Corneal elasticity after oxygen enriched high intensity corneal cross linking assessed using atomic force microscopy.

The purpose of this study was to assess anterior and mid corneal stromal elasticity after high intensity (HI) corneal cross linking (CXL), with and without oxygen (O2) enrichment, and compare these results to conventional CXL. Experiments were performed on 25 pairs of human cadaver eyes, divided into four different groups. Group 1 included corneas that did not receive treatment and served as controls; Group 2 included corneas that received conventional CXL treatment (Dresden Protocol: corneal epithelial debridement, 30 min of riboflavin pretreatment followed by 30 min of exposure to 3 mW/cm2 of ultraviolet light); Group 3 included corneas that received HI CXL treatment (corneal epithelial debridement, 30 min of riboflavin pretreatment followed by 3 min of exposure to 30mW/cm2 of ultraviolet light); and Group 4 included corneas that received the same treatment as Group 3, except that they were enriched with oxygen (4 L per minute pure O2 gas stream) during ultraviolet irradiation. In each group, corneas were subdivided to assess anterior stromal elasticity and mid stromal elasticity. Corneal stromal elasticity was quantified using Atomic Force Microscopy (AFM) through micro-indentation. Young's modulus for the anterior corneal stroma was 14.5 ± 6.0 kPa, 80.7 ± 44.6 kPa, 36.6 ± 10.5 kPa, and 30.6 ± 9.2 kPa, for groups 1, 2, 3 and 4 respectively. Young's modulus for the mid corneal stroma was 5.8 ± 2.0 kPa, 20.7 ± 4.3 kPa, 12.1 ± 4.9 kPa, and 11.7 ± 3.7 kPa, for groups 1, 2, 3 and 4, respectively. In the anterior stromal region, conventional CXL demonstrated a significantly different result from the control, whereas the two HI CXL protocols were not significantly different from the control. There were no statistical differences between the two HI CXL protocols, although only the HI CXL protocol with O2 enrichment was significantly different from the conventional CXL group. In the mid stromal region, once again only conventional CXL demonstrated a significantly different result from the control. There were no statistical differences between the two HI CXL protocols, and both HI CXL protocols were significantly different from the conventional CXL group. Oxygen enriched HI CXL seems to offer similar changes in corneal elasticity when compared to HI CXL without the presence O2. Conventional CXL increases corneal stiffness more than HI CXL both with and without O2 enrichment.

A layered magnetic iron/iron oxide nanoscavenger for the analytical enrichment of ng-L(-1) concentration levels of heavy metals from water.

Magnetically driven separation techniques have received considerable attention in recent decade because of their great potential application. In this study, we investigate the application of an unmodified layered magnetic Fe/Fe(2)O(3) nanoscavenger for the analytical enrichment and determination of sub-parts per billion concentrations of Cd(II), Pb(II), Ni(II), Cr(VI) and As(V) from water samples. The synthesized nanoscavenger was characterized by BET, TGA, XRD and IR and the parameters influencing the extraction and recovery of the preconcentration process were assessed by atomic absorption spectrometry. The possible mechanism of the enrichment of heavy metals on Fe/Fe(2)O(3) was proposed, which involved the dominant adsorption and reduction. The nanoscale size offers large surface area and high reactivity of sorption and reduction reactions. The obtained limits of detection for the metals studied were in the range of 20-125 ng L(-1) and the applicability of the nanomaterial was verified using a real sample matrix. The method is environmentally friendly as only 15 mg of nanoscavenger are used, no organic solvent is required for the extraction and the experiment is performed without the need for filtration or preparation of packed preconcentration columns.

Riboflavin's time-dependent degradation rate induced by ultraviolet A irradiation.

PURPOSE: To evaluate the time-dependent degradation rate of riboflavin after ultraviolet A (UVA) irradiation. METHODS: Two solutions of commercially available riboflavin solution (0.1%) were used; one served as control, while the second was irradiated using UVA light at 370 nm wavelength. Four samples of riboflavin solution were retrieved prior to irradiance and at 1, 5, 15, 30, and 60 minutes after irradiation (group A); at the same time points samples of riboflavin were retrieved from the control solution in order to assess environmental time-induced degradation of riboflavin (group B). All samples were immediately analyzed using liquid chromatograph mass spectrometry to detect riboflavin and its 2 subproducts, lumiflavin (LF) and lumichrome (LC). RESULTS: Mean percentage of riboflavin degradation was 0.0, 5.3, 9.1, 15.3, 20.6, and 33.3 at 0, 1, 5, 15, 30, and 60 minutes after UVA irradiation, respectively (group A). The time-dependent riboflavin degradation was statistically significant (p<0.05), while for group B there was no change in riboflavin concentration at all time intervals. In group A, mean LC concentration demonstrated a gradual concentration increase, reaching 2.386±1.526 ppm after 60 minutes of UVA exposure. CONCLUSIONS: The time-dependent degradation of riboflavin solution is significant, reaching 20.6% after 30 minutes of UVA exposure. It seems that only a small fraction of the overall riboflavin molecules break down since more than 65% remain intact even after 1 hour of UVA irradiation. Control riboflavin solution seems to be stable, as no degradation is evident even after 60 minutes.

Silica-modified magnetic nanoparticles functionalized with cetylpyridinium bromide for the preconcentration of metals after complexation with 8-hydroxyquinoline.

Magnetically driven separation technology has received considerable attention in recent decade for its great potential application. In this study, we investigate the application of silica-modified magnetite nanoparticles (NPs) coated with a cationic surfactant as adsorbent for microextraction and determination of trace amounts of Cu(II), Ni(II), Co(II), Cd(II), Pb(II) and Mn(II) from environmental water samples. The synthesized silica-coated NPs in combination with cetylpyridinium bromide have the ability to adsolubilize the metal ions after complexation with 8-hydroxyquinoline. The NPs bearing the target metals are easily separated from the aqueous solution by applying an external magnetic field and the complexed metals were desorbed using acidic methanol. The desorbed analytes are introduced into the graphite furnace of an atomic absorption spectrometer. The effect of pH, complexing agent, amount of cetylpyridinium bromide, microextraction time, desorption conditions, ionic strength on extraction efficiency of the metal ions are investigated and optimized. Under the optimized conditions, the detection limits for Cu(II), Ni(II), Co(II), Cd(II), Pb(II) and Mn(II) are 4.7, 9.1, 9.5, 2.3, 7.4 and 15.3 ng L(-1), respectively and the relative standard deviations (n=6) are less than 3.6%. The accuracy of the method was evaluated by recovery measurements on the spiked samples and good recoveries (93-113%) with low RSDs were achieved.

A revisit to the retention mechanism of hydrophilic interaction liquid chromatography using model organic compounds.

In this work, a revisit to the retention mechanism of HILIC was attempted to point out critical factors that contribute to the chromatographic regime as well as to bring out subtle details of the relative contribution of partitioning and surface adsorption. In this vein, the retention behaviour of a set of water-soluble vitamins (WSVs) and toluene on three silica based columns was evaluated under varying chromatographic conditions. The data obtained were associated with the hydration degree of the stationary phases and the ability of the organic solvents to disrupt the formation of the water-enriched layer. Moreover, the elution behaviour of toluene at different buffer salt concentrations in the mobile phase, confirmed the preferential partition of salt ions into the stagnant layer, as ACN content was increased. The results from the fitting of partitioning and surface adsorption models indicated differences in the contribution of the two retention mechanisms to both neutral and charged compounds. The occurrence of surface adsorption and the retentivity differences for neutral WSVs depend on the hydration degree and the hydrogen bonding properties of the solutes and the column surface, respectively. For charged solutes experiencing electrostatic repulsion, the contribution of the adsorption mechanism at highly organic mobile phases, emanates from both the weak effect of buffer salt ions on the electrostatic interaction and the strong effect of hydrophilic interactions. On the other hand, the chromatographic retention of electrostatically attracted solutes indicates that the surface adsorption dominates, even at mobile phases rich in water.

Effect of chromatographic parameters and detector settings on the response of HILIC-evaporative light-scattering detection system using experimental design approach and multicriteria optimization methodology.

Four polar compounds, i.e. pantothenic acid, inositol, taurine and caffeine were used as probe solutes in conjunction with chemometric methods to find out meaningful implications of chromatographic conditions and detector settings on the system performance. Putting a premium on the conditions of hydrophilic interaction liquid chromatography (HILIC) and settings of evaporative light-scattering detection (ELSD), we scrutinize the importance of certain factors on signal-to-noise ratio and its variability. The application of a central composite design reveals that caffeine, which sublimes, differentiates from the relatively thermosensitive pantothenic acid as well as from inositol and taurine, which are thermostable, do not sublime and have high melting points. It seems that prior knowledge of solute characteristics is critical to estimate the chromatographic response as a function of chromatographic conditions and detection settings. Reducing the responses to just one by combining them "ad hoc", results in an overall desirability function, which brings out the global optimal chromatographic conditions and detector settings.

Microwave-assisted phase-transfer catalysis for the rapid one-pot methylation and gas chromatographic determination of phenolics.

Microwave-assisted phase-transfer catalysis (PTC) is reported for the first time, for the one-step extraction-derivatization-preconcentration and gas chromatographic determination of twenty phenols and ten phenolic acids. The well established phase-transfer catalytic methylation is largely accelerated when heating is replaced with the "greener" microwave irradiation. The overall procedure was thoroughly optimized and the analytes were determined by GC/MS. The method presented adequate analytical characteristics being more sensitive in analyzing phenols than phenolic acids. The limits of detection without any additional preconcentration steps (e.g. solvent evaporation) were adequate and ranged from 0.4 to 15.8ng/mL while limits of quantitation were between 1.2 and 33.3ng/mL. The method was applied to the determination of phenols, in spiked environmental samples and phenolic acids in aqueous infusions of commercially available pharmaceutical dry plants. The recoveries of fortified composite lake water samples and Mentha spicata aqueous infusions ranged from 89.3% to 117.3% for phenols and 93.3% to 115.2% for phenolic acids.

HILIC separation and quantitation of water-soluble vitamins using diol column.

Hydrophilic interaction liquid-chromatography (HILIC) in conjunction with diode array detection has been applied for the separation of selected-water-soluble vitamins using an end-capped HILIC-diol column. Vitamins with significant biological importance, such as thiamine (B(1)), riboflavin (B(2)), nicotinic acid (B(3)), nicotinamide (B(3)), pyridoxine (B(6)), folic acid (B(9)), cyanocobalamin (B(12)) and ascorbic acid (vitamin C) were simultaneously separated. Chromatographic conditions including type and percentage of organic modifier in the mobile phase, pH, type and concentration of buffer salt and flow rate were investigated. ACN was shown to offer superior separation for the compounds tested as compared to methanol, isopropanol and THF. Isocratic separation and analysis were achieved for six vitamins (B(1), B(2), nicotinic acid/nicotinamide, B(6) and C) at ACN-H(2)O 90:10, containing ammonium acetate 10 mM, triethylamine 20 mM, pH 5.0, using a flow rate of 0.8 mL/min, while a gradient was necessary to resolve a mixture of all eight water-soluble vitamins. The HILIC method was validated and successfully applied to the analysis of a pharmaceutical formulation and an energy drink negating the need for time consuming clean-up steps.

Migration of di(2-ethylhexyl) adipate and acetyltributyl citrate plasticizers from food-grade PVC film into sweetened sesame paste (halawa tehineh): kinetic and penetration study.

Food-grade polyvinyl chloride (PVC) cling-film containing 5.3% (w/w) di(2-ethylhexyl) adipate (DEHA) and 3.0% (w/w) acetyltributyl citrate (ATBC) plasticizers was used to wrap halawa tehineh (halva) samples. Samples were split into two groups and stored at 25+/-1 degrees C. One group was analyzed for DEHA and ATBC content at intervals between 0.5 and 240h of contact (kinetic study) and a second group was cut into slices (1.5mm thick) after 240h of halva/PVC contact and was analyzed for DEHA and ATBC content (penetration study). Determination of both plasticizers was performed using a direct gas chromatographic (GC) method after extraction of DEHA from halva samples. DEHA readily migrated into halva samples: the equilibrium amount of DEHA in halva (3.31mg/dm(2) film or 81.4mg/kg halva) corresponding to a loss of 54.7% (w/w) DEHA from PVC film. This value is slightly higher than the limit of 3mg/dm(2) of film surface set by the European Union for DEHA. The equilibrium amount of ATBC in halva was 1.46mg/dm(2) (36.1mg/kg) corresponding to a loss of 42.7% ATBC from PVC film. With regard to the penetration of both placticizers into halva samples, migration of DEHA was detectable up to the 7th slice beneath the surface of halva (total depth 10.5mm) while the migration of ATBC was detectable up to the 5th slice (total depth 7.5mm).