Cyclobutane-based peptides/terpyridine conjugates : Their use in metal catalysis and as functional organogelators

Two new conjugates, hcptpyDP and hcptpyTP, of a terpyridine derivative incorporating artificial peptide moieties, have been synthesized and their use in the preparation of metal catalysts and organogelators has been investigated. Ru(II) complexes derived from these ligands showed electrochemical behavior and activity as catalysts in the epoxidation of olefins similar to that of Beller's catalyst. As organogelators, these conjugates were able to gelate a variety of solvents, from toluene to methanol, with satisfactory mgc (minimum gelation concentration) values. The presence of 4'-(4-carboxy)phenylterpyridine (hcptpy) moiety allows tuning the gelling properties and also influences the supramolecular self-assembling mode to produce chiral aggregates with respect to parent peptides DP and TP. In the case of the conjugates, π−π interactions provided by the aromatic moieties cooperate with inter-molecular hydrogen bonding between NH and CO in the amide groups. Further properties of peptide/terpyridine conjugates are under investigation in view of future applications

Cyclobutane scaffold in bolaamphiphiles : Effect of diastereoisomerism and regiochemistry on their surface activity aggregate structure

Cationic bolaamphiphiles have been synthesized starting from meso cis- or chiral trans-1,2-difunctionalized cyclobutane derivatives. They include cis/trans pairs of diastereoisomers, of N- or C-centered bisamides. The goal of this work was to investigate the influence of stereochemistry and regiochemistry on their abilities as surfactants and self-assembly. Very large differences in surface coverage (2-fold), critical micellar concentration (cmc, up to 2 orders of magnitude), and aggregate structure (from lamellae to fibers) for the four molecules are remarkable due to regio- and stereochemistry differences. Computational calculations were carried out to rationalize the experimental findings and a new methodology has been developed to calculate the structure of these bolaamphiphiles at the surface. Although the four surfactants adopt a wicket-like conformation, for N-centered trans, the distance between polar heads is much larger than that for the other three molecules, as suggested by calculations. We have shown that the interplay between the regiochemistry and stereoisomerism, enhanced by rigidity of the cyclobutane ring, affects different physicochemical properties quite differently. That is, the cmc value is mainly governed by stereochemistry, with regiochemistry only modulating this value. On the other hand, regiochemistry definitely governs the morphology of the supramolecular aggregates (i.e., long fibers versus plates or spherical assemblies), with stereochemistry finely modulating their structural parameters. All these results must help in the rational design of new bolaamphiphiles with predictable properties and useful potential applications

Techno-economic evaluation and comparison of PAC-MBR and ozonation-UV revamping for organic micro-pollutants removal from urban reclaimed wastewater

The presence of sewage-borne Organic Micro-Pollutants (OMP) in Wastewater Treatment Plants (WWTP) effluents represents an increasing concern when water is reclaimed for irrigation or even indirect potable reuse. During eighteen months, an innovative hybrid water reclamation scheme based on a Membrane Biological Reactor (MBR) enhanced with Powder Activated Carbon (PAC) was operated at pilot-scale (70 m3/d) in order to compare it with state-of-the art Wastewater Reclamation System (WWRS) also revamped with a final step of ozonation-UV. Removal of persistent OMP, water quality and treatment costs were evaluated and compared for the different treatment schemes. OMP removal efficiency results for the different schemes concluded that established technologies, such as physico-chemical and filtration systems as well as MBR, do not remove significantly (>15%) the most recalcitrant compounds. The upgrading of these two systems through the addition of ozonation-UV step and PAC dosing allowed improving average recalcitrant OMP removal to 85±2 and 75±5 %, respectively. In term of costs, PAC-MBR represents an increase of 37 % of costs regarding conventional systems but presents improvements of 50 % reduction in space and water quality. On the other hand, ozonation requires up to a 15% increase of foot-print; nevertheless, represents lower costs and lower carbon footprint. Ozonation-UV seems to be the best option for upgrading existing facilities, while PAC- MBR should be considered when space represents a critical limitation and produced water is reused for high water quality purposes.Postprint (author's final draft

What's in the water? – Target and suspect screening of contaminants of emerging concern in raw water and drinking water from Europe and Asia

There is growing worry that drinking water can be affected by contaminants of emerging concern (CECs), potentially threatening human health. In this study, a wide range of CECs ( n = 177), including pharmaceuticals, pesticides, perfluoroalkyl substances (PFASs) and other compounds, were analysed in raw water and in drinking water collected from drinking water treatment plants (DWTPs) in Europe and Asia ( n = 13). The impact of human activities was reflected in large numbers of compounds detected ( n = 115) and high variation in concentrations in the raw water (range 15-7995 ng L & minus;1 for E177 CECs). The variation was less pronounced in drinking water, with total concentration ranging from 35 to 919 ng L & minus;1 . Treatment efficiency was on average 65 +/- 28%, with wide variation between different DWTPs. The DWTP with the highest ECEC concentrations in raw water had the most efficient treatment procedure (average treatment efficiency 89%), whereas the DWTP with the lowest E177 CEC concentration in the raw water had the lowest average treatment efficiency (2.3%). Suspect screening was performed for 500 compounds ranked high as chemicals of concern for drinking water, using a prioritisation tool (SusTool). Overall, 208 features of interest were discovered and three were confirmed with reference standards. There was co-variation between removal efficiency in DWTPs for the target compounds and the suspected features detected using suspect screening, implying that removal of known contaminants can be used to predict overall removal of potential CECs for drinking water production. Our results can be of high value for DWTPs around the globe in their planning for future treatment strategies to meet the increasing concern about human ex-posure to unknown CECs present in their drinking water.(c) 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/

TFG 2014/2015

Amb aquesta publicació, EINA, Centre universitari de Disseny i Art adscrit a la Universitat Autònoma de Barcelona, dóna a conèixer el recull dels Treballs de Fi de Grau presentats durant el curs 2014-2015. Voldríem que un recull com aquest donés una idea més precisa de la tasca que es realitza a EINA per tal de formar nous dissenyadors amb capacitat de respondre professionalment i intel·lectualment a les necessitats i exigències de la nostra societat. El treball formatiu s’orienta a oferir resultats que responguin tant a paràmetres de rigor acadèmic i capacitat d’anàlisi del context com a l’experimentació i la creació de nous llenguatges, tot fomentant el potencial innovador del disseny.Con esta publicación, EINA, Centro universitario de diseño y arte adscrito a la Universidad Autónoma de Barcelona, da a conocer la recopilación de los Trabajos de Fin de Grado presentados durante el curso 2014-2015. Querríamos que una recopilación como ésta diera una idea más precisa del trabajo que se realiza en EINA para formar nuevos diseñadores con capacidad de responder profesional e intelectualmente a las necesidades y exigencias de nuestra sociedad. El trabajo formativo se orienta a ofrecer resultados que respondan tanto a parámetros de rigor académico y capacidad de análisis, como a la experimentación y la creación de nuevos lenguajes, al tiempo que se fomenta el potencial innovador del diseño.With this publication, EINA, University School of Design and Art, affiliated to the Autonomous University of Barcelona, brings to the public eye the Final Degree Projects presented during the 2014-2015 academic year. Our hope is that this volume might offer a more precise idea of the task performed by EINA in training new designers, able to speak both professionally and intellectually to the needs and demands of our society. The educational task is oriented towards results that might respond to the parameters of academic rigour and the capacity for contextual analysis, as well as to considerations of experimentation and the creation of new languages, all the while reinforcing design’s innovative potential

Drogues d’abús i fàrmacs en el medi aquàtic: Anàlisi, presencia i comportament

Les drogues d'abús i els fàrmacs estan considerats com contaminants d'interès emergent en el medi aquàtic, és a dir, són substàncies que no estan incloses en els programes habituals de control i monitorització d'aigües, tot i que s'ha demostrat la seva presència en el medi ambient. Donat que aquests contaminants són possibles candidats a ésser regulats en futures legislacions, l'objectiu d'aquesta memòria ha estat desenvolupar metodologies d'anàlisi a nivells traça per poder quantificar la seva presència en el medi aquàtic i conèixer el seu comportament al llarg dels tractaments, tant en les plantes depuradores com en les potabilitzadores. S'han desenvolupat metodologies d'anàlisi per drogues d'abús i fàrmacs, basades en l'extracció en fase sòlida i determinació per cromatografia de líquids acoblada a l'espectrometria de masses en tàndem. En tots els casos s'han trobat límits de quantificació, que permeten la detecció d'aquests contaminants en les tres matrius aquoses a nivells de ng/L. S'han analitzat les drogues d'abús en aigües residuals, a les entrades i sortides de les depuradores. Les eliminacions calculades a partir de les concentracions trobades van indicar que els tractaments aplicats no són suficientment efectius per eliminar completament aquests contaminants, i per tant es poden trobar en les aigües superficials on s'aboquen les aigües depurades. S'ha estudiat la presència de drogues i fàrmacs en les aigües superficials. En concret, l'aigua del riu Llobregat al llarg de tota la conca i exhaustivament a l'entrada de la planta potabilitzadora de Sant Joan Despí. Els estudis han demostrat que aquests contaminants es troben en l'aigua superficial en concentracions més baixes que a la sortida de les depuradores i que són susceptibles d'entrar a la planta potabilitzadora. Tanmateix, han permès tenir localitzats els punts més contaminats del riu per aquests tipus de compostos i veure que segueixen un comportament estacional, trobant les màximes concentracions a l'hivern i a la tardor. En aquest treball s’ha estudiat també la presència de drogues d’abús i fàrmacs en les aigües potables, tant a la sortida de la potabilitzadora de Sant Joan Despí com en aixetes de consumidors de les principals ciutats espanyoles i d’altres països europeus, sud-americans i del Japó. La conclusió és que alguns contaminants (p.ex. cafeïna, nicotina, benziolecgonina, ibuprofè) poden arribar a les aixetes dels consumidors encara que a nivells de traça (pocs ng(L). Un cop vist que les drogues d’abús i fàrmacs es poden trobar en les tres matrius d’aigua, es va portar a terme un estudi sobre el tractament avançat en aigua residual basat en membranes d’osmosi inversa, per a l’eliminació de les drogues d’abús, arribant a la conclusió que és molt més efectiu que els tractaments convencionals més comuns utilitzats avui en dia. A més es va provar que l’efectivitat amb tres membranes diferents és similar, de manera que es va triar la membrana que requeria menys energia pel seu funcionament. Així mateix s’ha estudiat com els tractaments que s’apliquen en la potabilitzadora de Sant Joan Despí eliminen els fàrmacs i les drogues d’abús. Els resultats obtinguts demostren que s’aconsegueixen bones eliminacions pràcticament per tots els compostos estudiats, tant amb el tractament convencional (que inclou ozonització i filtració per carbó) com amb el tractament avançat (que inclou membranes d’ultrafiltració i osmosi inversa), tot i que aquest darrer les millora fins a un 15% per compostos com la nicotinaDrugs of abuse and pharmaceuticals are considered contaminants of emerging concern in the aquatic environment. Given that these contaminants are potential candidates to be regulated in future legislations, the objective of this thesis has been devoted to develop a methodology for their analysis at trace levels; to quantify its presence in the aquatic environment as well as to improve the knowledge of their behaviour in different types of water treatments plants. Analytical methods for drugs of abuse and pharmaceuticals, based on solid phase extraction and liquid chromatography coupled to tandem mass spectrometry have been developed. In all cases, the quantification limits achieved, allowed the detection of contaminants at trace levels (ng/L). Drugs of abuse in influents and effluents of wastewaters treatment plants (WWTP) were analyzed. Results showed that the applied treatments are not enough effective and these pollutants can reach surface waters. The presence of drugs and pharmaceuticals in surface waters were studied in Llobregat river and their basin and at the intake of the drinking water treatment plant (DWTP) in Sant Joan Despi. Results showed that these compounds are present in surface waters at lower concentrations than in effluents of WWTPs and therefore they can enter to the DWTP. Moreover, it has also allowed to keep track of the most polluted river points, and to verify that they follow a seasonal pattern, with the highest concentrations in winter and autumn. This work has also studied the presence of drugs of abuse and pharmaceuticals in treated waters from the DWTP and from tap waters of main Spanish cities and other countries. The principal conclusion is that few of these contaminants (i.e. caffeine, nicotine, benzoilecgonine, ibuprofen) can reach tap waters at trace levels (few ng/L). A study on the advanced wastewater treatment based on reverse osmosis membranes showed that it is much more effective than conventional treatments commonly used in most WWTPs. No significant differences between the three kinds of membranes tested was observed and the membranes which requires less energy is proposed. Likewise, studies of how tratments applied in DWTPs of Sant Joan Despí eliminated pharmaceuticals and drugs of abuse were carried out. Good eliminations for almost all studied compounds in the conventional treatment (using ozonation and carbon filtration) as in advanced tratment (with ultrafiltration and reverse osmosis membranes) were achevied, although with the latter the elimination is improved up to 15% for compounds such as nicotine

Monitoring the complex occurrence of pesticides in the Llobregat basin, natural and drinking waters in Barcelona metropolitan area (Catalonia, NE Spain) by a validated multi-residue online analytical method

The European Directive 98/83/CE legislates the presence of pesticides in drinking water, but apart from a few compounds, nothing is said about which pesticides should be monitored. Nevertheless, water companies need to go beyond the accomplishment of the legislation and find out pesticide contamination in all sources of water in order to manage the hazard assessment, and to guarantee safe drinking water to all the population. The aim of this work was to develop an analytical multi-residue method for circa 100 compounds. The method analyses previously monitored compounds in Barcelona city and its metropolitan area, as well as many emerging pesticides and some transformation products. An on-line sample extraction (0.75 mL) coupled to fast UHPLC-MS/MS method was developed. Good linearity (r2 > 0.995, with less residuals than 15%), accuracies and precisions under 25%, and acceptable expanded uncertainties were obtained for most of the monitored compounds, according to ISO/IEC 17025, obtaining limits of quantification between 5 and 25 ng/L for all compounds. A monitoring campaign on natural and treated waters in the Barcelona metropolitan area was carried out during 2016–2017. Results showed that pesticide contamination at the low stretch of Llobregat River and in its aquifer is severe. The maximum concentrations were in the range of few μg/L for carbendazim, DEET, diuron and propiconazole, and in the range 0.1–0.5 μg/L for bentazone, imidacloprid, isoproturon, simazine, metazachlor, methomyl, terbutryn and tebuconazole. However, the efficiency of advanced treatments in the DWTPs involved in drinking water production in the Barcelona metropolitan area allows the complete removal of pesticides and a safe water production for consumers. The method shows a good analytical performance for most compounds with a fast sample preparation and analysis. In addition, it has updated the knowledge about the occurrence of pesticides in the Barcelona city area.We are grateful to Dr. Francesc Ventura for his critical revision of this work and to J. Martín-Alonso, M. Paraira, V. García-Tarriño, A. Cabeza and M. Ganzer for their knowledge and comments about the Llobregat River basin and drinking water distribution system. We are also grateful to all co-workers of the Analytical Organic Chemistry Department to deal with the daily work and for their time spent to move forward this study, as well as to the Sampling Department co-workers. This work has received funding from European Union's Horizon 2020 Research and Innovation Programme under grant agreement No. 727450. This presentation only reflects the authors' views and the Commission is not responsible for any use that may be made of the information it contains.Peer reviewe

Ceramic passive samplers for determining pharmaceuticals and drugs of abuse in river and drinking water

An important challenge today is to efficiently monitor the presence of polar pharmaceuticals and drugs in surface and drinking waters to ensure its safeness. Most studies rely on grab sampling techniques, which enable the determination of contaminants at a given point and given time. In this study, we propose the use of ceramic passive samplers (CPSs) to increase the representativeness and efficiency of organic contaminant monitoring in waters. Firstly, we have assayed the stability of 32 pharmaceuticals and drugs and found that five of those compounds were unstable. Moreover, we evaluated the retention capabilities of three sorbents (Sepra ZT, Sepra SBD-L, and PoraPak Rxn RP) in solid-phase extraction (SPE) mode and found no differences in terms of recoveries for all three sorbents. We then calibrated CPSs using the three sorbents for the 27 stable compounds over 13 days, with a suitable uptake for 22 compounds with sampling rates between 0.4 and 17.6 mL/day, which indicates high uptake efficiency. CPSs with the Sepra ZT sorbent were deployed in river water (n = 5) and drinking water (n = 5) for 13 days. Some of the studied compounds occurred with a time-weighted concentration, for instance, of 43 ng/L for caffeine, 223 ng/L for tramadol or 175 ng/L for cotinine in river water.The authors would like to acknowledge financial support received from ACCIO of the Generalitat de Catalunya and the European Regional Development Fund (ERDF) under project COMRDI16-1-0063, and from MCIN/AEI/10.13039/501100011033 and the European Regional Development Fund (ERDF) under projects PID2020-114587GB-I00 and PID2019-105732GBC21 and the Severo Ochoa project Grant CEX2018-000794-S to IDAEA-CSIC as Centre of Excellence.Peer reviewe

Identification of 3-(trifluoromethyl)phenol as the malodorous compound in a pollution incident in the water supply in Catalonia (N.E. Spain)

A study of organic compounds that caused a serious taste and odor episode of water supply in two residential areas in Catalonia (N.E. Spain) was carried out. Sweet and paint/solvent odor were the main descriptors used by consumers. Some cases of sickness and nausea were also associated with drinking water consumption by the consumers. Closed-loop stripping analysis (CLSA) combined with sensory gas chromatography and gas chromatography mass spectrometry detection were used to study the problem. As a result, 3-(trifluoromethyl)phenol (CAS number 98-17-9) was for the first time identified as a responsible of an odor incident in drinking water. Concentration levels of this compound were up to 17,000 ng/L in groundwater and up to 600 ng/L in distributed water. Odor threshold in water for 3-(trifluoromethyl)phenol was determined as 13 ng/L (45 °C). © 2019, Springer-Verlag GmbH Germany, part of Springer Nature.We are grateful to Dr. Auguste Bruchet for his explanations about past episodes in France involving fluoro-related compounds and to M.J. Domínguez-Cereijo for the details of the distribution system and sampling coordination. We are also grateful to all our colleagues of the Analytical Organic Chemistry Department for dealing with the daily work and spending time to move forward this study. We would also like to thank you I. Pérez and all the members and volunteers of the panel.Peer reviewe