Quantification of 31 illicit and medicinal drugs and metabolites in whole blood by fully automated solid-phase extraction and ultra-performance liquid chromatography–tandem mass spectrometry

An efficient method for analyzing illegal and medicinal drugs in whole blood using fully automated sample preparation and short ultra-high-performance liquid chromatography–tandem mass spectrometry (MS/MS) run time is presented. A selection of 31 drugs, including amphetamines, cocaine, opioids, and benzodiazepines, was used. In order to increase the efficiency of routine analysis, a robotic system based on automated liquid handling and capable of handling all unit operation for sample preparation was built on a Freedom Evo 200 platform with several add-ons from Tecan and third-party vendors. Solid-phase extraction was performed using Strata X-C plates. Extraction time for 96 samples was less than 3 h. Chromatography was performed using an ACQUITY UPLC system (Waters Corporation, Milford, USA). Analytes were separated on a 100 mm?×?2.1 mm, 1.7 μm Acquity UPLC CSH C₁₈ column using a 6.5 min 0.1 % ammonia (25 %) in water/0.1 % ammonia (25 %) in methanol gradient and quantified by MS/MS (Waters Quattro Premier XE) in multiple-reaction monitoring mode. Full validation, including linearity, precision and trueness, matrix effect, ion suppression/enhancement of co-eluting analytes, recovery, and specificity, was performed. The method was employed successfully in the laboratory and used for routine analysis of forensic material. In combination with tetrahydrocannabinol analysis, the method covered 96 % of cases involving driving under the influence of drugs. The manual labor involved in preparing blood samples, solvents, etc., was reduced to a half an hour per batch. The automated sample preparation setup also minimized human exposure to hazardous materials, provided highly improved ergonomics, and eliminated manual pipetting.

Synthesis,characterization and antimicrobial studies on 13-membered-N6-macrocyclic transition metal complexes containing trimethoprim

Asymmetrical macrocyclic complexes of Mn^II, Co^II, Ni^II, Cu^II and Zn^II have been synthesized by the template process using bis(benzil)ethylenediamine as precursor. Bis(benzil)ethylenediamine reacts with transition metal chlorides and trimethoprim in a 1:1:1 molar ratio in methanol to give several solid metal complexes of the general composition [M(L)X₂] (M = Mn^II, Co^II, Ni^II, Cu^II and Zn^II, L = ligand and X = Cl^?). They were characterized by physicochemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral structures. All the complexes are of the [M(L)X₂] type. The shifts of the ν(CN) (azomethine) stretches have been monitored. To find out the donor sites of the ligands, the activity data show that the metal complexes are more potent than the parent ligand. The [M(L)X₂] complexes showed a broad spectrum of antimicrobial activity in vitro against both gram-positive and gram-negative human pathogenic bacterial isolates and the antimicrobial spectrum enhanced only with a combination of metal chlorides and trimethoprim complex. From the results it is imperative that the synthesized macrocyclic [M(L)X₂] complexes exhibit potent broad spectrum antibacterial activity.     

Stereoselective Cycloaddition of Monosubstituted Ketene to a Methyl Glyoxylate- and Threonine-Derived Imine: Synthesis of Optically Pure β-Lactamic α-Amino Ester with High Functionality

The reaction of chloroacetyl chloride and triethylamine with a chiral imine derived from the combination of methyl glyoxylate and protected L-threonine gave two optically active α-amino acid derivatives with a cis-substituted β-lactam skeleton in a 72:28 ratio. The major product is obtained in 59% yield by simple crystallisation.     

A Novel and Cheap Synthesis of Artemisia Ketone1 (3,3,6-Trimethylhepta-L,5-Dien-4-One)

The Sequential dialkylation of dimethylaminoacetonitrile with first methallylchloride and then prenylbromide is performed at room temperature using K₂CO₃ in DMF. Subsequent hudrolysis and isomerisation offord artemisia ketone in 77% overall yield.     

WATER MOVEMENT CAUSED BY SPREADING SURFACTANTS IN UNSATURATED SYSTEMS OF PARTICLES OF NONUNIFORM SIZE

The movement of water originated by the spreading of two surfactants was analyzed in glass beads as well as on soil systems, both of particles of nonuniform size

The higher difference of surface tension produced in the system by 1 -hexadecanol compared to that of 1-tetradecanol led therefore to a higher amount of water moved. Decreased proportion of the smaller sized particles in glass beads system produced a decrease in the total water moved by both surfactants.

Organic matter acted in soil as a second surfactant in glass beads. This effect was compared in glass beads systems once 1-hexadecanol was evenly distributed among the particles as continuous film, which played a role alike that of organic matter in soil and then a second surfactant 1-tetradecanol was added. These additional surfactant effect diminished the difference between initial and final surface tension (surface tension depression) of the system and so the total water moved.

The soil organic matter (1.7%) modified the water movement curve in the presence of low (0.2g) content of 1-hexadecanol, whereas for high content of either alcohol (0.4g) or low content of 1-tetradecanol content (0.2g) the water movement curves were the same     

Synthesis of Insect Sex Pheromones and Their Homologues I. (Z,E)-9, 11-Alkadienyl Acetates

(Z, E)-9, 11-Tetradecadienyl-l-acetate (1), a major component of the sex pheromone of Spodoptera litura (F.), and (Z, E}-9, 11-pentadecadienyl-1-acetate (2) were synthesized by the Wittig reaction between (E)-2-alkenal (3) and the ylid derived from 9-hydroxynonyltriphenylphosphonium bromide (4).     

Densely-packed self-assembled monolayers on gold surfaces from a conformationally constrained helical hexapeptide

A novel hexapeptide was functionalized at the N-terminus by a lipoyl group for binding to gold substrates. Owing to the high content of α-aminoisobutyric acid residues, the peptide adopts a rigid helical conformation despite the shortness of its main chain. Binding of the peptide to gold was investigated by quartz crystal microbalance, cyclic voltammetry, X-ray photoelectron spectroscopy, and scanning tunneling microscopy under ultra-high vacuum conditions. Scanning tunneling microscopy experiments revealed that the peculiar self-assembly properties of this short helical peptide determine the complex morphology of the monolayer, showing ‘stripes’, i.e. peptide aggregates horizontally layered on the gold surface, and ‘holes’, i.e. Au vacancy islands coated by the peptide monolayer.     

Surface functionalization of electro-deposited nickel

A new in situ electrochemical method of functionalizing an oxide-free Ni surface is demonstrated using octanethiol. Initial adsorption results in a multilayer molecular film, which blocks both the hydrogen evolution reaction (HER) and re-oxidation of the Ni by ambient oxygen. However, excess octanethiol can be removed by rinsing with ethanol, leaving behind a monolayer that continues to protect against re-oxidation but gives rise to an unexpected enhancement in the HER, with a greater enhancement for longer film formation times. The presence of an octanethiol monolayer on the surface was confirmed by spectroscopic observation of the CH(2), CH(3) and thiolate groups using infra red spectroscopy, while X-ray photo-electron spectroscopy demonstrated the effectiveness of the thiol layer as a barrier to surface oxidation. The electrochemically prepared octanethiol film impedes oxidation of the Ni in air more effectively than a film formed by immersion in a solution of octanethiol in ethanol.