Consolidation of the Oxidant-Free Au(I)/Au(III) Catalysis Enabled by the Hemilabile Ligand Strategy.

In this minireview we survey the challenges and strategies in gold redox catalysis. Gold's reluctance to oxidative addition reactions due to its high redox potential limits its applicability. Initial attempts to overcome this problem focused on the use of sacrificial external oxidants in stoichiometric amounts to bring Au(I) compounds to Au(III) reactive species. Recently, innovative approaches focused on employing hemilabile ligands, which are capable of coordinating to Au(I) and stabilizing square-planar Au(III) intermediates, thus facilitating oxidative addition steps and enabling oxidant-free catalysis. Notable examples include the use of the (P^N) bidendate MeDalphos ligand to achieve various cross-coupling reactions via oxidative addition Au(I)/Au(III). Importantly, hemilabile ligand-enabled catalysis allows merging oxidative addition with π-activation, such as oxy- and aminoarylation of alkenols and alkenamines using organohalides, expanding gold's versatility in C-C and C-heteroatom bond formations and unprecedented cyclizations. Moreover, recent advancements in enantioselective catalysis using chiral hemilabile (P^N) ligands are also surveyed. Strikingly, versatile bidentate (C^N) hemilabile ligands as competitors of MeDalphos have appeared recently, by designing scaffolds where phosphine groups are substituted by N-heterocyclic or mesoionic carbenes. Overall, these approaches highlight the evolving landscape of gold redox catalysis and its tremendous potential in a broad scope of transformations.

Variation of the feeding/resting period in modified vertical treatment wetlands (depth, zeolite as medium) employed for treating rural domestic wastewater in tourist areas.

This work aimed to evaluate the performance of modified vertical flow treatment wetlands (VF-TWs) in terms of depth and medium to assess the effect of the feeding/resting periods and footprint (FP). The modifications were proposed for treating domestic wastewater in rural areas with flow variations such as tourist sites. The experimental setup included six laboratory-scale VF-TWs: (a) normal (VF-N), bed depth 1.0 m, filled with sand and (b) modified (VF-M), bed depth 0.5 m, filled with sand (upper) and zeolite (bottom, saturated). The operation was divided into three phases (3 months each), varying the feeding/resting period and FP: phase I, 5 d/10 d, 2.6 m2/person-equivalent (PE); phase II, 3.5 d/3.5 d, 1.7 m2/PE; and phase III, only feeding no resting, 0.85 m2/PE. Influent and effluent grab samples were taken every 2 weeks. The results showed effective removal (above 60%) of total solids, organic matter, and pathogens for both VF-N and VF-M. Regarding nutrients, VF-M showed a phosphate removal below 60%, but no consistent removal (15-60%) of total nitrogen. Thus, the results suggest that proposed modifications can be an option to be established in tourist sites, but further work should be conducted to improve and optimize total nitrogen removal.

Avocado Oil: Characteristics, Properties, and Applications.

Avocado oil has generated growing interest among consumers due to its nutritional and technological characteristics, which is evidenced by an increase in the number of scientific articles that have been published on it. The purpose of the present research was to discuss the extraction methods, chemical composition, and various applications of avocado oil in the food and medicine industries. Our research was carried out through a systematic search in scientific databases. Even though there are no international regulations concerning the quality of avocado oil, some authors refer to the parameters used for olive oil, as stated by the Codex Alimentarius or the International Olive Oil Council. They indicate that the quality of avocado oil will depend on the quality and maturity of the fruit and the extraction technique in relation to temperature, solvents, and conservation. While the avocado fruit has been widely studied, there is a lack of knowledge about avocado oil and the potential health effects of consuming it. On the basis of the available data, avocado oil has established itself as an oil that has a very good nutritional value at low and high temperatures, with multiple technological applications that can be exploited for the benefit of its producers.

Experimental and theoretical approaches to the influence of the addition of pyrene to a series of Pd and Ni NHC-based complexes: catalytic consequences.

A series of Ni and Pd complexes with three different N-heterocyclic carbene (NHC)-based ligands (imidazolylidene, benzimidazolylidene and pyrene-imidazolylidene) has been prepared and fully characterized. The influence of the addition of pyrene to solutions containing these complexes is studied by means of NMR and UV/Vis spectroscopies and by cyclic voltammetry. The addition of pyrene to the pyrene-NHC-containing Pd and Ni complexes gives rise to the formation of adducts by π-π stacking interactions between pyrene and the pyrene group of the NHC ligand. This interaction causes a modification of the electronic properties of the metal, as demonstrated by cyclic voltammetric studies of the Ni-NHC complexes. Theoretical calculations support this type of π-interactions, and justify the higher interactions observed with the pyrene-NHC containing complexes. The catalytic activities of the complexes were tested in the Suzuki-Miyaura C-C coupling and in the α-arylation of ketones. The addition of pyrene as an external π-stacking additive does not affect the activities of the complexes in the Suzuki-Miyaura coupling, but this observation may be justified due to the fact that the process is heterogeneously catalyzed, as indicated by the mercury-drop test. The addition of pyrene to the catalytic α-arylation of ketones results in a decrease in the activity of the reactions catalyzed by the pyrene-imidazolylidene palladium complex, whereas the other two catalysts do not modify their activity in the presence of this π-stacking additive.

Postmodification of the electronic properties by addition of π-stacking additives in N-heterocyclic carbene complexes with extended polyaromatic systems.

A series of iridium complexes containing phenanthro[4,5-abc]phenazino[11,12-d]imidazol-2-ylidene and acetonaphtho[1,2-b]quinoxaline[11,12-d]imidazol-2-ylidene ligands have been obtained and fully characterized. These complexes display highly extended polyaromatic systems attached to the backbone of the N-heterocyclic carbene. The presence of this extended polyaromatic system makes the electron-donating character of these ligands sensitive to the presence of π-stacking additives, such as pyrene and hexafluorobenzene. The computational studies predict that the addition of pyrene affords an increase of the electron-donating character of the polyaromatic ligand (Tolman electronic parameter (TEP) decreases), while the addition of hexafluorobenzene has the opposite effect (TEP increases). This prediction is experimentally corroborated by IR spectroscopy, by measuring the shift of the CO stretching bands of a series of IrCl(NHC)(CO)2 complexes, where NHC is the N-heterocyclic carbene ligand with the polyaromatic system. Finally, the energy of the π-stacking interaction of one of the key Ir(I) complexes with pyrene and hexafluorobenzene has been estimated by using the Benesi-Hildebrand treatment, based on the δ-shifts observed by (1)H NMR spectroscopy.

CCC-NHC Au(iii) pincer complexes as a reliable platform for isolating elusive species.

The reactivity of unprecedented CCC-NHC Au(iii) pincer complexes has been investigated, employing a novel methodology for their preparation. Notably, this marks the inaugural case of CCC-NHC Au(iii) pincer complexes with a central aryl moiety where the two arms of the pincer ligand consist of N-heterocyclic carbenes (NHC). The stability conferred by the CCC-NHC ligand facilitated the isolation of elusive Au(iii) species, encompassing Au(iii)-formate, Au(iii)-F, Au(iii)-Me, and Au(iii)-alkynyl. Our study also unveiled the elusive Au(iii)-H species, offering valuable insights into its formation, stability, and reactivity. While the CCC-NHC Au(iii)-H complex remains stable at room temperature, its decomposition becomes conspicuous at elevated temperatures (>60 °C), exhibiting a more pronounced tendency under acidic conditions compared to basic ones. Through comprehensive experiments, we indirectly demonstrated the potential of Au(iii)-formate to undergo ß-hydride elimination, becoming a key step in the dehydrogenation of formic acid. Theoretical calculations revealed variations in the reactivity of Au(iii)-H species towards sodium hydride and formic acid, highlighting a link between σ-donation from the pincer ligand and reaction energetics. Pincers with lower electron donation favored the reaction with sodium hydride but impeded the reaction with formic acid, whereas those with higher electron donation exhibited the opposite behavior. Additionally, the CCC-NHC Au(iii) pincer complex exhibited Lewis acid behavior, catalyzing the synthesis of phenols. In summary, the CCC-NHC Au(iii) pincer complex emerges as a versatile platform for isolating reactive species and unraveling elementary catalytic steps.

Hemilabile MIC

Oxidant-free Au-catalyzed reactions are emerging as a new synthetic tool for innovative organic transformations. Oxidant-free Au-catalyzed reactions are emerging as a new synthetic tool for innovative organic transformations. Still, a deeper mechanistic understanding is needed for a rational design of these processes. Here we describe the synthesis of two Au(i) complexes bearing bidentated hemilabile MIC^N ligands, [AuI(MIC^N)Cl], and their ability to stabilize square-planar Au(iii) species (MIC = mesoionic carbene). The presence of the hemilabile N-ligand contributed to stabilize the ensuing Au(iii) species acting as a five-membered ring chelate upon its coordination to the metal center. The Au(iii) complexes can be obtained either by using external oxidants or, alternatively, by means of feasible oxidative addition with strained biphenylene Csp2 -Csp2 bonds as well as with aryl iodides. Based on the fundamental knowledge gained on the redox properties on these Au(i)/Au(iii) systems, we successfully develop a novel Au(i)-catalytic procedure for the synthesis of γ-substituted γ-butyrolactones through the arylation-lactonization reaction of the corresponding γ-alkenoic acid. The oxidative addition of the aryl iodide, which in turn is allowed by the hemilabile nature of the MIC^N ligand, is an essential step for this transformation.

Bimetallic complexes that merge metallocene and pincer-metal building blocks: synthesis, stereochemistry and catalytic reactivity.

This perspective is to illustrate the synthesis and applications of bimetallic complexes by merging a metallocene and a (cyclopentadienyl/aryl) pincer metal complex. Four possible ways to merge metallocene and pincer-metal motifs are reported and representative examples are discussed in more detail. These bimetallic complexes have been employed in some important catalytic reactions such as cross-coupling, transfer hydrogenation or synthesis of ammonia. The metallocene fragment may tune the electronic properties of the pincer ligand, due to its redox reversible properties. Also, the presence of two metals in a single complex allows their electronic communication, which proved beneficial for, e.g., the catalytic activity of some species. The presence of the metallocene fragment provides an excellent opportunity to develop chiral catalysts, because the metallocene merger generally renders the two faces of the pincer-metal catalytic site diastereotopic. Besides, an extra chiral functionality may be added to the bimetallic species by using pincer motifs that are planar chiral, e.g. by using the different substituents of pincer ligand "arms" or non-symmetrical arene groupings. Post-functionalization of pre-formed pincer-metal complexes, via η6-coordination with an areneophile such as [CpRu]+ and [Cp*Ru]+ presents a striking strategy to obtain diastereomeric metallocene-pincer type derivatives, that actually involve half-sandwich metallocenes. This approach offers the possibility to create diastereomerically pure derivatives by using the chiral TRISPHAT anion. The authors hope that this report of the synthetic, physico-chemical properties and remarkable catalytic activities of metallocene-based pincer-metal complexes will inspire other researchers to continue exploring this realm.

Comparative Analysis of Conventional and Emerging Technologies for Seawater Desalination: Northern Chile as A Case Study.

The aim of this work was to study different desalination technologies as alternatives to conventional reverse osmosis (RO) through a systematic literature review. An expert panel evaluated thermal and membrane processes considering their possible implementation at a pilot plant scale (100 m3/d of purified water) starting from seawater at 20 °C with an average salinity of 34,000 ppm. The desalination plant would be located in the Atacama Region (Chile), where the high solar radiation level justifies an off-grid installation using photovoltaic panels. We classified the collected information about conventional and emerging technologies for seawater desalination, and then an expert panel evaluated these technologies considering five categories: (1) technical characteristics, (2) scale-up potential, (3) temperature effect, (4) electrical supply options, and (5) economic viability. Further, the potential inclusion of graphene oxide and aquaporin-based biomimetic membranes in the desalinization processes was analyzed. The comparative analysis lets us conclude that nanomembranes represent a technically and economically competitive alternative versus RO membranes. Therefore, a profitable desalination process should consider nanomembranes, use of an energy recovery system, and mixed energy supply (non-conventional renewable energy + electrical network). This document presents an up-to-date overview of the impact of emerging technologies on desalinated quality water, process costs, productivity, renewable energy use, and separation efficiency.

Reverse Osmosis Concentrate: Physicochemical Characteristics, Environmental Impact, and Technologies.

This study's aim is to generate a complete profile of reverse osmosis concentrate (ROC), including physicochemical characteristics, environmental impact, and technologies for ROC treatment, alongside element recovery with potential valorization. A systematic literature review was used to compile and analyze scientific information about ROC, and systematic identification and evaluation of the data/evidence in the articles were conducted using the methodological principles of grounded data theory. The literature analysis revealed that two actions are imperative: (1) countries should impose strict regulations to avoid the contamination of receiving water bodies and (2) desalination plants should apply circular economies. Currently, synergizing conventional and emerging technologies is the most efficient method to mitigate the environmental impact of desalination processes. However, constructed wetlands are an emerging technology that promise to be a viable multi-benefit solution, as they can provide simultaneous treatment of nutrients, metals, and trace organic contaminants at a relatively low cost, and are socially accepted; therefore, they are a sustainable solution.

Evaluation of Bed Depth Reduction, Media Change, and Partial Saturation as Combined Strategies to Modify in Vertical Treatment Wetlands.

The aim of this work was to evaluate the performance of vertical subsurface flow treatment wetlands (VSSF TWs) for treating rural domestic wastewater when strategies such as bed depth reduction and media change are used in combination with bottom saturation. Two treatment wetland systems were implemented: normal (VF-N), with a bed depth of 1.0 m, and modified (VF-M), with a bed depth of 0.5 m and a bottom layer of natural zeolite. Schoenoplectus californicus was used as experimental plant. These two treatment systems were operated at a hydraulic loading rate of 120 mm/d in two phases. Phase I did not use bottom saturation, while Phase II involved a bottom saturation of the zeolite layer of the VF-M system. The results show that bed depth reduction did not have a significant effect (p > 0.05) in terms of organic matter, solids, and ammonium removal. Conversely, it had a significant influence (p < 0.05) on phosphate as well as a negative effect on pathogen removal. This influence could be explained by initial media capacity for phosphorus removal and filtration importance in the case of pathogens. Partial saturation only had a positive influence on total nitrogen removal. The addition of a bottom layer of natural zeolite showed no positive effect on nutrient removal. The plant showed adaptation and positive development in both VF-N and VF-M. The water balance showed that water loss was not influenced by bed depth reduction. Therefore, according to the previous results, a combination of the proposal modifications to VSSF TWs can be introduced for treating rural domestic wastewater.

Fluorinated-NHC Transition Metal Complexes: Leading Characters as Potential Anticancer Metallodrugs.

In the last 20 years, N-Heterocyclic Carbene (NHC) ligands have been ubiquitous in biological and medicinal chemistry. Part of their success lies in the tremendous number of topologies that can be synthesized and thus finely tuned that have been described so far. This is particularly true in the case of those derivatives, including fluorine or fluorinated fragments on their NHC moieties, gaining much attention due to their enhanced biological properties and turning them into excellent candidates for the development of novel metallodrugs. Thus, this review summarizes the development that fluorinated-NHC transition metal complexes have had and their impact on cancer treatment.

Synthesis of Pt(II) complexes of the type [Pt(1,10-phenanthroline)(SArFn)2] (SArFn = SC6H3-3,4-F2; SC6F4-4-H; SC6F5). Preliminary evaluation of their in vitro anticancer activity.

A series of Pt(II) complexes of the type [Pt(1,10-phenanthroline)(SArFn)2] (SArFn = SC6H3-3,4-F2(1); SC6F4-4-H (2); SC6F5(3)) were synthesized from [Pt(1,10-phenanthroline)(Cl)2] and [Pb(SArFn)2] via metathesis reactions. The complexes were fully characterized including the unambiguous determination of their molecular structures by single-crystal X-ray diffraction techniques, showing the metal centers to be into a slightly distorted square-planar environments. The in vitro cytotoxic activity of the complexes was evaluated on six cancerous cell lines, i.e: glial cells of nervous central system (U-251), prostate (PC-3), leukemia (K-562), colon (HCT-15), breast (MCF-7) and lung (SKLU-1); we also included a healthy cell line of COS-7 (African green monkey kidney) for comparative purposes. We found that complex 2 was selective for PC-3. In addition, the IC50 values for the series of complexes were determined using the U-251, HCT-15 and SKLU-1 cancerous cell lines, as well as in the healthy cell line (COS-7), where complex 1 exhibited the best activity, with IC50 values going from 4.56 to 4.78 µM. These studies where further complemented with DNA docking theoretical calculations and DNA affinity experiments.