DAPNe with micro-capillary separatory chemistry-coupled to MALDI-MS for the analysis of polar and non-polar lipid metabolism in one cell

The cellular metabolome is considered to be a representation of cellular phenotype and cellular response to changes to internal or external events. Methods to expand the coverage of the expansive physiochemical properties that makeup the metabolome currently utilize multi-step extractions and chromatographic separations prior to chemical detection, leading to lengthy analysis times. In this study, a single-step procedure for the extraction and separation of a sample using a micro-capillary as a separatory funnel to achieve analyte partitioning within an organic/aqueous immiscible solvent system is described. The separated analytes are then spotted for MALDI-MS imaging and distribution ratios are calculated. Initially, the method is applied to standard mixtures for proof of partitioning. The extraction of an individual cell is non-reproducible; therefore, a broad chemical analysis of metabolites is necessary and will be illustrated with the one-cell analysis of a single Snu-5 gastric cancer cell taken from a cellular suspension. The method presented here shows a broad partitioning dynamic range as a single-step method for lipid analysis demonstrating a decrease in ion suppression often present in MALDI analysis of lipids.

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Comparison of distillation and ultrasound-assisted extraction methods for the isolation of sensitive aroma compounds from garlic (Allium sativum)

A comparative study of traditional simultaneous distillation extraction (SDE), microwave assisted hydrodistillation extraction (MWHD) and ultrasound-assisted extraction (USE) is presented, for the extraction of essential oils from fresh garlic (Allium sativum) cloves. Each method is evaluated in terms of qualitative and quantitative composition of the isolated essential oil. The highly reactive sulfur molecules of the garlic volatile fraction show variable response to the different isolation methods. The application of ultrasound for the extraction of the essential oil is considered to cause a lesser damage of thermal-sensitive molecules, thus, providing a better approach of the compounds primarily responsible for the characteristic odor and taste of freshly chopped garlic. All heat-involving isolation procedures have been shown to differentiate the volatile-fraction profile as analyzed by GC-MS. Especially when grouping the compounds into cyclic and acyclic, the percentage concentrations drop from 77.4% to 8.7% for the acyclic while that of the cyclic compounds increase from 4.7% to 70.8%. The observed fact may be attributed to the effect of the heat applied, which changes from harsh thermal treatment (SDE) to short time thermal (MWHD) and room-temperature isolation (USE). The use of USE proves to be crucial in order to provide reliable insight into garlic's chemistry.     

Quantum Covers in Quantum Measure Theory

Sorkin’s recent proposal for a realist interpretation of quantum theory, the anhomomorphic logic or coevent approach, is based on the idea of a “quantum measure” on the space of histories. This is a generalisation of the classical measure to one which admits pair-wise interference and satisfies a modified version of the Kolmogorov probability sum rule. In standard measure theory the measure on the base set Ω is normalised to one, which encodes the statement that “Ω happens”. Moreover, the Kolmogorov sum rule implies that the measure of any subset A is strictly positive if and only if A cannot be covered by a countable collection of subsets of zero measure. In quantum measure theory on the other hand, simple examples suffice to demonstrate that this is no longer true. We propose an appropriate generalisation, the quantum cover, which in addition to being a cover of A, satisfies the property that if the quantum measure of A is non-zero then this is also the case for at least one of the elements in the cover. Our work implies a non-triviality result for the coevent interpretation for Ω of finite cardinality, and allows us to cast the Peres-Kochen-Specker theorem in terms of quantum covers.     

Contrary Inferences in Consistent Histories and a Set Selection Criterion

The best developed formulation of closed system quantum theory that handles multiple-time statements, is the consistent (or decoherent) histories approach. The most important weaknesses of the approach is that it gives rise to many different consistent sets, and it has been argued that a complete interpretation should be accompanied with a natural mechanism leading to a (possibly) unique preferred consistent set. The existence of multiple consistent sets becomes more problematic because it allows the existence of contrary inferences [1]. We analyse the conceptual difficulties that arise from the existence of multiple consistent sets and provide a suggestion for a natural set selection criterion. This criterion does not lead to a unique physical consistent set, however it evades the existence of consistent sets with contrary inferences. The criterion is based on the concept of preclusion and the requirement that probability one propositions and their inferences should be non-contextual. The allowed consistent sets turn-out to be compatible with coevents which are the ontology of an alternative, histories based, formulation [2–4].     

A sort synthesis of polyhydroxylated pyrrolizidines via sequential 1,3-dipolar cycloaddition and reductive amination

Polyhydroxylated pyrrolizidines bearing a methyl group at C-5 have been synthesized by 1,3-dipolar cycloaddition of five membered cyclic nitrones with methyl vinyl ketone followed by a N–O reductive cleavage and in situ intramolecular reductive amination. The stereochemistry of the obtained compounds is examined in relation to the reactions mechanism.     

Rapid,quantitative, solvent-free synthesis of medium-ring diaza heterocycles from diketene–acetone adduct and diamines

The synthesis of medium-ring heterocycles remains a challenge largely due to unfavorable energetic factors. We are reporting syntheses of 7–9-member diaza heterocycles that go to completion in 5 min, require no solvents, and are quantitative with the only byproducts being acetone and water. The reaction products could be isolated in pure form by simply placing the mixture under vacuum. The reaction sequence possesses many of the hallmarks of a click reaction.     

Comparison of the thermal behavior and conformational changes in partially and fully hydrated dipalmitoylphosphatidylcholine systems

The temperature dependence of conformational changes for partially and fully hydrated DPPC systems through two physicochemical techniques, namely DSC and Raman spectroscopy, is studied. DSC experiments have shown a different thermal behavior between the two considered systems, indicating the effective role of water in the thermal behavior. A temperature resolution of inter- and intramolecular interactions during the main melting phase transition was achieved by using three different Raman intensity ratios, which confirm that the main phase transition represents a two-stage transition. Van’t Hoff plots for the C–C, C–H, C=O and C₄N⁺ stretching modes, in a temperature range just below the main transition temperature, have been used to compare the thermodynamic parameters extracted by the two physicochemical techniques. The significance of these results can be summarized as follows: (a) DSC and Raman spectroscopy have shown complementary results indicating that DPPC exists in partially or fully hydrated states; (b) thermodynamic parameters ΔΗ and ΔS calculated in both techniques for the two different hydration states of DPPC were in harmony; (c) water more significantly affects the thermal and dynamic properties of fully hydrated DPPC bilayers than of the partially hydrated DPPC; and (d) water disturbs the head-group packing, the alkyl chains interactions and the mesophase region. It appears that the amount of water plays a vital role in the bilayer structure. As more and more extensive studies appear in the literature on biomolecules or drug membrane interactions, this information will be valuable in understanding the role of water in these interactions.