UVA and UVB Photoprotective Capabilities of Topical Formulations Containing Mycosporine-like Amino Acids (MAAs) through Different Biological Effective Protection Factors (BEPFs).

The safety and stability of synthetic UV-filters and the procedures for evaluating the photoprotective capability of commercial sunscreens are under continuous review. The influence of pH and temperature stressors on the stability of certain Mycosporine-like amino acids (MAAs) isolated at high purity levels was examined. MAAs were highly stable at room temperature during 24 h at pH 4.5⁻8.5. At 50 °C, MAAs showed instability at pH 10.5 while at 85 °C, progressive disappearances were observed for MAAs through the studied pH range. In alkaline conditions, their degradation was much faster. Mycosporine-serinol and porphyra-334 (+shinorine) were the most stable MAAs under the conditions tested. They were included in four cosmetically stable topical sunscreens, of which the Sun Protection Factor (SPF) and other Biological Effective Protection Factors (BEPFs) were calculated. The formulation containing these MAAs showed similar SPF and UVB-BEPFs values as those of the reference sunscreen, composed of synthetic UV absorbing filters in similar percentages, while UVA-BEPFs values were slightly lower. Current in vitro data strongly suggest that MAAs, as natural and safe UV-absorbing and antioxidant compounds, have high potential for protection against the diverse harmful effects of solar UV radiation. In addition, novel complementary in vitro tests for evaluation of commercial sunscreens efficacy are proposed.

New Sources of Calcium (Chicken Eggshells, Chelates) - Preparation of Raw Material and Tablets.

BACKGROUND: There are many calcium supplements available in the market, especially those containing calcium in the form of carbonate, which unfortunately is not absorbed by the body to a sufficient degree. METHOD: Therefore, an attempt was made to prepare new sources of calcium, consuming the chicken eggshells as natural raw materials, which were used in preparation of tablets containing calcium carbonate and calcium citrate as well as tablets with calcium carbonate and calcium bisglycinate. The influence of raw material properties on the pharmaceutical availability of calcium from the obtained tablets was investigated. RESULTS: Based on the obtained calcium release profiles from the prepared tablets, it was found that the optimal source of calcium is a preparation containing calcium from chicken eggshells. It was found that both chicken eggshells and calcium bisglycinate (chelate) may be new, prospective sources of calcium. Calcium citrate prepared using eggshells as starting materials and bisglycinate is completely released within no more than 150 minutes. CONCLUSION: In turn, calcium carbonate added to calcium bisglycinate statistically significantly prolonges the release of calcium ions to 4 hours.

Surrogates for herbicide removal in stormwater biofilters.

Real time monitoring of suitable surrogate parameters are critical to the validation of any water treatment processes, and is of particularly high importance for validation of natural stormwater treatment systems. In this study, potential surrogates for herbicide removal in stormwater biofilters (also known as stormwater bio-retention or rain-gardens) were assessed using field challenge tests and matched laboratory column experiments. Differential UV absorbance at 254mn (ΔUVA254), total phosphorus (ΔTP), dissolved phosphorus (ΔDP), total nitrogen (ΔTN), ammonia (ΔNH3), nitrate and nitrite (ΔNO3+NO2), dissolved organic carbon (ΔDOC) and total suspended solids (ΔTSS) were compared with glyphosate, atrazine, simazine and prometryn removal rates. The influence of different challenge conditions on the performance of each surrogate was studied. Differential TP was significantly and linearly related to glyphosate reduction (R(2) = 0.75-0.98, P < 0.01), while ΔTP and ΔUVA254 were linearly correlated (R(2) = 0.44-0.84, P < 0.05) to the reduction of triazines (atrazine, simazine and prometryn) in both field and laboratory tests. The performance of ΔTP and ΔUVA254 as surrogates for herbicides were reliable under normal and challenge dry conditions, but weaker correlations were observed under challenge wet conditions. Of those tested, ΔTP is the most promising surrogate for glyphosate removal and ΔUVA254 is a suitable surrogate for triazines removal in stormwater biofilters.

Reverse osmosis followed by activated carbon filtration for efficient removal of organic micropollutants from river bank filtrate.

Drinking water utilities in Europe are faced with a growing presence of organic micropollutants in their water sources. The aim of this research was to assess the robustness of a drinking water treatment plant equipped with reverse osmosis and subsequent activated carbon filtration for the removal of these pollutants. The total removal efficiency of 47 organic micropollutants was investigated. Results indicated that removal of most organic micropollutants was high for all membranes tested. Some selected micropollutants were less efficiently removed (e.g. the small and polar NDMA and glyphosate, and the more hydrophobic ethylbenzene and napthalene). Very high removal efficiencies for almost all organic micropollutants by the subsequent activated carbon, fed with the permeate stream of the RO element were observed except for the very small and polar NDMA and 1,4-dioxane. RO and subsequent activated carbon filtration are complementary and their combined application results in the removal of a large part of these emerging organic micropollutants. Based on these experiments it can be concluded that the robustness of a proposed treatment scheme for the drinking water treatment plant Engelse Werk is sufficiently guaranteed.

Analysis of phosphorus herbicides by ion-pairing reversed-phase liquid chromatography coupled to inductively coupled plasma mass spectrometry with octapole reaction cell.

A reversed phase ion-pairing high performance liquid chromatographic (RPIP-HPLC) method is developed for the separation of two phosphorus herbicides, Glufosinate and Glyphosate as well as Aminomethylphosphonic acid (AMPA), the major metabolite of Glyphosate. Tetrabutylammonium hydroxide is used as the ion-pairing reagent in conjunction with an ammonium acetate/acetic acid buffering system at pH 4.7. An inductively coupled plasma mass spectrometer (ICP-MS) is coupled to the chromatographic system to detect the herbicides at m/z = 31P. Historically, phosphorus has been recognized as one of the elements difficult to analyze in argon plasma. This is due to its relatively high ionization potential (10.5 eV) as well as the inherent presence of the polyatomic interferences 14N16O1H+ and 15N16O+ overlapping its only isotope at m/z = 31. An octapole reaction cell is utilized to minimize the isobaric polyatomic interferences and to obtain the highest signal-to-background ratio. Detection limits were found to be in the low ppt range (25-32 ng/l). The developed method is successfully applied to the analysis of water samples collected from the Ohio River and spiked with a standard compounds at a level of 20 microg/l.

Synthesis of 2-[4'-(ethylcarbamoyl)phenyl]-N-acetylglycine, the proposed structure for giganticine.

A compound (1) with the structure proposed for giganticine, an antifeedant principle isolated from the root bark of Caloropis gigantea, has been successfully synthesized by two independent methods. Comparison of physical properties and spectroscopic data of 1 with giganticine revealed that they are different compounds. All available evidence suggests that the proposed structure of giganticine is incorrect.

Exclusion and retention of compensatory kosmotropes by HPLC columns.

With water as the elution solvent, zwitterionic solutes and polyols were retained on HPLC columns, more than was water, by totally hydrophobic packing materials. Relative retentions were systematically affected by oxygen functional groups in the packing material, explicable as specific retention of water. Reproducible elution sequences of 20 solutes at a variety of hydrophobic surfaces (aromatic and both long- and short-alkyl aliphatic surfaces) showed there is a general process, consistent with interactions with hydration water at the surface having solvent properties distinct from bulk water. Early eluting solutes included glycine, sarcosine and taurine. Glycine betaine followed both these and N,N-dimethylglycine. The natural betaines propionobetaine and dimethylsulfoniopropionate also preceded glycine betaine. Dimethylsulfoxide was strongly retained, as (to a lesser extent) was proline betaine. Polyols eluted in the sequence sorbitol, trehalose, glycerol. Changes in the chemical nature of the surface or base material affected relative retentions of water and solutes. The presence of hydrogen-bonding functions increased retention of polyols, as well as water, relative to zwitterionic solutes. Specific effects retention, constraining models based on the formation of low-density water.

Glyphosate degradation by immobilized bacteria: laboratory studies showing feasibility for glyphosate removal from waste water.

To evaluate immobilized bacteria technology for the removal of low levels of glyphosate (N-phosphonomethylglycine) from aqueous industrial effluents, microorganisms with glyphosate-degrading activity obtained from a fill and draw enrichment reactor inoculated with activated sludge were first exposed to glyphosate production wastes containing 500-2000 mg glyphosate/L. The microorganisms were then immobilized by adsorption onto a diatomaceous earth biocarrier contained in upflow Plexiglas columns. The columns were aerated, maintained at pH 7.0-8.0, incubated at 25 degrees C, supplemented with NH4NO3 (50 mg/L), and exposed to glyphosate process wastes pumped upflow through the biocarrier. Glyphosate degradation to aminomethylphosphonic acid was initially > 96% for 21 days of operation at flows yielding hydraulic residence times (HRTs) as short as 42 min. Higher flow rate studies showed > 98% removal of 50 mg glyphosate/L from the waste stream could be achieved at a HRT of 23 min. Glyphosate removal of > 99% at a 37-min HRT was achieved under similar conditions with a column inoculated with a pure culture of Pseudomonas sp. strain LBr, a bacterium known to have high glyphosate-degrading activity. After acid shocking (pH 2.8 for 18 h) of a column of immobilized bacteria, glyphosate-degrading activity was regained within 4 days without reinoculation. Although microbial growth and glyphosate degradation were not maintained under low organic nutrient conditions in the laboratory, the low levels of degradable carbon (45-94 mg/L) in the industrial effluent were sufficient to support prolonged glyphosate-degrading activity. The results demonstrated that immobilized bacteria technology is effective in removing low levels of glyphosate in high-volume liquid waste streams.

N-carbamoyl-2-(p-hydroxyphenyl)glycine from leaves of broad bean (Vicia faba L.).

1. dl-2-(p-Hydroxyphenyl)glycine was resolved through the bromocamphorsulphonate to give its d-isomer. The N-carbamoyl derivatives of these amino acids were synthesized. Circular-dichroism studies on these and related compounds, reported in a deposited Annex, helped to establish the optical configuration. 2. N-Carbamoyl-dl-2-(p-hydroxyphenyl)glycine was isolated from broad-bean leaves. It amounted to about 0.1% of the leaf dry matter. Racemization may or may not have occurred during the isolation. There were indications of the same compound in chicory and in savoy cabbage. Under weakly acidic conditions it was converted gradually into 5-(p-hydroxyphenyl)hydantoin. Both these compounds yielded 2-(p-hydroxyphenyl)glycine on acid hydrolysis. 3. The occurrence is discussed of 2-phenylglycine derivatives in Nature and of N-carbamoyl-amino acids and hydantoins in plants. 4. Gradient elution from anion-exchange resin with acetic acid, besides proving useful for the present work, gave useful separations of pyrrolidonecarboxylic acid and of some N-acetyl-amino acids. 5. Supplementary material (Annex 1: details of experimental work other than ultraviolet and circular-dichroism spectra; Annex 2: ultraviolet absorption and circular dichroism of d-2-phenylglycine and some related compounds) has been deposited as Supplementary Publication SUP 50003 at the National Lending Library for Science and Technology, Boston Spa, Yorks. LS23 7BQ, U.K., from whom copies can be obtained on the terms indicated in Biochem. J. (1971), 121, 7.