First enantioselective total synthesis of neocarazostatin B, determination of its absolute configuration and transformation into carquinostatin A

The first enantioselective total synthesis of neocarazostatin B, the determination of its absolute configuration and transformation into carquinostatin A are described.     

Occurrence and chemical speciation analysis of organotin compounds in the environment: A review

Environmental concerns regarding organotin compounds have increased remarkably in the past 20 years, due in large part to the use of these compounds as active components in antifouling paints [mainly tributyltin (TBT)] and pesticide formulations [mainly triphenyltin (TPhT)]. Their direct introduction into the environment, their bio-accumulation and the high toxicity of these compounds towards “non-target” organisms (for example: oysters and mussels) causes environmental and economic damage around the world. As a consequence, the presence and absence of organotin compounds is currently monitored in a range of environmental matrices (e.g., water, sediment and shellfish) to examine the utility of controls meant to regulate the level of contamination as required in some EC Directives and the Water Framework Directive 2000/60/EC. To evaluate the environmental distribution and fate of these compounds and to determine the effectives of legal provisions adopted by a number of countries, a variety of analytical methods have been developed for organotin determination in the environment. Most of these methods include different steps such as extraction, derivatisation and clean up. The aim of the present review is to evaluate the environmental distribution, fate and chemical speciation of organotin compounds in the environment.     

Production of Lactic Acid from Sucrose: Strain Selection, Fermentation, and Kinetic Modeling

Lactic acid is an important product arising from the anaerobic fermentation of sugars. It is used in the pharmaceutical, cosmetic, chemical, and food industries as well as for biodegradable polymer and green solvent production. In this work, several bacterial strains were isolated from industrial ethanol fermentation, and the most efficient strain for lactic acid production was selected. The fermentation was conducted in a batch system under anaerobic conditions for 50 h at a temperature of 34 °C, a pH value of 5.0, and an initial sucrose concentration of 12 g/L using diluted sugarcane molasses. Throughout the process, pulses of molasses were added in order to avoid the cell growth inhibition due to high sugar concentration as well as increased lactic acid concentrations. At the end of the fermentation, about 90% of sucrose was consumed to produce lactic acid and cells. A kinetic model has been developed to simulate the batch lactic acid fermentation results. The data obtained from the fermentation were used for determining the kinetic parameters of the model. The developed model for lactic acid production, growth cell, and sugar consumption simulates the experimental data well.     

A Phase Field Model for Martensitic Transformations

The martensitic transformation is described using a phase field model which is in mathematical terms the regularization of a sharp interface approach. In this work, up to two martensitic orientation variants are considered. The evolution of microstructure is assumed to follow a time dependent Ginzburg-Landau equation. The coupled problem of the mechanical balance equation and the evolution equations is solved using finite elements and an implicit time integration scheme. In this work, the global energy evolution during the martensitic transformation and the influence of external loads on the formation of the different martensitic phases are studied in 2d. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Depth-Sensing Indentation on REBa2Cu3O7?δ Single Crystals Obtained from Xenotime Mineral

A natural mixture of heavy rare-earth oxides extracted from xenotime mineral have been used to prepare large single crystals of the high-temperature REBa₂Cu₃O_7??? superconductor, grown using the CuO?CBaO self-flux method. Its mechanical properties along the ab-plane were characterized using instrumented indentation. Hardness and elastic moduli were measured by the Oliver and Pharr method, which yielded 7.4?±?0.2?GPa and the range 135?C175?GPa at small depths, respectively. Increased loads promote the nucleation of lateral cracks, which reduce hardness and measured elastic modulus, as indicated by instrumented indentation at higher loads. The indentation fracture toughness, estimated by measuring the radial crack length from cube corner indentations at various loads, was found to be 0.8?±?0.2?MPa m^1/2. The observed slip systems of REBa₂Cu₃O_7??? single crystals were [100](001) and [010](001), the same as for YBa₂Cu₃O_7??? single crystals. The initial stages of deformation and fracture in the indentation process were investigated. The hardness and elastic modulus are not strongly modified by the crystallographic orientation in the ab-plane. This was interpreted in terms of resolved shear stresses in the active slip systems. Evidence of cracking along the {100} and {110} planes on the ab-plane was observed. In conclusion, the mechanical properties of REBa₂Cu₃O_7??? single crystals prepared from xenotime are equivalent to those of YBa₂Cu₃O_7??? single crystals from conventional rare-earth oxides.     

Green Synthesis of Spiro Compounds with Potential Anticancer Activity through Knoevenagel/Michael/Cyclization Multicomponent Domino Reactions Organocatalyzed by Ionic Liquid and Microwave-Assisted

In this work a microwave-assisted Knoevenagel/Michael/cyclization multicomponent domino methodology, using ethanol as solvent and the ionic liquid 1-methylimidazolium chloride as catalyst was developed for the synthesis of spiro compounds. The reaction conditions considered ideal were determined from a methodological study varying solvent, catalyst, amount of catalyst, temperature, and heating mode. Finally, the generality of the methodology was evaluated by exploring the scope of the reaction, varying the starting materials (isatin, malononitrile, and barbituric acid). Overall, the twelve spiro compounds were synthesized in good yields (43–98%) and the X-ray structure of compound 1b was obtained. In addition, the in vitro antiproliferative activities of the spirocycles against four types of human cancer cell lines including HCT116 (human colon carcinoma), PC3 (prostate carcinoma), HL60 (promyelocytic leukemia), and SNB19 (astrocytoma) were screened by MTT-based assay. It is noteworthy that spiro compound 1c inhibited the four cell lines tested with the lowest IC₅₀ values: 52.81 µM for HCT116, 74.40 µM for PC3, 101 µM for SNB19, and 49.72 µM for HL60.     

Bioamperometric Systems with Fructose Dehydrogenase From Gluconobacter japonicus for D-Tagatose Monitoring

D-Tagatose is a rare natural sugar, which is promising alternative for popular dietary sweeteners. To optimize and make D-tagatose production more cost-effective, a portable (bio)sensor would be beneficial for D-tagatose quantification in bioreactor media during D-tagatose (bio)synthesis. In this study, a pilot study of D-tagatose quantification by a bioamperometric system is reported. A key feature of the system is usage of fructose dehydrogenase from Gluconobacter japonicus, widely known as a highly fructose-specific enzyme, and 2-arylamino-1,4-benzoquinone derivatives, as electron transfer mediators from the enzyme to carbon electrodes. The system has been validated as biosensor for D-tagatose quantification in the fermentation medium.