Acidic Electrocatalytic Semihydrogenation of Alkynols to Alkenols on Copper Phosphide at Industrial‐Level Current Density

Acidic Electrocatalytic Semihydrogenation of Alkynols to Alkenols on Copper Phosphide at Industrial-Level Current Density

We demonstrate a novel electrocatalytic strategy for selectively hydrogenating alkynols to corresponding high-value-added alkenols under ambient temperature and pressure. In acidic solution, the as-fabricated Cu3P nanoarrays on Cu foam exhibit high alkynol conversion, high alkenol selectivity, and superior long-term stability at an industrial-level current density.


Comprehensive Summary

Alkenols are important intermediates for the industrial manufacture of various commodities and fine chemicals. At present, alkenols are produced via thermocatalytic semihydrogenation of corresponding alkynols using precious metal Pd-based catalysts in pressurized hydrogen atmosphere. In this work, we highlight an efficient electrocatalytic strategy for selectively reducing alkynols to alkenols under ambient conditions. Using 2-methyl-3-butyn-2-ol as a model alkynol, Cu3P nanoarrays anchored on Cu foam remarkably deliver an industrial-level partial current density of 0.79 A·cm–2 and a specific selectivity of 98% for 2-methyl-3-buten-2-ol in acidic solution. Over a 40-runs stability test, Cu3P nanoarrays maintain 90% alkynol conversion and 90% alkenol selectivity. Even in a large two-electrode flow electrolyser, the single-pass alkynol conversion and alkenol selectivity of Cu3P nanoarrays exceed 90%. Moreover, this selective electrocatalytic hydrogenation approach is broadly feasible for the production of various water-soluble alkenols. Electrochemical analyses, theoretical simulation and electrochemical in-situ infrared investigations together reveal that exothermic alkynol hydrogenation, facile alkenol desorption and formation of active H on Cu3P surfaces account for the excellent electrocatalytic performance.

Sensitivity of the Neotropical Solitary Bee Centris analis F. (Hymenoptera, Apidae) to the Reference Insecticide Dimethoate for Pesticide Risk Assessment

Abstract

Currently, only Apis mellifera is used in environmental regulation to evaluate the hazard of pesticides to pollinators. The low representativeness of pollinators and bee diversity in this approach may result in insufficient protection for the wild species. This scenario is intensified in tropical environments, where little is known about the effects of pesticides on solitary bees. We aimed to calculate the medium lethal dose (LD50) and medium lethal concentration (LC50) of the insecticide dimethoate in the Neotropical solitary bee Centris analis, a cavity-nesting, oil-collecting bee distributed from Brazil to Mexico. Males and females of C. analis were exposed orally to dimethoate for 48 h under laboratory conditions. Lethality was assessed every 24 h until 144 h after the beginning of the test. After the LD50 calculation, we compared the value with available LD50 values in the literature of other bee species using the species sensitivity distribution curve. In 48 h of exposure, males showed an LD50 value 1.33 times lower than females (32.78 and 43.84 ng active ingredient/bee, respectively). Centris analis was more sensitive to dimethoate than the model species A. mellifera and the solitary bee from temperate zones, Osmia lignaria. However, on a body weight basis, C. analis and A. mellifera had similar LD50 values. Ours is the first study that calculated an LD50 for a Neotropical solitary bee. Besides, the results are of crucial importance for a better understanding of the effects of pesticides on the tropical bee fauna and will help to improve the risk assessment of pesticides to bees under tropical conditions, giving attention to wild species, which are commonly neglected. Environ Toxicol Chem 2023;00:1–10. © 2023 SETAC

Laboratory Determination of Particulate‐Matter–Bound Agrochemical Toxicity among Honeybees, Mason Bees, and Painted Lady Butterflies

Abstract

Pollinator population declines are global phenomena with severe consequences for native flora and agriculture. Many factors have contributed to pollinator declines including habitat loss, climate change, disease and parasitism, reductions in abundance and diversity of foraging resources, and agrochemical exposure. Particulate matter (PM) serves as a carrier of toxic agrochemicals, and pollinator mortality can occur following exposure to agrochemical-contaminated PM. Therefore, laboratory-controlled experiments were conducted to evaluate impacts of individual PM-bound agrochemicals. Honeybees (Apis mellifera), blue orchard mason bees (Osmia lignaria), and painted lady butterfly (Vanessa cardui) larvae were exposed to bifenthrin, permethrin, clothianidin, imidacloprid, abamectin, and ivermectin via suspended, airborne PM. Agrochemical concentrations in PM to which pollinators were exposed were based on concentrations observed in fugitive beef cattle feedyard PM including a “mean” treatment and a “max” treatment reflective of reported mean and maximum PM-bound agrochemical concentrations, respectively. In general, pollinators in the mean and max treatments experienced significantly higher mortality compared with controls. Honeybees were most sensitive to pyrethroids, mason bees were most sensitive to neonicotinoids, and painted lady butterfly larvae were most sensitive to macrocyclic lactones. Overall, pollinator mortality was quite low relative to established toxic effect levels derived from traditional pollinator contact toxicity tests. Furthermore, pollinator mortality resulting from exposure to individual agrochemicals via PM was less than that reported to occur at beef cattle feedyards, highlighting the importance of mixture toxicity to native and managed pollinator survival and conservation. Environ Toxicol Chem 2023;00:1–9. © 2023 SETAC

Ionothermal Synthesis and Photoactivity of Ti17 and Ti19‐Oxo Clusters Functionalized by Sulfate and 1,10‐Phenanthroline Ligands

Ionothermal Synthesis and Photoactivity of Ti17 and Ti19-Oxo Clusters Functionalized by Sulfate and 1,10-Phenanthroline Ligands

Sulfate and 1,10-phenanthroline ligands decorated Ti17 and Ti19-oxo clusters are prepared by ionothermal synthesis and show structure dependent photocatalytic MB dye degradation and photoelectrochemical photocurrent behaviors.


Comprehensive Summary

In this study, we successfully synthesized two titanium-oxo clusters, namely Ti193-O)192-O)10(1,10-phn)2(OiPr)18] (PTC-178) and (EMIm)3[Ti174-O)43-O)162-O)4(SO4)32-OiPr)4(OiPr)13] (PTC-179). These clusters were synthesized using an ionothermal reaction and possess similar nuclearity (Ti19 vs. Ti17) moieties. Additionally, we observed that these complexes exhibit varying activities for photocatalytic degradation of Methylene Blue (MB) dye and distinct photocurrent responses for photoelectrochemical studies due to their different surface-decorated ligands. This study provides valuable insights into the design of Ti-oxo molecular clusters with similar nuclearity but different surface environments, allowing for the establishment of critical structure-property relationships. Furthermore, our research contributes to the exploration of sustainable synthetic methods for high nuclearity TOCs using ionic liquids.

Metal Mixture Toxicity of Ni, Cu, and Zn in Freshwater Algal Communities and the Correlation of Single‐Species Sensitivities Among Single Metals: A Comparative Analysis

Abstract

The effects assessment of metals is mainly based on data of single metals on single species, thereby not accounting for effects of metal mixtures or effects of species interactions. Both of these effects were tested in combination, thereby hypothesizing that the sensitivity of a community to synergistic mixture toxicity depends on the correlation of single-species sensitivities among the single metals. Single-metal and metal-mixture effects were tested in full concentration–response experiments (fixed ray of 1:1:3 and 5:1:13 mass ratio Ni:Cu:Zn) on eight single freshwater algal species and 14 algal communities of four species each. The mean correlation of single-species median effect concentrations among the single metals (Ni–Cu, Cu–Zn, and Zn–Ni) for all species in a community (r ̅ $\mathop{r}\limits^{̅}$) ranged from −0.4 to 0.9 among the communities; most of these (12/14) were positive. Functional endpoints (total biomass) were overall less sensitive than structural endpoints (Bray-Curtis similarity index) for communities with positively correlated single-species sensitivities among the single metals (r ̅ > 0.33 $\mathop{r}\limits^{̅}\gt 0.33$), suggesting that such correlations indicate functional redundancy under metal-mixture stress. Antagonistic metal-mixture interactions were predominantly found in single species, whereas metal-mixture interactions were antagonistic and surprisingly synergistic for the communities, irrespective of the reference mixture model used (concentration addition or independent action). The mixture interactions close to the carrying capacity (day 7) of communities gradually shifted from antagonism to more noninteractions with increasing correlation of single-species sensitivities among the single metals. Overall, this suggests that functional redundancy under mixed-metal stress comes at the cost of reduced biodiversity and that synergisms can emerge at the community level without any synergisms on the single-species level. Environ Toxicol Chem 2023;00:1–18. © 2023 SETAC.

Cobalt‐Catalyzed Difunctionalization of Styrenes via Ligand Relay Catalysis

Cobalt-Catalyzed Difunctionalization of Styrenes via Ligand Relay Catalysis†

Here, we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity. Not only di- and tri-substituted hydrosilanes, but also alkoxysilane is suitable, which does explore the scope of the family of 1-amino-2-silyl compounds. The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time in this one-pot, two-step transformations.


Comprehensive Summary

Here, we report a cobalt-catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1-amino-2-silyl compounds with excellent regioselectivity. This difunctionalization reaction could undergo smoothly using 1 mol% catalyst loading with good functional group tolerance. Not only di- and tri-substituted hydrosilanes, but also alkoxysilane is suitable, which does explore the scope of the family of 1-amino-2-silyl compounds. The ligand relay phenomenon between neutral tridentate NNN ligand and anionic NNN ligand is observed for the first time via absorption spectral analysis in this one-pot, two-step transformations. The primary mechanism has been proposed based on the control experiments.

Using Multiple Metal Mixture Models to Predict Toxicity of Riverine Sediment Porewater to the Benthic Life Stage of Juvenile White Sturgeon (Acipenser transmontanus)

ABSTRACT

Five metal mixture dose-response models are used to predict toxicity of porewater to young sturgeon at areas of interest in the Upper Columbia River and to evaluate these models as tools for risk assessments. Dose components of metal mixture models include exposure to free metal ion activities or metal accumulation by biotic ligands or humic acid, whereas links of dose to response use logistic equations, independent joint action equations, or additive toxicity functions. Laboratory bioassay studies of single metal exposures to juvenile sturgeon, porewater collected in-situ in the fast-flowing Upper Columbia River, and metal mixture models are used to evaluate toxicity.

The five metal mixture models are very similar in their predictions of adverse response of juvenile sturgeon and in identifying copper (Cu) as the metal responsible for the most toxic conditions. Although the modes of toxic action and EC20 values are different among the dose models, predictions of adverse response are consistent among models because all doses are tied to the same biological responses. All models indicate that 56+5% of 122 porewater samples are predicted to have <20% adverse response, 25+5% of samples are predicted to have 20-80% adverse response, and 20+4% are predicted to have >80% adverse response of juvenile sturgeon.

The approach of combining bioassay toxicity data, compositions of field porewater, and metal mixture models to predict lack of growth and survival of aquatic organisms due to metal toxicity is an important tool that can be integrated with other information (e.g., survey studies of organism populations, lifecycle and behavior characteristics, sediment geochemistry, and food sources) to assess risks to aquatic organisms in metal-enriched ecosystems.

Effects of Acute and Sub‐Chronic Waterborne Thallium Exposure on Ionoregulatory Enzyme Activity and Oxidative Stress in Rainbow Trout (Oncorhynchus mykiss)

ABSTRACT

The mechanisms of acute (96 h) and sub-chronic (28-d) toxicity of the waterborne trace metal thallium (Tl) to rainbow trout (Oncorhynchus mykiss) were investigated. Specifically, effects on branchial and renal ionoregulatory enzymes (sodium/potassium ATPase and proton ATPase) and hepatic oxidative stress endpoints (protein carbonylation, glutathione content and activities of catalase and glutathione peroxidase) were examined. Fish (19-55 g) were acutely exposed to 0 (control), 0.9 (regulatory limit), 2004 (half the acute median lethal concentration) or 4200 (acute median lethal concentration) µg Tl L-1 or sub-chronically exposed to 0, 0.9 or 141 (an elevated environmental concentration) µg Tl L-1. The only effect following acute exposure was a stimulation of renal H+-ATPase activity at the highest Tl exposure concentration. Similarly, the only significant effect of sub-chronic Tl exposure was an inhibition of branchial NKA activity at 141 µg Tl L-1, an effect that may reflect the interaction of Tl with potassium ion handling. Despite significant literature evidence for effects of Tl on oxidative stress, there were no effects of Tl on any such endpoint in rainbow trout, regardless of exposure duration or exposure concentration. Elevated basal levels of antioxidant defences may explain this finding. These data suggest that ionoregulatory perturbance is a more likely mechanism of Tl toxicity than oxidative stress in rainbow trout, but is an endpoint of relevance only at elevated environmental Tl concentrations.

Double stranded DNA binding stapled peptides, an emerging tool for transcriptional regulation

Stapled peptides have rapidly established themselves as a powerful technique to mimic α-helical interactions with a short peptide sequence. There are many examples of stapled peptides that successfully disrupt α-helix-mediated protein-protein interactions, with an example currently in clinical trials. DNA-proteins interactions are also often mediated by α-helices and are involved in all transcriptional regulation processes. Unlike DNA-binding small molecules, which typically lack DNA sequence selectivity, DNA-binding proteins bind with high affinity and high selectivity. These are ideal candidates for the design DNA-binding stapled peptides. Despite the parallel to protein-protein interaction disrupting stapled peptides and the need for sequence specific DNA binders, there are very few DNA-binding stapled peptides. In this review we examine all the known DNA-binding stapled peptides. Their design concepts are compared to stapled peptides that disrupt protein-protein interactions and based on the few examples in the literature, DNA-binding stapled peptide trends are discussed.

Total Synthesis of Syringin and Its Natural Analogues via C—C Bond Activation of Aryl Ketones

Total Synthesis of Syringin and Its Natural Analogues via C—C Bond Activation of Aryl Ketones†


Comprehensive Summary

Syringin is found in the root of Acanthopanax senticosus (Rupr. Maxim.) Harms and belongs to the lignin chemical compound with many biological activities. In this study, we employed commercially available starting materials and accomplished the total synthesis of syringin in 5 steps with an overall yield of 58%. Palladium-catalyzed C(O)–C bond activation and subsequent cross coupling reaction is the key to construct syringin and its natural analogues.