A Review of Microdialysis Sampling Systems

The most important aspects of microdialysis are a theoretical understanding of the process, the microdialysis membrane and the design of the microdialysis probe including the inner cannula dimensions. Several efforts have been made to theoretically account for the processes that take place during microdialysis. These have been employed to develop optimal sampling conditions so as to increase the applicability of the technique for in situ sampling and as a sample clean-up technique prior to chromatography. On the occasion of Prof. Lo Gorton’s 60th birthday, this review highlights the challenge presented by low analyte recoveries that is the major bottleneck in the wider use of microdialysis. The discussion concludes by considering how to increase analyte recovery through a multiple probe approach or by an increase in recovery in the light of the advantages of nanotechnology. Both approaches could impact on the use of microdialysis as a sampling and sample clean-up technique for liquid chromatography.     

Sample preparation for chromatography: an African perspective

Africa as a continent has its unique challenges for analytical chemists in sample preparation for chromatographic analyses. The areas of agriculture, environment, food and health provide formidable challenges when it comes to method development, for example, drought can result in inadequate supplies of good quality water. The testing of water quality necessitates the development of assay methods that can be employed to not only determine the quantities of pesticides associated with malaria and tsetse fly eradication programmes, but also to monitor mycotoxins or neurotoxins. Urbanisation has also meant that endocrine disruptors such as phthalate esters need to be monitored. This review will profile some of the activities by analytical chemists practising in the African continent, who seek to address some of the challenges in sample preparation for chromatographic analyses.     

Preparation and Characterization of Graphite‐Epoxy Composite Modified with Zinc Hexacyanoferrate and Their Electrochemical Behaviour in Presence of Substituted Anilines

The growth of zinc hexacyanoferrate (ZnHCF) hybrid film on the surface of graphite‐epoxy composite (GEC) electrodes was demonstrated by cyclic voltammetry. Surface morphology of the hybrid film was investigated by using scanning electron microscopy. The effect of the type of monovalent cations on the redox behaviour of hybrid film was also studied. This effect indicated that the radius of the hydrated cation mainly determines the ion permeability of the film.     

Hierarchical Functionalized Polymeric‐Ceramic Coatings on Mg‐Ca Alloys for Biodegradable Implant Applications

Magnesium‐based implants present several advantages for clinical applications, in particular due to their biocompatibility and degradability. However, degradation products can affect negatively the cell activity. In this work, a combined coating strategy to control the implant degradation and cell regulation processes is evaluated, including plasma electrolytic oxidation (PEO) that produces a 13 µm‐thick Ca, P, and Si containing ceramic coating with surface porosity, and breath figures (BF) approach that produces a porous polymeric poly(ε‐caprolactone) surface. The degradation of PCL‐PEO‐coated Mg hierarchical scaffold can be tailored to promote cell adhesion and proliferation into the porous structure. As a result, cell culture can colonize the inner PEO‐ceramic coating structure where higher amount of bioelements are present. The Mg/PEO/PCL/BF scaffolds exhibit equally good or better premyoblast cell adhesion and proliferation compared with Ti CP control. The biological behavior of this new hierarchical functionalized scaffold can improve the implantation success in bone and cardiovascular clinical applications.     

Electrospun Nanofibers Sorbents for Pre-Concentration of 1,1-dichloro-2,2 bis-(4-chlorophenyl)ethylene with Subsequent Desorption by Pressurized Hot Water Extraction

Electrospun polystyrene (PS) nanofibers (130–500 nm) incorporating a potassium salt of imidazole-1-carbodithioate were evaluated as potential sorbents for the pre-concentration of a model organochlorine pesticide; 1,1-dichloro-2,2bis-(4-chlorophenyl)ethylene (DDE). The efficiencies of DDE (0.25–1.0 μg L^?1) adsorption by the nanofiber sorbent followed by desorption employing pressurized hot water extraction (PHWE) were investigated and monitored using gas chromatography with electron capture detection (GC-ECD). Parameters such as time, temperature and pressure of extraction, sample volume, DDE concentration and sorbent mass were optimized. The maximum adsorption of DDE (0.50 μg L^?1) on electrospun PS and carbodithioate incorporated PS nanofibers was at 43.7 and 94.6%, respectively, in 20 min. Incorporation of carbodithiote doubled the adsorption efficiency of PS and achieved LOD of 0.000234 μg L^?1 for DDE. The optimal DDE desorption on the PHWE system was 93.8% in 10 min. It would seem that the use of electrospun nanofibers as sorbent material with subsequent desorption by PHWE has great potential and thus warrants further investigations. This approach as it uses water as an extraction solvent for an organochlorine pesticide provides an opportunity to eliminate organic solvents, especially for procedures aimed at monitoring organic pollutants in the environment.     

Thermal and odd–even behaviour in a homologous series of lithium n-alkanoates

Thermotropic phase transition temperatures, enthalpies and entropies of phase changes and odd–even alternation, in a homologous series of anhydrous lithium n-alkanoates, LiC_nH_2n?1O₂ (LiC_8–19 inclusive), have been investigated by differential scanning calorimetry (d.s.c.), hot stage polarizing microscopy and solid state ¹³C NMR spectroscopy. The number of phases observed, between the room temperature microcrystalline solid and isotropic melt, shows a clear dependence on chain length. For LiC_8–13, only one intermediate lamellar II crystalline phase is observed. For LiC_14–19, a lamellar II and high temperature phase are evident. The high temperature phase is characterized by pre-melting and disordering of hydrocarbon chains as they change from nearly all-trans to one with increased gauche conformers. It is probably a solid rotator phase. Odd–even alternation in melting temperature, density and some thermodynamic data result from the relative distance between methyl groups, from opposite layers in a bi-layer. Molecular models indicate that the methyl groups in odd chains are more favourably orientated which lead to a more energetically favoured staggered conformer. As a consequence, the methyl groups, for odd chains, are in closer proximity than even chains. This subtle change in the molecular lattice could account for the presence of polymorphic structures on cooling from the melt.     

Electrochemical Behavior of a Glassy Carbon Electrode Chemically Modified with Nickel Pentacyanonitrosylferrate in Presence of Sulfur Compounds

The glassy carbon electrode was modified with a nickel pentacyanonitrosylferrate film by electrodeposition of Ni and subsequent derivatization with NaPCNF. The film was characterized by XPS and electrochemical methods. Cyclic voltammetry of the NiPCNF onto the GC shows a redox couple (Fe^III/Fe^II) with E°′ of 538 mV (I_pa/I_pc around 1) and ΔE_p of 93 mV in 0.5 mol L^?1 KNO₃, with a diffusion‐controlled process. There was a decrease of anodic peak currents of the film in the presence of sulfide and 2‐propanethiol due to a precipitation reaction on the film surface by nucleophilic attack.     

Hybrid system of nickel<Emphasis Type="Bold">–</Emphasis>cobalt hydroxide on carbonised natural cellulose materials for supercapacitors

Advanced carbon materials formed from abundant biomass are an exciting and promising class for energy devices due to the clear advantages of low cost, sustainability and good physical and electrochemical properties. However, these materials typically do not compete well with their metal functionalised counterparts. In this work, we demonstrate that xCo(OH)₂–(1?x)Ni(OH)₂ with various Ni:Co ratios can be deposited onto biomass-derived carbon to make a hybrid inorganic-carbon electrode with tuneable physical features and electrochemical performance. These features were tuned by adjusting the Ni:Co ratio within precursor solutions. The electrodes had shown a capacitance ranging from 780.7 to 2041 F g^?1, which is very close to the theoretical value for Ni(OH)₂ (2365 F g^?1). A hypothesis is presented to help explain this performance for a modified, biomass-derived carbon electrode.     

Penetration of mercury-adsorbed phospholipid monolayers by polynuclear aromatic hydrocarbons

The penetration of phospholipid monolayers (dioleoyl lecithin) adsorbed on mercury by polynuclear aromatic hydrocarbons (PAH) is described. The PAH studied were anthracene, phenanthrene, pyrene, benzo[a]anthracene, fluoranthene and perylene. The penetration is monitored by measuring the differential capacitance of the monolayer; the uptake of PAH causes a potential shift (up to ?0.25 V) in the cathodic capacitance peaks. This occurs without displacement of the lipid from the mercury. The differential capacitance is measured by out-of-phase (90°) a.c. voltammetry and rapid cyclic voltammetry. The PAH permeate the mercury-adsorbed lipid layers from dilute aqueous solution; the order of affinity is benzo[a]anthracene > fluoranthrene = pyrene > anthracene = phenanthrene. The rates of penetration vary for the different compounds and depend on their water solubility.