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The synthesis of zwitterionic dithiocarboxylate adducts was achieved by deprotonating various aldiminium or 1,2,3-triazolium salts with a strong base, followed by the nucleophilic addition of the in situ-generated cyclic (alkyl)(amino) or mesoionic carbenes (CAACs or MICs) onto carbon disulfide. Nine novel compounds were isolated and fully characterized by 1H and 13C NMR, FTIR, and HRMS techniques. Moreover, the molecular structures of two CAAC·CS2 and two MIC·CS2 betaines were determined by X-ray diffraction analysis. The analytical data recorded for all these adducts were compared with those reported previously for related NHC·CS2 betaines derived from imidazolinium or (benz)imidazolium salts. Due to the absence of electronic communication between the CS2 unit and the orthogonal heterocycle, all the CAAC·CS2, MIC·CS2, and NHC·CS2 zwitterions displayed similar electronic properties and featured the same bite angle. Yet, their steric properties are liable to ample modifications by varying the exact nature of their cationic heterocycle and its substituents.

This article describes the development of a nickel-catalyzed regio- and diastereoselective formal [3+2] cycloaddition between N-substituted indoles and donor–acceptor cyclopropanes to synthesize cyclopenta[b]indoles. Optimized reaction conditions provide the desired nitrogen-containing cycloadducts in up to 93% yield and dr 8.6:1 with complete regioselectivity. The substrate scope showed high tolerance to various substituted indoles and cyclopropanes, resulting in the synthesis of six new cyclopenta[b]indoles and the isolation of five derivatives previously reported in the literature. In addition, a mechanistic proposal for the reaction was studied through online reaction monitoring by ESI-MS, allowing for the identification of the reactive intermediates in the Ni(II) catalyzed process. X-ray crystallography confirmed the structure and relative endo stereochemistry of the products. This method enables the fast and efficient construction of fused indolines from readily accessible starting materials.

Water and energy are two strategic drivers of sustainable development, intimately interlaced and vital for a secure future of humanity. Given that water resources are limited, whereas global population and energy demand are exponentially growing, the competitive balance between these resources, referred to as the water-energy nexus, is receiving renewed focus. The desalination industry alleviates water stress by producing freshwater from saline sources, such as seawater, brackish or groundwater. Since the last decade, the market has been dominated by membrane desalination technology, offering significant advantages over thermal processes, such as lower energy demand, easy process control and scale-up, modularity for flexible productivity, and feasibility of synergic integration of different membrane operations. Although seawater reverse osmosis (SWRO) accounts for more than 70% of the global desalination capacity, it is circumscribed by some significant technological limitations, such as: (i) the relatively low water recovery factor (around 50%) due to the negative impact of osmotic and polarization phenomena; (ii) an energy consumption in the range of 3–5 kWh m ^−3 , still far from the theoretical energy demand (1.1 kWh m ^−3 ) to produce potable water from seawater (at 50% water recovery factor). Ultimately, desalination is an energy intensive practice and research efforts are oriented toward the development of alternative and more energy-efficient approaches in order to enhance freshwater resources without placing excessive strain on limited energy supplies. Recent years have seen a relevant surge of interest in membrane distillation (MD), a thermally driven membrane desalination technology having the potential to complement SWRO in the logic of Process Intensification and Zero Liquid Discharge paradigm. Due to its peculiar transport mechanism and negligibility of osmotic phenomena, MD allows high-quality distillate production (theoretically, non-volatile species are completely rejected) with a recovery factor of up to 80% at a relatively low operative temperature (typically 60 °C–80 °C). Although low operative temperatures make MD technology attractive for renewable power applications (e.g. solar thermal, wind or geothermal energy sources) or for efficient exploitation of low-grade or waste heat streams, the low energy efficiency intrinsically due to heat losses—and specifically to temperature polarization—has so far hindered the application at industrial scale. Nowadays, photothermal materials able to absorb and convert natural or artificial irradiation into heat have gained great attention, demonstrating the potential to mitigate the ‘anthropic’ energy input to MD and to mitigate the impact of thermal inefficiencies. On this road, a step-change improvement in light-to-heat conversion is expected through high-throughput computational screening over thermoplasmonic materials based on electronic and optical properties of advanced materials including novel topological phases of matter used as nanofillers in polymeric membranes. Coherently with the concept of Circular Economy, waste hypersaline solutions rejected from desalination process (referred as ‘brine’) are now the subject of valorization activities along two main exploitation routes: (1) recovery of valuable minor and trace metals and minerals, with special focus on critical raw materials (including, among others, Mg, Na, Ca, K, Sr, Li, Br, B, and Rb); (2) production of salinity gradient power (SGP) renewable energy resulting from the recovery of the Gibbs energy of mixing (mainly represented by the entropic contribution) of two solutions having different ionic concentration. The exciting new frontier of sustainable mining of seawater concentrates is accelerating the appearance of a plethora of innovative membrane materials and methods for brine dehydration and selective extraction of trace ions, although under the sword of Damocles represented by cost feasibility for reliable commercial application. On the other hand, among several emerging technologies, reverse electrodialysis (SGP-RED) was already proven capable—at least at the kW scale–of turning the chemical potential difference between river water, brackish water, and seawater into electrical energy. Efforts to develop a next generation of ion exchange membranes exhibiting high perm-selectivity (especially toward monovalent ions) and low electrical resistance, to improve system engineering and to optimize operational conditions, pursue the goal of enhancing the low power density so far achievable (in the order of a few W per m ^2 ). This Roadmap takes the form of a series of short contributions written independently by worldwide experts in the topic. Collectively, such contributions provide a comprehensive picture of the current state of the art in membrane science and technology at the water-energy nexus, and how it is expected to develop in the future. In addition, this Roadmap acknowledges the challenges and advances in membrane systems, particularly emphasizing the interplay of material innovation and system optimization, which collectively contribute to advancing the desalination field within the water-energy nexus framework.

Abstract There is interest for desalination technologies powered by solar energy as arid areas are typically bestowed with good solar potential. In response to a US DOE call for solar desalination analysis tools, we developed an open-source solar energy desalination analysis tool, sedat, for techno-economical evaluation of desalination technologies and selection of regions with the highest potential for using solar energy to power desalination plants. It is expected that this software will simplify the planning, design, and valuation of solar desalination systems in the U.S. and worldwide. Sedat uses Dash for integrating various layers of large volumes of GIS data with Python-based models of solar energy generation and desalination technologies. It derives time-series of energy generation and water production, with details of plant performance and suggestions for improving the solar-desalination coupling. This paper summarizes the various phases of the tool’s development, presents example results showing the potential, under multiple objectives, of solar desalination in parts of the U.S. southwest, and discusses method details that would be useful for future model development.

Membrane distillation (MD) is a thermal desalination technique proposed for the valorization of residual brines that other operations such as reverse osmosis cannot treat. Previous studies have shown that vacuum-assisted air gap (V-AGMD) operation in commercial multi-envelope modules improves the performance of MD noticeably. However, the permeate quality at pilot scale has not been thoroughly characterized so far. The aim of this study is, therefore, to assess and model the effect of the main operating conditions (feed flow rate, inlet temperatures, and feed salinity) on the permeate quality. Results from different steady-state experiments allowed to estimate descriptive metrics such as the salt rejection factor (SRF) and the membrane leak ratio (MLR). Given their non-linear behavior, these metrics were subsequently modeled using artificial neural networks (ANN) to estimate the permeate quality in the whole scope of operating conditions. Acceptable SRF results with MLR values lower than 0.2% confirmed the validity of MD as an operation for the treatment of concentrated brines, although the salinity of the resulting permeate does not comply in all cases with that permitted for human consumption.

In this work, the salinity of permeate obtained with membrane distillation (MD) in pilot scale systems was analyzed. Experiments were performed with three different spiral-wound commercial modules, one from Solar Spring with 10 m2 surface membrane area and two from Aquastill with 7.2 and 24 m2. Intermittent operation meant that high permeate conductivity was measured in the beginning of each experiment, which was gradually decreasing until reaching a constant value (3−143 µS·cm−1 for seawater feed). The final quality reached did not depend on operating conditions, only the time it took to reach it. This can be because the permeate flux dilutes the minimal feed leak taking place through pinholes in the membranes. Larger feed leak through the membrane was observed when operating in vacuum-enhanced air-gap MD configuration (V-AGMD), which is compatible with this explanation. However, for the increase of feed leak with salinity (up to 1.8 M), a conclusive explanation cannot be given. Pore wetting due to crystallization is discarded because the high permeate quality was recovered after washing with distilled water. More studies at higher salinities and also at membrane level are required to investigate this.

A performance analysis of a salinity gradient heat engine (SGP-HE) is presented for the conversion of low temperature heat into power via a closed-loop Reverse Electrodialysis (RED) coupled with Multi-Effect Distillation (MED). Mathematical models for the RED and MED systems have been purposely developed in order to investigate the performance of both processes and have been then coupled to analyze the efficiency of the overall integrated system. The influence of the main operating conditions (i.e., solutions concentration and velocity) has been quantified, looking at the power density and conversion efficiency of the RED unit, MED Specific Thermal Consumption (STC) and at the overall system exergy efficiency. Results show how the membrane properties (i.e., electrical resistance, permselectivity, water and salt permeability) dramatically affect the performance of the RED process. In particular, the power density achievable using membranes with optimized features (ideal membranes) can be more than three times higher than that obtained with current reference ion exchange membranes. On the other hand, MED STC is strongly influenced by the available waste heat temperature, feed salinity and recovery ratio to be achieved. Lowest values of STC below 25 kWh/m3 can be reached at 100 °C and 27 effects. Increasing the feed salinity also increases the STC, while an increase in the recovery ratio is beneficial for the thermal efficiency of the system. For the integrated system, a more complex influence of operating parameters has been found, leading to the identification of some favorable operating conditions in which exergy efficiency close to 7% (1.4% thermal) can be achieved for the case of current membranes, and up to almost 31% (6.6% thermal) assuming ideal membrane properties.

The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymene)Ru(μ-Cl)3RuCl(3-phenyl-1-indenylidene)(PCy3)] (1) to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II)–Ru(III) mixed-valence compound [(p-cymene)Ru(μ-Cl)3RuCl2(PCy3)], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

The solid state structure of 1-((1H-benzotriazol-1-yl)methyl)naphthalen-2-ol, C17H13N3O, shows that this Mannich base crystallizes forming intermolecular N···HO hydrogen bonds, rather than intramolecular ones. Factors contributing to this choice of hydrogen-bonding mode are discussed. The compound crystallizes in the monoclinic system, P21/c space group, with lattice constants: a = 11.7934(9) Å, b = 14.3002(14) Å, c = 8.4444(8) Å, β = 106.243(5) deg, V = 1367.3(2) Å3, Z = 4, F(000) = 576, R1 = 6.96%, wR2 = 11.4%.

The coordinative chemistry of the tridentate thiosemicarbazone ligand 2-pyridinecarboxaldehyde 4-N-ethylthiosemicarbazone (HLEt) has been explored by using an electrochemical methodology. All the complexes have been characterized using analytical and spectroscopic techniques. In the case of copper we have isolated two different complexes, with Cu(LEt)2·4H2O (6) and [Cu2(LEt)2(SO4)] (7) formulae. The sulfate group coordinated to the copper atoms in 7was probably released to the media as a consequence of a desulfurization process. Single X-ray crystallography has been carried out for the ligand HLEtand the complexes 7, [Ag6(LEt)6]·CH3CN (9) and [Pb(LEt)2] (12). The copper(ii) complex 7is a dimer compound in which two antiparallel monodeprotonated ligands are coordinated to two copper centres by establishment of μ2-thiolate bridges and the additional coordination of a sulfate group bridging the two metal atoms. The silver complex 9is an unusual hexanuclear cluster compound with a wheel-type conformation, while the lead complex 12is a monomer which exhibits the lone pair effect. A structural comparative study of the electrochemically obtained complexes derived from HLXligands (X= Me, Et and Ph) have been performed. Finally, the solution behaviour of the complexes was checked by NMR, UV and fluorescence studies. [ABSTRACT FROM AUTHOR]

We have prepared some transition and post-transition metal complexes derived from the pentadentate thiosemicarbazone ligand bis(4-N-ethylthiosemicarbazone)-2,6-diacetylpyridine H2LEt, by both chemical and electrochemical procedures. The complexes have been synthesised and fully characterised, including the crystal structures for the ligand H2LEtand its manganese, cadmium and lead complexes. We have also performed multinuclear 109Ag, 113Cd, 119Sn and 207Pb studies for silver, cadmium, tin and lead compounds, respectively. Moreover we present here a comparative study on the different structures found for pentadentate thiosemicarbazonate complexes, trying to check the influence of different factors, such as experimental procedure, size of metal, structure of the ligand, and metal oxidation state, on the final structure of the complex formed. Our aim is gaining a better insight into the coordination trends of pentadentate thiosemicarbazone ligands. [ABSTRACT FROM AUTHOR]