Behaviour of FRP-to-concrete bonded joints

The bond behaviour between FRP (fibre-reinforced polymer) and concrete is a consideration in the design of FRP strengthening mechanisms for structurally deficient or functionally obsolete concrete structures. In the past, a number of empirical models and fracture mechanics based theoretical models have been proposed for determining the effective bond length and bond strength of FRP sheets/plates bonded to concrete. However, these methods have yielded large discrepancies in the predictions of effective bond length and bond strength. In this paper, the results of an experimental investigation into effective bond length and bond strength are presented. Comparison of experiments results with predictions from three empirical and three fracture mechanics based theoretical models shows that a recently proposed fracture mechanics based local-bond slip model provides a conservative prediction of the effective bond length and an accurate prediction of bond strengt

Simultaneous measurement of free and conjugated estrogens in surface water using capillary liquid chromatography tandem mass spectrometry

Given detrimental impacts induced by estrogens at trace level, determination of them is significant but challenging due to their low content in environmental samples and inherent weak ionisation. A modified derivatisation-based methodology was applied for the first time to detect estrogen in free and conjugated forms including some isomers simultaneously using liquid chromatography tandem mass spectrometry (LC-MSn). Derivatisation reaction with previously used 1,2-dimethyl-1H-imidazole-5-sulphonyl chloride allowed significant increase of mass spectrometric signal of analytes and also provided distinctive fragmentation for their confirmation even in complicated matrix. Then satisfactory recovery (>75%) for the majority of analytes was achieved following optimisation of solid phase extraction (SPE) factors. The linearity was validated over a wide concentration with the correlation coefficient around 0.995. The repeatability of this methodology was also confirmed via the intra-day and inter-day precision and was less than 11.73%. Validation of method quantification limits (MQLs) for all chosen estrogens was conducted using 1000 mL surface water, ranging from 7.0 to 132.3 pg L−1. The established methodology was applied to profile presence of targeted estrogens in natural surface water samples. Out of the ten compounds of interest, three free estrogens (E1, E2, E3) and two sulphate estrogens (E1-3S and E2-3S) were found over their MQLs, being in the range of 0.05–0.32 ng L−1

The structure of tagetitoxin

Based on detailed analysis of newly acquired NMR data, we show that the previously revised structure of tagetitoxin is incorrect. A new structure of tagetitoxin is proposed which is consistent with the NMR and MS data

A highly sensitive liquid chromatography electrospray ionization mass spectrometry method for quantification of TMA, TMAO and creatinine in mouse urine

Our method describes the quantification in mouse urine of trimethylamine (TMA), trimethylamine N-oxide (TMAO) and creatinine. The method combines derivatization of TMA, with ethyl bromoacetate, and LC chromatographic separation on an ACE C18 column. The effluent was continuously electrosprayed into the linear ion trap mass spectrometer (LTQ), which operated in selective ion monitoring (SIM) modes set for targeted analytes and their internal standards (IS). All validation parameters were within acceptable ranges of analytical method validation guidelines. Intra- and inter-day assay precision and accuracy coefficients of variation were <3.1%, and recoveries for TMA and TMAO were 97–104%. The method developed uses a two-step procedure. Firstly, TMA and TMAO are analyzed without a purification step using a 5-min gradient cap-LC- SIMs analysis, then creatinine is analyzed using the same experimental conditions. The method is robust, highly sensitive, reproducible and has the high-throughput capability of detecting TMA, TMAO and creatinine at on-column concentrations as low as 28 pg/mL, 115 pg/mL and 1 ng/mL, respectively. The method is suitable for analysis of TMA, TMAO and creatinine in both male and female mouse urine. / The key benefits of the method are: The small sample volume of urine required, which overcomes the difficulties of collecting sufficient volumes of urine at defined times. / No sample pre-treatment is necessary. / The quantification of TMA, TMAO and creatinine using the same cap-LC-MS method

Removal of antibiotics in sand, GAC, GAC sandwich and anthracite/sand biofiltration systems

Drinking water biofiltration offers the possibility of the removal of trace level micropollutants from source water. Sand, granular activated carbon (GAC), GAC sandwich (a layer of GAC loaded in the middle of sand bed), and anthracite-sand dual biofilters were set-up in duplicate at bench-scale to mimic the filtration process in real drinking water treatment works. During the 3-month system operation, removal of five antibiotics (amoxicillin, clarithromycin, oxytetracycline, sulfamethoxazole, and trimethoprim) and overall biofilter performance were evaluated. Natural surface water spiked with a mixture of the target antibiotics was used as feedwater to the biofilters. Results showed that the target antibiotics were substantially removed (>90%) by GAC-associated biofilters and partially removed (≤20%) by sand alone and anthracite-sand biofilters. In particular, the GAC sandwich biofilter exhibited superior performance compared to sand/anthracite biofilter, and the comparisons among all biofilters indicated that both adsorption and biodegradation contributed to the removal of the target antibiotics in the GAC-associated biofilters. Adsorption kinetics showed that sulfamethoxazole fitted with pseudo-first-order adsorption model, while trimethoprim, amoxicillin, oxytetracycline and clarithromycin fitted the pseudo-second-order model. All antibiotics fitted the Langmuir model according to the isotherm experiment. To date, this is the first study evaluating the removal of antibiotics by GAC sandwich biofilters. Overall, this research will provide useful information which can be used for optimising or updating existing biofiltration processes in industry to reduce antibiotic residues from source water

Analysis of transferred fragrance and its forensic implications

Perfumes are widely used by many people in developed countries, and a large number of both men and women wear perfumes on a daily basis. Analysis of perfume trace materials from clothing is not commonly employed within forensic casework, yet as a form of trace evidence it has the potential to provide valuable intelligence. In order to appreciate the value of trace evidence there is a fundamental need for an evidence base that can both offer insight into how a trace material behaves under different scenarios and activities, and from which inferences can be made. With this purpose a gas chromatography-mass spectrometry method for trace analysis of perfumes was developed. This paper presents two different series of experiments that investigate the dynamics of perfume transfer as a factor of perfume ageing time, and as a factor of perfume contact time. Empirical data showed that both perfume ageing time, and perfume contact time play a key role in the number of perfume components transferred. These studies have implication for forensic protocols, specifically for perfume trace evidence collection, analysis, interpretation, and presentation, and there is potentially great value in analysing perfumes from clothing exhibits in forensic enquiries that involve close contact between individuals, such as sexual assaults

Cysteine-to-lysine transfer antibody fragment conjugation

The modification of lysine residues with acylating agents has represented a ubiquitous approach to the construction of antibody conjugates, with the resulting amide bonds being robustly stable and clinically validated. However, the conjugates are highly heterogeneous, due to the presence of numerous lysines on the surface of the protein, and greater control of the sites of conjugation are keenly sought. Here we present a novel approach to achieve the targeted modification of lysines distal to an antibody fragment's binding site, using a disulfide bond as a temporary ‘hook’ to deliver the acylating agent. This cysteine-to-lysine transfer (CLT) methodology offers greatly improved homogeneity of lysine conjugates, whilst retaining the advantages offered by the formation of amide linkages

Convex Polytopes and Quasilattices from the Symplectic Viewpoint

We construct, for each convex polytope, possibly nonrational and nonsimple, a family of compact spaces that are stratified by quasifolds, i.e. each of these spaces is a collection of quasifolds glued together in an suitable way. A quasifold is a space locally modelled on $\R^k$ modulo the action of a discrete, possibly infinite, group. The way strata are glued to each other also involves the action of an (infinite) discrete group. Each stratified space is endowed with a symplectic structure and a moment mapping having the property that its image gives the original polytope back. These spaces may be viewed as a natural generalization of symplectic toric varieties to the nonrational setting.Comment: LaTeX, 29 pages. Revised version: TITLE changed, reorganization of notations and exposition, added remarks and reference

Identification of diverse lipid-binding modes in the groove of zinc α2 glycoprotein reveals its functional versatility

ZAG is a multifunctional glycoprotein with a class I MHC-like protein fold and an α1-α2 lipid-binding groove. The intrinsic ZAG ligand is unknown. Our previous studies showed that ZAG binds the dansylated C11 fatty acid, DAUDA, differently to the boron dipyrromethane C16 fatty acid, C16-BODIPY. Here, the molecular basis for this difference was elucidated. Multi-wavelength analytical ultracentrifugation confirmed that DAUDA and C16-BODIPY individually bind to ZAG and compete for the same binding site. Molecular docking of lipid-binding in the structurally related CD1-proteins predicted nine conserved ligand contact residues in ZAG. Twelve mutants were accordingly created by alanine scanning site directed mutagenesis for characterisation. Mutation of Y12 caused ZAG to misfold. Mutation of K147, R157 and A158 abrogated C16-BODIPY but not DAUDA binding. L69 and T169 increased the fluorescence emission intensity of C16-BODIPY but not of DAUDA compared to wild-type ZAG and showed that C16-BODIPY binds close to T169 and L69. Distance measurements of the crystal structure revealed K147 forms a salt bridge with D83. A range of bioactive bulky lipids including phospholipids and sphingolipids displaced DAUDA from the ZAG binding site but unexpectedly did not displace C16-BODIPY. We conclude that the ZAG α1-α2 groove contains separate but overlapping sites for DAUDA and C16-BODIPY and is involved in binding to a bulkier and wider repertoire of lipids than previously reported. This work suggested that the in vivo activity of ZAG may be dictated by its lipid ligand

LC-MS analysis to determine the biodistribution of a polymer coated ilomastat ocular implant

Ilomastat is a matrix metalloproteinase inhibitor (MMPi) that has shown the potential to inhibit scarring (fibrosis) by mediating healing after injury or surgery. A long lasting ocular implantable pharmaceutical formulation of ilomastat is being developed to mediate the healing process to prevent scarring after glaucoma filtration surgery. The ilomastat implant was coated with water permeable and biocompatible phosphoryl choline polymer (PC1059) displayed extended slow release of ilomastat in vitro and in vivo. The ocular distribution of ilomastat from the implant in rabbits at day 30 post surgery was determined by the extraction of ilomastat and its internal standard marimastat from the ocular tissues, plasma, aqueous humour and vitreous fluid followed by capillary-flow liquid chromatography (cap-LC), the column effluent was directed into a triple quadrupole mass spectrometer operating in product scan mode. The lower limits of quantification (LLOQs) were 0.3 pg/μL for ocular fluids and plasma, and 3 pg/mg for ocular tissues. The extraction recoveries were 90-95% for ilomastat and its internal standard from ocular tissues. Ilomastat was found in ocular fluids and tissues at day 30 after surgery. The level of ilomastat was 18 times higher in the aqueous humour than vitreous humour. The concentration ranking of ilomastat in the ocular tissues was sclera > bleb conjunctiva > conjunctiva (rest of the eye) > cornea. Mass spectrometry analysis to confirm the presence of ilomastat in the ocular tissues and fluids at day 30 post-surgery establishes the extended release of ilomastat can be achieved in vivo, which is crucial information for optimisation of the ilomastat coated implant