Passive sampling combined with ecotoxicological and chemical analysis of pharmaceuticals and biocides - evaluation of three Chemcatcher™ configurations

Passive sampling is a tool to monitor the presence and concentrations of micropollutants in the aquatic environment. We investigated the duration of integrative sampling and the effects of flow rate on the performance of three configurations of the Chemcatcher - a sampler for polar organic compounds. Chemcatchers were fitted with Empore™ styrenedivinylbenzene (SDB) XC disks (XC), SDB-RPS disks (RPS) or SDB-RPS disks covered with a polyethersulfone membrane (RPS-PES). Samplers were either exposed to treated sewage effluent for 5 days at various flow rates, or at a single flow rate with overlapping exposures of 3-24 days. Chemical analysis focused on a set of pharmaceuticals and biocides and ecotoxicological analysis measured inhibition of photosystem II in algae. For compounds with log K_OW > 2, both XC and RPS disks respond dynamically to higher flow rates; uptake increased up to five-fold when flow increased from 0.03 to 0.37 m s⁻¹. At a flow rate of 0.13 m s⁻¹ the integrative window of SDB disks approached 6 days for more hydrophobic compounds (log K_OW > 3.5). The RPS-PES configuration was less affected by flow and also showed an extended integrative window (up to 24 days). The membrane causes a lag phase of up to 2.3 days which thwarts a sound interpretation of data from sampling periods of less than 10 days.     

The efficacy of nisin can drastically vary when produced in situ in model cheeses

Nisin, a bacteriocin produced by strains of Lactococcus lactis, has a broad inhibitory effect against Gram-positive bacteria. This study investigated the efficacy of nisin Z against Lactobacillus sakei when produced by a nisin-producing strain L. lactis in model cheeses manufactured with ultrafiltrated milk. These cheeses, containing 0, 4 or 10% of gelatin in their dry matter, were inoculated with both strains. Measurement of Lb. sakei loss of viability was an indirect indicator of nisin in situ efficacy. After 24 h, the loss of viability of Lb. sakei was from 0.73 ± 0.14 to 3.30 ± 0.60 log₁₀ cfu g⁻¹ in the cheeses with 0 and 10% of gelatin, respectively, indicating a better in situ efficacy of nisin when gelatin was incorporated. However, the concentration of nisin produced by Lactococcus was similar (3.5 μg g⁻¹) in all model cheeses when measured using an enzyme-linked immune sorbent assay (ELISA). The growth of Lactococcus was slightly improved when gelatin was incorporated, leading to a higher lactate concentration, which is one of the factors explaining the increased nisin efficacy. These results reinforced previous observations that prediction of nisin efficacy in complex food systems remains difficult.     

A pH‐Based High‐Throughput Assay for Transketolase: Fingerprinting of Substrate Tolerance and Quantitative Kinetics

A pH‐based high‐throughput assay method has been developed for the rapid and reliable measurement of transketolase (TK) activity. The method is based on the decarboxylation of lithium hydroxypyruvate (HPA) as a hydroxyacetyl donor with an aldehyde acceptor, using phenol red as the pH indicator. Upon release of carbon dioxide from HPA, the pH increase in the reaction mixture can be determined photometrically by the color change of the pH indicator. At low buffer concentration (2 mM triethanolamine, pH 7.5), the method is highly sensitive and allows continuous monitoring, for quantitative determination of the kinetic parameters. By using this method, the substrate specificities of the TK enzymes from Escherichia coli and Saccharomyces cerevisiae, as well as two active‐site‐modified variants of the E. coli TK (D469E, H26Y) were evaluated against a panel of substrate analogues; specific activities and kinetic constants could be rapidly determined. Substrate quality indicated by assay determination was substantiated with novel TK applications by using achiral 3‐hydroxypropanal and 4‐hydroxybutanal for preparative synthesis of chiral deoxyketose‐type products. Determination of ee for the latter could be performed by chiral GC analysis, with an unambiguous correlation of the absolute configuration from rotation data. This pH‐based assay method is broadly applicable and allows rapid, sensitive, and reliable screening of the substrate tolerance of known TK enzymes and variants obtained from directed evolution.     

Occurrence and composition of extracellular lipids and polysaccharides in a full-scale membrane bioreactor

The aim of this study was to characterize the polysaccharides and lipid fractions of membrane foulants in a full-scale membrane bioreactor (MBR) treating municipal wastewater. Both of these polymeric compounds are major components of bacterial lipopolysaccharides and are impacting membrane fouling; however most of the data so far have been collected by determining sum parameters rather than the detailed composition of these polymers.Photometric analysis of sugars showed that uronic acids (glucuronic, mannuronic and galacturonic acid) as common units of bacterial polysaccharides accounted for 8% (w/w) of extracellular polymeric substances (EPS) in activated sludge flocs. Further the so-called polysaccharide peak of EPS, with a molecular weight >10 kDa according to size exclusion chromatography, was proven to contain bacterial sugar units as shown by high resolution LC-MS. Interestingly, only traces of uronic acids could be detected in EPS of the membrane fouling layer.A far more dramatic enrichment in the fouling layer was revealed for the lipid fraction of EPS, which was determined as fatty acid methyl esters by GC-MS. The weight percentage of fatty acids in EPS extracted from fouled ultrafiltration membranes was much higher (10%) than in the activated sludge itself (1-3%). The fatty acids accumulated on the membrane fouling layer were obviously not only of microbial origin (C16:0, C18:0) but also derived from the raw wastewater itself (C9:0). Hydrophobic interaction of lipids with the PVDF (polyvinylidene fluoride) membrane material therefore seems a plausible explanation for the observed fouling phenomenon. The results suggest that fatty acids from bacterial lipopolysaccharides as well as from synthetic sources are of much higher relevance to membrane fouling than previously assumed.     

杭州RAFFLES城

杭州Raffles城发展坐落于浙江省省会杭州市的钱塘江边，是嘉德置地继新加坡、上海、北京、成都和巴林之后的第六栋，将零售店、办公楼、住户和酒店设施融于一体，成为新城区的文化地标。     

Analysis of a new type of high pressure homogeniser. A study of the flow pattern

High-pressure homogenisation is a key unit operation used to disrupt fat globules or cells containing intracellular bioproducts (AIChE J. 43(4) (1997) 1100). Modelling and optimisation of a small homogenising unit are often restrained by a lack of information on the flow conditions within the homogeniser valve. A numerical investigation of the flow within such a new homogenising valve, capable to reach pressure as high as (Stansted Fluid Power Ltd, UK) is presented. Results are obtained using the finite-volume technique and a RNG k-ε turbulence model with low Reynolds number near wall treatment conditions. An experimental measurement of the size of the valve gap is presented in order to validate mathematical relations that give valve gap sizes versus homogenising pressure. The modelling results give detailed information on the mechanical stresses and the high shear rates in small disruption valves, and also reveal other phenomena that could not be easily determined experimentally.     

Mechanical behavior of alumina and alumina-feldspar based ceramics in an acetic acid (4%) environment

This study investigates the mechanical properties of alumina-feldspar based ceramics when exposed to an aggressive environment (acetic acid 4%). Alumina ceramics containing different concentrations of feldspar (0%, 1%, 5%, 10%, or 40%) were sintered at either 1300, 1600, or 1700 °C. Flaws (of width 0%, 30%, or 50%) were introduced into the specimens using a saw. Half of these ceramic bodies were exposed to acetic acid. Their flexural strength, K_IC, and porosity were measured and the fractured samples were evaluated using scanning electronic- and optical microscopy. It was found that in the ceramic bodies sintered at 1600 °C, feldspar content up to 10% improved flexural strength and K_IC, and reduced porosities. Generally, it was found that acetic acid had a weakening effect on the flexural strength of samples sintered at 1700 °C but a beneficial effect on K_IC of ceramics sintered at 1600 °C. It was concluded that alumina-based ceramics with feldspar content up to 10% and sintered at higher temperatures would perform better in an aggressive environment similar to oral cavity.     

Überwachung von NSO-Heterocyclen an Teeröl-kontaminierten Standorten

In addition to well-characterized contaminants like homocyclic aromatic hydrocarbons, NSO-heterocyclic hydrocarbons typically occur at creosote-contaminated sites. Despite requirements by the German Federal Ordinance of Soil Protection to monitor NSO-heterocycles, this work has not routinely been done. Within the “KORA” project (“Natural Attenuation: Retention and Degradation Processes Reducing Contaminations in Groundwater and Soil”) funded by the German Federal Ministry of Education and Research, several creosote-contaminated sites were investigated. In conjunction with literature data on toxicity and persistence, priority substances were identified for inclusion in standard measurements for the evaluation of natural attenuation processes. Several analytical methods were developed for the detection and quantification of these compounds.     

Enhanced oral bioavailability of a poorly water soluble drug PNU-91325 by supersaturatable formulations

Supersaturatable cosolvent (S-cosolvent) and supersaturatable self-emulsifying drug delivery systems (S-SEDDS) are designed to incorporate water soluble cellulosic polymers such as hydroxypropyl methylcellulose (HPMC), which may inhibit or retard drug precipitation in vivo. A poorly soluble drug, PNU-91325, was used as a model drug in this study to illustrate this formulation approach. The comparative in vitro studies indicated that the presence of a small amount HPMC in the formulation was critical to achieve a stabilized supersaturated state of PNU-91325 upon mixing with water. An in vivo study was conducted in dogs for assessment of the oral bioavailability of four formulations of PNU-91325. A five-fold higher bioavailability (∼ 60%) was observed from a S-cosolvent formulation containing propylene glycol (PG) + 20 mg/g HPMC as compared to that (∼ 12%) of a neat polyethylene glycol (PEG) 400 formulation. The low bioavailability of the PEG 400 formulation is attributed to the uncontrolled precipitation of PNU-91325 upon dosing, a commonly observed phenomenon with the cosolvent approach. A S-SEDDS formulation composed of 30% w/w Cremophor (surfactant), 9% PEG 400, 5% DMA, 18% Pluronic L44, 20% HPMC, and other minor components showed an oral bioavailability of ∼ 76%, comparable to that of a neat tween formulation (bioavailability: ∼ 68%). The significant improvement of the oral bioavailability of the supersaturatable S-cosolvent and S-SEDDS formulations is attributed to a high free drug concentration in vivo as a result of the generation and stabilization of the supersaturated state due to the incorporation of polymeric precipitation inhibitor.