Identification of new transformation products during enzymatic treatment of tetracycline and erythromycin antibiotics at laboratory scale by an on-line turbulent flow liquid-chromatography coupled to a high resolution mass spectrometer LTQ-Orbitrap

This work describes the formation of transformation products (TPs) by the enzymatic degradation at laboratory scale of two highly consumed antibiotics: tetracycline (Tc) and erythromycin (ERY). The analysis of the samples was carried out by a fast and simple method based on the novel configuration of the on-line turbulent flow system coupled to a hybrid linear ion trap – high resolution mass spectrometer. The method was optimized and validated for the complete analysis of ERY, Tc and their transformation products within 10 min without any other sample manipulation. Furthermore, the applicability of the on-line procedure was evaluated for 25 additional antibiotics, covering a wide range of chemical classes in different environmental waters with satisfactory quality parameters. Degradation rates obtained for Tc by laccase enzyme and ERY by EreB esterase enzyme without the presence of mediators were ∼78% and ∼50%, respectively. Concerning the identification of TPs, three suspected compounds for Tc and five of ERY have been proposed. In the case of Tc, the tentative molecular formulas with errors mass within 2 ppm have been based on the hypothesis of dehydroxylation, (bi)demethylation and oxidation of the rings A and C as major reactions. In contrast, the major TP detected for ERY has been identified as the “dehydration ERY-A”, with the same molecular formula of its parent compound. In addition, the evaluation of the antibiotic activity of the samples along the enzymatic treatments showed a decrease around 100% in both cases

Improving the molecular diagnosis of Chlamydia psittaci and Chlamydia abortus infection with a species-specific duplex real-time PCR.

Chlamydia psittaci and Chlamydia abortus are closely related intracellular bacteria exhibiting different tissue tropism that may cause severe but distinct infection in humans. C. psittaci causes psittacosis, a respiratory zoonotic infection transmitted by birds. C. abortus is an abortigenic agent in small ruminants, which can also colonize the human placenta and lead to foetal death and miscarriage. Infections caused by C. psittaci and C. abortus are underestimated mainly due to diagnosis difficulties resulting from their strict intracellular growth. We developed a duplex real-time PCR to detect and distinguish these two bacteria in clinical samples. The first PCR (PCR1) targeted a sequence of the 16S-23S rRNA operon allowing the detection of both C. psittaci and C. abortus. The second PCR (PCR2) targeted the coding DNA sequence CPSIT_0607 unique to C. psittaci. The two PCRs showed 100 % detection for ≥ 10 DNA copies per reaction (1000 copies ml- 1). Using a set of 120 samples, including bacterial reference strains, clinical specimens and infected cell culture material, we monitored 100 % sensitivity and 100 % specificity for the detection of C. psittaci and C. abortus for PCR1. When PCR1 was positive, PCR2 could discriminate C. psittaci from C. abortus with a positive predictive value of 100 % and a negative predictive value of 88 %. In conclusion, this new duplex PCR represents a low-cost and time-saving method with high-throughput potential, expected to improve the routine diagnosis of psittacosis and pregnancy complication in large-scale screening programs and also during outbreaks.

Multivitamins/multiminerals in Switzerland: a first assessment The fallacy of slimming products: a case analysis in Switzerland

Purpose: To assess the composition and compliance with legislation of multivitamin/multiminerals (MVM) in Switzerland. Methods: Information on the composition of vitamin/minerals supplements was obtained from the Swiss drug compendium, the Internet, pharmacies, parapharmacies and supermarkets. MVM was defined as the presence of at least 5 vitamins and/or minerals. Results: 95 MVM were considered. The most frequent vitamins were B6 (73.7%), C (71.6%), B2 (69.5%) and B1 (67.4%); the least frequent were K (17.9%), biotin (51.6%), pantothene (55.8%) and E (56.8%). Around half of MVMs provided >150% of the ADI for vitamins. The most frequent minerals were zinc (66.3%), calcium (55.8%), magnesium (54.7%) and copper (48.4%), and the least frequent were fluoride (3.2%), phosphorous (17.9%) and chrome (22.1%). Only 25% of MVMs contained iodine. More than two thirds of MVMs provided between 15 and 150% of the ADI for minerals, and few MVMs provided >150% of the ADI. While few MVMs provided <15% of the ADI for vitamins, a considerable fraction did so for minerals (32.7% for magnesium, 26.1% for copper and 22.6% for calcium). Conclusion: There is a great variability regarding the composition and amount of MVMs in Switzerland. Several MVM do not comply with the Swiss legislation.

Identification of metabolites and thermal transformation products of quinolones in raw cow milk by liquid chromatography coupled to high resolution mass spectrometry

The presence of residues of antibiotics, metabolites, and thermal transformation products (TPs), produced during thermal treatment to eliminate pathogenic microorganisms in milk, could represent a risk for people. Cow"s milk samples spiked with enrofloxacin (ENR), ciprofloxacin (CIP), difloxacin (DIF), and sarafloxacin (SAR) and milk samples from cows medicated with ENR were submitted to several thermal treatments. The milk samples were analyzed by liquid chromatography-mass spectrometry (LC-MS) to find and identify TPs and metabolites. In this work, 27 TPs of 4 quinolones and 24 metabolites of ENR were found. Some of these compounds had been reported previously, but others were characterized for the first time, including lactose-conjugated CIP, the formamidation reaction for CIP and SAR, and hydroxylation or ketone formation to produce three different isomers for all quinolones studied.

Heterogeneous products and tests for an appropriate aggregation level considering different qualities: evidence from fresh hake at Barcelona’s wholesale market

[cat] Aquest estudi destaca la importància de considerar un nivell d’agregació adequat en els anàlisis de demanda, ja que treballar utilitzant un nivell d’agregació inadequat pot donar lloc a estimacions esbiaixades. Aquest fet es mostra a través de l’anàlisi de diferents productes de lluç fresc comercialitzats a Mercabarna, el mercat majorista de Barcelona. La literatura sobre la demanda de peix tracta al lluç com un únic producte i espècie. No obstant això, en el mercat espanyol, es comercialitzen molts peixos com a lluç, els quals mostren comportaments molt diferents (des de béns inferiors fins a béns de luxe). Els resultats obtinguts, en concordança amb les observacions empíriques, demostren que l’anàlisi s’ha de realitzar amb un major grau de detall que a nivell d’espècie. Això qüestiona els resultats d’anteriors estudis de demanda i la majoria de les bases de dades, on l’observació del nivell d’agregació adequat dels productes no es té en compte.

Heterogeneous products and tests for an appropriate aggregation level considering different qualities: evidence from fresh hake at Barcelona’s wholesale market

[cat] Aquest estudi destaca la importància de considerar un nivell d’agregació adequat en els anàlisis de demanda, ja que treballar utilitzant un nivell d’agregació inadequat pot donar lloc a estimacions esbiaixades. Aquest fet es mostra a través de l’anàlisi de diferents productes de lluç fresc comercialitzats a Mercabarna, el mercat majorista de Barcelona. La literatura sobre la demanda de peix tracta al lluç com un únic producte i espècie. No obstant això, en el mercat espanyol, es comercialitzen molts peixos com a lluç, els quals mostren comportaments molt diferents (des de béns inferiors fins a béns de luxe). Els resultats obtinguts, en concordança amb les observacions empíriques, demostren que l’anàlisi s’ha de realitzar amb un major grau de detall que a nivell d’espècie. Això qüestiona els resultats d’anteriors estudis de demanda i la majoria de les bases de dades, on l’observació del nivell d’agregació adequat dels productes no es té en compte.

Identification of metabolites and thermal transformation products of quinolones in raw cow milk by liquid chromatography coupled to high resolution mass spectrometry.

The presence of residues of antibiotics, metabolites, and thermal transformation products (TPs), produced during thermal treatment to eliminate pathogenic microorganisms in milk, could represent a risk for people. Cow"s milk samples spiked with enrofloxacin (ENR), ciprofloxacin (CIP), difloxacin (DIF), and sarafloxacin (SAR) and milk samples from cows medicated with ENR were submitted to several thermal treatments. The milk samples were analyzed by liquid chromatography-mass spectrometry (LC-MS) to find and identify TPs and metabolites. In this work, 27 TPs of 4 quinolones and 24 metabolites of ENR were found. Some of these compounds had been reported previously, but others were characterized for the first time, including lactose-conjugated CIP, the formamidation reaction for CIP and SAR, and hydroxylation or ketone formation to produce three different isomers for all quinolones studied.

New methods for the concentration of viruses from urban sewage using quantitative PCR.

Viruses are among the most important pathogens present in water contaminated with feces or urine and represent a serious risk to human health. Four procedures for concentrating viruses from sewage have been compared in this work, three of which were developed in the present study. Viruses were quantified using PCR techniques. According to statistical analysis and the sensitivity to detect human adenoviruses (HAdV), JC polyomaviruses (JCPyV) and noroviruses genogroup II (NoV GGII): (i) a new procedure (elution and skimmed-milk flocculation procedure (ESMP)) based on the elution of the viruses with glycine-alkaline buffer followed by organic flocculation with skimmed-milk was found to be the most efficient method when compared to (ii) ultrafiltration and glycine-alkaline elution, (iii) a lyophilization-based method and (iv) ultracentrifugation and glycine-alkaline elution. Through the analysis of replicate sewage samples, ESMP showed reproducible results with a coefficient of variation (CV) of 16% for HAdV, 12% for JCPyV and 17% for NoV GGII. Using spiked samples, the viral recoveries were estimated at 30-95% for HAdV, 55-90% for JCPyV and 45-50% for NoV GGII. ESMP was validated in a field study using twelve 24-h composite sewage samples collected in an urban sewage treatment plant in the North of Spain that reported 100% positive samples with mean values of HAdV, JCPyV and NoV GGII similar to those observed in other studies. Although all of the methods compared in this work yield consistently high values of virus detection and recovery in urban sewage, some require expensive laboratory equipment. ESMP is an effective low-cost procedure which allows a large number of samples to be processed simultaneously and is easily standardizable for its performance in a routine laboratory working in water monitoring. Moreover, in the present study, a CV was applied and proposed as a parameter to evaluate and compare the methods for detecting viruses in sewage samples.

New methods for the concentration of viruses from urban sewage using quantitative PCR.

Viruses are among the most important pathogens present in water contaminated with feces or urine and represent a serious risk to human health. Four procedures for concentrating viruses from sewage have been compared in this work, three of which were developed in the present study. Viruses were quantified using PCR techniques. According to statistical analysis and the sensitivity to detect human adenoviruses (HAdV), JC polyomaviruses (JCPyV) and noroviruses genogroup II (NoV GGII): (i) a new procedure (elution and skimmed-milk flocculation procedure (ESMP)) based on the elution of the viruses with glycine-alkaline buffer followed by organic flocculation with skimmed-milk was found to be the most efficient method when compared to (ii) ultrafiltration and glycine-alkaline elution, (iii) a lyophilization-based method and (iv) ultracentrifugation and glycine-alkaline elution. Through the analysis of replicate sewage samples, ESMP showed reproducible results with a coefficient of variation (CV) of 16% for HAdV, 12% for JCPyV and 17% for NoV GGII. Using spiked samples, the viral recoveries were estimated at 30-95% for HAdV, 55-90% for JCPyV and 45-50% for NoV GGII. ESMP was validated in a field study using twelve 24-h composite sewage samples collected in an urban sewage treatment plant in the North of Spain that reported 100% positive samples with mean values of HAdV, JCPyV and NoV GGII similar to those observed in other studies. Although all of the methods compared in this work yield consistently high values of virus detection and recovery in urban sewage, some require expensive laboratory equipment. ESMP is an effective low-cost procedure which allows a large number of samples to be processed simultaneously and is easily standardizable for its performance in a routine laboratory working in water monitoring. Moreover, in the present study, a CV was applied and proposed as a parameter to evaluate and compare the methods for detecting viruses in sewage samples.

Medicinal chemistry in the development of societies. Biodiversity and natural products

This document here has been elaborated by the IUPAC Medicinal Chemistry section and is backed by a large number of scientists, many of whom have had direct involvement and whose names appear at the end of the article. This work discusses the role that the discovery of new medicinal agents has in the development of societies as well as in the conservation of biodiversity in terms of the work carried out on natural products. Also included are several recommendations for countries which are presently in search of their own scientific and technological development in medicinal agents. The IUPAC Medicinal Chemistry section would appreciate the collaboration of the scientific societies in every country to aid in the diffusion of this document.

Merchandising Strategies and Retail Performance for Seasonal Fashion Products

This study presents mathematical methods for evaluation of retail performance with special regard to product sourcing strategies. Forecast accuracy, process lead time, offshore / local sourcing mix and up front / replenishment buying mix are defined as critical success factors in connection with sourcing seasonal products with a fashion content. As success measures, this research focuses on service level, lost sales, product substitute percentage, gross margin, gross margin return on inventory and mark down rate. The accuracy of demand forecast is found to be a fundamental success factor. Forecast accuracy depends on lead time. Lead times are traditionally long and buying decisions are made seven to eight months prior to the start of the selling season. Forecast errors cause stockouts and lost sales. Some of the products bought for the selling season will not be sold and have to be marked down and sold at clearance, causing loss of gross margin. Gross margin percentage is not the best tool for evaluating sourcing decisions and in the context of this study gross margin return on inventory, which combines profitability and assets management, is used. The findings of this research suggest that there are more profitable ways of sourcing products than buying them from low cost offshore sources. Mixing up front and inseason replenishment deliveries, especially when point of sale information is used for improving forecast accuracy, results in better retail performance. Quick Response and Vendor Managed Inventory strategies yield better results than traditional up front buying from offshore even if local purchase prices are higher. Increasing the number of selling seasons, slight over buying for the season in order to

Iron oxide and pyrocatechol: a spectroscopy study of the reaction products

The reaction of 1,2-dihydroxy-benzene (pyrocatechol) (C6H6O2) with iron oxide (Fe2O3) and sodium thiosulfate (Na2S2O3) in aqueous medium (pH 7) was investigated. Pyrocatechol suffers autoxidation and coordinates with Fe3+ in solution. The presence of S2O3(2-) in solution was fundamental to generate and stabilize the pyrocatechol oxidation products as o-semiquinones. This compound was isolated and its structure characterized using FT-IR, EPR and UV-Vis Spectroscopy as [CTA][Fe(SQ)2(Cat)]. A thermal mass loss mechanism was proposed based on Thermogravimetric Analysis (TG) to support the structural characterization.

The impact of FTAs on MENA trade in agricultural and industrial products

This paper analyses the impact of Free Trade Agreements (FTAs) on Middle East and North African Countries (MENA) trade for the period 1994-2010. The analysis distinguishes between industrial and agricultural trade to take into account the different liberalisation schedules. An augmented gravity model is estimated using up-to-date panel data techniques to control for all time-invariant bilateral factors that influence bilateral trade as well as for the so-called multilateral resistance factors. We also control for the endogeneity of the agreements and test for self-selection bias due to the presence of zero trade in our sample. The main findings indicate that North-South-FTAs and South-South- FTAs have a differential impact in terms of increasing trade in MENA countries, with the former being more beneficial in terms of exports for MENA countries, but both showing greater global market integration. We also find that FTAs that include agricultural products, in which MENA countries have a clear comparative advantage, have more favourable effects for these countries than those only including industrial products. JEL code: F10, F15