA analysis

The nature of the complexing agents used in the bioscouring process of cotton fabrics aiming to eliminate the non-cellulosic compounds (pectin, waxes, etc.) and to improve the hydrophilic and wetting properties influences the thermal behaviour and the FT-IR spectra of the textile materials. In this paper, we study the influence of the experimental conditions and complexing agent nature (sodium citrate or disodium EDTA salt) on the pectin elimination in bioscouring treatment of cotton fabric by FT-IR and TG/DTG/DTA analysis. The changes from FT-IR spectra of the specific bands (absorbance intensity at 2916, 2852, 1732 and 1640/1642 cm^?1) were evaluated. The thermal behaviour of the investigated samples’ fabric by using TG/DTG/DTA analysis was studied at 30–600 °C temperature range, in air atmosphere. All samples showed three mass-loss steps due to the elimination of humidity, decomposition of the non-cellulosic and cellulosic components (main degradation stage of the samples) and thermo-oxidative decomposition of the formed degradation products. The T_onset values corresponding to the main decomposition step, the mass-loss values (%Δm) and the % residual mass (at 600 °C) were influenced by the complexing agent nature as well as the concentration and the action time of the commercial enzyme product. In addition, the calcium content of some samples treated with and without ultrasound was determined using atomic absorption spectroscopy method (AAS) in order to correlate the results with TG/DTG/DTA analysis. The obtained results have shown that the synergistic action of experimental conditions (enzyme concentration, pH, enzyme product action time, ultrasound) and the presence of sodium citrate as a biodegradable complexing agent led to the elimination of a higher amount of pectin from the cotton samples than that eliminated when using EDTA.     

Sol-gel synthesis of ZnO/Zn<Subscript>2-x</Subscript>Fe<Subscript>x</Subscript>TiO<Subscript>4</Subscript> powders: structural properties,electrical conductivity and dielectric behavior

The aim of this work was an investigation of structural and electrical properties of ZnO/Zn_2-xFe_xTiO₄ (x?=?0.7, 1, 1.4) powders. The compounds obtained by sol-gel method are characterized by several techniques: X-ray diffraction (XRD), N₂ adsorption–desorption isotherms, scanning and transmission electron microscopy (SEM and TEM), X-ray photoelectron spectroscopy (XPS), electrical and dielectrical measurements. The XRD, SEM and XPS analysis confirmed the formation of ZnFeTiO₄ inverse spinel structure. The electrical and dielectrical properties of ZnO/Zn_2-xFe_xTiO₄ (x?=?0.7, 1, 1.4) were measured by impedance spectroscopy, revealing a decrease in the electrical conductivity and the dielectric constant with Fe content.

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Characterization of Magnetic Nanoiron Oxides for the Removal of Metal Ions from Aqueous Solution

ABSTRACT

Two nanostructured hybrid materials are reported that include uncoated magnetic nanoiron oxides and magnetic nanoiron oxides treated with rose leaf extract. Atomic and molecular absorption spectrometry were used to evaluate the sensitivity of these materials for the isolation of Cr(VI), Zn(II), Pb(II), and Ca(II) from aqueous solution. The structure and physicochemical properties of the resulting nanohybrids were characterized by scanning electron microscopy coupled with energy-dispersive spectroscopy, atomic force microscopy, and X-ray diffraction. The results show that following 15?min of contact in acidic solution, the uncoated magnetic nanoiron oxides removed approximately 90% of Cr(VI), while the magnetic nanoiron oxides coated with rose leaf extract removed 92% of the analyte. These correspond to most industrial wastewater conditions. For the removal of Ca(II) and Zn(II), it was necessary to adjust the pH to neutral to maximize the efficiency. Pb(II) showed maximum removal efficiency when the solution is basic. The simple rose extract suspension was also used for metal removal with high capacity. The results demonstrate that the magnetic nanoiron oxides were uniformly distributed in the rose leaf extract. The extract served as a capping agent due to the presence of polyphenolics.