Diphenyl Diselenide Research Articles

Copper Catalyzed Fluoroalkyl‐Selenization of Olefins

An efficient copper catalyzed fluoroalkyl‐selenization reaction of olefins has been developed, providing 1,2‐difluoroarylselenides in moderate to excellent yields. The readily available ethyl bromodifluoroacetate and diphenyl diselenide (Ph2Se2) have been employed as efficient radical precursor and selenization reagents to react with olefins. The reaction features a broad substrate scope, including substituted alkenes with various functional groups.

Revival of Degraded CsPbI3 Nanocrystals by Diselenide Ligand and Nanocrystal Self-Assembly on Nanofibrilar Ligand Template.

Among the lead halide perovskite (LHP) family, CsPbI3 is known to be significantly vulnerable to moisture, which hinders its use in real device applications. It is reported that chalcogen-based ligands can better stabilize CsPbI3 and revive nanocrystals (NCs). Here, diphenyl diselenide (DPhDSe) ligand is used to revive the degraded CsPbI3 NCs through a post-synthetic treatment of adding a small amount of DPhDSe in the degraded NC dispersion. DPhDSe in the dispersion formed nanofibrillar crystals at a low temperature through the π-π stacking of the phenyl ring. The nanofibrils played as a template on which the NCs self-assembled and they are attached side-by-side to form microfibers. The microfiber powder containing the NCs is optically stable at ambient conditions and morphologically self-healable by mild thermal annealing due to the dynamic Se─Se bond. The mechanism of the structural changes, optical transitions, and chemical changes has been systematically characterized through electron microscopy, diffraction, spectroscopy, and elemental analysis.

A Green Synthesis of 3-Selanyl-Isoflavones via Lipase Mediated Selenylation/Cyclization of Enaminones

Herein, a green biocatalytic approach using lipase as a catalyst has been developed for the synthesis of 3-selanyl-isoflavones through the selenylation/cyclization of 2-hydroxyphenyl enaminones and diphenyl di-selenide under mild conditions. The environmentally friendly method reached high yields of 87–95% in a short time at 30 °C, with 17 examples of 3-selanyl-isoflavones successfully prepared. Furthermore, we have investigated the possible mechanisms underlying this reaction.

Four-Component Radical 1,2-Selenosulfonylation of Allenes.

Selenosulfones, as pivotal pharmaceutical molecule frameworks, have become a research hotspot in modern organic synthesis due to their vital need for efficient preparation. Herein, we have developed an iron-catalyzed four-component controllable radical tandem reaction of allenes involving cycloketone oxime esters, 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO), and diphenyl diselenides for the synthesis of complex selenosulfones. This is the first case of achieving the 1,2-selenosulfonylation of allenes via a radical process, wherein precise control of radical rates and polarity matching enhance high regioselective conversion. The reaction conditions are ecofriendly and mild with step-efficiency by forming two new C-S bonds and one C-Se bond in one pot. Moreover, the 1,2-selenosulfonylation of allenes can be achieved by replacing cycloketone oxime esters with aryldiazonium tetrafluoroborates in this system.

Aromatic diselenide catalytic reactions for the efficient formation of multiple disulfide bonds in peptides

Multiple disulfide bonds (MBDs) play a critical role in maintaining the three-dimensional structure of peptides and proteins affording their pharmaceutical and biological activities. The efficient synthesis of correct MBDs in peptides and proteins remains a challenging task in chemical synthesis these compounds. In this work, aromatic diselenides including diphenyl diselenide (DPDS), bis(2-carboxyphenyl)diselenide (BCPDS), and 2,2′-dipyridyl diselenide (DPDDS) played as catalysts and were successfully used for the synthesis of correct MBDs in peptides. Good yields were achieved by use of the catalytic reactions under mild conditions, and the reaction time decreased with the trend of DPDDS < BCPDS < DPDS. A reaction mechanism was proposed, in which the formation of a selenenylsulfide intermediate played a critical role in the formation of correct MBDs in peptides. On the other hand, phenylselenenyl chloride (PSC) can oxidize fully reduced peptides to their correct MDBs forms.

Methyl jasmonate and diphenyl diselenide attenuate diethylnitrosamine and carbon tetrachloride-induced nephrotoxicity in rats via modulation of inflammation and oxidative stress processes

The pathogenesis of toxicity-mediated renal injury has been linked to reactive oxygen species. Therefore, intervention with antioxidant agents as part of therapeutic strategies is necessary. This study investigated the modulatory effects of Diphenyldiselenide (PhSe)2 and Methyl Jasmonate (MJ) against Diethylnitrosamine (DEN) and Carbon tetrachloride (CCL4)-induced nephrotoxicity in male Wistar rats. Forty-eight (48) rats were assigned into six groups of eight animals each. Group 1 served as control, Group 2 received DEN (100mg/kg) + CCL4 (0.5mg/kg), Group 3 received [DEN+CCL4] and treated with MJ (50 mg/kg), Groups 4 and 5 received [DEN+CCL4] and treated with (PhSe)2 (5 mg/kg and 10 mg/kg), and Group 6 received [DEN+CCL4] and treated with quercetin (50mg/kg). Administration of DEN and CCL4 increased serum urea, creatinine and kidney injury molecule-1 (KIM-1) by 97%, 62% and 73%. Furthermore, activities of glutathione-S-transferase, superoxide dismutase and catalase significantly (P&lt;0.05) decreased in [DEN+CCL4] rats. The BCL-2 associated X, caspases -3 and -9 increased in rats administered-[DEN+CCL4]. In addition, TNF-α increased by 117%, myeloperoxidase and nitric oxide level increased by 385% and 65%, respectively in [DEN+CCL4]-administered rats. Histology showed mild vascular congestion and infiltration of inflammatory cells in interstitial spaces in [DEN+CCL4] rats. Interestingly, treatment with methyl jasmonate and diphenyl diselenide attenuated kidney function markers, reduced tissue inflammation and apoptosis status of [DEN+CCL4]-rats. Methyl jasmonate and diphenyldiselenide abate nephrotoxicity caused by combined administration of DEN- and CCL4- via induction of antioxidative and anti-inflammatory activities.

In situ formation of the electrophilic phenylselenenyl sulfate triggered by light

Ammonium persulfate is a mild oxidant capable of oxidizing the selenium-selenium bond through thermal activation or under drastic acid catalysis. In this paper we highlight that this reaction can be activated photochemically, starting from diphenyl diselenide in the absence of any organic or and/or metallic photocatalyst or additive. The protocol was applied to a well-known panel of selenoalkoxylation reactions and the obtained results clearly indicate the involvement of an electrophilic selenium reagent.

Electrochemically driven regioselective organoselenation for selective synthesis of β- hydroxy substituted selanylated ketones

A simple yet efficient approach towards the synthesis of β-hydroxy selanylated ketones was developed from easily accessible chalcones and diphenyl diselenide through an electrochemical pathway. In this technique, diphenyl diselenide and water are the source of PhSe. and hydroxyl (–OH) groups that can be inserted at the α and β positions respectively producing β-hydroxy selanylated ketones in moderate to good yields. The reaction features difunctionalization of ketones, catalyst free, mild reaction conditions, stereo and regioselectivity in an undivided electrochemical cell at room temperature. For this transformation, a plausible radical mechanism has been put out.

Inorganic-Organic Hybrid Layered Semiconductor AgSePh: Quasi-Solution Synthesis, Optical Properties, and Thermolysis Behavior.

Two-dimensional inorganic-organic hybrid layered semiconductors are actively studied because of their naturally formed multiquantum well (MQW) structures and associated optical, photoelectric, and quantum optics characteristics. Silver benzeneselenolate (AgSePh, Ph = C6H5) is a new member of such hybrid layered materials, but has not fully been exploited. Herein, we present a quasi-solution method to prepare high quality free-standing AgSePh flake-like microcrystals by reacting diphenyl diselenide (Ph2Se2) with silver nanoparticles. The resultant AgSePh microflakes exhibit room-temperature (RT) resolvable MQW-induced quasi-particle quantization and interesting optical properties, such as three distinct excitonic resonance absorptions X1 (2.67 eV), X2 (2.71 eV), and X3 (2.83 eV) in the visible region, strong narrow-line width blue photoluminescence at ∼2.64 eV (470 nm) from the radiative recombination of the X1 exciton state, and a large exciton binding energy (∼0.35 eV). Furthermore, AgSePh microcrystals show high stability under water, oxygen, and heat environments, while above 220 °C, they will thermally decompose to silver and Ph2Se2 as evidenced by a combination of thermogravimetry and differential scanning calorimetry and pyrolysis-coupled gas chromatography-mass spectrometry studies. Finally, a comparison is extended between AgSePh and other metal benzeneselenolates, benzenethiolates, and alkanethiolates to clarify differences in their solubility, decomposition/melting temperature, and pyrolytic products.

Interplay between diphenyl diselenide and copper: Impact on D. melanogaster survival, behavior, and biochemical parameters

Copper (Cu2+) is a biologically essential element that participates in numerous physiological processes. However, elevated concentrations of copper have been associated with cellular oxidative stress and neurodegenerative diseases. Organo‑selenium compounds such as diphenyl diselenide (DPDS) have in vitro and in vivo antioxidant properties. Hence, we hypothesized that DPDS may modulate the toxicity of Cu2+ in Drosophila melanogaster. The acute effects (4 days of exposure) caused by a high concentration of Cu2+ (3 mM) were studied using endpoints of toxicity such as survival and behavior in D. melanogaster. The potential protective effect of low concentration of DPDS (20 μM) against Cu2+ was also investigated. Adult flies aged 1–5 days post-eclosion (both sexes) were divided into four groups: Control, DPDS (20 μM), CuSO4 (3 mM), and the combined exposure of DPDS (20 μM) and CuSO4 (3 mM). Survival, biochemical, and behavioral parameters were determined. Co-exposure of DPDS and CuSO4 increased acetylcholinesterase (AChE) activity and the generation of reactive oxygen species (ROS as determined by DFCH oxidation). Contrary to our expectation, the co-exposure reduced survival, body weight, locomotion, catalase activity, and cell viability in relation to control group. Taken together, DPDS potentiated the Cu2+ toxicity.

Upper Rim-Bridged Calix[4]arenes via Cyclization of meta Alkynyl Intermediates with Diphenyl Diselenide.

A Sonogashira coupling of meta-iodocalix[4]arene with various terminal acetylenes confirmed that the meta position of calixarene is well addressable, and that both thermal and microwave protocols led to good yields of alkynylcalixarenes. Alkynes thus obtained were subjected to the ferric chloride and diphenyl diselenide-promoted electrophilic closure. It turns out that the calix[4]arenes give completely different bridging products than those described for the non-macrocyclic starting compounds. This can be demonstrated not only by the isolation of products with a six-membered ring (6-exo-dig), but mainly by the smooth formation of the 5-endo-dig cyclization, which has never been observed in the aliphatic series. An attempt at electrocyclization led to a high yield of the 1,2-diketone (oxidation of the starting alkyne), again in contrast to the reaction described for the acyclic derivatives. The structures of the unexpected products were unequivocally established by X-ray analysis and clearly demonstrate how the preorganized macrocyclic skeleton favors a completely different regioselectivity of cyclization reactions compared to common aliphatic compounds.

Synthesis of bis‐Naphthol based Organoselenium Antioxidants as Efficient Inhibitors against Biofilms

AbstractIn the present study, synthesis of bis‐naphthol based organoselenium compounds has been described. The synthetic strategy involves electrophilic aromatic addition of alkyl/aryl selenium species at the electron rich center of 2,7‐dihydroxynaphthalene. The reaction with electrophilic selenylating reagents in situ generated by potassium persulphate and diselenides produced desired selenides. Synthesized compounds were studied for their glutathione peroxidase (GPx)‐like antioxidant activities using thiophenol assay. It was observed that all compounds exhibited greater GPx‐like antioxidant activity than diphenyl diselenide used as reference. Further, these GPx mimics were introduced for their antibacterial properties against biofilm formation by Bacillus subtilis and Pseudomonas aeruginosa. To support experimental details, molecular docking studies were also performed to elucidate in silico interactions between the active sites of proteins TsaA and LasR found in Bacillus subtilis and Pseudomonas aeruginosa, respectively. The minimum inhibitory concentration assay was performed for all the antioxidants against Bacillus subtilis and Pseudomonas aeruginosa. Additionally, hemolytic assay has also been carried out to check the impact on red blood cells. Cytotoxicity assessments of antioxidants have also been carried using MTT assay.

Dynamically Ion‐Coordinated Bipolar Organodichalcogenide Cathodes Enabling High‐Energy and Durable Aqueous Zn Batteries

AbstractBipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high‐energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high‐voltage/capacity merits. Herein, we initially report dynamically ion‐coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron‐involved positive‐valence oxidation and negative‐valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe‐SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)− to (PhSe‐SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF−). When confined into ordered mesoporous carbon (CMK‐3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK‐3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe−1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe−1), and ultralong lifespan (12 000 cycles) at 10 A g−1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion‐type active site engineering for high‐voltage/capacity bipolar OCMs towards high‐energy AZBs.

Dynamically Ion-Coordinated Bipolar Organodichalcogenide Cathodes Enabling High-Energy and Durable Aqueous Zn Batteries.

Bipolar organic cathode materials (OCMs) implementing cation/anion storage mechanisms are promising for high-energy aqueous Zn batteries (AZBs). However, conventional organic functional group active sites in OCMs usually fail to sufficiently unlock the high-voltage/capacity merits. Herein, we initially report dynamically ion-coordinated bipolar OCMs as cathodes with chalcogen active sites to solve this issue. Unlike conventional organic functional groups, chalcogens bonded with conjugated group undergo multielectron-involved positive-valence oxidation and negative-valence reduction, affording higher redox potentials and reversible capacities. With phenyl diselenide (PhSe-SePh, PDSe) as a proof of concept, it exhibits a conversion pathway from (PhSe)- to (PhSe-SePh)0 and then to (PhSe)+ as unveiled by characterization and theoretical simulation, where the diselenide bonds are periodically broken and healed, dynamically coordinating with ions (Zn2+ and OTF-). When confined into ordered mesoporous carbon (CMK-3), the dissolution of PDSe intermediates is greatly inhibited to obtain an ultralong lifespan without voltage/capacity compromise. The PDSe/CMK-3 || Zn batteries display high reversibility capacity (621.4 mAh gPDSe -1), distinct discharge plateau (up to 1.4 V), high energy density (578.3 Wh kgPDSe -1), and ultralong lifespan (12 000 cycles) at 10 A g-1, far outperforming conventional bipolar OCMs. This work sheds new light on conversion-type active site engineering for high-voltage/capacity bipolar OCMs towards high-energy AZBs.

Diphenyl Diselenide Attenuates Mitochondrial Damage During Initial Hypoxia and Enhances Resistance to Recurrent Hypoxia.

Hypoxia plays a significant role in the development of various cerebral diseases, many of which are associated with the potential risk of recurrence due to mitochondrial damage. Conventional drug treatments are not always effective for hypoxia-related brain diseases, necessitating the exploration of alternative compounds. In this study, we investigated the potential of diphenyl diselenide [(PhSe)2] to ameliorate locomotor impairments and mitigate brain mitochondrial dysfunction in zebrafish subjected to hypoxia. Additionally, we explored whether these improvements could confer resistance to recurrent hypoxia. Through a screening process, an appropriate dose of (PhSe)2 was determined, and animals exposed to hypoxia received a single intraperitoneal injection of 100mg/kg of the compound or vehicle. After 1h from the injection, evaluations were conducted on locomotor deficits, (PhSe)2 content, mitochondrial electron transport system, and mitochondrial viability in the brain. The animals were subsequently exposed to recurrent hypoxia to assess the latency time to hypoxia symptoms. The findings revealed that (PhSe)2 effectively crossed the blood-brain barrier, attenuated locomotor deficits induced by hypoxia, and improved brain mitochondrial respiration by modulating complex III. Furthermore, it enhanced mitochondrial viability in the telencephalon, contributing to greater resistance to recurrent hypoxia. These results demonstrate the beneficial effects of (PhSe)2 on both hypoxia and recurrent hypoxia, with cerebral mitochondria being a critical target of its action. Considering the involvement of brain hypoxia in numerous pathologies, (PhSe)2 should be further tested to determine its effectiveness as a potential treatment for hypoxia-related brain diseases.

Diphenyl Diselenide Through Reduction of Inflammation, Oxidative Injury and Caspase-3 Activation Abates Doxorubicin-Induced Neurotoxicity in Rats.

Neurotoxicity associated with chemotherapy is a debilitating side effect of cancer management in humans which reportedly involves inflammatory and oxidative stress responses. Diphenyl diselenide (DPDS) is an organoselenium compound which exhibits its anti-tumoral, anti-oxidant, anti-inflammatory and anti-mutagenic effects. Nevertheless, its possible effect on chemotherapy-induced neurotoxicity is not known. Using rat model, we probed the behavioral and biochemical effects accompanying administration of antineoplastic agent doxorubicin (7.5mg/kg) and DPDS (5 and 10mg/kg). Anxiogenic-like behavior, motor and locomotor insufficiencies associated with doxorubicin were considerably abated by both DPDS doses with concomitant enhancement in exploratory behavior as demonstrated by reduced heat maps intensity and enhanced track plot densities. Moreover, with exception of cerebral glutathione (GSH) level, superoxide dismutase (SOD) and glutathione peroxidase (GPx) activities, biochemical data demonstrated reversal of doxorubicin-mediated decline in cerebral and cerebellar antioxidant status indices and the increase in acetylcholinesterase (AChE) activity by both doses of DPDS. Also, cerebellar and cerebral lipid peroxidation, hydrogen peroxide as well as reactive oxygen and nitrogen species levels were considerably diminished in rats administered doxorubicin and DPDS. In addition, DPDS administration abated myeloperoxidase activity, tumour necrosis factor alpha and nitric oxide levels along with caspase-3 activity in doxorubicin-administered rats. Chemoprotection of doxorubicin-associated neurotoxicity by DPDS was further validated by histomorphometry and histochemical staining. Taken together, DPDS through offsetting of oxido-inflammatory stress and caspase-3 activation elicited neuroprotection in doxorubicin-treated rats.

Gold-Promoted Biocompatible Selenium Arylation of Small Molecules, Peptides and Proteins.

A low pKa (5.2), high polarizable volume (3.8 Å), and proneness to oxidation under ambient conditions make selenocysteine (Sec, U) a unique, natural reactive handle present in most organisms across all domains of life. Sec modification still has untapped potential for site-selective protein modification and probing. Herein we demonstrate the use of a cyclometalated gold(III) compound, [Au(bnpy)Cl2 ], in the arylation of diselenides of biological significance, with a scope covering small molecule models, peptides, and proteins using a combination of multinuclear NMR (including 77 Se NMR), and LC-MS. Diphenyl diselenide (Ph-Se)2 and selenocystine, (Sec)2 , were used for reaction optimization. This approach allowed us to demonstrate that an excess of diselenide (Au/Se-Se) and an increasing water percentage in the reaction media enhance both the conversion and kinetics of the C-Se coupling reaction, a combination that makes the reaction biocompatible. The C-Se coupling reaction was also shown to happen for the diselenide analogue of the cyclic peptide vasopressin ((Se-Se)-AVP), and the Bos taurus glutathione peroxidase (GPx1) enzyme in ammonium acetate (2 mM, pH=7.0). The reaction mechanism, studied by DFT revealed a redox-based mechanism where the C-Se coupling is enabled by the reductive elimination of the cyclometalated Au(III) species into Au(I).

Reactions of hypobromous acid with dimethyl selenide, dimethyl diselenide and other organic selenium compounds: kinetics and product formation.

Selenium (Se) is an essential micronutrient for many living organisms particularly due to its unique redox properties. We recently found that the sulfur (S) analog for dimethyl selenide (DMSe), i.e. dimethyl sulfide (DMS), reacts fast with the marine oxidant hypobromous acid (HOBr) which likely serves as a sink of marine DMS. Here we investigated the reactivity of HOBr with dimethyl selenide and dimethyl diselenide (DMDSe), which are the main volatile Se compounds biogenically produced in marine waters. In addition, the reactivity of HOBr with further organic Se compounds was tested, i.e., SeMet (as N-acetylated-SeMet), and selenocystine (SeCys2 as N-acetylated-SeCys2), as well as the phenyl-analogs of DMSe and DMDSe, respectively, diphenyl selenide (DPSe) and diphenyl diselenide (DPDSe). Apparent second-order rate constants at pH 8 for the reactions of HOBr with the studied Se compounds were (7.1 ± 0.7) × 107 M-1 s-1 for DMSe, (4.3 ± 0.4) × 107 M-1 s-1 for DMDSe, (2.8 ± 0.3) × 108 M-1 s-1 for SeMet, (3.8 ± 0.2) × 107 M-1 s-1 for SeCys2, (3.5 ± 0.1) × 107 M-1 s-1 for DPSe, and (8.0 ± 0.4) × 106 M-1 s-1 for DPDSe, indicating a very high reactivity of all selected Se compounds with HOBr. The reactivity between HOBr and DMSe is lower than for DMS and therefore this reaction is likely not relevant for marine DMSe abatement. However, the high reactivity of SeMet with HOBr suggests that SeMet may act as a relevant quencher of HOBr.

Solvent effect on the 77Se NMR chemical shifts of diphenyl diselenides

Herein, we evaluated the solvent effect on the 77Se NMR chemical shifts of diphenyl diselenides. To gain a deeper insight into the 77Se NMR chemical shift behavior, DFT calculations have been performed.

Design and development of symmetric aromatic bischalcogenide-based photocatalysts for water treatment application: a concise study of diphenyl diselenide polypyrrole nanocatalysis.

Dopant engineering can be a very selective approach in designing hybrid materials. Incorporating the required functionality in a dopant effectively modulates its properties towards aimed applications. Consequently, this work through a comparative study envisaged the incorporation of chalcogenides (S, Se, and Te) in a biphenyl motif based on the analysis of major photocatalytic descriptors. Bischalcogenides as tuned dopants have been impressive in enhancing the surface area, increasing crystallinity and facilitating band gap shifts towards better light harvesting. In addition, the chalcogen effect was observed to induce preferential ion migration, leading to effective charge separation and attenuated recombination rates. Photocatalytic descriptors evaluated from electrochemical impedance spectroscopy and photoluminescence data corroborated the chalcogen effect in the observed trend (Ph)2 < (PhS)2 < (PhSe)2 < (PhTe)2. The diphenyl diselenide polypyrrole nanocomposite emerged to be better among the studied systems. (PhSe)2/PPY was characterized and comprehensively evaluated for its photocatalytic activity towards varied dye classes and the colorless isoniazid antibiotic under environmentally viable conditions. Its calculated band potential values and scavenger experiments indicate OH˙ and O2 ˙- as dominant species in its photocatalytic activity. Control experiments confirmed photocatalytic degradation over photolysis as the dye decolouration mechanism. Taken together, (PhSe)2/PPY emerges as a good propensity photocatalyst worthy of real time customization for wastewater treatment on a pilot scale.