Comparison of Coated and Immobilized Chiral Stationary Phases Based on Amylose tris-[(S)-α-Methylbenzylcarbamate] for the HPLC Enantiomer Separation of α-Lipoic Acid and Its Reduced Form

The couple of chiral sulfur compounds α-lipoic acid (ALA)/α-dihydrolipoic acid (DHALA) has attracted considerable attention in recent years owing to its remarkable anti-inflammatory and antioxidant properties. It is well known that the chirality of the C6 plays a key role in determining the biological activity of ALA. The natural occurring (R)-ALA enantiomer is an essential cofactor for key oxidative metabolism enzyme complexes and, after oral administration of the racemic mixture, it shows higher plasma concentration than (S)-ALA. Differently, the in vivo enantioselective action difference between the enantiomers of DHALA has not yet been studied. This lacking is perhaps due to the unavailability of analytical methods capable of determining the enantiomeric composition of biological samples during pharmacokinetic and pharmacodynamic events. In the present work, the direct and baseline enantioresolution of both chiral acids by HPLC on two amylose-derived chiral stationary phases is presented. The proposed chiral enantioselective protocol, therefore, does not require pre- or on-column derivatization. The performance of the coated Chiralpak AS-H CSP and the new immobilized Chiralpak IH-3 CSP, which have the same chiral selector amylose tris-[(S)-α-methylbenzylcarbamate], were compared using conventional normal-phase mobile phases containing ethanol or 2-propanol as alcoholic solvents and a fixed percentage of trifluoroacetic acid. Nonconventional eluents containing dichloromethane, ethyl acetate, and 2-methyltetrahydrofuran as organic cosolvents were applied in the separation of the enantiomers of two carboxylic acids on the immobilized Chiralpak IH-3 CSP. The effect of the column temperature was carefully evaluated in order to improve enantioselectivity. Adequate amounts of enantiomers were isolated by an analytical-size Chiralpak IH-3 column and submitted to chiroptical measurements. The absolute configuration assignment of the isolated enantiomers was determined by a multidisciplinary procedure based on the comparison of the experimental and calculated chiroptical properties.     

Clotting Activity of Polyphosphate‐Functionalized Silica Nanoparticles

We present a silica nanoparticle (SNP) functionalized with polyphosphate (polyP) that accelerates the natural clotting process of the body. SNPs initiate the contact pathway of the blood‐clotting system; short‐chain polyP accelerates the common pathway by the rapid formation of thrombin, which enhances the overall blood‐clotting system, both by accelerating fibrin generation and by facilitating the regulatory anticoagulation mechanisms essential for hemostasis. Analysis of the clotting properties of bare SNPs, bare polyP, and polyP‐functionalized SNPs in plasma demonstrated that the attachment of polyP to SNPs to form polyP‐SNPs creates a substantially enhanced synergistic effect that lowers clotting time and increases thrombin production at low concentrations. PolyP‐SNP even retains its clotting function at ambient temperature. The polyP‐SNP system has the potential to significantly improve trauma‐treatment protocols and outcomes in hospital and prehospital settings.     

Agronomical and chemical characterisation of Thymbra capitata (L.) Cav. biotypes from Sicily,Italy

In this study, the agronomical and chemical characterisation of 13 Sicilian biotypes of Thymbra capitata (L.) Cav., grown under the same agricultural and environmental condition, are reported. The main morpho-productive parameters and quali-quantitative profile of essential oils (EOs) were determined. The EOs were analysed by gas chromatography-flame ionisation detector and gas chromatography–mass spectrometry. Hierarchical cluster analysis and principal component analysis statistical methods were used to group biotypes according to the EOs chemical composition. The EO yield ranged between 4.6 and 8.1 (v/w). A total of 38 EO compounds have been identified. The compounds mostly represented were α-pinene, myrcene, α-terpinene, p-cymene, γ-terpinene, borneol, carvacrol and β-caryophyllene. In all biotypes, the carvacrol (67.4–79.5%) was the main compound, confirming that T. capitata is a carvacrol chemotype. The results showed that all Sicilian Thymbra biotypes have a good adaptation to the climatic conditions of the test environment.     

Characterization of water distribution in bread during storage using magnetic resonance imaging

A soy bread of fully acceptable quality and containing 49% soy ingredients (with or without 5% almond powder) has been recently developed in our laboratory.

An investigation on water distribution and mobility, as probed by proton signal intensity and T₂ magnetic resonance images, during storage was designed to examine possible relations between water states and hindered staling rate upon soy or soy–almond addition.

Water proton distribution throughout soy-containing loaves was found to be very homogeneous in fresh breads with and without almond, with minimal water migration occurring during prolonged storage. In contrast, traditional wheat bread displayed an inhomogeneous water proton population that tended to change (with higher moisture migration towards the outer perimeter of the slice) during storage. Similar results were found for water mobility throughout the loaves, as depicted in T₂ images. On intensity images of all considered bread varieties, the outer perimeter corresponding to the crust exhibited lower signal intensity due to decreased water content. Higher T₂ values were found in the crust of soy breads with and without almond, which were attributed to lipids.

The results indicated that the addition of soy to bread improved the homogeneous distribution of water molecules, which may hinder the staling rate of soy-containing breads. However, incorporation of almond had little effect on the water proton distribution or mobility of soy breads.     

Photophysical properties and photobiological behavior of amodiaquine, primaquine and chloroquine

This article describes the results of a coupled photophysical and photobiological study aimed at understanding the phototoxicity mechanism of the antimalarial drugs amodiaquine (AQ), primaquine (PQ) and chloroquine (CQ). Photophysical experiments were carried out in aqueous solutions by steady-state and time-resolved spectrometric techniques to obtain information on the different decay pathways of the excited states of the drugs and on the transient species formed upon laser irradiation. The results showed that all three drugs possess very low fluorescence quantum yields (10(-2)-10(-4)). Laser flash photolysis experiments proved the occurrence of photoionization processes leading to the formation of a radical cation in all three systems. In the case of AQ the lowest triplet state was also detected. Together with the photophysical properties the photobiological properties of the antimalarial drugs were investigated under UV irradiation, on various biological targets through a series of in vitro assays. Phototoxicity on mouse 3T3 fibroblast and human keratinocyte cell lines NCTC-2544 was detected for PQ and CQ but not for AQ. In particular, PQ- and CQ-induced apoptosis was revealed by the externalization of phosphatidylserine. Furthermore, upon UV irradiation, the drugs caused significant variations of the mitochondrial potential (Deltapsi(mt)) measured by flow cytometry. The photodamages produced by the drugs were also evaluated on proteins, lipids and DNA. The combined approaches were useful in understanding the mechanism of phototoxicity induced by these antimalarial drugs.     

Attenuated Total Reflection-Fourier transform infrared microspectroscopic mapping for the characterisation of paint cross-sections

Paint cross-sections have been analysed using the attenuated total reflection technique combined with FTIR mapping microspectroscopy in order to characterise the nature of the compounds present and map their localisation in the stratigraphy. The study reveals the possibilities offered by micro-ATR devices for obtaining informations about the organic substances employed in painting techniques and in particular their distribution in the different layers, showing a real improvement over traditional analytical investigations in use for the detection of organic substances. Limitations, such as the contamination of the embedding resin and the typical spectral resolution (20 μm) are presented and alternative methods were proposed to obtain better results. In particular, the use of an infrared transparent salt (KBr) as embedding material for the cross-sections is evaluated and seems to be very promising. Furthermore, ATR mapping represent a useful non-destructive analytical technique complementary to others molecular and elemental analyses to be performed afterwards such as SEM-EDX.     

Recent Investigations on Thiocyanate-Free Ruthenium(II) 2,2′-Bipyridyl Complexes for Dye-Sensitized Solar Cells

Three decades ago, dye-sensitized solar cells (DSSCs) emerged as a method for harnessing the energy of the sun and for converting it into electricity. Since then, a lot of work has been devoted to create better global photovoltaic efficiencies and long term stability. Among photosensitizers for DSSCs, thiocyanate-free ruthenium(II) complexes have gained increasing interest due to their better stability compared to conventional thiocyanate-based complexes, such as benchmark dyes N719 and Z907. In this mini-review, two classes of thiocyanate-free Ru(II) complexes are presented: (a) bis-bipyridyl compounds bearing an ancillary cyclometalating bidentate ligand; (b) bipyridyl compounds bearing non-cyclometalating ancillary ligands. The coverage, mainly from 2014 up to now, is not exhaustive, but illustrates the most recent design strategies and photovoltaic properties of these two families of ruthenium(II) dyes.     

Determination of beef tallow in lard through a multidimensional off-line non-aqueous reversed phase-argentation LC method coupled to mass spectrometry

The presence of tallow in lard is not easy to determine, due to the similarity of the composition of these two animal fats, which differ mainly in the distribution of fatty acids (FA) in the three positions of the glycerol molecule. The determination of the composition of the triacylglycerol (TAG) fraction of lard, tallow, and their mixtures was investigated by HPLC in combination with atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The presence of tallow in lard was determined through the study of the sn-POP/sn-PPO ratio by multidimensional HPLC. The off-line bidimensional system was attained through the coupling of non-aqueous reversed phase (NARP)-HPLC and silver ion (Ag)-HPLC. The primary column eluate was fractionated and the fraction containing POP/PPO isomers was injected onto the secondary column, allowing the separation of positional isomers, unresolved in the first dimension. Peak assignment was carried out by combining retention data with APCI-MS spectral information. The fatty acid distribution along the glycerol backbone, determined by Ag-HPLC, was confirmed through diglyceride ion ratios derived from APCI-MS analysis. Method validation was carried out in preliminary applications on standard TAGs. The analytical results obtained show that even a 5% addition of tallow to lard modifies the distribution of positional isomers.     

Growth Performance,Biochemical Composition and Nutrient Recovery Ability of Twelve Microalgae Consortia Isolated from Various Local Organic Wastes Grown on Nano-Filtered Pig Slurry

This paper demonstrated the growth ability of twelve algae-microbial consortia (AC) isolated from organic wastes when a pig slurry-derived wastewater (NFP) was used as growth substrate in autotrophic cultivation. Nutrient recovery, biochemical composition, fatty acid and amino acid profiles of algae consortia were evaluated and compared. Three algae-microbial consortia, i.e., a Chlorella-dominated consortium (AC_1), a Tetradesmus and Synechocystis co-dominated consortium (AC_10), and a Chlorella and Tetradesmus co-dominated consortium (AC_12) were found to have the best growth rates (µ of 0.55 ± 0.04, 0.52 ± 0.06, and 0.58 ± 0.03 d⁻¹, respectively), which made them good candidates for further applications. The ACs showed high carbohydrates and lipid contents but low contents of both proteins and essential amino acids, probably because of the low N concentration of NFP. AC_1 and AC_12 showed optimal ω6:ω3 ratios of 3.1 and 3.6, which make them interesting from a nutritional point of view.