Formation Of Hydrogen Research Articles

Simultaneous Photocatalytic Production of H2 and Acetal from Ethanol with Quantum Efficiency over 73% by Protonated Poly(heptazine imide) under Visible Light.

In this work, protonated poly(heptazine imide) (H-PHI) was obtained by adding acid to the suspension of potassium PHI (K-PHI) in ethanol. It was established that the obtained H-PHI demonstrates very high photocatalytic activity in the reaction of hydrogen formation from ethanol in the presence of Pt nanoparticles under visible light irradiation in comparison with K-PHI. This enhancement can be attributed to improved efficiency of photogenerated charge transfer to the photocatalyst's surface, where redox processes occur. Various factors influencing the system's activity were evaluated. Notably, it was discovered that the conditions of acid introduction into the system can significantly affect the size of Pt (cocatalyst metal) deposition on the H-PHI surface, thereby enhancing the photocatalytic system's stability in producing molecular hydrogen. It was established that the system can operate efficiently in the presence of air without additional components on the photocatalyst surface to block air access. Under optimal conditions, the apparent quantum yield of molecular hydrogen production at 410 nm is around 73%, the highest reported value for carbon nitride materials to date. The addition of acid not only increases the activity of the reduction part of the system but also leads to the formation of a value-added product from ethanol-1,1-diethoxyethane (acetal) with high selectivity.

Third Metal Ion Dictates the Catalytic Activity of the Two-Metal-Ion Pre-Ribosomal RNA-Processing Machinery.

Nucleic acid processing enzymes use a two-Mg2+-ion motif to promote the formation and cleavage of phosphodiester bonds. Yet, recent evidence demonstrates the presence of spatially conserved second-shell cations surrounding the catalytic architecture of proteinaceous and RNA-dependent enzymes. The RNase mitochondrial RNA processing (MRP) complex, which cleaves the ribosomal RNA (rRNA) precursor at the A3 cleavage site to yield mature 5'-end of 5.8S rRNA, hosts in the catalytic core one atypically-located Mg2+ ion, in addition to the ions forming the canonical catalytic motif. Here, we employ biased quantum classical molecular dynamics simulations of RNase MRP to discover that the third Mg2+ ion inhibits the catalytic process. Instead, its displacement in favour of a second-shell monovalent K+ ion propels phosphodiester bond cleavage by enabling the formation of a specific hydrogen bonding network that mediates the essential proton transfer step. This study points to a direct involvement of a transient K+ ion in the catalytic cleavage of the phosphodiester bond and implicates cation trafficking as a general mechanism in nucleic acid processing enzymes and ribozymes.

Shear‐Strained Pd Single‐Atom Electrocatalysts for Nitrate Reduction to Ammonia

AbstractElectrochemical nitrate reduction method (NitRR) is a low‐carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper‐based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO3. However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by‐product NO2−. In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd−CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol. gcat−1. h−1, and a Faraday efficiency of 90 % for ammonia production at −0.5 V vs. RHE. Electrochemical in situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress obviously promote the production of active hydrogen, reduce the reaction energy barrier of the decision‐making step for nitrate conversion to ammonia, further promote ammonia generation.

Shear-Strained Pd Single-Atom Electrocatalysts for Nitrate Reduction to Ammonia.

Electrochemical nitrate reduction method (NitRR) is a low-carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper-based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO3. However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by-product NO2 -. In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd-CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol. gcat -1. h-1, and a Faraday efficiency of 90 % for ammonia production at -0.5 V vs. RHE. Electrochemical in situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress obviously promote the production of active hydrogen, reduce the reaction energy barrier of the decision-making step for nitrate conversion to ammonia, further promote ammonia generation.

Bio-spectroscopic investigation linking changes of retinal structure with short-term administration of Amiodarone and revealing the ameliorative effect of vitamin E supplementation

Long term use of Amiodarone (AMIO) is associated with the development of ocular adverse effects. This study investigates the short term effects, and the ameliorative consequence of vitamin E on retinal changes that were associated with administration of AMIO. This is accomplished by investigating both retinal structural and conformational characteristics using Fourier transform infrared spectroscopy (FTIR) and Fundus examination. Three groups of healthy rabbits of both sexes were used; the first group served as control. The second group was orally treated with AMIO (160 mg /kg body weight) in a daily basis for two weeks. The last group orally received AMIO as the second group for two weeks then, oral administration of vitamin E (100 mg/kg body weight) for another two weeks as well. FTIR results revealed significant structural and conformational changes in retinal tissue constituents that include lipids and proteins due to AMIO administration. AMIO treatment was associated with fluctuated changes (increased/decreased) in the band position and bandwidth of NH, OH, and CH bonds. This was concomitant with changes in the percentage of retinal protein constituents in particularly α-helix and Turns. AMIO facilitates the formation of intra-molecular hydrogen bonding and turned retinal lipids to be more disordered structure. In conclusion, the obtained FTIR data together with principal component analysis provide evidence that administration of vitamin E following the treatment with AMIO can ameliorate these retinal changes and, these biophysical changes are too early to be detected by Fundus examination.

Transition Metal-Gallium Intermetallic Compounds with Tailored Active Site Configurations for Electrochemical Ammonia Synthesis.

Gallium (Ga) with a low melting point can serve as a unique metallic solvent in the synthesis of intermetallic compounds (IMCs). The negative formation enthalpy of transition metal-Ga IMCs endows them with high catalytic stability. Meanwhile, their tunable crystal structures offer the possibility to tailor the configurations of active sites to meet the requirements for specific catalytic applications. Herein, we present a general method for preparing a range of transition metal-Ga IMCs, including Co-Ga, Ni-Ga, Pt-Ga, Pd-Ga, and Rh-Ga IMCs. The structurally ordered CoGa IMCs with body-centered cubic (bcc) structure are uniformly dispersed on the nitrogen-doped reduced graphene oxide substrate (O-CoGa/NG) and deliver outstanding nitrate reduction reaction (NO3RR) performance, making them excellent catalysts to construct highly efficient rechargeable Zn-NO3- battery. Operando studies and theoretical simulations demonstrate that the electron-rich environments around the Co atoms enhance the adsorption strength of *NO3 intermediate and simultaneously suppress the formation of hydrogen, thus improving the NO3RR activity and selectivity.

Panthenol Additives with Multiple Coordination Sites Induce Uniform Zinc Deposition and Inhibited Side Reactions for High Performance Aqueous Zinc Metal Battery.

Application of aqueous zinc metal batteries (AZMBs) in large-scale new energy systems (NESs) is challenging owing to the growth of dendrites and frequent side reactions. Here, this study proposes the use of Panthenol (PB) as an electrolyte additive in AZMBs to achieve highly reversible zinc plating/stripping processes and suppressed side reactions. The PB structure is rich in polar groups, which led to the formation of a strong hydrogen bonding network of PB-H2O, while the PB molecule also builds a multi-coordination solvated structure, which inhibits water activity and reduces side reactions. Simultaneously, PB and OTF- decomposition, in situ formation of SEI layer with stable organic-inorganic hybrid ZnF2-ZnS interphase on Zn anode electrode, can inhibit water penetration into Zn and homogenize the Zn2+ plating. The effect of the thickness of the SEI layer on the deposition of Zn ions in the battery is also investigated. Hence, this comprehensive regulation strategy contributes to a long cycle life of 2300h for Zn//Zn cells assembled with electrolytes containing PB additives. And the assembled Zn//NH4V4O10 pouch cells with homemade modules exhibit stable cycling performance and high capacity retention. Therefore, the proposed electrolyte modification strategy provides new ideas for AZMBs and other metal batteries.

Role of MgO in Al2O3‐supported Fe catalysts for hydrogen and carbon nanotubes formation during catalytic methane decomposition

AbstractCatalytic methane decomposition is a promising technology for reducing the reliance on fossil fuels and mitigating the effects of climate change by producing clean hydrogen and value‐added carbon without the emission of greenhouse gases. The aim of the study was to investigate the use of Al2O3‐modified MgO doped iron‐based catalysts for the catalytic decomposition of methane. The catalysts were synthesized using the impregnation method and characterized using various analysis techniques, including Brunauer, Emmett, and Teller, temperature programmed reduction, temperature programmed oxidation, X‐ray diffraction, thermal gravimetric analysis, Raman, scanning electron microscopy, and transmission electron microscopy. The activity of the synthesized catalysts was tested in a packed‐bed reactor with a gas flow rate of 20 mL/min at a temperature of 800°C. The investigation focuses on the influence of incorporating magnesium into alumina catalysts with MgO concentration ranging from (20%–70%), where higher magnesium levels improve catalytic activity by creating more active sites, positively impacting methane decomposition. Enhanced catalyst reducibility and increased particle dispersion lead to improved catalytic properties despite the reduced surface area. The FA70M and FA63M catalysts exhibited almost the same catalytic characteristics and the highest stability and methane conversion among the catalysts investigated, reaching 87% and 85% at 800°C for 120 min. Moreover, both catalysts showed hydrogen yields of 86% and 85%, respectively. The introduction of MgO further increased the total carbon yield from 103% with FA and 39% for FM to 114% and 120% for the respective catalysts (FA70M and FA63M). During the methane decomposition reaction, carbon nanotubes of varying diameters were produced. Higher iron loading resulted in a positive trend.

Discovery of white etching areas in high nitrogen bearing steel X30CrMoN15-1: A novel finding in rolling contact fatigue analysis

White etching areas (WEA) and white etching cracks (WEC) are frequently linked to premature bearing failure in conventional high carbon bearing steels like 100Cr6 (SAE 52100). In contrast, no WEA/WEC has yet been reported for the high nitrogen bearing steel X30CrMoN15-1 (SAE AMS 5898). Thus, the present study proves for the first time that X30CrMoN15-1 is also susceptible to develop WEA/WEC under rolling contact fatigue (RCF) when pre-charged with hydrogen. RCF tests conducted in parallel without hydrogen pre-charging resulted in RCF damage only, which identifies hydrogen as an active agent for WEA/WEC formation in X30CrMoN15-1. These findings correspond to the fact that hydrogen diffusion during RCF is often considered to cause or accelerate the formation of WEA/WEC. Additionally, it is observed that the M2(C, N) and M23C6 precipitates of the martensitic microstructure of the X30CrMoN15-1 do not entirely decompose during the WEA formation process as observed for M3C precipitates in 100Cr6. In conclusion, the results for X30CrMoN15-1 strongly suggest that the formation of WEA is driven by a hydrogen-activated local severe plastic deformation process, which initiates continuous dynamic recrystallisation, leading to the characteristic nano-ferritic grains observed in WEA. Also, the highly stable and self-regenerating passive chromium-oxide layer of X30CrMoN15-1 mitigates the risk of WEA/WEC failure during typical RCF operation by hindering the formation and adsorption of ionic hydrogen. Hence, this study emphasises the importance of protecting the base material against hydrogen ingress to delay WEA/WEC formation.

Direct Collapse Supermassive Black Holes from Relic Particle Decay.

We investigate the formation of high-redshift supermassive black holes (SMBHs) via the direct collapse of baryonic clouds, where the unwanted formation of molecular hydrogen is successfully suppressed by a Lyman-Werner (LW) photon background from relic particle decay. We improve on existing studies by dynamically simulating the collapse, accounting for the adiabatic contraction of the DM halo, as well as the insitu production of the LW photons within the cloud which reduce the impact of the cloud's shielding. We find a viable parameter space where the decay of either some of the dark matter or all of a subdominant decaying species successfully allows direct collapse of the cloud to a SMBH.

Molecular Hydrogen Formation via Vibrational Excitation of Partially Superhydrogenated Pyrenes

While polycyclic aromatic hydrocarbons (PAHs) are now accepted to be abundant in interstellar space, the abundance and influence of superhydrogenated PAHs (HPAHs) in the interstellar medium (ISM) are still under investigation. HPAHs may act as catalysts for or reactants in small-molecule formation via hydrogen abstraction reactions, H2 evaporation, and carbon skeleton fragmentation. Here, we present a gas-phase infrared (IR) action spectroscopy study of the HPAH 4, 5, 9, 10-tetrahydropyrene (THP; C16H14), performed at the Free Electron Lasers for Infrared eXperiments facility. IR action spectroscopy was performed on the THP cation, protonated THP, and their fragments produced by collision-induced dissociation in the range from 600 to 1800 cm−1. Calculated IR spectra, at the density functional theory level, agree with experimental IR spectra to a high degree and were utilized to determine molecular structures of the HPAH fragments. Molecular dynamics simulations compared with experimental mass spectra reveal favorable HPAH fragmentation pathways. Molecular hydrogen (H2) is observed to be a primary fragment of [THP+H]+ with superhydrogenated duo groups. This contrasts the notion that HPAHs typically undergo carbon skeleton fragmentation leading to C x H y formation. These observations show that lowered symmetry and duo or trio aliphatic groups on HPAHs uniquely change their IR spectra, stability, and fragmentation patterns. As a result, these species may contribute to H2 formation in the ISM.

Crucial role of extracellular polymeric substances from anammox sludge in wastewater phosphorus recovery via magnesium phosphate crystallization

The magnesium phosphate (Mg-P) crystallization based on anaerobic ammonia oxidation is of interest for simultaneous nitrogen and phosphorus removal in wastewater treatment due to cost-effectiveness. Understanding the role of extracellular polymeric substances (EPS) in crystal growth is pivotal for bio-induced Mg-P crystallization. In this work, the effects of EPS in Mg-P crystallization were thoroughly investigated. Results indicated that EPS decreased the initial crystallization rate but slightly improved the final crystallization yield. The maximum removal efficiencies of Mg and P ions increased by 2.8 % and 3.1 %, respectively, when EPS concentration was 80 mg/L. Additionally, the presence of EPS enhanced Mg3(PO4)2·10 H2O production and facilitated the formation of larger rhombic plate-like structures crystals (maximum particle size increased by 215 %). Analysis of EPS composition changes during the crystallization process and characterization of the final crystals suggested that tryptophan-like proteins preferentially involved in the Mg-P crystallization process, while β-sheet proteins potentially influencing crystal morphology. Furthermore, the formation of phosphate ester groups, hydrogen bonding, and COOH-Mg2+ complexes were considered triggering factors for the interaction between EPS and Mg-P crystals. This study elucidated the underlying mechanism of EPS on Mg-P crystallization, further enhancing the understanding of the interaction between inorganic mineralization processes and microorganisms.

Theoretical description of hydride-hydride interactions in selected hydrogen storage materials.

The high content of hydride-hydride contacts Hδ-···δ-H in hydrogen storage materials appears to be relevant for hydrogen formation. At present time there is no consensus whether these contacts are attractive or repulsive. Accordingly, the main goal of this article is to shed light on physical factors which constitute homopolar hydride-hydride interactions Hδ-···δ-H in selected transition metal complexes i.e. HCoL4, L = CO,PPh3,PH3. In order to achieve this goal, the charge and energy decomposition ETS-NOCV approach along with the Interacting Quantum Atoms (IQA) and reduced density gradient (NCI) are applied for the bonded adducts L4CoH···HCoL4. Based on DFT and correlated methods it has been shown, that hydride-hydride interactions might be attractive and even far stronger than classical hydrogen bonds. The stability of the adducts is increased by phosphine ligand installation: overall Hδ-···δ-H bonding energy changes in the order: CO << PPh3 ~ PH3. It has been revealed that depending on monomer's conformations Hδ-···δ-H bonds are dominated by charge delocalization or London dispersion forces and the electrostatic term is also relevant. It is finally determined by IQA energy decomposition, that diatomic hydride-hydride interaction CoH···HCo is chameleon-like, namely, it is attractive in CO4CoH···HCoCO4, whereas the repulsion is unveiled in (CO)3(PPh3)CoH···HCo(CO)3(PPh3).

Spectral-Sensing System for Distinguishing CH3OH and CD3OD.

Spectrally discriminating CH3OH and CD3OD, and even detecting CH3OH contents in the CD3OD solvent, are important yet have not been achieved so far, likely owing to their very similar chemical/physical properties. Herein, dynamic transesterification reactions, which can be achieved via two-step proton transfers, can be signaled via ultraviolet UV-visible (UV/vis) absorption and fluorescence spectroscopies under mild experimental conditions. Introduction of strong electron-withdrawing groups, such as -NO2, to the aromatic ring (benzoic acid moiety or phenol moiety) of carboxylate esters to activate the esters is important for transesterification reactions and is an intriguing method for modulating the selectivity of the spectral response. The rate constant of the transesterification reaction enhanced with increasing the total number of strong electron-withdrawing groups. Furthermore, the rate constants of esters in which substituent(s) are connected to the phenol moiety are higher than those of corresponding esters in which substituent(s) are connected to the benzoic acid moiety. In transesterification systems, added aliphatic amines mainly play two roles: (i) lowering the energy barrier of the first transesterification step via the formation of intermolecular hydrogen bonding in ternary systems and (ii) deprotonating the released 4-nitrophenol in UV/vis absorption spectral systems to generate an UV/vis absorption spectral signal reporter, i.e., nitrophenolate anions. As a result of the methanol-mediated transesterification reaction, spectral-sensing systems can be established for discriminating CH3OH and CD3OD and even detecting low CH3OH contents in the CD3OD solvent, owing to the kinetic isotope effect. This is the first example of spectral recognition between CD3OD and CH3OH.

THE EFFECT OF CHEMICAL STRUCTURE OF VINYL CHLORIDE BASED POLYMERS ON ITS THE COMPATIBILITY WITH POLYURETHANEUREA ELASTOMER

The effect of the chemical structure of vinyl chloride-based polymers, such as poly(vinyl chloride) (PVC), chlorinated PVC (cPVC), vinyl chloride/vinylidene chloride copolymer VCVD-40TM, vinyl chloride/vinyl acetate copolymer А-15TM on its compatibility with poly(ether-urethane)urea elastomer (PUU) was studied by DSC and FTIR spectroscopy. The segmented PUU was synthesized by prepolymer approach in N,N-dimethylformamide (DMF) solution using poly(propylene glycol) of number-averaged molecular weight (Mn) of 1000 Da, 2,4-tolylenediisocyanate and tolylene 2,4-diamine as a chain extender at a molar ratio of 1:2:1. PUU/vinyl chloride-based polymer blends was prepared by solution casting technique vie DMF solution. It was found a compatibility of PUU based blends containing 30 % PVC (PUU/30PVC blend) or cPVC (PUU/30cPVC) were initiated by strong hydrogen bonding. As a result, the blends are characterized by single wide relaxation transition. A glass transition temperature (Тс) of PUU/30PVC composite is similar to the theoretical one (ТFс), which is calculated using the Flory-Fox equation, whereas Тс value of PUU/30cPVC composite is higher than ТFс. Introducing polar vinyl acetate or vinylidene chloride fragments into vinyl chloride-based polymer macrochains suppresses the compatibility of components of the polymer blends and initiates the formation of a biphase microheterogeneous structure. The formation of intermolecular hydrogen bonding network at the interface in polymer-polymer blends is confirmed by FTIR spectroscopy. Comparative analysis of experimental and theoretically calculated (additive) tensile characteristics of polymer blends demonstrates their substantial dependence on interface interactions between the constituents. The highest strengthening effect was observed for cPVC or PVC-containing nanocomposites.

Citric Acid and Polyvinyl Alcohol Induced PEDOT: PSS with Enhanced Electrical Conductivity and Stretchability for Eco-Friendly, Self-Healable, Wearable Organic Thermoelectrics.

Poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT: PSS) is a promising material for organic thermoelectric (TE) applications. However, it is challenging to achieve PEDOT: PSS composites with stretchable, self-healable, and high TE performance. Furthermore, some existing self-healing TE materials employ toxic reagents, posing risks to human health and the environment. In this study, a novel intrinsically self-healable and wearable composite is developed by incorporating environmentally friendly, highly biocompatible, and biodegradable materials of polyvinyl alcohol (PVA) and citric acid (CA) into PEDOT: PSS. This results in the formation of double hydrogen bonding networks among CA, PVA, and PEDOT: PSS, inducing microstructure alignment and leading to simultaneous enhancements in both TE performance and stretchability. The resulting composites exhibit a high electrical conductivity and power factor of 259.3 ± 11.7 S·cm-1, 6.9 ± 0.4 µW·m-1·K-2, along with a tensile strain up to 68%. Furthermore, the composites display impressive self-healing ability, with 84% recovery in electrical conductivity and an 85% recovery in tensile strain. Additionally, the temperature and strain sensors based on the PEDOT: PSS/PVA/CA are prepared, which exhibit high resolution suitable for human-machine interaction and wearable devices. This work provides a reliable and robust solution for the development of environmentally friendly, self-healing and wearable TE thermoelectrics.

Properties of Hydrogen Species in n‐Type Silicon Deduced from In‐Diffusion Profiles

Reported depth profiles of hydrogen in plasma‐exposed n‐Si samples can be fitted with a simple model of hydrogen transport by negative and neutral species (H− and H0) accompanied by a reversible formation of hydrogen–donor pairs (HD) and by an irreversible production of mobile dimers H2A—in particular by a bulk pairing reaction of the H− and H0 species. Contrary to a complicated behavior of hydrogen found in p‐Si (with multiple independent states for positive ions and passivated boron), the situation in n‐Si appears to be much simpler as only single states for H−, H0, and HD are sufficient for profile reproduction. The parameters deduced from the profiles are the diffusivity of H−, the characteristic electron concentration marking equal contributions of H− and H0 into hydrogen transport, and the diffusivity of H2A dimers (in the available temperature range 120–225 °C).

Ignisphaera cupida sp. nov., a hyperthermophilic hydrolytic archaeon from a hot spring of Uzon (Kamchatka), and emended description of the genus Ignisphaera

A novel strictly anaerobic hyperthermophilic archaeon, strain 4213-coT, was isolated from a terrestrial hot spring in the Uzon Caldera, Kamchatka (Russian Federation). Coccoid cells were present singly, in pairs, or aggregates, and occasionally were motile. The strain grew at 75–100 °C and within a pH range of 5.4–8.2 with the optimum at 92 °C and pH 6.4–6.7. Strain 4213-coT was a chemoorganoheterotroph, growing on proteinaceous substrates and mono-, di- and polysaccharides (starch, guar gum, xanthan gum). It did not require sodium chloride for growth. The complete genome of strain 4213-coT was 1.74 Mbp in size; its G+C content was 36.18 %. Genome analysis allowed to identify 25 genes encoding glycosidases involved in polysaccharide hydrolysis as well as genes of ADP-forming acetate-CoA ligase, lactate dehydrogenase and two [NiFe] hydrogenases responsible for acetate, lactate and hydrogen formation during fermentation. Moreover gene cluster encoding archaellum subunits was found. According to the phylogenomic analysis strain 4213-coT formed a species-level phylogenetic lineage within Ignisphaera genus. Our phylogenomic analysis also supports the delineation of the Ignisphaera genus into a separate family Ignisphaeraceae, as recently published. Here we propose a novel species Ignisphaera cupida, sp. nov. with type strain 4213-coT (=JCM 39446T=VKM B-3715T=UQM 41593T). Ecogenomic analysis showed that representatives of the Ignisphaera are thermophilic archaea, the majority of them were found in terrestrial hot springs and deep-sea hydrothermal vents. This study allowed a better understanding of physiology and ecology of Ignisphaeraceae – a rather understudied archaeal group.

Benzimidazole-oxindole hybrids: A novel class of selective dual CDK2 and GSK-3β inhibitors of potent anticancer activity.

A new series of benzimidazole-oxindole hybrids 8a-x was discovered as dual cyclin-dependent kinase (CDK2) and glycogen synthase kinase-3-beta (GSK-3β) inhibitors with potent anticancer activity. The synthesized hits displayed potent anticancer activity against national cancer institute cancer cell lines in single-dose and five-dose assays. Moreover, the derivatives 8k, 8l, 8n, 8o, and 8p demonstrated potent cytotoxic activity against PANC-1 cells with IC50 = 1.88-2.79 µM. In addition, the hybrids 8l, 8n, 8o, and 8p displayed potent antiproliferative activity on the MG-63 cell line (IC50 = 0.99-1.90 µM). Concurrently, the benzimidazole-oxindole hybrid 8v exhibited potent dual CDK2/GSK-3β inhibitory activity with IC50 values of 0.04 and 0.021 µM, respectively. In addition, 8v displayed more than 10-fold higher selectivity toward CDK2 and GSK-3 β over CDK1, CDK5, GSK-3α, vascular endothelial growth factor receptor-2, and B-rapidly accelerated fibrosarcoma. Screening of the effect of 8n and 8v on the cell cycle and apoptosis of PANC-1 and MG-63 cells displayed their ability to arrest their cell cycle at the G2-M phase and to potentiate the apoptosis of both cell lines. In silico docking of the benzimidazole-oxindole hybrid 8v into the catalytic pocket of both CDK2 and GSK-3β revealed its perfect fitting through the formation of hydrogen bonding and hydrophobic interactions with the key amino acids in the binding sites. In addition, in silico absorption, distribution, metabolism, excretion studies proved that 8a-x exhibit satisfactory drug-likeness properties for drug development.

In Situ and Continuous Decoding Hydrogen Generation in Solar Water-Splitting Cells.

Photoelectrochemical (PEC) water splitting is gaining recognition as an effective method for producing green hydrogen. However, the absence of in situ, continuous decoding hydrogen generation tools hampers a detailed understanding of the physics and chemistry involved in hydrogen generation within PEC systems. In this article, we present a quantitative, spatiotemporally resolved optical sensor employing a fiber Bragg grating (FBG) to probe hydrogen formation and temperature characteristics in the PEC system. Demonstrating this principle, we observed hydrogen formation and temperature changes in a novel cappuccino cell using a BiVO4/TiO2 photoanode and a Cu2O/CuO/TiO2 photocathode. Our findings demonstrate that FBG sensors can probe dynamic hydrogen formation at 0.5 s temporal resolution; these sensors are capable of detecting hydrogen concentrations as low as 0.6 mM. We conducted in situ and continuous monitoring of hydrogen and temperature to ascertain various parameters: the rate of hydrogen production at the photocathode surface, the time to reach hydrogen saturation, the distribution of hydrogen and temperature, and the rate of hydrogen transfer in the electrolyte under both external bias and unbiased voltage conditions. These results contribute valuable insights into the design and optimization of PEC water-splitting devices, advancing the in situ comprehensive monitoring of PEC water-splitting processes.