New antiproliferative 14,15-secopregnane glycosides from Solenostemma argel

Eight new 14,15-secopregnane glycosides, namely argelosides C-J, possessing two ketal functions involved in three five-membered rings, have been isolated from the hairy seeds of Solenostemma argel. Their structures have been established by MS and NMR experiments, combined with quantum mechanical calculations of the ¹³C chemical shifts for the interpretation of the experimental data. On the basis of the obtained results, the structures of argelosides A and B have been revised. Additionally, the effect of these compounds on the VEGF-induced in Kaposi's sarcoma cell proliferation was evaluated. Results indicated that all the compounds reduced the cell proliferation in a dose-dependent manner.     

Cyclopentathiadiazines, new heterocyclic materials from cyclic enaminonitriles

Indene and cyclopentene enaminonitriles were reacted with SCl2, iBu3N and NCS to give the first cyclopenta[1,2,6]thiadiazines that showed unusual characteristics, one as a NIR dye and another as a liquid crystal.     

Correction to: Foreword to the memorial issue for Professor Roberto Marassi

Journal of Solid State Electrochemistry -     

Analysis of Fatty Acids,Amino Acids and Volatile Profile of Apple By-Products by Gas Chromatography-Mass Spectrometry

Apple industrial by-products are a promising source of bioactive compounds with direct implications on human health. The main goal of the present work was to characterize the Jonathan and Golden Delicious by-products from their fatty acid, amino acid, and volatile aroma compounds’ point of view. GC-MS (gas chromatography-mass spectrometry) and ITEX/GC-MS methods were used for the by-products characterization. Linoleic and oleic were the main fatty acids identified in all samples, while palmitic and stearic acid were the representant of saturated ones. With respect to amino acids, from the essential group, isoleucine was the majority compound identified in JS (Jonathan skin) and GS (Golden skin) samples, lysine was the representant of JP (Jonathan pomace), and valine was mainly identified in GP (Golden pomace). A total number of 47 aroma volatile compounds were quantified in all samples, from which the esters groups ranged from 41.55–53.29%, aldehydes 29.75–43.99%, alcohols from 4.15 to 6.37%, ketones 4.14–5.72%, and the terpenes and terpenoids group reached values between 2.27% and 4.61%. Moreover, the by-products were valorized in biscuits manufacturing, highlighting their importance in enhancing the volatile aroma compounds, color, and sensorial analysis of the final baked goods.     

Investigation on corrosion inhibition and adsorption mechanism of azomethine derivatives at mild steel/0.5 ​M ​H2SO4 solution interface: Gravimetric,electrochemical, SEM and EDX studies

The inhibition performance of five azomethine derivatives such as: 1-(4-Methyloxy phenylimino)-1-(phenylhydrazono)-propan-2-one (SB₁), 1-(4-Methylphenylimino)-1-(phenylhydrazono) propan-2-one (SB₂), 1-(phenylimino)-1(phenylhydrazono)-propan-2-one (SB₃), 1-(4-Bromo phenylimino)-1(phenylhydrazono)-propan-2-one (SB₄) and 1-(4-Chlorophenylimino)-1(phenylhydrazono) -propan-2-on (SB₅) as corrosion inhibitors for mild steel in sulfuric acid 0.5 ?M were investigated using different methods. All experimental results demonstrate that these compounds are eficients inhibitors. The inhibition efficiencies ($IE$) increase with inhibitors concentration. At 7.5 $\times$ 10^?5 ?M, the $IE$ was 97.27%, 96.31%, 94.23%, 93.19 and 91.64% for SB₁, SB₂, SB₃, SB₄ and SB₅, respectively. The potentiodynamic polarization results indicated that all the studied inhibitors act as mixed type. The adsorption process on mild steel surface obeyed Langmuir isotherm. The associated activation parameters and thermodynamic have been calculated and discussed. The adsorbed film formed on the metal surface was characterized by SEM and EDX.     

Organotin (IV) complexes derived from tridentate Schiff base ligands: Synthesis,spectroscopic analysis,antimicrobial and antioxidant activity

Organotin complexes of Schiff bases (derived from the condensation of hydrazides with salicylaldehyde derivatives) were prepared and their characterization was done using several spectroscopic techniques like FTIR, NMR (¹H, ¹³C, and ¹¹⁹Sn) and mass spectrometry. The spectroscopic data of the ligands and their corresponding complexes revealed that the Schiff bases chelated to the tin metal in a tridentate manner through –ONO atoms (oxygen atom of the hydroxyl group of the salicylaldehydic derivatives, the nitrogen atom of azomethine group, and the oxygen atom of enolic group present in the carboxylic acid hydrazides). Around tin atom pentacoordinated geometry was exhibited. The synthesized ligands and their complexes have been assessed for their biological potency (antibacterial, antifungal and antioxidant using Ciprofloxacin, Fluconazole and Ascorbic acid as reference compounds) and few of the compounds showed optimistic activity. The ligands having electron withdrawing group attached showed greater antimicrobial activity as compared to the other ligands. The complexes showed the better activity than the ligands. The general trend followed by the complexes was diphenyl ?> ?dibutyl ?> ?dimethyl substituted complexes. Compound 11 was the most active against microbes. The antioxidant activity increased with electron donating group. The phenyl substituted complexes showed better activity as compared to the dibutyl and dimethyl substituted complexes. Compound 20 was the best antioxidant.     

Reduced formation of peroxide and radical species stabilises iron-based hybrid catalysts in polymer electrolyte membrane fuel cells

The incorporation of Pt into an iron-nitrogen-carbon(Fe NC)catalyst for the oxygen reduction reaction(ORR)was recently shown to enhance catalyst stability without Pt directly contributing to the ORR activity.However,the mechanistic origin of this stabilisation remained obscure.It is established herein with rotating ring disc experiments that the side product,H₂O₂,which is known to damage FeNC catalysts,is suppressed by the presence of Pt.The formation of reactive oxygen species is additionally inhibited,independent of intrinsic H₂O₂ formation,as determined by electron paramagnetic resonance.Transmission electron microscopy identifies an oxidised Fe-rich layer covering the Pt particles,thus explaining the inactivity of the latter towards the ORR.These insights develop understanding of Fe NC degradation mechanisms during ORR catalysis,and crucially establish the required properties of a precious metal free protective catalyst to improve Fe NC stability in acidic media.     

Organic‐acid mediated bulk polymerization of ε‐caprolactam and its copolymerization with ε‐caprolactone

Polyamides (PA) constitute one of the most important classes of polymeric materials and have gained strong position in different areas, such as textiles, fibers, and construction materials. Whereas most PA are synthesized by step‐growth polycondensation, PA 6 is synthesized by ring opening polymerization (ROP) of ε‐caprolactam (ε‐CLa). The most popular ROP methods involve the use of alkaline metal catalyst difficult to handle at large scale. In this article, we propose the use of organic acids for the ROP of ε‐CLa in bulk at 180 °C (below the polymer's melting point). Among evaluated organic acids, sulfonic acids were found to be the most effective for the polymerization of ε‐CLa , being the Brønsted acid ionic liquid: 1‐(4‐sulfobutyl)?3‐methylimidazolium hydrogen sulfate the most suitable due to its higher thermal stability. End‐group analysis by ¹H nuclear magnetic resonance and model reactions provided mechanistic insights and suggested that the catalytic activity of sulfonic acids was a function of not only the acid strength, but of the nucleophilic character of conjugate base as well. Finally, the ability of sulfonic acid to promote the copolymerization of ε‐CLa and ε‐caprolactone is demonstrated. As a result, poly(ε‐caprolactam‐co‐ε‐caprolactone) copolymers with considerably randomness are obtained. This benign route allows the synthesis of poly(ester amide)s with different thermal and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2394–2402     

Fluoride-induced coupling of perfluoroketene dithioacetals with silyl alkynes: A way towards new polyfunctionalized trifluoromethyl building blocks

Under fluoride activation, the vinyl fluorine of perfluoroketene dithioacetal may be substituted by silylated nucleophiles. Using silyl alkynes, a formal transition metal free sila-Sonogashira cross-coupling reaction occurred. The resulting enynes were hydrolyzed giving new polyfunctional trifluoromethyl building blocks.     

Polymer‐Bound Thiol Groups on Poly(2‐oxazoline)s

A new 2‐oxazoline monomer with a protected thiol group, 2‐[2‐(4‐methoxybenzylsulfanyl)ethyl]‐2‐oxazoline, MOB‐SOx , was synthesized from commercially available compounds. MOB‐SOx and 2‐ethyl‐2‐oxazoline (EtOx) were simultaneously polymerized yielding well defined copolymers with narrow molar mass distributions and target polymer chain length. The copolymerization was initiated by N‐methyl‐2‐methyl‐2‐oxazolinium triflate ( MeOxOTf ). After quantitative deprotection, poly(2‐oxazoline) with pendant thiol groups was obtained. The thiol groups were quantitatively added to the double bond of N‐phenyl‐acrylamide ( PhA ) and benzylmaleimide ( BzM ). Graft copolymers were obtained by reaction of those SH containing polymers with poly(2‐methyl‐2‐oxazoline)s bearing acrylamide ( PMeOx ₁₀ A ) and maleimide ( PMeOx ₁₀ M ) as terminal reactive groups.