Volume 69, Issue 2

Since the late 1990’s there has been a tremendous growth in literature on ionic liquids (ILs) for a broad range of applications, i.e. catalysis, electrolytes for batteries, in solvolysis of biomass, and also in separation technology. ILs can be applied as solvents for absorption (e.g. of CO2), extractive distillation and extraction processes. That ILs are not magic solvents but have their limitations has also become evident during the past years. Especially the high costs associated with ILs and the lack of experience with these materials in the industrial practice are factors limiting industrial adoption of ILs. The often praised versatility of properties that can be achieved through combination of different cations and anions generates a huge amount of options and makes it difficult to decide where to start when selecting/designing a solvent. This paper focuses on solvent selection/design for applications in extractive distillations and liquid-liquid extractions; also, solvent performance in several specific case studies taken from the open literature is discussed. Important recommendations include: a) make a conceptual process design including the recovery step, regeneration of the IL may be a critical parameter; b) if extractions from aqueous streams are studied, the uptake of water by the IL is an important factor because such co-extracted water is evaporated during the regeneration; c) compare the process with conventional processes to check whether it performs better than the state-of-the-art in industry.

Although various attempts have been made to eliminate doping in sport, hitherto they all have proved futile. Moreover, the main class of substances that jeopardises the fair play rule remains the same - anabolic androgenic steroids (AAS). To date, longitudinal monitoring of the fluctuations of the endogenous steroids content for a given athlete is regardeded as the most effective approach to the detection of AAS abuse. This is based on the fact that the activity of the steroid biosynthesis pathway may undergo significant changes in response to the AAS administration. This paper presents the entire analytical procedure for quantification of steroids crucial for the Athlete Biological Passport (ABP): testosterone, epitestosterone, dehydroepiandrosterone, androsterone, etiocholanolone, 5-α-androstandiol and 5-β-androstandiol. The procedure consists of a four-step sample preparation process followed by analysis by gas chromatography coupled with mass spectrometry. The limits of quantification for the substances listed above were; 0.44 ng mL −1 , 2.07 ng mL −1 , 1.24 ng mL −1 , 62.49 ng mL −1 , 36.20 ng mL −1 , 16.90 ng mL −1 and 14.92 ng mL -1 , respectively. Aqueous solutions containing deuterated and non-deuterated steroids were used for calibration purposes. Subsequently, the validation parameters, e.g., precision, accuracy and recovery were evaluated for each substance individually.

A method was developed for the fabrication of microfluidic paper-based analytical devices (μPAD). This method was based on the silanisation of cellulose in filter paper using alkyltrimethoxysilane coupled with UV radiation. The filter paper sheet was hydrophobised by immersion in an octadecyltrimethoxysilane/heptane (OTMS/heptane) solution (0.25 vol. %) containing 5 vol. % of ethyl acetate (EtOAc). The hydrophobic-hydrophilic contrast was generated on the filter paper after the hydrophobised paper sheet was exposed to UV light with a metal mask creating the desired pattern on the sheet. The exposed area was oxidised to create a hydrophilic area, while the hydrophobic area was protected by the metal mask. The optimal conditions for the fabrication of μPAD were studied; these included ethyl acetate concentration (CEtOAc), immersion time, octadecyltrimethoxysilane concentration (COTMS) and exposure time. This method is costeffective and simple. In addition, different functional groups could be further grafted for various assay purposes. To demonstrate the feasibility of the μPAD in analytical applications, a flowershaped μPAD with eight channels and eight detection units was fabricated and used to determine the nitrite content in pickled vegetables. The nitrite content (124 μg g −1 ) in the sample determined by this method compared favourably with that measured using a standard method (137 μg g −1 ).

Ag + - and Sn 2+ -substituted KSbTeO 6 were prepared by a facile ion-exchange method at ambient temperature. All the samples were characterised by scanning electron microscopy, energydispersive spectra, thermogravimetric analysis, powder X-ray diffraction, Raman spectra and UV-VIS diffuse reflectance spectra. Both Sn 2+ - and Ag + -substituted KSbTeO 6 were crystallised in a cubic lattice with the Fd3̅m space group. The band-gap energy of all the samples was deduced from their UV-VIS diffuse reflectance spectral profiles. The visible light-induced photocatalytic oxidation of the methylene blue (MB) dye was examined in the presence of all the as-prepared materials. The Ag + - and Sn2 + -substituted KSbTeO 6 exhibited a higher photocatalytic activity than the parent KSbTeO 6 in degradation of the MB dye under visible light irradiation.

The pertraction of dysprosium (Dy) through a supported liquid membrane (SLM) system consisting of PTFE (polytetrafluoroethylene) support, D2EHPA (di-2-ethylhexyl phosphoric acid) dissolved in kerosene as membrane solution, and HNO3 solution as stripping solution, was studied. The experiments were designed by the Taguchi method in order to investigate the effects of initial Dy concentration, feed phase pH, different stripping solution concentration, and D2EHPA concentration in the membrane phase on Dy pertraction. Optimal experimental conditions for Dy pertraction were obtained using an analysis of variance (ANOVA) (feed concentration: 130 mg L −1 , D2EHPA concentration: 0.90 M, feed phase pH: 5, stripping phase concentration: 2 M). In addition, the stability of the carrier in terms of its leaching from the membrane support was studied over a period of 6 days and was found to be satisfactory over that time.

Characterization of volatile compounds composition and evaluation of antioxidant properties of bee pollen collected in Lithuania is presented in the paper, which is the first study on pollen of Lithuanian origin to our knowledge. Three polyfloral pollen samples collected by honey bees were analyzed. Characterization of volatile compounds was performed using solid phase microextraction (SPME) and GC-MS. Styrene was predominant in all samples contributing 19.6-27.0 mass %. Sample A distinguished by a high amount of limonene, 9.0 mass %, sample B differed from the rest by a high content of hexanal, 9.3 mass %, and nonanal, 12.3 mass %, while sample C showed the highest content of 1-tridecene, 43.3 mass %. Screening of antioxidant properties was carried out by spectrophotometric methods and liquid chromatography coupled with a post-column 1,1- diphenyl-2-picrylhydrazyl (DPPH) reaction detector and electrochemical detector. Total phenolic and flavonoid contents together with radical scavenging activity in the free radical (DPPH) model system were evaluated in the tested samples. Total phenolic content varied from 24.4 mg g −1 to 38.9 mg g −1 , total flavonoid content was in the range of 7.3-10.0 mg g −1 and radical scavenging activity was found between 30.7 mg g −1 and 34.9 mg g −1 , all data are expressed in rutin equivalents. To process the collected data statistically and classify the bee pollen samples to clusters according to their volatile composition and antioxidant activity, principal component analysis, hierarchical cluster analysis and non-linear discriminant analysis were applied.

Two new interesting entangled structures, namely, [Ni 1.5 (L)(bpy) 2 (H 2 O) 3 ] n ·3nH 2 O (I) and [Cd 3 (L) 2 (bbi) 2 ] n · nH 2 O (II) (where H 3 L is 4-(4-carboxyphenoxy)-phthalic acid, bpy is 4,4´- bipyridine, and bbi is 1,1´-(1,4-butanediyl)bis(imidazole)) have been synthesized and characterized by elemental analysis (EA), infrared spectra (IR), X-ray powder diffraction (XRPD), solid fluorescence and thermogravimetric analysis (TGA). Single-crystal X-ray diffraction analysis revealed that complex I possesses a 3D self-penetrating framework constructed from ladder-like and fishbone-like subunits. Complex II shows a 3D framework of two-fold interpenetration assembled from trinuclear Cd(II) clusters bridged by bbi and L 3− ligands.

As one of the most recently developed membrane separation processes, nanofiltration (NF) has found a number of industrial applications. Ceramic NF membranes are also regarded as the appropriate choice in many applications, due to their higher chemical and physical stability. In this study, the rejection of the chloride ion is investigated using bi-layered γ-Al 2 O 3 -TiO 2 NF membranes based on α-alumina supports. Compression is used in preparation of the supports and sol-gel dip-coating for the top-layer formation. SEM micrographs, XRD, and nitrogen adsorption/desorption isotherms are used for membrane characterisation. The results show that the calcination temperature (600◦C) results in different crystal structures including the brookite phase of TiO 2 , the γ phase of Al 2 O 3 , and a combined phase of aluminium-titanium oxides. The average pore size of the membrane was identified as 1.6 nm using an adsorption/desorption isotherm. The rejection was also studied for the chloride ion, using a cross-flow filtration module. Filtration tests were carried out under different pressures, pH values, and salt concentrations; these showed a smoother behaviour particularly around the isoelectric points (IEPs) due to the dual-layer structure, with the best rejection at pH of approximately 5.

The incorporation of 1 mass % of group VI metals (chromium, molybdenum, and tungsten) into 4 mass % of Ni/MgO catalysts was evaluated for the synthesis of carbon nanotubes (CNTs) by the catalytic chemical vapour deposition of ethylene. All materials were characterised by XRD, surface area, TEM, SEM, Raman spectroscopy, and TGA-DTA. The resulting data demonstrated that the addition of group VI metals improved the surface area and metal dispersion, thereby achieving a remarkable enhancement in catalytic growth activity. Among the metals of group VI, Mo was found to be the most effective promoter for catalysing the CNTs’ growth. From TEM observation, long CNTs with a higher degree of graphitization were obtained on the Ni-Mo/MgO catalyst. TGA and DTA analysis showed that the as-grown CNTs over both Ni-Mo and Ni-W/MgO catalysts exhibited higher thermal stability.

A solvent-free microwave-assisted method for the synthesis of 2-substituted-4,5-di(2-furyl)-1H-imidazoles was developed. Imidazoles with moderate to good yields were produced by condensation of furil with aldehydes over acidic alumina impregnated with ammonium acetate, and they were characterized by FT-IR, HRMS, 1 H NMR and 13 C NMR spectroscopy. Crystal structure of 2,4,5- tri-2-furyl-1H-imidazole (I ) in the orthorhombic space group Pbca was reported, which showed more coplanarity than the reported crystal structure of I in the monoclinic space group Cc. Moreover, their luminescent properties were investigated. It was found that the organic small molecule compounds synthesized possess higher fluorescence quantum efficiency (up to 0.508) in a 0.1 M H 2 SO 4 aqueous solution dissolved in 0.5 mL of CH 3 OH; along with higher stability; also the emission of some compounds synthesized in the solution was sensitive to the polarity of the solvents.

Based on rational design of the transition state analog inhibitors of glycosyltransferases, four model glycomimetics of this type, viz. benzyl 2-thio-α-D-fructofuranoside 1-diethylphosphate (XIa), its β-anomer (XIb), and their ethyl 2-thio analogs - α-anomer (XIIa) and β-anomer (XIIb), were synthesized. In addition, fourteen precursors arising during the synthesis of the desired final model compounds (XI and XII), partially or fully acetylated benzyl and/or ethyl 2-thiofructofuranoside 1-diethyl phosphates, were isolated and characterized with the aim to prepare complete series of glycomimetics, representing donor UDP-GlcNAc designated for biological assays on human GnT’s, viz. GnT-I, Core2GnT, and GnT-V.

New potential transition state analogue inhibitors for N-acetylglucosyltransferases (GnTs) were synthesised. These compounds based on psico- and tagatofuranose (structure) scaffold contained a 2-thiophenyl-1-O-diethylphosphate moiety mimicking the proposed model of the transition state of the enzymatic reaction catalysed by N-acetylglucosyltransferases. The synthesised compounds as well as their precursors were fully characterised by NMR, optical rotation and mass techniques. Anomeric configuration of tagatofuranose derivatives was confirmed by X-ray crystallography. Two types of potential human glycosyltransferase (GnTs) inhibitors representing donor UDP-GlcNAc, assigned for biological assays on human GnTs, were prepared.

The control of HIV infection using antiretroviral agents, especially through targeted delivery, has attracted extensive attention in the last decade. Recently, the vaginal route of administration has become the one most recommended for HIV infections during pregnancy. Efavirenz is a non-nucleoside reverse transcriptase inhibitor anti-HIV drug and its prolonged half-life helps achieve long-term preexposure prophylaxis of HIV-1 infections; it is used as a first-line drug in the treatment using combination therapy. Nanotechnology has received attention as a major area of research into drug delivery in recent years. The aerosol foam formulation is packed under pressure and contains therapeutically active ingredients that are released as foam on the activation of an appropriate valve system. The objective of this study was to develop an aerosol foam formulation of efavirenz nanoparticles for vaginal drug delivery. The nanoparticles were prepared using the emulsion solvent evaporation method and converted into an aerosol foam formulation with the addition of 0.1 mass % of sodium lauryl sulphate as a foaming agent and pressurised with 1,1,1,2-tetrafluroethane. The nanoparticles containing the formulation and aerosol foam formulation were individually characterised by applying various tests such as particle size, zeta potential, pH, viscosity, drug content, entrapment efficiency, drug release studies and release kinetics. The compatibility of the materials was evaluated using FT-IR, polymorphic changes by TGA-DSC and also the morphological properties using SEM study. Foam density, bubble size and collapse time were evaluated in the aerosol-foam formulation; in addition, the drug content and release studies were compared with nanoparticle formulation. The results revealed that the nanoparticle-containing formulation and aerosol formulations were stable and the foam emerged as grade one with fine bubbles and became coarser over time.

A new Schiff base compound, 4-[[(5-hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)methylidene] amino]-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one (I ), was synthesised and characterised by elemental analysis and LC-MS, FTIR and 1H NMR spectra. The photochromic property of the synthesised compound investigated under 365 nm UV irradiation can be observed by solid state absorption and fluorescence spectra. The kinetic study showed that the photochromic reaction was of the pseudo-first-order. The photo-isomerisation was due to photo-induced intermolecular hydrogen bonding, which resulted in enol to keto transformation. The molecular switching behaviour was studied in solution with two inputs in three different systems (OH − and Ag + ), (OH − and Cd 2+ ) and (OH − and Th 4+ ) based on the UV absorption spectra. It exhibited the logic behaviour of XNOR, AND and NOR for Ag + , Cd 2+ and Th 4+ in alkaline media, respectively.

This study proposes changes to the design and evaluation of the CO 2 headspace test, which is used as a simple method for assessment of the complete biodegradability of surfactants. It presents a modified equation for the calculation of biodegradation. It is proposed that the solution of 7 mol L −1 sodium hydroxide commonly used in the process involving alkalinisation of the vial contents be replaced with 15 mol L −1 sodium hydroxide. The use of the higher hydroxide concentration leads to a significant reduction in the value of the blank CO 2 headspace test.

A mixture of stereoisomers of the corn rootworm pheromones was synthesised via the Grignard coupling of protected bromohydrins with alkylcuprate as a key step. The synthesis of 8-methyldec-2- yl propanoate (I ), the northern corn rootworm Diabrotica longicornis Say pheromone, was achieved from pentane-1,5-diol in four steps with an overall yield of 35.1 % and 10-methyltridecan-2-one (II ), the southern corn rootworm Diabrotica undecimpunctata howardi Barber pheromone, was synthesised from octane-1,8-diol as commercially available starting material in five steps with an overall yield of 28.7 %.