Assessment of Self-Compacting Concrete Immersed in Acidic Solutions

Ettringite and thaumasite can be found among the deterioration products of cementitious materials exposed to sulfate and hydrochloric attack. The results of a test program to investigate the acid resistance of self-compacting concrete (SCC) and conventional concrete (CC), immersed up to 18 weeks at 20°C in sulfuric and hydrochloric acid solutions, are described. The SCC was prepared with 47% carboniferous limestone powder, as a replacement for cement, and an ordinary portland cement. The CC was prepared with portland cement only. The water-binder ratios of the SCC and CC were 0.36 and 0.46, respectively. The parameter investigated was the time, in weeks, taken to cause 10% mass loss of fully immersed concrete specimens in a 1% solution of sulfuric acid and the same amount of loss in a 1% solution of hydrochloric acid. The investigation indicated that the SCC performed better than the CC in sulfuric solution but was slightly more vulnerable to hydrochloric acid attack compared to CC. The mode of attack between the two solutions was different.

Adsorption of sulfur dioxide on chemically modified natural clinoptilolite. Acid modification

Natural Bulgarian clinoptilolite from the south-eastern Rhodopes mountain was modified through treatment with hydrochloric acid with various normality, both single and repeatedly, as well as through a charring of a preliminary obtained NH4-form. The parameters concerning the uptake of the ion-exchangeable cations (Ca2+, Na+ and K+), as well as the uptake of aluminium from the natural material were calculated on the basis of the chemical contents. The highest extent of cations removal was attained in the case of the treatment with NH4Cl solution, while the highest aluminium deficiency was established in the samples treated by hydrochloric acid solutions with increasing concentration. Sulfur dioxide adsorption on the obtained decationised and dealuminised samples was studied according to the frontal-dynamic method. The parameters of the breakthrough curves, namely breakthrough time, saturation time and some of the statistical moments of the curve distribution, were determined. The dynamic adsorption capacities were also specified. Comparing the momentum values it was established that as a result of the natural zeolite treatment with NH4Cl and with low concentrated acid, the diffusion resistance decreases because of the dominant exchange of the presenting exchangeable cations in the samples with the smaller size protons and because of enlargement of the pores opening. Intensified dealuminisation was observed when more concentrated acid solutions are used. The capacity is enhanced, probably due to an increase in the total pore volume.

Dioxouranium(VI) extraction in microchannels using ionic liquids

The extraction of uranium(VI) from aqueous nitric acid solutions by tributylphosphate {TBP; 30%(v/v)} dissolved in the ionic liquid 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide was investigated. The experiments were performed in a Teflon microchannel of 0.5 mm internal diameter, while the dioxouranium(VI) concentrations in the aqueous and the ionic liquid phases were determined by UV-Vis spectroscopy. The effects of initial nitric acid concentration (0.01-3 M), residence time, and phase flow rate ratio were studied. It was found that, with increasing nitric acid concentration, the percentage of dioxouranium(VI) extracted decreased and then increased again, while the extraction efficiency followed a slightly different trend. Overall mass transfer coefficients varied between 0.049 s and 0.312 s . © 2012 Elsevier B.V. All rights reserved.

Drug Delivery of Aminolevulinic Acid from Topical Formulations Intended for Photodynamic Therapy

Topical photodynamic therapy is used for a variety of malignant and pre-malignant skin disorders, including Bowen's Disease and Superficial Basal Cell Carcinoma. A haem precursor, typically 5-aminolevulinic acid (ALA), acting as a prodrug, is absorbed and converted by the haem biosynthetic pathway to photoactive protoprophyrin IX (PpIX), which accumulates preferentially in rapidly dividing
cells. Cell destruction occurs when PpIx is activated by an intense light source of appropriate wavelength. Topical delivery of ALA avoids the prolonged photosensitivity reactions associated with systemic administration of photosensitisers but its clinical utility is influenced by the tissue penetration characteristics of the drug, its ease of application and the stability of the active agent in the applied dose. This review, therefore, focuses on drug delivery applications for topical, ALA-based PDT. Issues considered in detail include physical and chemical enhancement strategies for tissue penetration of ALA and subsequent intracellular accumulation of PpIX, together with formulation strategies and drug delivery design solutions appropriate to various clinical applications. The fundamental aspects of drug diffusion in
relation to the physicochemical properties of ALA are reviewed and specific consideration is given to the degradation pathways of ALA in formulated systems that, in turn, influence the design of stable topical formulations.

Quantitative surface-enhanced Raman spectroscopy of dipicolinic acid - towards rapid anthrax endospore detection

Dipicolinic acid (DPA) is an excellent marker compound for bacterial spores, including those of Bacillus anthracis ( anthrax). Surface-enhanced Raman spectroscopy (SERS) potentially has the sensitivity and discrimination needed for trace DPA analysis, but mixing DPA solutions with citrate-reduced silver colloid only yielded measurable SERS spectra at much higher (> 80 ppm) concentrations than would be desirable for anthrax detection. Aggregation of the colloid with halide salts eliminated even these small DPA bands but aggregation with Na2SO4(aq) resulted in a remarkable increase in the DPA signals. With sulfate aggregation even 1 ppm solutions gave detectable signals with 10 s accumulation times, which is in the sensitivity range required. Addition of CNS- as an internal standard allowed quantitative DPA analysis, plotting the intensity of the strong DPA 1010 cm(-1) band (normalised to the ca. 2120 cm(-1) CNS- band) against DPA concentration gave a linear calibration (R-2 = 0.986) over the range 0 - 50 ppm DPA. The inclusion of thiocyanate also allows false negatives due to accidental deactivation of the enhancing medium to be detected.

Room Temperature, Electrochemical Generation of Ozone with 50% Current Efficiency in 0.5M Sulfuric Acid at Cell Voltages <3V.

The electrochemical generation of ozone by Ni/Sb-SnO2 anodes immersed in 0.5M H2SO4 was assessed in both flow and recycle systems using the same electrochemical cell. The anodes were found to exhibit current efficiencies of up to 50% for ozone generation under flow conditions at room temperature, with an optimum mole ratio in the precursor solutions of ca. 500:8:3 Sn:Sb:Ni and optimum cell voltage of 2.7V. A comparison of the data obtained under flow and recycle conditions suggests that the presence of ozone in the anolyte inhibits its formation. The minimum electrical energy cost achieved, of 18 kWh kg1 compares favorably with estimated costs for Cold Corona Discharge generally reported in the literature, especially when the very significant advantages of electrochemical ozone generation are taken into account.

Mandelohydroxamic acid as ligand for copper(II) 15-metallacrown-5 lanthanide(III) and copper(II) 15-metallacrown-5 uranyl complexes

The formation of pentanuclear copper(ii) complexes with the mandelohydroxamic ligand was studied in solution by electrospray ionization mass spectrometry (ESI-MS), absorption spectrophotometry, circular dichroism and H-1 NMR spectroscopy. The presence of lanthanide(iii) or uranyl ions is essential for the self-assembly of the 15-metallacrown-5 compounds. The negative mode ESI-MS spectra of solutions containing copper(II), mandelohydroxamic acid and lanthanide(iii) ions (Ln = La, Ce, Nd, Eu, Gd, Dy, Er, Tm, Lu, Y) or uranyl in the ratio 5:5:1 showed only the peaks that could be unambiguously assigned to the following intact molecular ions: {Ln(NO3)(2)[15-MCuIIN(MHA)-5](2-)}(-) and {Ln(NO3)[15-MCCuIIN(MHA)-5](3-)}(-), where MHA represents doubly deprotonated mandelohydroxamic acid. The NMR spectra of the pentanuclear species revealed only one set of peaks indicating a fivefold symmetry of the complex. The pentanuclear complexes synthesized with the enantiomerically pure R- or S-forms of mandelohydroxamic acid ligand, showed circular dichroism spectra which were mirror images of each other. The pentanuclear complex made from the racemic form of the ligand showed no signals in the CD spectrum. The UV/ Vis titration experiments revealed that the order in which the metal salts are added to the solution of the mandelohydroxamic acid ligand is crucial for the formation of metallacrown complexes. The addition of copper(ii) to the solutions containing mandelohydroxamic acid and neodymium(iii) in a 5:1 ratio lead to the formation of a pentanuclear complex in solution. In contrary, titration of lanthanide(iii) salt to the solution containing copper(ii) and mandelohydroxamic acid did not show any evidence for the formation of pentanuclear species. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Characterisation of the Thermal, Spectroscopic and Drug Dissolution Properties of Mefenamic Acid and Polyoxyethylene–Polyoxypropylene Solid Dispersions

The aim of this study was to investigate the solubility of mefenamic acid (MA), a highly cohesive, poorly water-soluble drug in a copolymer of polyoxyethylene–polyoxypropylene (Lutrol F681), and to understand the effect drug polymer solubility has on in vitro dissolution of MA. Solid dispersions (SD) of MA were prepared by a hot melt method, using Lutrol F681 as a thermoplastic polymeric platform. High-speed differential scanning calorimetry (Hyper-DSC), Raman spectroscopy, powder X-ray diffractometry (PXRD) and hot-stage/?uorescence microscopy were used to assess the solubility of the drug in molten and solid polymer. Drug dissolution studies were subsequently conducted on single-phase solid solutions and biphasic SD using phosphate buffer pH 6.8 as dissolution media. Solubility investigations using Hyper-DSC, Raman spectroscopy and hot-stage microscopy suggested MA was soluble in molten Lutrol F681 up to a concentration of 35% (w/w). Conversely, the solubility in the solidstate matrix was limited to<15% (w/w); determined by Raman spectroscopy, PXRD and ?uorescence microscopy. As expected the dissolution properties of MA were signi?cantly in?uenced by the solubility of the drug in the polymer matrix. At a concentration of 10% (w/w) MA (a single phase solid solution) dissolution of MA in phosphate buffer 6.8 was rapid, whereas at a concentration of 50% (w/w) MA (biphasic SD) dissolution was signi?cantly slower. This study has clearly demonstrated the complexity of drug– polymer binary blends and in particular de?ning the solubility of a drug within a polymeric platform. Moreover, this investigation has demonstrated the signi?cant effect drug solubility within a polymeric matrix has upon the in vitro dissolution properties of solid polymer/drug binary blends.

Immunobiosensor detection of domoic acid as a screening test in bivalve molluscs: Comparison with liquid chromatography-based analysis

A rapid and sensitive immuno-based screening method was developed to detect domoic acid (DA) present in extracts of shellfish species using a surface plasmon resonance-based optical biosensor. A rabbit polyclonal antibody raised against DA was mixed with standard or sample extracts and allowed to interact with DA immobilized onto a sensor chip surface. The characterization of the antibody strongly suggested high cross-reactivity with DA and important isomers of the toxin. The binding of this antibody to the sensor chip surface was inhibited in the presence of DA in either standard solutions or sample extracts. The DA chip surface proved to be highly stable, achieving approximately 800 analyses per chip without any loss of surface activity. A single analytical cycle (sample injection, chip regeneration, and system wash) took 10 min to complete. Sample analysis (scallops, mussels, cockles, oysters) was achieved by simple extraction with methanol. These extracts were then filtered and diluted before analysis. Detection limits in the ng/g range were achieved by the assay; however, the assay parameters chosen allowed the test to be performed most accurately at the European Union's official action limit for DA of 20 mu g/g. At this concentration, intra- and interassay variations were measured for a range of shellfish species and ranged from 4.5 to 7.4% and 2.3 to 9.7%, respectively.

Parallel Peptidome and Transcriptome Analyses of Amphibian Skin Secretions Using Archived Frozen Acid-Solvated Samples

Amphibian skin secretions are unique sources of bioactive peptides and their donor species are currently rapidly disappearing from the biosphere. Here, we report that both peptides and polyadenylated mRNAs from skin granular glands remain amenable to study in samples of stimulated skin secretions following their storage in 0.1 % aqueous trifluoroacetic acid at -20 °C for many years. Frozen acidified solutions of toad (Bombina variegata) skin secretions, stored for 12 years, were thawed and samples removed for direct reverse phase HPLC fractionation. Additional samples were removed, snap frozen and lyophilised for construction of cDNA libraries following polyadenylated mRNA capture using magnetic oligo-dT beads and reverse transcription. Using the bombesin and bradykinin peptides found in bombinid toad skin as models, individual variant peptides of each type were located in reverse phase HPLC fractions and their corresponding biosynthetic precursor-encoding mRNA transcripts were cloned from the cDNA library using a RACE PCR strategy. This study illustrates unequivocally that both amphibian skin secretion peptides and their biosynthetic precursor-encoding polyadenylated mRNAs are stable in frozen acid-solvated skin secretion samples for considerable periods of time-a finding that may have fundamental implications in the study of archived materials but also in the wider field of molecular biology.

Phase Equilibria of Binary and Ternary Systems Containing ILs, Dodecane, and Cyclohexanecarboxylic Acid

This paper reports both the binary and ternary phase behavior of ionic liquids for extracting cyclohexanecarboxylic acid (CCA) from dodecane. This system is a model for the extraction of acids representative of naphthenic acids found in crude oils. In order to develop an effective ternary liquid-liquid extraction system the preliminary selection of ionic liquids was based on CCA miscibility and the dodecane immiscibility with selected ILs. A wide range of ILs based on different cations, anions, cation alkyl-chain length, as well as the effect of temperature on the overall fluid phase behavior is reported. Factors such as variation of cation group, anion effect, alkyl-chain length, and temperature all impact the extraction to various degrees. The largest effects were found to be the lipophilicity of the IL cation and the co-ordination ability of the anion. While CCA capacity increased with lipophilicity of the cation, as did the dodecane. Highly coordinating anions such as trifluoroacetate and triflate demonstrated that highly efficient extraction could be obtained producing favorable tie-lines in the ternary phase diagram. Overall, this study demonstrates that ILs can selectively extract acids from hydrocarbon streams and offers possible treatment solutions for problems associated with the processing of high acid crude oils.

Endodontic 'Solutions'. Part 2:An audit comparing current practice in Belfast with UK and Republic of Ireland Dental Schools

Endodontic lubricants, irrigating solutions and medicaments help reduce the microbial load within root canals. Primary and secondary cases involve different microbes. Each'solution'or combinations thereof could play a significant role but no detailed guidelines exist on their use. An audit was undertaken to compare current practice in Belfast Dental School to the others across the UK and Republic of Ireland (ROI). This audit highlighted three main differences between Belfast and other dental schools. Many other institutions utilized other irrigants besides sodium hypochlorite (NaOCl), different intracanal medicaments, including calcium hydroxide, and higher concentrations of NaOCl. Having gathered this information, we ask, 'Is there sufficient evidence to change the endodontic regime currently used at Belfast Dental School?'. Using the findings from the literature review (Part 1), we introduce new evidence-based protocols for primary and secondary cases for use in Belfast Dental School. Clinical Relevance: In the absence of detailed clinical guidelines on the use of endodontic lubricants, irrigants and medicaments in primary and secondary cases, it is important to be aware of current practice in UK and ROI dental schools where dentists and specialists are trained.

Performance Evaluation of Two-Stage Electrokinetic Washing as Soil Remediation Method for Lead Removal using Different Wash Solutions

The study explores the application of a two-stage electrokinetic washing system on remediation of lead (Pb) contaminated soil. The process involved an initial soil washing, followed by an electrokinetic process. The use of electrokinetic process in soil washing not only provided additional driving force for transporting the desorbed Pb away from the soil but also reduced the high usage of wash solution. In this study, the effect of NaNO3, HNO3, citric acid and EDTA as wash solutions on two-stage electrokinetic washing system were evaluated. The results revealed that a two-stage electrokinetic washing process enhanced Pb removal efficiency by 2.52-9.08% and 4.98-20.45% in comparison to a normal electrokinetic process and normal washing process, respectively. Low pH and adequate current were the most important criteria in the removal process as they provided superior desorption and transport properties. The effect of chelating by EDTA was less dominant as it delayed the removal process by forming a transport loop in anode region between Pb ion and complexes. HNO3 was not suitable as wash solution in electrokinetic washing in spite of offering highest removal efficiency as it caused pH fluctuation in the cathode chamber, corroded graphite anode and showed high power consumption. In contrast, citric acid not only yielded high Pb removal efficiency with low power consumption but also maintained a low soil: solution ratio of 1 g: <1 mL, stable pH and electrode integrity. Possible transport mechanisms for Pb under each wash solution are also discussed in this work.