EPR on Medically Relevant NO Adsorbed to Zn-LTA

For medical purposes, materials are required that store and target specifically deliver exogenous nitric oxide (NO). Partially zinc-exchanged Na-LTA (Linde type A) zeolite (Zn-LTA) has high potential in this respect due to its non-toxicity and adsorption capacity for NO. In contrast to NO adsorbed to LTA zeolites prepared for catalytic purposes, lower dehydration temperature prior to NO adsorption is used to achieve a balance between production cost and high activity. In order to study the interaction of NO with the metal sites in the samples prepared under these medical conditions, continuous-wave X-band electron paramagnetic resonance has been applied. In contrast to Na-LTA with only one weakly interacting NO monomer, three different monomers, having stronger interaction to the metal sites than in Na-LTA, were observed in Zn-LTA. To improve the storage capacity of Zn-LTA, higher dehydration temperatures would be necessary.     

Residual determination and risk assessment of buprofezin in plum (Prunus domestica) grown in open‐field conditions following the application of three different formulations

This study was conducted to characterize the residual level and perform a risk assessment on buprofezin formulated as an emulsifiable concentrate, wettable powder, and suspension concentrate over various treatment schedules in plum (Prunus domestica). The samples were extracted with an AOAC quick, easy, cheap, effective, rugged, and safe, ‘QuEChERS’, method after major modifications. As intrinsic interferences were observed in blank plum samples following dispersive‐solid phase extraction (consisting of primary secondary amine and C₁₈ sorbents), amino cartridges were used for solid‐phase extraction. Analysis was carried out using liquid chromatography with diode array detection and confirmed by liquid chromatography–tandem mass spectrometry. The method showed excellent linearity with determination coefficient (R² = 1) and satisfactory recoveries (at two spiking levels, 0.5 and 2.5 mg/kg) between 90.98 and 94.74% with relative standard deviation (RSD) ≤8%. The limit of quantification (0.05 mg/kg) was considerably lower than the maximum residue limit (2 mg/kg) set by the Codex Alimentarius. Absolute residue levels for emulsifiable concentrates were highest, perhaps owing to the dilution rate and adjuvant. Notably, all formulation residues were lower than the maximum residue limit, and safety data proved that the fruits are safe for consumers. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrochemical determination of traces lead ions using a new nanocomposite of polypyrrole/carbon nanofibers

Journal of Solid State Electrochemistry - In this paper, a new nanocomposite of polypyrrole (PPy) and carbon nanofibers (CNFs)-modified carbon paste electrode (CPE) has been reported for the...     

Ozonization: An Efficient Method for the Oxidation of Halophosphines

Abstract

The ozonization of various halophosphines 1a-j leads with quantitative yields to the corresponding phosphine oxides 2a-j.

Ozonization is a convenient method of oxidation, in particular of compounds with bulky ligands (1c, 1d, 1e).     

Thio Analogues of Pyrimidine Bases: Syntheses and Spectral Study of New Potentially Biologically Active 2,4-Di-Ortho-(Meta- and Para-)Bromo- (Chloro and Nitro)-Benzylthio-5-Bromouracils (and 6-Methyluracils)

Eighteen new 2,4-di-ortho- (meta- and para-) bromo-(chloro- and nitro-)benzylthio-5-bromouracils (and 6-methyluracils) have been prepared. The structures of these compounds were confirmed by spectral (IR, UV/vis, ¹H NMR) and elemental analyses. Estimation of pharmacotherapeutic potential has been made for synthesized compounds on the basis of prediction of activity spectra for substances (PASS).     

Chemical Preparation,Thermal Behavior,Kinetic, and IR Studies of MnK4(P3O9)2.2H2O,Crystallographic Data of a New Cyclotriphosphate MnK4(P3O9)2, and Quantum Chemical Calculations for the P3O3− 9 Ion

Abstract

Chemical presparation, thermal behavior, and infrared (IR) studies are discussed for the cyclotriphosphate MnK₄(P₃O₉)₂.2H₂O and its anhydrous form MnK₄(P₃O₉)₂. The total dehydration of MnK₄(P₃O₉)₂.2H₂O, between 200 and 550 °C, leads to its anhydrous form MnK₄(P₃O₉)₂. MnK₄(P₃O₉)₂ is a new cyclotriphosphate crystallizing in the rhombohedral system and is stable until its melting point at 560 °C. The thermal behavior of MnK₄(P₃O₉)₂.2H₂O has been investigated and interpreted by comparison with IR absorption spectrometry and X-ray diffraction experiments. Two different methods, Ozawa and KAS (Kissinger-Akahira-Sunose), were selected in studying the kinetics of thermal behavior of the title compound. Quantum chemical calculations were made for the P₃O ^3? ₉ ion.

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.

GRAPHICAL ABSTRACT     

Polyazomethines Bearing Furan Moieties. Solution Polycondensation of Bis(furanic diamine)s and Aromatic Dialdehydes

A series of new polyazomethines containing furan moieties was synthesized by polycondensation of bifuranic diamine monomers with commercially available aromatic dialdehydes viz., terephthaldehyde (TPA), isophthaldehyde (IPA). Inherent viscosities and number average molecular weights of polyazomethines were in the range 0.90–1.56 dL/g and 10460–17850 (SEC, polystyrene standard), respectively indicating formation of medium to reasonably high molecular weight polymers. The resulting polyazomethines were characterized by solubility tests, viscosity measurements, FTIR, NMR, UV spectroscopy, differential scanning calorimetric (DSC), and thermogravimetric analysis (TGA). These furan-based polyazomethines were essentially amorphous and exhibited glass transition temperatures (Tg) in the 150–190°C range. The temperature at 10% wt loss (T₁₀), determined from TGA of polyazomethines were in the range 300–380°C, indicating their good thermal stability.     

Dapson in Heterocyclic Chemistry,Part III: Synthesis,Antimicrobial, and Antitumor Activities of Some New Bisheterocyclic Compounds Containing Biologically Active Diphenylsulfone Moiety

The key intermediate diisothiocyanate 2 was allowed to react with 5-amino-3-methyl-pyrazole-4-carbonitrile 3, ethyl 5-amino-1-phenyl-pyrazole-4-carboxylate 6, 2-amino-tetrahydrobenzo[b]thiophene-3-car-bonitrile 9, ethyl-2-amino-tetra-hydrobenzo[b]thiophene-3-carboxylate 12, and/or 1,2,4-triazole 15 to give the corresponding biscompounds 4, 5, 7, 8, 10, 11, 13, 14, and 16, respectively. The structure of the synthesized compounds was elucidated by elemental analyses and spectral data. Some of the prepared compounds were tested for their antimicrobial and antitumor activities.     

Identification and functional characterization of a novel α-conotoxin (EIIA) from Conus ermineus

Nicotinic acetylcholine receptors (nAChRs) are one of the most important families in the ligand-gated ion channel superfamily due to their involvement in primordial brain functions and in several neurodegenerative pathologies. The discovery of new ligands which can bind with high affinity and selectivity to nAChR subtypes is of prime interest in order to study these receptors and to potentially discover new drugs for treating various pathologies. Predatory cone snails of the genus Conus hunt their prey using venoms containing a large number of small, highly structured peptides called conotoxins. Conotoxins are classified in different structural families and target a large panel of receptors and ion channels. Interestingly, nAChRs represent the only subgroup for which Conus has developed seven distinct families of conotoxins. Conus venoms have thus received much attention as they could represent a potential source of selective ligands of nAChR subtypes. We describe the mass spectrometric-based approaches which led to the discovery of a novel α-conotoxin targeting muscular nAChR from the venom of Conus ermineus. The presence of several posttranslational modifications complicated the N-terminal sequencing. To discriminate between the different possible sequences, analogs with variable N-terminus were synthesized and fragmented by MS/MS. Understanding the fragmentation pathways in the low m/z range appeared crucial to determine the right sequence. The biological activity of this novel α-conotoxin (α-EIIA) that belongs to the unusual α4/4 subfamily was determined by binding experiments. The results revealed not only its selectivity for the muscular nAChR, but also a clear discrimination between the two binding sites described for this receptor.