-
International Journal of Molecular... Jun 2023In this paper, three imidazolium-based ionic liquids, viz., 1-butyl-3-undecyl imidazolium bromide ([BUIm]Br), 1-butyl-3-octyl imidazolium bromide ([BOIm]Br), and...
In this paper, three imidazolium-based ionic liquids, viz., 1-butyl-3-undecyl imidazolium bromide ([BUIm]Br), 1-butyl-3-octyl imidazolium bromide ([BOIm]Br), and 1-butyl-3-hexadecyl imidazolium bromide ([BCIm]Br), were synthesized. Three novel microemulsions systems were constructed and then were used to recover Pd (II) from cyanide media. Key extraction parameters such as the concentration of ionic liquids (ILs), equilibration time, phase ratio (R), and pH were evaluated. The [BUIm]Br/n-heptane/n-pentanol/sodium chloride microemulsion system exhibited a higher extraction percentage of Pd (II) than the [BOIm]Br/n-heptane/n-pentanol/sodium chloride and [BCIm]Br/n-heptane/n-pentanol/sodium chloride microemulsion systems. Under the optimal conditions (equilibrium time of 10 min and pH 10), the extraction percentages of these metals were all higher than 98.5% when using the [BUIm]Br/n-heptane/n-pentanol/sodium chloride microemulsion system. Pd(CN) was separated through a two-step stripping procedure, in which Fe (III) and Co (III) were first separated using KCl solution, then Pd(CN) was stripped using KSCN solution (separation factors of Pd from Fe and Co exceeded 10). After five extraction-recovery experiments, the recovery of Pd (II) through the microemulsion system remained over 90%. The Pd (II) extraction mechanism of the ionic liquid [BUIm]Br was determined to occur via anion exchange, as shown by spectral analysis (UV, FTIR), Job's method, and DFT calculations. The proposed process has potential applications for the comprehensive treatment of cyanide metallurgical wastewater.
Topics: Cyanides; Ionic Liquids; Palladium; Bromides; Sodium Chloride
PubMed: 37445887
DOI: 10.3390/ijms241310709 -
Autophagy Nov 2023Proteolysis-targeting chimeras (PROTACs) based on the ubiquitin-proteasome system have made great progress in the field of drug discovery. There is mounting evidence...
Proteolysis-targeting chimeras (PROTACs) based on the ubiquitin-proteasome system have made great progress in the field of drug discovery. There is mounting evidence that the accumulation of aggregation-prone proteins or malfunctioning organelles is associated with the occurrence of various age-related neurodegenerative disorders and cancers. However, PROTACs are inefficient for the degradation of such large targets due to the narrow entrance channel of the proteasome. Macroautophagy (hereafter referred to as autophagy) is known as a self-degradative process involved in the degradation of bulk cytoplasmic components or specific cargoes that are sequestered into autophagosomes. In the present study, we report the development of a generalizable strategy for the targeted degradation of large targets. Our results suggested that tethering large target models to phagophore-associated ATG16L1 or LC3 induced targeted autophagic degradation of the large target models. Furthermore, we successfully applied this autophagy-targeting degradation strategy to the targeted degradation of HTT65Q aggregates and mitochondria. Specifically, chimeras consisting of polyQ-binding peptide 1 (QBP) and ATG16L1-binding peptide (ABP) or LC3-interacting region (LIR) induced targeted autophagic degradation of pathogenic HTT65Q aggregates; and the chimeras consisting of mitochondria-targeting sequence (MTS) and ABP or LIR promoted targeted autophagic degradation of dysfunctional mitochondria, hence ameliorating mitochondrial dysfunction in a Parkinson disease cell model and protecting cells from apoptosis induced by the mitochondrial stress agent FCCP. Therefore, this study provides a new strategy for the selective proteolysis of large targets and enrich the toolkit for autophagy-targeting degradation. ABP: ATG16L1-binding peptide; ATG16L1: autophagy related 16 like 1; ATTEC: autophagy-tethering compound; AUTAC: autophagy-targeting chimera; AUTOTAC: autophagy-targeting chimera; Baf A1: bafilomycin A; BCL2: BCL2 apoptosis regulator; CALCOCO2/NDP52: calcium binding and coiled-coil domain 2; CASP3: caspase 3; CPP: cell-penetrating peptide; CQ: chloroquine phosphate; DAPI: 4',6-diamidino-2-phenylindole; DCM: dichloromethane; DMF: N,N-dimethylformamide; DMSO: dimethyl sulfoxide; EBSS: Earle's balanced salt solution; FCCP: carbonyl cyanide 4-(trifluoromethoxy)phenylhydrazone; FITC: fluorescein-5-isothiocyanate; GAPDH: glyceraldehyde-3-phosphate dehydrogenase; GFP: green fluorescent protein; HEK293: human embryonic kidney 293; HEK293T: human embryonic kidney 293T; HPLC: high-performance liquid chromatography; HRP: horseradish peroxidase; HTT: huntingtin; LIR: LC3-interacting region; MAP1LC3/LC3: microtubule associated protein 1 light chain 3; MFF: mitochondrial fission factor; MTS: mitochondria-targeting sequence; NBR1: NBR1 autophagy cargo receptor; NLRX1: NLR family member X1; OPTN: optineurin; P2A: self-cleaving 2A peptide; PB1: Phox and Bem1p; PBS: phosphate-buffered saline; PE: phosphatidylethanolamine; PINK1: PTEN induced kinase 1; PRKN: parkin RBR E3 ubiquitin protein ligase; PROTACs: proteolysis-targeting chimeras; QBP: polyQ-binding peptide 1; SBP: streptavidin-binding peptide; SDS-PAGE: sodium dodecyl sulfate-polyacrylamide gel electrophoresis; SPATA33: spermatogenesis associated 33; TIMM23: translocase of inner mitochondrial membrane 23; TMEM59: transmembrane protein 59; TOMM20: translocase of outer mitochondrial membrane 20; UBA: ubiquitin-associated; WT: wild type.
Topics: Humans; Male; Autophagy; Autophagy-Related Proteins; Carbonyl Cyanide p-Trifluoromethoxyphenylhydrazone; HEK293 Cells; Mitochondria; Mitochondrial Proteins; Proteasome Endopeptidase Complex; Protein Aggregates; Proto-Oncogene Proteins c-bcl-2; Ubiquitins
PubMed: 37424101
DOI: 10.1080/15548627.2023.2234797 -
Advanced Materials (Deerfield Beach,... Sep 2023The majority of waste-heat energy exists in the form of low-grade heat (<100 °C), which is immensely difficult to convert into usable energy using conventional...
The majority of waste-heat energy exists in the form of low-grade heat (<100 °C), which is immensely difficult to convert into usable energy using conventional energy-harvesting systems. Thermally regenerative electrochemical cycles (TREC), which integrate battery and thermal-energy-harvesting functionalities, are considered an attractive system for low-grade heat harvesting. Herein, the role of structural vibration modes in enhancing the efficacy of TREC systems is investigated. How changes in bonding covalency, influenced by the number of structural water molecules, impact the vibration modes is analyzed. It is discovered that even small amounts of water molecules can induce the A stretching mode of cyanide ligands with strong structural vibration energy, which significantly contributes to a larger temperature coefficient (ɑ) in a TREC system. Leveraging these insights, a highly efficient TREC system using a sodium-ion-based aqueous electrolyte is designed and implemented. This study provides valuable insights into the potential of TREC systems, offering a deeper understanding of the intrinsic properties of Prussian Blue analogs regulated by structural vibration modes. These insights open up new possibilities for enhancing the energy-harvesting capabilities of TREC systems.
PubMed: 37395728
DOI: 10.1002/adma.202303199 -
Biochemical and Biophysical Research... Sep 2023Atopic dermatitis (AD) is a common disease with a considerable impact on the patient's quality of life and limited treatment options. Sodium thiosulfate (STS) is a...
Atopic dermatitis (AD) is a common disease with a considerable impact on the patient's quality of life and limited treatment options. Sodium thiosulfate (STS) is a traditional medicine used in the rescue of cyanide poisoning, and some pruritus dermatosis. However, the exact efficacy and mechanism of its application on AD are not clear. In this work, comparing to other traditional therapy, STS was found to effectively improve the severity of skin lesions and the quality of life in AD patients with a dose-dependent manner. Mechanically, STS downregulated the expression of IL-4, IL-13, IgE in the serum of AD patients, as well as reduce the concentration of eosinophils. Furthermore, in the AD-like mice model triggered by ovalbumin (OVA) and calcitriol, STS was found to reduce the epidermal thickness, scratching times, and the infiltration of dermal inflammatory cells in AD mice, as well as the reactive oxygen species (ROS) production and the expression levels of inflammatory cytokines in the skin tissue. In HacaT cells, STS inhibited the accumulation of ROS and activation of NLRP3 inflammasome and its downstream IL-1β expression. Therefore, this study revealed that STS plays an important therapeutic role in AD, and the mechanism may be that STS inhibits the activation of NLRP3 inflammasome and the subsequent release of inflammatory cytokines. Thus, the role of STS in treating AD was clarified and the possible molecular mechanism was revealed.
Topics: Animals; Mice; Cytokines; Dermatitis, Atopic; Disease Models, Animal; Inflammasomes; Mice, Inbred BALB C; NLR Family, Pyrin Domain-Containing 3 Protein; Quality of Life; Reactive Oxygen Species; Skin
PubMed: 37392479
DOI: 10.1016/j.bbrc.2023.06.072 -
Langmuir : the ACS Journal of Surfaces... Jul 2023Aqueous biphasic systems (ABSs) that are based on deep eutectic solvents (DESs) are environmentally benign systems to use for metal ion separation. In this work, a...
Aqueous biphasic systems (ABSs) that are based on deep eutectic solvents (DESs) are environmentally benign systems to use for metal ion separation. In this work, a series of DESs was synthesized for the first time with PEG 400 as hydrogen bond donors and tetrabutylphonium bromide (PBr), tetrabutylammonium bromide (NBr), or tetrabutylammonium chloride (NCl) as hydrogen bond acceptors, and then they were combined with citrate (NaCHO), which is eco-friendly, to construct an ABS for use in the separation of Au(I) from an aurocyanide solution. Phase diagrams of DESs + NaCHO + HO systems were constructed using the experimentally measured data. Multiple factors that affect the efficiency of the gold extraction were studied; these factors were the species of salt or DES and their content, the equilibrium pH, the oscillation time, and the initial gold concentration. Gold(I) is preferentially retained in the DES-rich phase, and the PBr:PEG 1:2 + NaCHO + HO system has a high extraction efficiency of 100.0% under optimized conditions. FT-IR, NMR, and TEM characterizations and DFT calculations show that the migration of Au(I) from the salt-rich to the DES-rich phase follows an ion exchange mechanism. Specifically, Au(CN) replaces Br in the original PBr and generates a stable ion pair with the quaternary phosphonium salt cation, P, and this replacement is driven by electrostatic attractions. A new strong hydrogen bond network simultaneously forms between the anionic Au(CN) and the -OH group in the PEG 400 component. Finally, the gold of Au(I)-loaded PBr:PEG 1:2 can be successfully reduced by sodium borohydride with an efficiency of 100.0%. The strategy to extract gold(I) from alkaline cyanide solutions using an ABS based on DESs as proposed in this work provides a potential platform for developing green technology for recovering gold.
PubMed: 37366178
DOI: 10.1021/acs.langmuir.3c01076 -
The Journal of Organic Chemistry Jul 2023This work describes the unprecedented intramolecular cyclization occurring in a set of α-azido-ω-isocyanides in the presence of catalytic amounts of sodium azide....
This work describes the unprecedented intramolecular cyclization occurring in a set of α-azido-ω-isocyanides in the presence of catalytic amounts of sodium azide. These species yield the tricyclic cyanamides [1,2,3]triazolo[1,5-]quinoxaline-5(4)-carbonitriles, whereas in the presence of an excess of the same reagent, the azido-isocyanides convert into the respective C-substituted tetrazoles through a [3 + 2] cycloaddition between the cyano group of the intermediate cyanamides and the azide anion. The formation of tricyclic cyanamides has been examined by experimental and computational means. The computational study discloses the intermediacy of a long-lived -cyanoamide anion, detected by NMR monitoring of the experiments, subsequently converting into the final cyanamide in the rate-determining step. The chemical behavior of these azido-isocyanides endowed with an aryl-triazolyl linker has been compared with that of a structurally identical azido- isomer, experiencing a conventional intramolecular [3 + 2] cycloaddition between its azido and cyanide functionalities. The synthetic procedures described herein constitute metal-free approaches to novel complex heterocyclic systems, such as [1,2,3]triazolo[1,5-]quinoxalines and 9-benzo[]tetrazolo[1,5-][1,2,3]triazolo[1,5-][1,4]diazepines.
Topics: Azides; Cyanides; Cyclization; Molecular Structure; Cyanamide; Quinoxalines
PubMed: 37338459
DOI: 10.1021/acs.joc.3c00558 -
Planta May 2023The consortium inoculation with strains R1 and R4 modified the root system to boost seedling growth, increase the zinc content of French bean pods, and reduce salinity...
Assessing the role of ACC deaminase-producing bacteria in alleviating salinity stress and enhancing zinc uptake in plants by altering the root architecture of French bean (Phaseolus vulgaris) plants.
The consortium inoculation with strains R1 and R4 modified the root system to boost seedling growth, increase the zinc content of French bean pods, and reduce salinity stress. The present study demonstrated the effect of two 1-aminocyclopropane-1-carboxylic acid (ACC) deaminase-producing plant growth-promoting rhizobacteria (Pantoea agglomerans R1 and Pseudomonas fragi R4) alone and consortia on the root system development, French bean growth, and zinc content as well as salinity stress tolerance. Both the strains were characterized for ACC utilization activity (426.23 and 380.54 nmol α-ketobutyrate mg protein h), indole acetic acid (IAA) production, phosphate solubilization, ammonia, hydrogen cyanide (HCN), and siderophore production. The strains exhibited zinc solubilization in both plate and broth assays with zinc oxide and zinc carbonate as zinc sources as validated by atomic absorption spectroscopy (AAS). Single or combined inoculations with the selected strains significantly modulated the architectural and morphological traits of the root system of French bean plants. Furthermore, the application of R1and R4 consortia has enhanced zinc content in roots (60.83 mg kg), shoots (15.41 mg kg), and pods (30.04 mg kg) of French bean plants grown in ZnCO amended soil. In another set of pot experiments, the consortium bacterization has significantly enhanced length as well as fresh and dry biomass of roots and shoots of the French bean plant under saline stress conditions. Additionally, inoculation with ACC-degrading rhizobacterial strains has increased chlorophyll and carotenoid contents, osmoprotectant content, and antioxidative enzyme (catalase and peroxidase) activity in comparison to their counterparts exposed to salt treatments only. Current findings suggested ACC deaminase-producing rhizobacterial strains hold the potential to improve root architecture which in turn promotes plant growth under salt-stressed conditions as well as enhances micronutrient concentration in host plants.
Topics: Phaseolus; Bacteria; Carbon-Carbon Lyases; Sodium Chloride; Salt Stress; Zinc; Soil Microbiology; Plant Roots; Salinity
PubMed: 37212904
DOI: 10.1007/s00425-023-04159-3 -
Ecotoxicology (London, England) May 2023Artisanal and small-scale gold mining (ASGM) is the largest source of anthropogenic Hg emissions on the planet. In addition, Hg-contaminated tailings are often...
Artisanal and small-scale gold mining (ASGM) is the largest source of anthropogenic Hg emissions on the planet. In addition, Hg-contaminated tailings are often reprocessed with sodium cyanide (NaCN) to extract the residual gold remaining in the material. This leads to the formation of mercury cyanide (Hg(CN)) complexes, which are often discharged in untreated form into local drainages, leading to large amounts of free cyanide being released. However, data on mercury-cyanide interactions are scarce. In this study, we investigated the impact of cyanide and Hg bioavailability in zebrafish when added as Hg(CN). Different concentrations of Hg(CN) and NaCN were used, leading to an LC of 0.53 mg.L for NaCN and 0.16 mg.L for Hg(CN). Analyzing free cyanide concentrations in aquarium water, >40% dissociation was observed for NaCN and about 5% for Hg(CN). The accumulation of total Hg (THg) in the brain, gills, muscle and kidney was quantified. All fish exposed to Hg(CN) had higher THg levels than their controls and kidney was the tissue with higher Hg(CN) accumulation. Histological effects on the kidney and gills of both cyanides in D. rerio tissues were investigated, suggesting renal alterations in fish exposed to Hg(CN) and showing hyperplasia in the gills of animals exposed to NaCN and Hg(CN). The results alert to the risks of the presence of these complexes in aquatic environments.
Topics: Animals; Zebrafish; Mercury; Ecotoxicology; Gold; Cyanides; Environmental Monitoring
PubMed: 37055677
DOI: 10.1007/s10646-023-02651-w -
Molecules (Basel, Switzerland) Apr 2023Cross-coupling reactions with [BHI] as one partner have been used successfully for Kumada and Buchwald Hartwig couplings with Pd catalysis. Here, we found that the...
Cross-coupling reactions with [BHI] as one partner have been used successfully for Kumada and Buchwald Hartwig couplings with Pd catalysis. Here, we found that the iodide could be substituted easily, and unexpectedly, with other halides such as Br and Cl, and with pseudohalides such as cyanide, azide, and isocyanate. We found that for Cl, Br, N, and NCO, tetrabutylammonium salts-or sodium salts-were successful halide sources, whereas for cyanide, CuCN was the only halide source that allowed a successful exchange. The azide could be reacted further in a click reaction with triazoles. While no substitution with fluoride occurred, tetrabutylammonium fluoride in the presence of water led to [BHOH]. Yields were high to very high, and reaction times were short when using a microwave oven as a heating source.
PubMed: 37050008
DOI: 10.3390/molecules28073245