Biphenyl Ether Research Articles

Exposure of an endangered seabird species to persistent organic pollutants: Assessing levels in blood and link with reproductive parameters

Ocean contamination, particularly from persistent organic pollutants (POPs), remains a significant threat to marine predators that occupy high trophic positions. Long-lived procellariform seabirds are apex predators in marine ecosystems and tend to accumulate contaminants. Prolonged exposure to pollutants negatively affects their fitness including reproductive success. Low breeding success may represent a hurdle for the restoration of small and endangered seabird populations, including several highly threatened gadfly petrels. Here we investigated the annual variation (2019 and 2022) in organochlorine pesticide (OCP), polychlorinated biphenyl ether (PCB), polybrominated diphenyl ether (PBDE), and polycyclic aromatic hydrocarbon (PAH) exposure in the endangered Bermuda petrel (Pterodroma cahow), and the relationship between female contaminant burden and breeding parameters. We found that petrels were exposed to a wide range of pollutants (33 out of 55 showed measurable levels) with PCBs dominating the blood contaminant profiles in both years. Only 9 compounds were detected in >50 % of the birds. Specifically, among OCPs, p, p’-DDE and hexaclorobenzene were the most frequently detected while fluorene and acenaphthene were the most common PAH. The concentrations of ∑5PCBs and ∑7POPs were higher in older birds. Furthermore, females with greater contaminant burdens laid eggs with a lower probability of hatching. However, female investment in egg production (size and volume) was unrelated to their blood contaminant load. Overall, this study highlights the presence of a wide range of contaminants in the petrel's food web, and it sheds light on the potential impact of chronic exposure to sub-lethal levels of PCBs on the breeding success of seabirds. We claim that toxicological testing should be a practice integrated in the management of seabirds, particularly of endangered species to monitor how past and present anthropogenic activities impact their conservation status.

Highly efficient non-doped organic light emitting diodes based on phenanthreneimidazole derivatives with hot exciton mechanism

Organic light-emitting diodes (OLEDs) promise many advantages for next-generation illumination and future display applications. Developing organic metal-free fluorescent emitter with wide bandgap and high efficiency is both significant and challenging in OLEDs. Here, phenanthroimidazole (PI) unit possessing ultraviolet emission is connected with biphenyl, diphenylmethane and diphenyl ether moieties to construct a series of blue luminogens of PPIDPh, PPIDPhC and PPIDPhO with hot exciton character. PPIDPh with biphenyl substituent at C2 position of PI group exhibits emission peak at 454 nm in non-doped film. The integration of diphenylmethane and diphenyl ether units with PI group in PPIDPhC and PPIDPhO further limits the π-conjugation owing to sp3 hybridized carbon atom and oxygen atom, which results in bluer emission peaking at 433 nm and 437 nm in the aggregated state, respectively. Particularly, the maximum external quantum efficiency (EQEmax) of PPIDPh-based non-doped OLED reaches 10.33 % with CIE coordinates of (0.15, 0.10) and subtle efficiency roll-off of only 7.4 % at high brightness of 1000 cd m−2. The PPIDPhC and PPIDPhO-based non-doped devices display even better color purity with high EQEmax of 8.56 % and 7.90 %, Commission Internationale de ĺEclairage (CIE) coordinates of (0.17, 0.08) and (0.16, 0.08), respectively, matching well with National Television Standards Committee (NTSC) requirement for saturated blue color. Such result is among the best outcomes of non-doped blue fluorescent OLEDs with the same emission color. This result will also shed light on the further development of efficient organic wide bandgap emitter and corresponding high-performance OLED.

Protective Effects of Isoliquiritigenin and Licochalcone B on the Immunotoxicity of BDE-47: Antioxidant Effects Based on the Activation of the Nrf2 Pathway and Inhibition of the NF-κB Pathway.

2,2',4,4'-Tetrabrominated biphenyl ether (BDE-47) is a polybrominated diphenyl ether (PBDE) homologue that is ubiquitous in biological samples and highly toxic to humans and other organisms. Prior research has confirmed that BDE-47 can induce oxidative damage in RAW264.7 cells, resulting in apoptosis and impaired immune function. The current study mainly focused on how Isoliquiritigenin (ISL) and Licochalcone B (LCB) might protect against BDE-47's immunotoxic effects on RAW264.7 cells. The results show that ISL and LCB could increase phagocytosis, increase the production of MHC-II, and decrease the production of inflammatory factors (TNF-α, IL-6, and IL-1β) and co-stimulatory factors (CD40, CD80, and CD86), alleviating the immune function impairment caused by BDE-47. Secondly, both ISL and LCB could reduce the expressions of the proteins Bax and Caspase-3, promote the expression of the protein Bcl-2, and reduce the apoptotic rate, alleviating the apoptosis initiated by BDE-47. Additionally, ISL and LCB could increase the levels of antioxidant substances (SOD, CAT, and GSH) and decrease the production of reactive oxygen species (ROS), thereby counteracting the oxidative stress induced by BDE-47. Ultimately, ISL and LCB suppress the NF-κB pathway by down-regulating IKBKB and up-regulating IκB-Alpha in addition to activating the Nrf2 pathway and promoting the production of HO-1 and NQO1. To summarize, BDE-47 causes oxidative damage that can be mitigated by ISL and LCB through the activation of the Nrf2 pathway and inhibition of the NF-κB pathway, which in turn prevents immune function impairment and apoptosis. These findings enrich the current understanding of the toxicological molecular mechanism of BDE-47 and the detoxification mechanism of licorice.

Preparation and Properties of Low-Dielectric Polyimide Films Containing Tert-Butyl.

The design of high-performance polyimide (PI) films and understanding the relationship of the structure-dielectric property are of great significance in the field of the microelectronics industry, but are challenging. Herein, we describe the first work to construct a series of novel tert-butyl PI films (denoted as PI-1, PI-2, PI-3, and PI-4) based on a low-temperature polymerization strategy, which employed tetracarboxylic dianhydride (pyromellitic anhydride, 3,3',4,4'-biphenyl tetracarboxylic anhydride, 4,4'-diphenyl ether dianhydride, and 3,3',4,4'-benzophenone tetracarboxylic anhydride) and 4,4'-diamino-3,5-ditert butyl biphenyl ether as monomers. The results indicate that introducing tert-butyl branches in the main chain of PIs can enhance the free volume of the molecular chain and reduce the interaction between molecular chains of PI, resulting in a low dielectric constant. Particularly, the optimized PI-4 exhibits an excellent comprehensive performance with a high (5) wt% loss temperature (454 °C), tensile strength (117.40 MPa), and maximum hydrophobic angle (80.16°), and a low dielectric constant (2.90), which outperforms most of the results reported to date.

Mechanism-Based Macrocyclic Inhibitors of Serine Proteases.

Protease inhibitor drug discovery is challenged by the lack of cellular and oral permeability, selectivity, metabolic stability, and rapid clearance of peptides. Here, we describe the rational design, synthesis, and evaluation of peptidomimetic side-chain-cyclized macrocycles which we converted into covalent serine protease inhibitors with the addition of an electrophilic ketone warhead. We have identified potent and selective inhibitors of TMPRSS2, matriptase, hepsin, and HGFA and demonstrated their improved protease selectivity, metabolic stability, and pharmacokinetic (PK) properties. We obtained an X-ray crystal structure of phenyl ether-cyclized tripeptide VD4162 (8b) bound to matriptase, revealing an unexpected binding conformation. Cyclic biphenyl ether VD5123 (11) displayed the best PK properties in mice with a half-life of 4.5 h and compound exposure beyond 24 h. These new cyclic tripeptide scaffolds can be used as easily modifiable templates providing a new strategy to overcoming the obstacles presented by linear acyclic peptides in protease inhibitor drug discovery.

Acute and chronic effects of triclosan on the behavior, physiology, and multigenerational characteristics of the water flea Moina macrocopa

Triclosan, a chlorinated biphenyl ether is widely used in industrial products and cosmetics due to its antibiotic activity. Although relatively levels of triclosan have been detected in aquatic ecosystems, limited information is available regarding the acute and chronic impacts of triclosan on aquatic invertebrates, especially planktonic crustaceans. In this study, we analyzed the acute (24 h) and chronic (14 days exposure across three generations) effects of different concentrations of triclosan [1/10 of the no observed effect concentration (NOEC), the NOEC, and 1/10 of the LC50] calculated from the 24 h acute toxicity value, on the water flea Moina macrocopa. In the acute exposure experiment, the 1/10 LC50 value of triclosan significantly reduced survival, feeding rate, thoracic limb activity, heart activity, and acetylcholinesterase activity. In response to the 1/10 LC50 value, intracellular reactive oxygen species increased along with elevated levels of malondialdehyde and glutathione. Enzymatic activities of catalase, superoxide dismutase, glutathione peroxidase, and glutathione reductase were significantly increased by the 1/10 LC50 value, suggesting active protection of the antioxidant defense system against oxidative stress. Chronic exposure to the 1/10 NOEC and NOEC values revealed multigenerational adverse impacts of triclosan. The second generation was found to be the most sensitive to triclosan, as the NOEC value significantly reduced the survival rate, body length, and the number of neonates per brood, along with a delayed hatching period. Taken together, these results indicate that even sublethal levels of triclosan can have detrimental effects on the water flea population's maintenance through intergenerational toxicity.

Discovery and Crystallography Study of Novel Biphenyl Ether and Oxadiazole Thioether (Non-Arylmethylamine)-Based Small-Molecule PD-1/PD-L1 Inhibitors as Immunotherapeutic Agents.

Current small-molecule PD-1/PD-L1 inhibitors are mainly based on the arylmethylamine/biphenyl core scaffold. Herein, we designed for the first time a series of non-arylmethylamine analogues (oxadiazole thioether derivatives) as small-molecule PD-1/PD-L1 inhibitors. Among them, compound LP23 exhibited the most potent PD-L1 inhibitory activity with an IC50 of 16.7 nM, 3.2-fold better than the lead BMS-202 (IC50 = 53.6 nM). The X-ray crystal structure of LP23 in complex with PD-L1 was solved at a resolution of 2.6 Å, which further confirmed the high binding affinity of LP23 to PD-L1. In the HepG2/Jurkat T cell co-culture model, LP23 effectively promoted HepG2 cell death by restoring the immune function of T cells. In addition, LP23 showed excellent in vivo antitumor efficacy (TGI = 88.6% at 30 mg/kg) and benign toxicity profiles in a B16-F10 tumor model by modulating PD-L1. In summary, LP23 represents the first non-arylmethylamine-based small-molecule PD-1/PD-L1 inhibitor worthy of further investigation.

BDE-47 Induces Immunotoxicity in RAW264.7 Macrophages through the Reactive Oxygen Species-Mediated Mitochondrial Apoptotic Pathway

Polybrominated diphenyl ethers (PBDEs) are classic and emerging pollutants that are potentially harmful to the human immune system. Research on their immunotoxicity and mechanisms suggests that they play an important role in the resulting pernicious effects of PBDEs. 2,2',4,4'-Tetrabrominated biphenyl ether (BDE-47) is the most biotoxic PBDE congener, and, in this study, we evaluated its toxicity toward RAW264.7 cells of mouse macrophages. The results show that exposure to BDE-47 led to a significant decrease in cell viability and a prominent increase in apoptosis. A decrease in mitochondrial membrane potential (MMP) and an increase in cytochrome C release and caspase cascade activation thus demonstrate that cell apoptosis induced by BDE-47 occurs via the mitochondrial pathway. In addition, BDE-47 inhibits phagocytosis in RAW264.7 cells, changes the related immune factor index, and causes immune function damage. Furthermore, we discovered a significant increase in the level of cellular reactive oxygen species (ROS), and the regulation of genes linked to oxidative stress was also demonstrated using transcriptome sequencing. The degree of apoptosis and immune function impairment caused by BDE-47 could be reversed after treatment with the antioxidant NAC and, conversely, exacerbated by treatment with the ROS-inducer BSO. These findings indicate that oxidative damage caused by BDE-47 is a critical event that leads to mitochondrial apoptosis in RAW264.7 macrophages, ultimately resulting in the suppression of immune function.

Biological effects related to exposure to polychlorinated biphenyl (PCB) and decabromodiphenyl ether (BDE-209) on cats.

As an animal familiar to humans, cats are considered to be sensitive to chemicals; cats may be exposed to polychlorinated biphenyls (PCBs) and decabromodiphenyl ether (BDE-209) from indoor dust, household products, and common pet food, leading to adverse endocrine effects, such as thyroid hormone dysfunction. To elucidate the general biological effects resulting from exposure of cats to PCBs and PBDEs, cats were treated with a single i.p. dose of a principal mixture of 12 PCBs and observed for a short-term period. Results revealed that the testis weight, serum albumin, and total protein of the treated group decrease statistically in comparison with those in the control group. The negative correlations suggested that the decrease in the total protein and albumin levels may be disturbed by 4'OH-CB18, 3'OH-CB28 and 3OH-CB101. Meanwhile, the serum albumin level and relative brain weight decreased significantly for cats subjected to 1-year continuous oral administration of BDE-209 in comparison to those of control cats. In addition, the subcutaneous fat as well as serum high-density lipoprotein (HDL) and triglycerides (TG) levels increased in cats treated with BDE-209 and down-regulation of stearoyl-CoA desaturase mRNA expression in the liver occurred. These results suggested that chronic BDE-209 treatment may restrain lipolysis in the liver, which is associated with lipogenesis in the subcutaneous fat. Evidence of liver and kidney cell damage was not observed as there was no significant difference in the liver enzymes, blood urea nitrogen and creatinine levels between the two groups of both experiments. To the best of our knowledge, this is the first study that provides information on the biochemical effects of organohalogen compounds in cats. Further investigations on risk assessment and other potential health effects of PCBs and PBDEs on the reproductive system, brain, and lipid metabolism in cats are required.

A review of the endocrine disrupting effects of micro and nano plastic and their associated chemicals in mammals.

Over the years, the vaste expansion of plastic manufacturing has dramatically increased the environmental impact of microplastics [MPs] and nanoplastics [NPs], making them a threat to marine and terrestrial biota because they contain endocrine disrupting chemicals [EDCs] and other harmful compounds. MPs and NPs have deleteriouse impacts on mammalian endocrine components such as hypothalamus, pituitary, thyroid, adrenal, testes, and ovaries. MPs and NPs absorb and act as a transport medium for harmful chemicals such as bisphenols, phthalates, polybrominated diphenyl ether, polychlorinated biphenyl ether, organotin, perfluorinated compounds, dioxins, polycyclic aromatic hydrocarbons, organic contaminants, and heavy metals, which are commonly used as additives in plastic production. As the EDCs are not covalently bonded to plastics, they can easily leach into milk, water, and other liquids affecting the endocrine system of mammals upon exposure. The toxicity induced by MPs and NPs is size-dependent, as smaller particles have better absorption capacity and larger surface area, releasing more EDC and toxic chemicals. Various EDCs contained or carried by MPs and NPs share structural similarities with specific hormone receptors; hence they interfere with normal hormone receptors, altering the hormonal action of the endocrine glands. This review demonstrates size-dependent MPs' bioaccumulation, distribution, and translocation with potential hazards to the endocrine gland. We reviewed that MPs and NPs disrupt hypothalamic-pituitary axes, including the hypothalamic-pituitary-thyroid/adrenal/testicular/ovarian axis leading to oxidative stress, reproductive toxicity, neurotoxicity, cytotoxicity, developmental abnormalities, decreased sperm quality, and immunotoxicity. The direct consequences of MPs and NPs on the thyroid, testis, and ovaries are documented. Still, studies need to be carried out to identify the direct effects of MPs and NPs on the hypothalamus, pituitary, and adrenal glands.

Toughening and strengthening of low-temperature resistant epoxy resins by introducing high-performance thermoplastic resin with phthalazinone structure

This paper used phthalazinone-based copoly(biphenyl ether nitrile) (co-PPEN) to improve the low-temperature toughness of epoxy resin E51. The effects of co-PPEN content on the normal/low-temperature mechanical properties, thermomechanical properties, and thermal stability of epoxy resins were studied. Results showed that co-PPEN significantly improved the normal/low-temperature mechanical properties of E51. At room temperature, the impact strength, flexural strength, and tensile strength of co-PPEN/E51 blends increased by 144.0%, 12.8%, and 28.1%, respectively; at low temperature, the impact strength, flexural strength, and tensile strength of co-PPEN/E51 blends increased by 87.9%, 43.6%, and 18.5%, respectively. From the cross-sectional analysis, the crack deflection and crack bridging of co-PPEN are the main toughening mechanisms of the blends. The blend system has high thermal property, and the glass transition temperature of the co-PPEN/E51 blend increased by about 50 °C. Simultaneously, all blends exhibited better thermal stability.

Molecular structural dataset of lignin macromolecule elucidating experimental structural compositions

Lignin is one of the most abundant biopolymers in nature and has great potential to be transformed into high-value chemicals. However, the limited availability of molecular structure data hinders its potential industrial applications. Herein, we present the Lignin Structural (LGS) Dataset that includes the molecular structure of milled wood lignin focusing on two major monomeric units (coniferyl and syringyl), and the six most common interunit linkages (phenylpropane β-aryl ether, resinol, phenylcoumaran, biphenyl, dibenzodioxocin, and diaryl ether). The dataset constitutes a unique resource that covers a part of lignin’s chemical space characterized by polymer chains with lengths in the range of 3 to 25 monomer units. Structural data were generated using a sequence-controlled polymer generation approach that was calibrated to match experimental lignin properties. The LGS dataset includes 60 K newly generated lignin structures that match with high accuracy (~90%) the experimentally determined structural compositions available in the literature. The LGS dataset is a valuable resource to advance lignin chemistry research, including computational simulation approaches and predictive modelling.

Synthesis and Characterization of Bio-Based Poly(amide imide)s Derived from 11-Aminoundecanoic Acid and 1,10-Diaminodecane

Three diimide diacid (DIDA) monomers possessing different rigid groups (phenyl, biphenyl and diphenyl ether group) between two imide rings were prepared through the dehydration cyclization reaction of 11-aminoundecanoic acid and aromatic dianhydride. These DIDA monomers were polymerized with 1,10-diaminodecane to produce bio-based poly(amide imide)s (PAIs) by the ecofriendly and low-cost two-step polymerization method. All the PAIs have high thermal stabilities, and their initial thermal decomposition temperatures are above 400 °C at 5% weight loss. When the rigid group between two imide rings is changed from phenyl to diphenyl ether group, the glass transition temperature of PAI shows a decreasing trend from 54.7 °C to 42.4 °C, the tensile strength also reduces from 62.4 MPa to 49.5 MPa, but elongation at break increases from 3.7% to 6.8%. Moreover, the PAI with phenyl group between two imide rings is a semicrystalline polymer, while the PAI with biphenyl or diphenyl ether group is an amorphous polymer. It is a viable way to regulate the properties of PAIs by changing the structure of rigid group between two imide rings. Such bio-based PAIs with high thermal stabilities, low glass transition temperatures and good mechanical strength will provide great promise for their wider applications.

Biphenyl Ether Analogs Containing Pomalidomide as Small-Molecule Inhibitors of the Programmed Cell Death-1/Programmed Cell Death-Ligand 1 Interaction

New biphenyl-based chimeric compounds containing pomalidomide were developed and evaluated for their activity to inhibit and degrade the programmed cell death-1/programmed cell death- ligand 1 (PD-1/PD-L1) complex. Most of the compounds displayed excellent inhibitory activity against PD-1/PD-L1, as assessed by the homogenous time-resolved fluorescence (HTRF) binding assay. Among them, compound 3 is one of the best with an IC50 value of 60 nM. Using an ex vivo PD-1/PD-L1 blockade cell line bioassay that expresses human PD-1 and PD-L1, we show that compounds 4 and 5 significantly restore the repressed immunity in this co-culture model. Western blot data, however, demonstrated that these anti-PD-L1/pomalidomide chimeras could not reduce the protein levels of PD-L1.

Densities for Sulfur in Benzene and Densities with Solubilities for a Eutectic Mixture of Biphenyl plus Diphenyl Ether: A General Solubility Equation for the Treatment of Aromatic Physical Sulfur Solvents

Physical sulfur solvents are utilized in (i) the mitigation of sulfur deposition in sour gas wells and gathering lines and (ii) as a process medium for small-scale sulfur recovery. Non-aqueous aromatic solvents have two distinct advantages, where they are less reactive with elemental sulfur and provide for relatively large sulfur solubilities. Understanding the solubilities and physical properties within aromatic sulfur solvents over a wide range of temperature and pressure is important for both the previous applications. In this study, high-pressure densities for sulfur in benzene and a eutectic mixture of biphenyl and diphenyl ether were measured for T = (298.15–373.15) K and p < 100 MPa, where the densities were used to calculate the molar volume change upon dissolution. New sulfur solubility measurements are reported for sulfur in the eutectic mixture of biphenyl and diphenyl from T = (298.15–403.15) K and compared to benzene, toluene, and xylenes (BTX). The calculated volumetric changes and measured solubilities at atmospheric pressure were used to determine the enthalpy of dissolution, ΔX→slH°, and the change in heat capacity, ΔX→slCp°, for the α-sulfur, β-sulfur, and the liquid-sulfur phase dissolution using a van’t Hoff model. The eutectic solvent showed a higher solubility when compared to BTX at higher temperatures (β-sulfur and the liquid-sulfur regions) and both solubilities calculated to have a very small pressure dependence.

An Overview: Organophosphate Flame Retardants in the Atmosphere

Organophosphate flame retardants (OPFRs) have been adopted as safer alternatives to polybrominated biphenyl ether flame retardants. However, because of their ubiquitous presence in the environment and the growing evidence of health risks, there has been growing research interest in understanding the fate and effects of these compounds in the environment. This review focuses on the current knowledge of OPFRs in the atmosphere. There is no consensus on the target OPFR for analysis, making comparisons challenging. However, we can still conclude that OPFRs partition mainly in the particulate phase, and chlorinated-OPFRs are the main compounds in the atmosphere. The general concentration trends from the literature were: PM2.5 > TSP > air. However, the gas-phase OPFRs in the published studies might be significantly underestimated because of sampling artifacts. OPFRs were also found in remote environments in Antarctica, the Arctic, and high mountains, suggesting long-range transport potential. For example, concentrations up to 92.3 ± 13.8 pg m-3 in the air have been measured in the Antarctic. Lastly, atmospheric transformations of some OPFRs have been reported as more toxic and persistent than parent compounds, indicating additional risk. However, they are currently not measured or included during risk assessment.

Rhodium Indenyl NHC and Fluorenyl-Tethered NHC Half-Sandwich Complexes: Synthesis, Structures and Applications in the Catalytic C-H Borylation of Arenes and Alkanes.

Indenyl (Ind) rhodium N‐heterocyclic carbene (NHC) complexes [Rh(η 5‐Ind)(NHC)(L)] were synthesised for 1,3‐bis(2,6‐diisopropylphenyl)‐4,5‐dihydroimidazol‐2‐ylidene (SIPr) with L=C2H4 (1), CO (2 a) and cyclooctene (COE; 3), for 1,3‐bis(2,4,6‐trimethylphenyl)‐4,5‐dihydroimidazol‐2‐ylidene (SIMes) with L=CO (2 b) and COE (4), and 1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene (IMes) with L=CO (2 c) and COE (5). Reaction of SIPr with [Rh(Cp*)(C2H4)2] did not give the desired SIPr complex, thus demonstrating the “indenyl effect” in the synthesis of 1. Oxidative addition of HSi(OEt)3 to 3 proceeded under mild conditions to give the Rh silyl hydride complex [Rh(Ind){Si(OEt)3}(H)(SIPr)] (6) with loss of COE. Tethered‐fluorenyl NHC rhodium complexes [Rh{(η 5‐C13H8)C2H4N(C)C2H x NR}(L)] (x=4, R=Dipp, L=C2H4: 11; L=COE: 12; L=CO: 13; R=Mes, L=COE: 14; L=CO: 15; x=2, R=Me, L=COE: 16; L=CO: 17) were synthesised in low yields (5–31 %) in comparison to good yields for the monodentate complexes (49–79 %). Compounds 3 and 1, which contain labile alkene ligands, were successful catalysts for the catalytic borylation of benzene with B2pin2 (Bpin=pinacolboronate, 97 and 93 % PhBpin respectively with 5 mol % catalyst, 24 h, 80 °C), with SIPr giving a more active catalyst than SIMes or IMes. Fluorenyl‐tethered NHC complexes were much less active as borylation catalysts, and the carbonyl complexes were inactive. The borylation of toluene, biphenyl, anisole and diphenyl ether proceeded to give meta substitutions as the major product, with smaller amounts of para substitution and almost no ortho product. The borylation of octane and decane with B2pin2 at 120 and 140 °C, respectively, was monitored by 11B NMR spectroscopy, which showed high conversions into octyl and decylBpin over 4–7 days, thus demonstrating catalysed sp3 C−H borylation with new piano stool rhodium indenyl complexes. Irradiation of the monodentate complexes with 400 or 420 nm light confirmed the ready dissociation of C2H4 and COE ligands, whereas CO complexes were inert. Evidence for C−H bond activation in the alkyl groups of the NHC ligands was obtained.

Activation of persulfate by swine bone derived biochar: Insight into the specific role of different active sites and the toxicity of acetaminophen degradation pathways

Recently, persulfate (PS) activation system has grown up as a primary branch of advanced oxidation processes, and biochar has been recognized as a potential nonmetal material in this field. However, few studies have focused on the corresponding relationship between actives sites on biochar and active species in AOPs. To pave this way, similar biochar (obtained from different pyrolysis temperature) with different functional structures were involved. In this study, biochar derived from swine bone (BBC) was applied in PS activation system to degrade acetaminophen (ACT). The results showed that both radical and non-radical pathway worked in the PS/BBCs systems, and the degradation rate (from 0.1042 to 0.4364 min−1) climbed with the increase of pyrolysis temperature (from 700 to 900 °C). To probe into the corresponding relationship between functional structure and active species, the effect of pyrolysis temperature on functional structure was analyzed. It came out that 1) defects could act as active sites for various active species; 2) persistent free radicals could do favor to the generation of 1O2 and O2−; 3) hydroxyapatite in swine bone only served as hard templet for the porous structure. ACT degradation process was measured by Liquid chromatograph-mass spectrometer, and Scendesmus obliquus was applied to investigate the toxicity of PS/BBCs system. It illustrated that the existence of SO4− mainly contributed to the generation of high toxic intermediates (such as biphenyl and diphenyl ether) in the PS/BBCs system. Furthermore, the enhancement of adsorption capacity would mitigate the toxicity of PS/BBCs systems to some extent.

Liquid-phase sulfur recovery within a eutectic solvent coupled with low temperature carbon disulfide hydrolysis

Liquid phase sulfur recovery was explored in a eutectic solvent to demonstrate proof-of-concept for an alternative Claus tail gas cleanup process. A simulated tail gas feed containing 3% H2S and 1.5% SO2 was converted to elemental sulfur within a biphenyl and diphenyl ether eutectic solvent. The formed sulfur accumulates at the bottom of the reactor upon solvent saturation, allowing for liquid–liquid separation if the temperature is maintained above 120 °C. Alternatively, crystallization of elemental sulfur could be performed with lower sulfur solubility in the solvent at room temperature. In the temperature range of 120 – 150 °C, a Claus equilibrium conversion of > 99% was achieved when care was taken to maintain the H2S/SO2 ratio at 2:1. While lower temperature favours Claus equilibrium, destruction of other sulfur containing species such as CS2 often suffers at these lower temperatures. Therefore, CS2 destruction was explored within the eutectic solvent over both alumina and titania catalysts, which are commonly used in commercial applications. Good conversions were observed for both alumina and titania when maintaining the H2S/SO2 ratio at 2:1. Better CS2 conversions of 95% (over alumina) and 98% (over titania) were observed at 150 °C when operating at an H2S/SO2 ratio at 2.3:1. The total sulfur conversions, when assuming theoretical equilibrium conversion in the sulfur recovery unit, combined with the liquid-phase tail gas cleanup process ranged from 99.3 to 99.9%. Addition of water to the feed negatively affected the CS2 destruction on titania but had little effect on alumina. At sulfur saturation conditions, CS2 destruction was not affected on titania, but was negatively affected on alumina at 150 °C.

Anthraquinones, Diphenyl Ethers, and Their Derivatives from the Culture of the Marine Sponge-Associated Fungus Neosartorya spinosa KUFA 1047.

Previously unreported anthraquinone, acetylpenipurdin A (4), biphenyl ether, neospinosic acid (6), dibenzodioxepinone, and spinolactone (7) were isolated, together with (R)-6-hydroxymellein (1), penipurdin A (2), acetylquestinol (3), tenellic acid C (5), and vermixocin A (8) from the culture of a marine sponge-associated fungus Neosartorya spinosa KUFA1047. The structures of the previously unreported compounds were established based on an extensive analysis of 1D and 2D NMR spectra as well as HRMS data. The absolute configurations of the stereogenic centers of 5 and 7 were established unambiguously by comparing their calculated and experimental electronic circular dichroism (ECD) spectra. Compounds 2 and 5–8 were tested for their in vitro acetylcholinesterase and tyrosinase inhibitory activities as well as their antibacterial activity against Gram-positive and Gram-negative reference, and multidrug-resistant strains isolated from the environment. The tested compounds were also evaluated for their capacity to inhibit biofilm formation in the reference strains.