Chemoselectivity Control in the Reactions of 1,2‐Cyclic Sulfamidates with Amines

Although 1,2‐cyclic sulfamidates derived from α‐methylisoserine undergo nucleophilic displacement at the quaternary center, to the best of our knowledge their behavior with amines as nucleophiles has never been explored. We have found that a broad range of amines can be used, demonstrating the scope of the reaction, and that excellent control of the chemoselectivity can be achieved. Application of this methodology for the synthesis of a chiral α,β‐diamino acid and an important piperazinone heterocycle is also presented. Additionally, we have found that DMF and DMSO behave not only as polar aprotic solvents but also as O‐nucleophilic reagents, allowing the incorporation of an oxygen atom at a quaternary center of the electrophile, with inversion of configuration.     

Cosurfactant effects on the microemulsion polymerization of styrene

The polymerization of styrene in o/w microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB) with or without cosurfactant (n-butanol, n-hexanol or n-octanol) is examined here. The addition of a cosurfactant enhances the one-phase region in the order: n-butanol > n-hexanol > n-octanol. The kinetics of polymerization slows down in the presence of the alcohol. With the alcohol, the molar masses increase, but no particular trend was noticed on particle size of the lattices. However, by changing the surfactant counter-ion to chloride, alcohol effects on the kinetics almost vanish. Possible explanations to these results are given here. To cite this article: J.E. Puig et al., C. R. Chimie 6 (2003).     

Effect of the carbon dioxide modifier on the lipid composition of wool wax extracted from raw wool

Wool wax or lanolin is a unique substance secreted by sheep and forms a natural protective coating on wool fibres. It is widely used in pharmaceutical and cosmetic formulations. However, different systems of wool wax recovery from scouring liquour provide a dark impurified greasy product. This product has a lipid composition that differs from the wool wax present on wool fibres. The wool wax extraction method from raw wool with pressurised CO₂ and different modifiers at constant pressure and temperature was studied. Thin-layer chromatography coupled to an automated flame ionisation detection system (TLC/FID) was used to analyse the different lipid classes present in the collected extracts. Moreover, a detailed structural comparison of the cholesteryl esters and hydroxycholesteryl esters was carried out by means of sub-ambient pressure chromatography mass spectrometry in the electron impact and in the ammonia positive chemical ionisation modes. For comparison, qualitative and quantitative analyses of the lanolin extracted in Soxhlet with dichloromethane and commercial cosmetic lanolin were carried out. Differences in the quantity of wool wax extraction and in the lipid composition of different wool wax extracts were detected by changing the modifier polarity.     

In Silico Analysis and In Vitro Characterization of the Bioactive Profile of Three Novel Peptides Identified from 19 kDa α-Zein Sequences of Maize

In this study, we characterized three novel peptides derived from the 19 kDa α-zein, and determined their bioactive profile in vitro and developed a structural model in silico. The peptides, 19ZP1, 19ZP2 and 19ZP3, formed α-helical structures and had positive and negative electrostatic potential surfaces (range of −1 to +1). According to the in silico algorithms, the peptides displayed low probabilities for cytotoxicity (≤0.05%), cell penetration (10–33%) and antioxidant activities (9–12.5%). Instead, they displayed a 40% probability for angiotensin-converting enzyme (ACE) inhibitory activity. For in vitro characterization, peptides were synthesized by solid phase synthesis and tested accordingly. We assumed α-helical structures for 19ZP1 and 19ZP2 under hydrophobic conditions. The peptides displayed antioxidant activity and ACE-inhibitory activity, with 19ZP1 being the most active. Our results highlight that the 19 kDa α-zein sequences could be explored as a source of bioactive peptides, and indicate that in silico approaches are useful to predict peptide bioactivities, but more structural analysis is necessary to obtain more accurate data.     

CpTiCl2-Catalyzed Cross-Coupling between Internal Alkynes and Ketones: A Novel Concept in the Synthesis of Halogenated,Conjugated Dienes

A novel concept for the synthesis of halogenated, conjugated dienes is disclosed: the CpTiCl₂-catalyzed coupling of keto-alkynes, in the presence of Me₃SiBr/Et₃N ⋅ HBr. This reaction provided five-, six-, and seven-membered carbocycles, nitrogenated heterocycles, as well as six-membered oxygenated heterocycles leading to a brominated conjugate diene. These products showed high reactivity in the Diels–Alder, Suzuki, and Sonogashira reactions, giving complex chemical structures in only three steps from the corresponding acyclic keto-alkyne. Hopefully, this strategy will pave the way towards the synthesis of bioactive natural products and new materials.     

Self-degassing SARA ATRP mediated by Na2S2O4 with no external additives

The supplemental activator and reducing agent (SARA) atom transfer radical polymerization (ATRP) mediated by Na₂S₂O₄ in the presence of air, without external deoxygenation or additional oxygen scavengers, is reported for several vinyl monomers: methyl acrylate (MA), n-butyl acrylate (n-BA), methyl methacrylate (MMA), 2-(dimethylamino)ethyl methacrylate (DMAEMA), poly(ethylene glycol) methyl ether acrylate (OEOA), and styrene (Sty). The polymerizations can be conducted in aqueous medium or using organic/water mixtures as solvent, with low concentration of copper, near room temperature. In the absence of any external deoxygenation, several well-defined homopolymers and block copolymers were obtained (Ð < 1.3). The evolution of the oxygen concentration during the polymerizations was monitored with an optical oxygen sensor. The consumption of oxygen prior polymerization in ethanol/water mixtures was attributed to the combined presence of Na₂S₂O₄ and alkyl halide initiator, which led to a lower initiation efficiency (I_eff). This could be overcome by decreasing the headspace volume of the reaction. The system reported exhibited the potential to be scalable, which is very relevant from an industrial standpoint. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 145–153     

Stability of triglyceride liquid films on hydrophilic and hydrophobic glasses

Wetting and dewetting of solid surfaces by oily fluids were investigated in terms of the stability of the liquid film formed between an air bubble and the solid surface. With the objective of understanding how molecules with low polarity but relatively complex molecular structure behave at the solid/liquid interface, three liquid triglycerides with different chain length and saturation were chosen, namely, tributyrin, tricaprylin, and triolein. Tributyrin and tricaprylin exist in milkfat while triolein is present in vegetable oils. The stability of the liquid films may be inferred from the shape of the disjoining pressure isotherms, which represent the dependence of the disjoining pressure on the film thickness. Disjoining pressure isotherms for films of the three triglycerides on hydrophilic and hydrophobic glasses were obtained using a recently developed apparatus, based on the interferometric technique. The experimental curves are compared with the theoretical predictions of London-Hamaker. The deviations between theory and experiment are interpreted in terms of a structural component of the disjoining pressure. All triglycerides form metastable films on both hydrophilic and hydrophobic glasses which means that for disjoining pressures higher than a critical value, pi(c), a wetting transition occurs and the film ruptures. The mechanisms for film rupture are discussed and a correlation between film stability and the apolar (Lifshitz-van der Waals) and the polar components of the spreading coefficient is proposed.     

1H and 13C assignments of cyclo[N-(Lys-Phe)-Orn-Val], a semicyclic imide tetrapeptide from Burkholderia cepacia

The rhizobacteria Burkholderia cepacia biosynthesized the new tetrapeptide Cyclo[N-(Lys-Phe)-Orn-Val] (1), a 2,5-diketopiperazine, and the known siderophore azurechelin (salicylic acid). The structure of 1 was established by means of IR, UV, 1H and 13C NMR, double dimension experiments and MS.     

A simple light-emitted diode-induced fluorescence detector using optical fibers and a charged coupled device for direct and indirect capillary electrophoresis methods

We constructed a simple fluorescence detector for both direct and indirect CE methods using a blue light-emitted diode (470 nm) as excitation source, a bifurcated optical fiber as a waveguide, and a CCD camera as a detector. The connection of all the components is fairly easy even for nonexperts and the use of a CCD camera improves the applicability of this detector compared to the others using PMTs because it permits the recording of 2-D electropherograms or phosphorescence measurements. This detector provides a compact, low cost, and rapid system for the determination of native fluorescence compounds which have high quantum yields by CE with direct fluorescence detection, showing an LOD of 2.6 x 10(-6) M for fluorescein; the determination of fluorescence derivative compounds by CE with direct fluorescence detection, showing an LOD of 1.6 x 10(-7) M for FITC-labeled 1,6-diaminohexane; and nonfluorescence compounds by CE with indirect fluorescence detection with an LOD of 2.7 x 10(-6) M for gallic acid.     

Metal-catalyzed oxidation and epoxidation of alpha-hydroxy vinyl and dienyl sulfoxides

Treatment of acyclic alpha-hydroxyalkyl alpha,beta-unsaturated sulfoxides with t-BuOOH/VO(acac)2 results in rapid oxidation to the unsaturated sulfones followed by an unusual regio- and stereoselective epoxidation at the unsaturated sulfones; this methodology has been applied to the preparation of carbohydrate-like fragments.