Fast screening of 88 pharmaceutical drugs and metabolites in whole blood by ultrahigh-performance liquid chromatography–tandem mass spectrometry

Forensic investigations involving acute or lethal intoxication, drug-facilitated sexual assault, driving or workplace impairment frequently require the analysis of fresh or postmortem blood samples to check out a wide variety of pharmaceutical and illicit drugs, even after single-dose consumption. A sensitive and selective ultrahigh-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) screening method was developed for fast screening of 88 psychoactive drugs and metabolites in blood samples, including the ones most frequently involved in acute intoxications and forensic investigations in Italy. The new method allows short sample processing and analysis time (the whole procedure can be accomplished in less than 30 min) together with the simultaneous monitoring of a large number of pharmaceutical substances. These features represent crucial factors in the approach of acute intoxications, when the patient requires urgent and appropriate therapy. Blood sample treatment was limited to protein precipitation. Two UHPLC–MS/MS runs in positive and negative electrospray ionization modes were performed. The data were acquired at unit mass resolution in the selected reaction monitoring mode. According to international guidelines, linearity range, precision, trueness, detection and quantification limits, recovery, selectivity, specificity, carryover, and matrix effect phenomena were determined. Despite the limited sample purification and the inherent decreased chance of eliminating any potential interference, the present multiresidue screening method proved extremely effective and sensitive, allowing the detection of all tested drugs, even those belonging to structurally different classes of substances. Moreover, the developed method is easily susceptible to further expansion to encompass more drugs, either new or those becoming important for criminal investigation. This protocol was also applied to the analysis of authentic blood samples collected from victims of various crimes in routine casework, whose relevance in forensic investigations is presented in five cases.     

Investigation of the solubilization of car-emitted Pt,Pd and Rh in street dust and spiked soil samples

A sequential extraction procedure (three-step), proposed by the Standards, Measurements and Testing Programme (formerly BCR) of the European Union, was applied to street dust and spiked soil samples for the determination of PGEs. Analyses were carried out using inductively coupled plasma-mass spectrometry (ICP-MS). The results indicate that up to 5% from Pt, 70% from Pd and 14% from Rh are in mobile forms in street dust. The results for the soil samples spiked with crushed catalytic converter are significantly lower indicating that PGEs are oxidised more efficiently in natural conditions. Additionally Pt and Pd bound to humic acids were investigated.     

Steric and Electronic Effects on the Configurational Stability of Residual Chiral Phosphorus‐Centered Three‐Bladed Propellers: Tris‐aryl Phosphane Oxides

A series of tris‐aryl phosphane oxides existing as residual enantiomers or diastereoisomers with substituents on the aryl rings differing in size and electronic properties were synthesized and characterized. Their electronic properties were evaluated on the basis of their electrochemical oxidation and reduction potentials together with those of the corresponding “blade bromides” (i.e., the naphthalene derivatives displaying the same substitution pattern of the tris‐naphthyl phosphane oxide blades, with a bromo substituent where the phosphorus atom is located) determined by CV. The residual stereoisomeric phosphane oxides were isolated in a stereochemically pure state and were found to be highly configurationally stable at room temperature (stereoisomerization barriers of about 27 kcal mol^?1). The chiroptical properties of the residual stereoisomers and the assignments of absolute configuration are discussed. The configurational stability of residual tris‐aryl phosphane oxides was found to be scarcely influenced by the electronic properties of the substituents present on the aromatic rings constituting the blades, while steric effects play the most relevant role. Detailed theoretical calculations are in agreement with the experimental results and also contribute to a rational interpretation of the stereodynamics of these systems.     

Isoflavonoid-Antibiotic Thin Films Fabricated by MAPLE with Improved Resistance to Microbial Colonization

Staphylococcus aureus (Gram-positive) and Pseudomonas aeruginosa (Gram-negative) bacteria represent major infectious threats in the hospital environment due to their wide distribution, opportunistic behavior, and increasing antibiotic resistance. This study reports on the deposition of polyvinylpyrrolidone/antibiotic/isoflavonoid thin films by the matrix-assisted pulsed laser evaporation (MAPLE) method as anti-adhesion barrier coatings, on biomedical surfaces for improved resistance to microbial colonization. The thin films were characterized by Fourier transform infrared spectroscopy, infrared microscopy, and scanning electron microscopy. In vitro biological assay tests were performed to evaluate the influence of the thin films on the development of biofilms formed by Gram-positive and Gram-negative bacterial strains. In vitro biocompatibility tests were assessed on human endothelial cells examined for up to five days of incubation, via qualitative and quantitative methods. The results of this study revealed that the laser-fabricated coatings are biocompatible and resistant to microbial colonization and biofilm formation, making them successful candidates for biomedical devices and contact surfaces that would otherwise be amenable to contact transmission.     

Smart Coatings Prepared via MAPLE Deposition of Polymer Nanocapsules for Light-Induced Release

Herein, smart coatings based on photo-responsive polymer nanocapsules (NC) and deposited by laser evaporation are presented. These systems combine remotely controllable release and high encapsulation efficiency of nanoparticles with the easy handling and safety of macroscopic substrates. In particular, azobenzene-based NC loaded with active molecules (thyme oil and coumarin 6) were deposited through Matrix-Assisted Pulsed Laser Evaporation (MAPLE) on flat inorganic (KBr) and organic (polyethylene, PE) and 3D (acrylate-based micro-needle array) substrates. SEM analyses highlighted the versatility and performance of MAPLE in the fabrication of the designed smart coatings. DLS analyses, performed on both MAPLE- and drop casting-deposited NC, demonstrated the remarkable adhesion achieved with MAPLE. Finally, thyme oil and coumarin 6 release experiments further demonstrated that MAPLE is a promising technique for the realization of photo-responsive coatings on various substrates.     

Identification of Organic Volatile Markers Associated with Aroma during Maturation of Strawberry Fruits

In the present study, organic volatile markers of three strawberry varieties (Albion, Festival and Frontera) during the maturation process were investigated. Forty metabolites associated with aroma in fresh strawberries were monitored during seven stages of maturation using gas chromatography–mass spectrometry (GC-MS) equipped with headspace-solid phase microextraction (HS-SPME). The data were evaluated using multivariate analysis to observe correlations between the organic volatile compound profile and the seven phenological stages of maturation for each strawberry variety. The dynamic levels of butanoic acid methyl ester, hexanoic acid methyl ester, octylcyclohexane, cyclohexane,1,1,2-trimethyl, linalool, tetradecane, and α-muurolene underwent distinctive changes in concentration during the maturation process. The multivariate analysis also allowed the identification of these compounds as possible volatile markers to measure the maturation of strawberry fruits in all three varieties. These findings highlight the importance of the timing of harvest and maturation stage in each variety to preserve or improve the desirable aromatic characteristics of strawberry fruits.     

Volatiles and Antifungal-Antibacterial-Antiviral Activity of South African Salvia spp. Essential Oils Cultivated in Uniform Conditions

Spontaneous emissions of S. dentata Aiton and S. scabra Thunb., as well as the essential oil (EO) composition of the cited species, together with S. aurea L., were investigated. The chemical profile of the first two species is reported here for the first time. Moreover, in vitro tests were performed to evaluate the antifungal activity of these EOs on Trichophyton mentagrophytes, Microsporum canis, Aspergillus flavus, Aspergillus niger, and Fusarium solani. Secondly, the EO antibacterial activity against Escherichia coli, Staphylococcus aureus, and Staphylococcus pseudointermedius was examined, and their antiviral efficacy against the H1N1 influenza virus was assessed. Leaf volatile organic compounds (VOCs), as well as the EOs obtained from the arial part of Salvia scabra, were characterized by a high percentage of sesquiterpene hydrocarbons (97.8% and 76.6%, respectively), mostly represented by an equal amount of germacrene D (32.8% and 32.7%, respectively). Both leaf and flower spontaneous emissions of S. dentata, as well as the EO composition, showed a prevalence of monoterpenes divided into a more or less equal amount of hydrocarbon and oxygenated compounds. Interestingly, its EO had a non-negligible percentage of oxygenated sesquiterpenes (29.5%). S. aurea EO, on the contrary, was rich in sesquiterpenes, both hydrocarbons and oxygenated compounds (41.5% and 33.5%, respectively). S. dentata EO showed good efficacy (Minimal Inhibitory Concentration (MIC): 0.5%) against M. canis. The tested EOs were not active against E. coli and S. aureus, whereas a low inhibition of S. dentata EO was observed on S. pseudointermedius (MIC = 10%). Once again, S. dentata EO showed a very good H1N1 inhibition; contrariwise, S. aurea EO was completely inactive against this virus. The low quantity of S. scabra EO made it impossible to test its biological activity. S. dentata EO exhibited interesting new perspectives for medicinal and industrial uses.     

Reverse roughening transition in carbon dioxide

We report the observation of a roughening transition in carbon dioxide along the melting line of phase I, which we call reverse as faceting appears with increasing temperature. The characteristics of the transition are discussed in light of modern theories of roughening and the causes of its reverse behavior investigated. We propose that high temperature faceting is related to a pressure-induced increase of the surface stiffness.     

Firing-Induced Microstructural Properties of Quasi-Diamagnetic Carbonate-Based Porous Ceramics: a <Superscript>1</Superscript>H NMR Relaxation Correlation Study

This study deals with the application of two-dimensional proton nuclear magnetic resonance relaxometry (2D ¹H NMR-R) to the characterization of porous ceramics nearly free of magnetic compounds. Different microstructural properties were obtained by firing a diamagnetic mixture of kaolin, calcium, and magnesium carbonate over a wide range of maximum temperatures (600–1100 °C) and firing times at the maximum temperature (soaking times) (0–10 h). The 2D ¹H NMR-R method relies on the correlated measurement of ¹H longitudinal (T ₁) and transverse (T ₂) relaxation times of pore-filling water by which the properties of the interconnected pore space may be investigated. In the absence of significant magnetic susceptibility effect due to para- and ferro-magnetic compounds, the 2D ¹H NMR-R maps allow studying the conjoint effects on pore size distribution and inter-pore coupling due to the variations in both time and temperature of firing. The NMR experiments were performed with a low-field ¹H NMR sensor, which allows non-destructive and in situ analysis. For ceramic specimens fired at 600 and 700 °C, the fraction of smallest pores increases with firing time at the expenses of those with intermediate size. The pore shrinkage occurring at this stage, and likely associated with the transformation of kaolinite in metakaolinite, is affected in a similar way by soaking time and firing temperature, in line with the concept of equivalent firing temperature. At temperatures from 800 to 1100 °C, the structural modifications involving interconnectivity and average pore size are driven primarily by firing temperature and, secondarily, by soaking time. The 2D ¹H NMR-R results are confirmed by more traditional, but destructive, mineralogical, and structural analyses like X-ray powder diffraction, helium pycnometry, mercury intrusion porosimetry, and nitrogen adsorption/desorption method.