Stopping Hydrogen Migration in its Tracks: The First Successful Synthesis of Group Ten Scorpionate Complexes Based on Azaindole Scaffolds

The first successful synthesis and characterization of group 10 complexes featuring flexible scorpionate ligands based on 7-azaindole heterocycles are reported herein. Addition of 2 equiv of either K­[HB­(azaindolyl)3] or Li­[HB­(Me)­(azaindolyl)2] to [M­(μ-Cl)­(η,1η2-COEOMe)]2 leads to the formation of 2 equiv of the complexes [M­{κ3-N,N,H-HB­(azaindolyl)3}­(η,1η2-COEOMe)] and [M­{κ3-N,N,H-HB­(Me)­(azaindolyl)2}­(η,1η2-COEOMe)] (where M = Pt, Pd; COEOMe = 8-methoxycyclooct-4-en-1-ide), respectively. In these reactions, the borohydride group is directed toward the metal center forming square based pyramidal complexes. In contrast to analogous complexes featuring other flexible scorpionate ligands, no hydrogen migration from boron is observed in the complexes studied. The fortuitous line widths observed in some of the 11B NMR spectra allow for a closer inspection of the B–H···metal unit in scorpionate complexes than has previously been possible

The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK

The presence and fate of 56 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) were investigated in the South Wales region of the UK. Two contrasting rivers: River Taff and River Ely were chosen for this investigation and were monitored for a period of 10 months. The impact of the factors affecting the levels of concentration of PPCPs and illicit drugs in surface water such as surrounding area, proximity to wastewater effluent and weather conditions, mainly rainfall was also investigated. Most PPCPs were frequently found in river water at concentrations reaching single μg L−1 and their levels depended mainly on the extent of water dilution resulting from rainfall. Discharge of treated wastewater effluent into the river course was found to be the main cause of water contamination with PPCPs. The most frequently detected PPCPs represent the group of pharmaceuticals dispensed at the highest levels in the Welsh community. These were antibacterial drugs (trimethoprim, erythromycin-H2O and amoxicillin), anti-inflammatories/analgesics (paracetamol, tramadol, codeine, naproxen, ibuprofen and diclofenac) and antiepileptic drugs (carbamazepine and gabapentin). Only four PPCPs out of 56 (simvastatin, pravastatin, digoxin and digoxigenin) were not quantified over the course of the study. Several PPCPs were found to be both ubiquitous and persistent in the aqueous environment (e.g. erythromycin-H2O, codeine, carbamazepine, gabapentin and valsartan). The calculated average daily loads of PPCPs indicated that in total almost 6 kg of studied PPCPs are discharged daily into the studied rivers. The illicit drugs studied were found in rivers at low levels of ng L−1. Average daily loads of amphetamine, cocaine and its main metabolite benzoylecgonine were as follows: 8, 1.2 and 39 g day−1, respectively. Their frequent occurrence in surface water is primarily associated with their high illegal usage and is strongly associated with the discharge of insufficiently treated wastewater effluent

The effect of signal suppression and mobile phase composition on the simultaneous analysis of multiple classes of acidic/neutral pharmaceuticals and personal care products in surface water by solid-phase extraction and ultra performance liquid chromatography–negative electrospray tandem mass spectrometry

A new multi-residue method for the determination of 25 acidic/neutral pharmaceuticals (antibiotics, anti-inflammatory/analgesics, lipid regulating agents, diuretics, triazides, H2-receptor antagonists, cardiac glicozides and angiotensin II antagonists) and personal care products (sunscreen agents and preservatives) in surface water with the usage of a new technique: ultra performance liquid chromatography–negative electrospray tandem mass spectrometry (UPLC–MS/MS) was developed and validated. The novel UPLC system with 1.7 μm particle-packed column allowed for good resolution of analytes with the application of low mobile phase flow rates (0.05 mL min−1) and short retention times (from 4.7 min to 13.3 min) delivering a fast and cost-effective multi-residue method. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for sample clean-up and concentration. The influence of mobile-phase composition, matrix assisted ion suppression and SPE recovery on the sensitivity of the method was identified and quantified. The instrumental limits of quantification varied from 0.2 μg L−1 to 30 μg L−1. The method limits of quantification were at low nanogram per litre levels and ranged from 0.3 ng L−1 to 30 ng L−1. The instrumental and method intra-day and inter-day repeatabilities were on average less than 5%. The method was successfully applied for the determination of PPCPs in River Taff. Thirteen compounds were determined in river water at levels ranging from a single to a few hundred nanograms per litre. Among them were ten pharmaceuticals (aspirin, salicylic acid, ketoprofen, naproxen, diclofenac, ibuprofen, mefenamic acid, furosemide, sulfasalazine and valsartan) and three personal care products (methyl- and ethylparaben and 4-benzophenon

Illicit drugs and pharmaceuticals in the environment – Forensic applications of environmental data. Part 1: Estimation of the usage of drugs in local communities

Pharmaceuticals and recently also illicit drugs have been recognised as emerging environmental contaminants due to their potential environmental impact: frequent occurrence, persistence and risk to aquatic life and humans. This manuscript is part one of the two-part study aiming to provide a better understanding and application of environmental data not only for environmental aims but also to meet forensic objectives. An attempt to use wastewater data is made in order to verify patterns of the usage of drugs (in particular illicit) in local communities. The average usage of cocaine in South Wales was estimated at 0.9 g day−1 1000 people−1, which equals 1 tonne of this drug used or disposed of to sewage annually in Wales. The calculated usage of amphetamine denoted 2.5 g day−1 1000 people−1 and is suspected to be an overestimate. Because no analysis of enantiomers of amphetamine was undertaken, no distinction between amphetamine's legal and illicit usage could be made. Wastewater as an indicative source of information can be used in forensic applications

Multiresidue methods for the analysis of pharmaceuticals, personal care products and illicit drugs in surface water and wastewater by solid-phase extraction and ultra performance liquid chromatography–electrospray tandem mass spectrometry

The main aim of the presented research is to introduce a new technique, ultra performance liquid chromatography–positive/negative electrospray tandem mass spectrometry (UPLC–ESI/MS/MS), for the development of new simultaneous multiresidue methods (over 50 compounds). These methods were used for the determination of multiple classes of pharmaceuticals (acidic, basic and neutral compounds: analgesic/anti-inflammatory drugs, antibiotics, antiepileptics, beta-adrenoceptor blocking drugs, lipid regulating agents, etc.), personal care products (sunscreen agents, preservatives, disinfectant/antiseptics) and illicit drugs (amphetamine, cocaine and benzoylecgonine) in surface water and wastewater. The usage of the novel UPLC system with a 1.7 μm particle-packed column allowed for good resolution of analytes with the utilisation of low mobile phase flow rates (0.05–0.07 mL min−1) and short retention times (method times of up to 25 min), delivering a fast and cost-effective method. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for sample clean-up and concentration. The influence of mobile phase composition, matrix-assisted ion suppression in ESI–MS and SPE recovery on the sensitivity of the method was extensively studied. The method limits of quantification were at low nanogram per litre levels and ranged from tenths of ng L−1 to tens of ng L−1 in surface water and from single ng L−1 to a few hundreds of ng L−1 in the case of wastewater. The instrumental and method intraday and interday repeatabilities were on average less than 5%. The method was successfully applied for the determination of pharmaceuticals in the River Taff (South Wales) and a wastewater treatment plant (WWTP Cilfynydd). Several pharmaceuticals and personal care products were determined in river water at levels ranging from single ng L−1 to single μg L−1

Illicit drugs and pharmaceuticals in the environment – Forensic applications of environmental data, Part 2: Pharmaceuticals as chemical markers of faecal water contamination

This manuscript is part two of a two-part study aiming to provide a better understanding and application of environmental data not only for environmental aims but also to meet forensic objectives. In this paper pharmaceuticals were investigated as potential chemical indicators of water contamination with sewage. The monitoring program carried out in Wales revealed that some pharmaceuticals are particularly persistent and/or ubiquitous in contaminated river water and therefore might be considered as potential conservative or labile wastewater indicators. In particular, these include some anti-inflammatory/analgesics, antiepileptics, beta-blockers, some H2-receptor antagonists and antibacterial drugs. Wastewater as an indicative source of information can be used in forensic applications

The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters

A 5-month monitoring program was undertaken in South Wales in the UK to determine the fate of 55 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) in two contrasting wastewater plants utilising two different wastewater treatment technologies: activated sludge and trickling filter beds. The impact of treated wastewater effluent on the quality of receiving waters was also assessed. PPCPs were found to be present at high loads reaching 10 kg day−1 in the raw sewage. Concentrations of PPCPs in raw sewage were found to correlate with their usage/consumption patterns in Wales and their metabolism. The efficiency of the removal of PPCPs was found to be strongly dependent on the technology implemented in the wastewater treatment plant (WWTP). In general, the WWTP utilising trickling filter beds resulted in, on average, less than 70% removal of all 55 PPCPs studied, while the WWTP utilising activated sludge treatment gave a much higher removal efficiency of over 85%. The monitoring programme revealed that treated wastewater effluents were the main contributors to PPCPs concentrations (up to 3 kg of PPCPs day−1) in the rivers studied. Bearing in mind that in the cases examined here the WWTP effluents were also major contributors to rivers' flows (dilution factor for the studied rivers did not exceed 23 times) the effect of WWTP effluent on the quality of river water is significant and cannot be underestimated

Multi-residue method for the determination of basic/neutral pharmaceuticals and illicit drugs in surface water by solid-phase extraction and ultra performance liquid chromatography - positive electrospray ionisation tandem mass spectrometry

The paper presents the development and validation of a new multi-residue method for the determination of 28 basic/neutral pharmaceuticals (antiepileptics, antibacterial drugs, β-blockers, analgesics, lipid-regulating agents, bronchodilators, histamine-2-blockers, anti-inflammatory agents, calcium channel blockers, angiotensin-II antagonists and antidepressants) and illicit drugs in surface water with the usage of a new technique: ultra performance liquid chromatography–positive electrospray tandem mass spectrometry (UPLC–MS/MS). The usage of the novel UPLC system with 1.7 μm particle size and 1 mm internal diameter column allowed for low mobile phase flow rates (0.07 mL min−1) and short retention times (from 1.3 to 15.5 min) for all compounds analysed. As a result, a fast and cost-effective method was developed. SPE with the usage of Oasis MCX strong cation-exchange mixed-mode polymeric sorbent was chosen for pharmaceuticals extraction from environmental samples. The influence of matrix-assisted ion suppression and low SPE recovery on the sensitivity of the method was studied. The instrumental limits of quantification varied from 0.2 to 10 μg L−1. The method limits of quantification were at low nanogram per litre levels and ranged from 0.3 to 50 ng L−1. The instrumental and method intra- and inter-day repeatabilities were on average less than 10%. The method was applied for the determination of pharmaceuticals in Rivers Taff (UK) and Warta (Poland). Fifteen compounds were determined in river water at levels ranging from single nanograms to single micrograms per litre