Comparison and prediction of the retention in micellar electrokinetic chromatography and microemulsion electrokinetic chromatography for disubstituted benzenes

Retention index (I), rather than retention factor (k), was found to be a more reasonable parameter for comparison of the relative affinity of disubstituted benzenes in MEEKC and MEKC, due to independent of I with the SDS surfactant concentration. MEKC and MEEKC may give similar or different I values, depending on types of moieties. With known I and K_ow for alkylbenzenes as references in MEKC and MEEKC, the values of K_ow for disubstituted benzenes can be estimated from the observed I values, where K_ow is the octanol–water distribution constant. In addition, a group additive approach can be used to predict I for disubstituted benzenes with different moieties from the average observed I for the disubstituted benzenes with same moieties. However, electronic effects and/or intramolecular interaction may result in the different observed I from prediction.     

Convenient synthetic route to a dehydrorotenoid via selective intramolecular aldol condensation of 1,2-diaryl diketone

Synthesis of dehydrorotenoid (1) was successfully achieved via an intramolecular aldol reaction of the corresponding 1,2-diaryl diketone intermediate. The 1,2-diaryl diketone was prepared using a ruthenium-catalyzed oxidation of the corresponding substituted diaryl acetylene. Treatment of this 1,2-diketone with l-proline induced a selective intramolecular aldol condensation reaction, forming the desired benzopyranone over the alternative benzofuran. Deprotection, cyclization, and dehydration gave the target compound in good overall yield.     

Hydrogen bonding in labdane diterpenoids, labda-7,12(E),14-triene-17-oic acid and labda-12(Z),14,17-triene-18-oic acid

Two labdane diterpenoids, labda-7,12(E),14-triene-17-oic acid (1) and labda-12(Z),14,17-triene-18-oic acid (2), C₂₀H₃₀O₂, have been isolated from Croton oblongifolius. Both 1 and 2 crystallized in the monoclinic system, space group C2, with cell dimensions of a = 21.912(1) Å, b = 7.4002(4) Å, c = 11.5079(7) Å, = 101.999(1)^o and a = 21.308(2) Å, b = 11.9067(9) Å, c = 7.5606(6) Å, = 100.763(1)^o, respectively. Compound 1, a rare example of carboxylic group bound to a cyclohexene ring, forms an infinite intermolecular hydrogen-bonded polymer [O1 O2(–x + 1/2, y + 1/2, –z + 2) 2.697(2) Å], whereas molecules of compound 2 are linked to form an asymmetric hydrogen-bonded dimer [O1 O2(–x, y, –z) 2.657(3) Å].     

Encapsulation of octadecane in poly(divinylbenzene-co-methyl methacrylate) using phase inversion emulsification for droplet generation

Octadecane (OD), a heat storage material, was encapsulated into poly(divinylbenzene-co-methyl methacrylate) or P(DVB-co-MMA) matrix via the microsuspension polymerization. The oil droplets were first generated by using the phase inversion emulsification, i.e., adding a sodium dodecyl sulphate (SDS) aqueous solution into an oil phase (monomers:OD = 1:1) containing various concentrations of poly(vinyl alcohol) (PVA). Results showed that 0.1 wt% of SDS in aqueous medium with the additional rate of 2 mL/min and 3 wt% of PVA in oil phase were the optimal conditions for the formation of nonspherical microcapsules. The smallest number- (d_n) and weight- (d_w) average diameters of P(DVB-co-MMA)/OD were, respectively, 3.1 and 3.2 µm with a narrow particle size distribution (d_w/d_n) of 1.02. The latent heats of the encapsulated OD increased with increasing MMA content of microcapsules. The heat of melting (ΔH_m; 223 J/g-OD) and crystallization (ΔH_c; 230 J/g-OD) of the OD encapsulated in microcapsules using DVB:MMA of 30:70 were higher than those using only PDVB (189 and 193 J g-OD for ΔH_m and ΔH_c, respectively) and comparable to those of bulk OD (233 and 234 J/g-OD for ΔH_m and ΔH_c, respectively). The obtained P(DVB-co-MMA)/OD microcapsules would be useful as high performance heat storage material.     

Gas Chromatographic Fingerprint Analysis for the Comparison of Seized Cannabis Samples

Cannabis sativa L. is widely used as recreational illegal drugs. Illicit Cannabis profiling, comparing seized samples, is challenging due to natural Cannabis heterogeneity. The aim of this study was to use GC–FID and GC–MS herbal fingerprints for intra (within)- and inter (between)-location variability evaluation. This study focused on finding an acceptable threshold to link seized samples. Through Pearson correlation-coefficient calculations between intra-location samples, ‘linked’ thresholds were derived using 95% and 99% confidence limits. False negative (FN) and false positive (FP) error rate calculations, aiming at obtaining the lowest possible FP value, were performed for different data pre-treatments. Fingerprint-alignment parameters were optimized using Automated Correlation-Optimized Warping (ACOW) or Design of Experiments (DoE), which presented similar results. Hence, ACOW data, as reference, showed 54% and 65% FP values (95 and 99% confidence, respectively). An additional fourth root normalization pre-treatment provided the best results for both the GC–FID and GC–MS datasets. For GC–FID, which showed the best improved FP error rate, 54 and 65% FP for the reference data decreased to 24 and 32%, respectively, after fourth root transformation. Cross-validation showed FP values similar as the entire calibration set, indicating the representativeness of the thresholds. A noteworthy improvement in discrimination between seized Cannabis samples could be concluded.     

Chiral separation in capillary electrophoresis using dual neutral cyclodextrins: theoretical models of electrophoretic mobility difference and separation selectivity

Simple equations and theoretical models, related to enantioselectivity (kappa) and C, have been developed for prediction of electrophoretic mobility difference (Deltamu) and separation selectivity (alpha) for enantiomers in CE using dual CDs, where alpha and kappa are defined as the ratio of mu and the ratio of binding constant (K) for enantiomers to each CD, respectively, C the CD concentration, and the average K for enantiomers and each CD. Experiments were carried out using dual CDs as beta-CD and dimethyl-beta-cyclodextrin (DM-beta-CD) and test analytes as five pairs of amphetamine drug enantiomers. A change in observed Deltamu and alpha of enantiomers in dual CDs was found to be in excellent agreement with the theoretical models. For example, in comparison with single CD1, dual CDs can enhance Deltamu and alpha up to the maximum value when enantiomers migrate with the same order in CD1 and CD2, and have the value of rho > 1.0, where rho is the enantioselectivity ratio for CD2 to CD1, while worse Deltamu and alpha are obtained for enantiomers with rho < 1.0.     

Influence of water domain formed in hexadecane core inside cross-linked capsule particle on thermal properties for heat storage application

The influence of a water domain formed in n-hexadecane (HD) core in cross-linked polymer capsule particles on the thermal properties of encapsulated HD was studied from the view point of heat storage application. The capsule particles were prepared by micro-suspension polymerization of divinylbenzene at 70 °C utilizing the Self-assembling of Phase-Separated Polymer (SaPSeP) method that the authors proposed. The water domain was not observed for particles taken just after the polymerization and kept at 70 °C, but it was gradually formed with an increase of the size during cooling process from 70 °C to room temperature. In differential scanning calorimetric thermograms, pure HD had a single peak because of solidification (T _s) at 15 °C, and the encapsulated HD containing the water domain had two peaks of T _s1 and T _s2, at 6 and 1 °C, respectively. That is, the encapsulated HD containing the water domain required longer time and lower temperature to complete the solidification than the pure HD, which is negative for its application. However, the lower temperature-side peak at T _s2 gradually disappeared with an increase of capsule particle diameter, which seems to be based on the decrease of total interfacial area between the water domains and encapsulated HD in the capsule particles.     

Electron Transfer from Thioethers

Abstract

Oxidation of thioethers is greatly facilitated by neighboring group participation by carboxylate, alcohol, and thioether moieties.