Further studies on the synthesis of α-fluoro carbonyl compounds [1]

The trimethylsilyl enol ethers of cycloalkanones and acid esters are converted in high yields (70–90%) to the corresponding α-fluoro carbonyl derivative using XeF₂ in CH₂Cl₂. Non-cyclic α-hydroxy ketones such as ethyl mandelate are efficiently transformed to the α-fluoro product by DAST and by Ishikawa's reagent. Nucleophilic displacement of halogen by fluoride failed in cyclic systems, giving instead, α,β-unsaturated ketones in DMF or CH₃CN (18-crown-6) and 1,2-diones in DMSO, with KF acting as a base. Attempts at DMSO oxidation of I(Br)F adducts failed to give the α-fluoro ketones, but resulted in dehydrohalogenation to the $\text{trans}$-vinyl fluorides.     

Essential Oil Composition and Bioactivity of Two Juniper Species from Bulgaria and Slovakia

Juniperus excelsa M. Bieb and J. sabina L. contain essential oil (EO), while J. sabina also contains podophyllotoxin, which is used as a precursor for anti-cancer drugs. Two studies were conducted. The first assessed the variability in the EO profile and podophyllotoxin concentration of the two junipers, depending on the location and tree gender. The main EO constituents of J. excelsa were α-cedrol, α-limonene and α-pinene, while the constituents in J. sabina were sabinene, terpinen-4-ol, myrtenyl acetate and α-cadinol. The podophyllotoxin yield of 18 J. sabina accessions was 0.07–0.32% (w/w), but this was not found in any of the J. excelsa accessions. The second study assessed the effect of hydrodistillation (Clevenger apparatus) and steam distillation (in a semi-commercial apparatus) on the EO profile and bioactivity. The extraction type did not significantly alter the EO composition. The EO profiles of the two junipers and their accessions were different and may be of interest to the industry utilizing juniper leaf EO. Breeding and selection programs could be developed with the two junipers (protected species) in order to identify chemotypes with (1) a high EO content and desirable composition, and (2) a high concentration of podophyllotoxin in J. sabina. Such chemotypes could be established as agricultural crops for the commercial production of podophyllotoxin and EO.     

Phytochemical Variability of Essential Oils of Two Balkan Endemic Species: Satureja pilosa Velen. and S. kitaibelii Wierzb. ex Heuff. (Lamiaceae)

Satureja pilosa and S. kitaibelii (Lamiaceae) are Balkan endemic plant species, and the composition of their essential oil (EO) is highly variable. The aim of the present study was to establish: (1) the EO variability in two populations of S. pilosa (the intrapopulation), and (2) the EO variation in S. kitaibelii between nine populations (interpopulation) from Bulgaria and two from Serbia. The EOs of two Satureja species were obtained from aboveground plant parts by hydrodistillation and were analyzed by GC/MS/FID. Overall, the EO yield on the intrapopulation level of S. pilosa varied from 0.54% to 2.15%, while the EO of S. kitaibelii varied from 0.04% to 0.43% (interpopulation). The EO of S. pilosa was found to contain thymol and carvacrol as the main constituents, with other major constituents being p-cymene and γ-terpinene. S. pilosa samples in both studied populations formed six chemical groups. The major constituents (p-cymene, terpinen-4-ol, bornyl acetate, γ-muurolene, endo-borneol, cis-β-ocimene, trans-β-ocimene, carvacrol, α-pinene, thymoquinone, geranial, geranyl acetate, spathulenol, and caryophyllene oxide) of S. kitaibelii EO were considered for grouping the populations into ten chemotypes. The present study is the first report on the interpopulation diversity of S. kitaibelii EOs in Bulgaria. It demonstrated variability of the EOs between and within the populations of S. kitaibelii from Bulgaria. This study identified promising genetic material that could be further propagated and developed into cultivars for commercial production of S. kitaibelii and S. pilosa, thereby reducing the impact of collection on wild populations.     

Resilience in reaction-diffusion systems

Reaction-diffusion systems with zero-flux Neumann boundariesare widely used to model various kinds of interaction in, forexample, the scientific fields of ecology, biology, chemistry,medicine and industry. The physical systems within these fieldsare often known to be (conditionally or unconditionally) resilientwith respect to shocks, disturbances or catastrophies in theimmediate environment. In order to be good mathematical modelsof such situations the reaction-diffusion systems must havethe same resilient or asymptotic behaviour as that of the physicalsituation. Three fundamentally different kinds of reaction termsare usually distinguished according to the entry signs of thereaction Jacobian: mutualism, mixed (predator-prey) interactionand competition. The asymptotic stability (in the Poincarésense) of mutualistic systems has already been studied extensively,but the results cannot be generalized (globally) to the othertwo fundamental types, which are not order-preserving. A partial(local) generalization is, however given here for these twotypes, involving simple Jacobian inequalities and knowledge(often prompted by the underlying physical situation) of invariantsets in solution space. The return time of resilient systemsand the approach rate of asymptotically stable solutions arealso estimated.     

Quantitative assessment of fatigue damage accumulation in wavy slip metals from acoustic harmonic generation

A comprehensive, analytical treatment is presented of the microelastic–plastic nonlinearities resulting from the interaction of a stress perturbation with dislocation substructures and cracks that evolve during cyclic fatigue of wavy slip metals. The interaction is quantified by a material nonlinearity parameter β extracted from acoustic harmonic generation measurements. The contribution to β from the substructures is obtained from the Cantrell model. The contribution to β from cracks is obtained by applying the Paris law to the Nazarov–Sutin crack nonlinearity equation. The nonlinearity parameter resulting from the two contributions is predicted to increase monotonically by hundreds of percent during fatigue from the virgin state to fracture. The increase in β during the first 80–90% fatigue life is dominated by the evolution of dislocation substructures, while the last 10–20% is dominated by crack growth. Application of the model to aluminium alloy 2024-T4 in stress-controlled loading at 276?MPa yields excellent agreement between theory and experiment.