Chemical Epitaxy of Iridium Oxide on Tin Oxide Enhances Stability of Supported OER Catalyst.

Significantly reducing the iridium content in oxygen evolution reaction (OER) catalysts while maintaining high electrocatalytic activity and stability is a key priority in the development of large-scale proton exchange membrane (PEM) electrolyzers. In practical catalysts, this is usually achieved by depositing thin layers of iridium oxide on a dimensionally stable metal oxide support material that reduces the volumetric packing density of iridium in the electrode assembly. By comparing two support materials with different structure types, it is shown that the chemical nature of the metal oxide support can have a strong influence on the crystallization of the iridium oxide phase and the direction of crystal growth. Epitaxial growth of crystalline IrO2 is achieved on the isostructural support material SnO2, both of which have a rutile structure with very similar lattice constants. Crystallization of amorphous IrOx on an SnO2 substrate results in interconnected, ultrasmall IrO2 crystallites that grow along the surface and are firmly anchored to the substrate. Thereby, the IrO2 phase enables excellent conductivity and remarkable stability of the catalyst at higher overpotentials and current densities at a very low Ir content of only 14 at%. The chemical epitaxy described here opens new horizons for the optimization of conductivity, activity and stability of electrocatalysts and the development of other epitaxial materials systems.

Evaluation of High-Affinity Monoclonal Antibodies and Antibody-Drug Conjugates by Homogenous Time-Resolved FRET.

The rapid growth of therapeutic monoclonal antibodies demands greater accessibility to scalable methods of evaluating antigen binding. Homogenous TR-FRET is ideal for preliminary screening but has not been reported to assay these interactions due to their high-affinity and complex solution-phase kinetics. Here we report the development of a competition assay to rank-order the relative affinities of these drugs for a common antigen. The assay is compatible with automation, requires no modification of the analytes, and measures affinities as low as single-digit picomolar. We further demonstrate applications to inform the development of antibody-drug conjugates. The assay may aid discovery and manufacturing of therapeutic antibodies as a low-cost, high-throughput alternative to existing technologies.

Nanosized-laser-induced sub-20nm homogenous alloy nanoparticles.

Alloy nanoparticles (NPs) have great potential in nanosized 3D-printing, surface coating, plasmonic enhancement, information coding, and so forth. However, chemical-pollution-free and homogeneous sub-20nm NPs maintain still a challenge in preparation. Here we present a smart nanosecond laser scan strategy of alloy-NPs preparation on a bilayer metal film by using a nanosized focused beam, sucessfully realizing controllable fabrication of the sub-20nm homogeneous alloy NPs without pollution. As demonstration, various sub-20nm AgCu GPs with different volume ratios have been prepared, all GPs show narrow size distribution and uniform interparticle spacing. The simple and cost-effective method is a stable and adaptable for other alloy-GPs such as AuAg GPs. In addition, such alloy NPs exhibit two-peak plasma resonance feature and information cording capacity. We believe that homogenous alloy sub-20nm GPs will provide new application opportunities in many fields. .

Homogenizing The Low-Dimensional Phases for Stable 2D-3D Tin Perovskite Solar Cells.

2D-3D tin-based perovskites are considered as promising candidates for achieving efficient lead-free perovskite solar cells (PSCs). However, the existence of multiple low-dimensional phases formed during the film preparation hinders the efficient transport of charge carriers. In addition, the non-homogeneous distribution of low-dimensional phases leads to lattice distortion and increases the defect density, which are undesirable for the stability of tin-based PSCs. Here, mixed spacer cations [diethylamine (DEA+) and phenethylamine (PEA+)] are introduced into tin perovskite films to modulate the distribution of the 2D phases. It is found that compared to the film with only PEA+, the combination of DEA+ and PEA+ favors the formation of homogeneous low-dimensional perovskite phases with three octahedral monolayers (n = 3), especially near the bottom interface between perovskite and hole transport layer. The homogenization of 2D phases help improve the film quality with reduced lattice distortion and released strain. With these merits, the tin PSC shows significantly improved stability with 94% of its initial efficiency retained after storing in a nitrogen atmosphere for over 4600 h, and over 80% efficiency maintained after continuous illumination for 400 h.

Inclusion of TAT and NLS sequences in lipopeptide molecules generates homogenous nanoparticles for gene delivery applications.

PURPOSES: The objective of this study is to develop a versatile gene carrier based on lipopeptides capable of delivering genetic material into target cells with minimal cytotoxicity. METHODS: Two lipopeptide molecules, palmitoyl-CKKHH and palmitoyl-CKKHH-YGRKKRRQRRR-PKKKRKV, were synthesized using solid phase peptide synthesis and evaluated as transfection agents. Physicochemical characterization of the lipopeptides included a DNA shift mobility assay, particle size measurement, and transmission electron microscopy (TEM) analysis. Cytotoxicity was assessed in CHO-K1 and HepG2 cells using the MTT assay, while transfection efficiency was determined by evaluating the expression of the green fluorescent protein-encoding gene. RESULTS: Our findings demonstrate that the lipopeptides can bind, condense, and shield DNA from DNase degradation. The inclusion of the YGRKKRRQRRR sequence, a transcription trans activator, and the PKKKRKV sequence, a nuclear localization signal, imparts desirable properties. Lipopeptide-based TAT-NLS/DNA nanoparticles exhibited stability for up to 20 days when stored at 6-8 °C, displaying uniformity with a compact size of approximately 120 nm. Furthermore, the lipopeptides exhibited lower cytotoxicity compared to the poly-L-lysine. Transfection experiments revealed that protein expression mediated by the lipopeptide occurred at a charge ratio ranging from 4.0 to 8.0. CONCLUSION: These results indicate that the lipopeptide, composed of a palmitoyl alkyl chain and TAT and NLS sequences, can efficiently condense and protect DNA, form stable and uniform nanoparticles, and exhibit promising characteristics as a potential gene carrier with minimal cytotoxicity.

Ball-Milling toward Nickel(II) Diphosphine Complexes for Direct Use in Catalysis.

Mechanochemistry turned out to be a powerful synthetic tool enabling the first efficient synthesis of nickel(II) complexes with diphosphines. It has been demonstrated that solventless ball-milling of nickel(II) halides with diphosphines leads to the [NiX2(diphosphine)] type compounds, which can be directly used in catalysis without any purification. Moreover, it was confirmed that despite the presence of impurities in the resulting complexes, their catalytic activity remains identical to those obtained via traditional solvent-based methods.

A novel distributed meta-module motion design for modular robotic systems based on grid partition method.

This article studies a meta-module motion design approach for homogenous modular robotic systems in self-configuration. By utilizing configuration diversity, scalability and unit-substitutability, homogenous modular robotic systems can be a promising approach to life detection and space exploration in the future. Based on the requirements of the potential applications, self-configuration can be considered as the precondition. As similar to swarm robotic systems, the distributed control strategy in which the modular robots are operated in a sequence of motion circles consist of 'detection'- 'decision'- 'execution' is of great significance. However, there is a limitation to the applicability of previously proposed work on the self-configuration topic, due to the fact that the self-configuration strategy execution suffers from the motion constraints of modular robots. In order to solve the problem, we propose a grid partition method that removes the gap between the locomotion of a single modular robot and the reconfiguration of the whole system. Under the analysis of the grid partition, the meta-module motion design is proposed to realize the distributed self-configuration strategy. We simulated the self-configuration in M-Lattice, a two-dimensional homogenous modular robotic system.

Recyclable Homogeneous Catalysis Enabled by Dynamic Coordination on Rhodium(II) Axial Sites of Metal-Organic Polyhedra.

The activity of catalytic nanoparticles is strongly dependent on their surface chemistry, which controls colloidal stability and substrate diffusion toward catalytic sites. In this work, we studied how the outer surface chemistry of nanostructured Rh(II)-based metal-organic cages or polyhedra (Rh-MOPs) impacts their performance in homogeneous catalysis. Specifically, through post-synthetic coordination of aliphatic imidazole ligands onto the exohedral Rh(II) axial sites of Rh-MOPs, we solubilized a cuboctahedral Rh-MOP in dichloromethane, thereby enabling its use as a homogeneous catalyst. We demonstrated that the presence of the coordinating ligand on the surface of the Rh-MOP does not hinder its catalytic activity in styrene aziridination and cyclopropanation reactions, thanks to the dynamic Rh-imidazole coordination bond. Finally, we used similar ligand exchange post-synthetic reactions to develop a ligand-mediated approach for precipitating the Rh-MOP catalyst, facilitating the recovery and reuse of Rh-MOPs as homogeneous catalysts.

Mechanism of Alkaline Earth Metal Amide Catalyzed Hydrogenation of Challenging Alkenes and Arenes.

Recently, bulky alkaline earth (Ae=Mg, Ca, Sr, Ba) metal amide complexes AeN"2 (N"=N[Si(iPr)3]2) are shown to be active for catalyzing the hydrogenation of unactivated alkenes and arenes, presumably via the monomer N"AeH as catalyst. In sharp contrast, our extensive DFT calculations disclose that the double Ae-H-Ae bridged dimer (N"AeH)2 is kinetically more favorable in catalytic hydrogenation with H2, although rate-limited by the initial hydrogenolysis of AeN"2 to form the monomer N"AeH.

Modelling competitive adsorption of organic micropollutants onto powdered activated carbon in continuous stirred tank reactors for advanced wastewater treatment.

This work investigates the validation and application of a competitive model approach for full-scale wastewater treatment plants (WWTP) with external recirculation of partially loaded powdered activated carbon (PAC) for removal of organic micropollutants (OMP). It is based on the ideal adsorbed solution theory (IAST) for multisolute mixtures combined with calibration of fictive organic components and correction of single-solute model parameters for OMP by use of the tracer model (TRM). Adsorption kinetics are represented by a pseudo first order reaction (PFO) and compared to mass transfer calculated with the homogenous surface diffusion model (HSDM). Model validation with operational data from two different WWTPs showed a strong dependency of model results on the batch sample quality used for model calibration. In contrast, the kinetic approach is of less importance for predicting full-scale OMP removal with long PAC sludge retention times. Further model application demonstrated that external PAC recirculation significantly improves the OMP removal with regard to both adsorption capacity and compensation of competitive effects of Dissolved Organic Carbon (DOC).

In-syringe homogeneous liquid-phase microextraction followed by filtration-based phase separation for on-site extraction of chloroanilines from water samples.

This study introduces a new in-syringe homogeneous liquid-phase microextraction method for the rapid on-site extraction of chloroanilines from water samples. Extraction was performed using a plastic syringe, eliminating the use of any electrical power source. Di-(2-ethylhexyl) phosphoric acid (DEHPA) served as the extractant. The process initially involved dissolving DEHPA in an alkaline solution to obtain a homogeneous solution. Subsequently, the sodium salt of DEHPA was precipitated by salting-out, and the resulting heterogeneous mixture was filtered using a syringe filter. The precipitate containing the analytes was then dissolved in methanol for analysis by high-performance liquid chromatography. Under optimal conditions, extraction recovery for chloroanilines ranged from 26% to 71%. Method linearity was evaluated within a concentration range of 1.0-100 µg/L, resulting in coefficients of determination exceeding 0.9987 for all analytes. Method detection limits ranged from 0.28 to 0.41 µg/L. Intra and inter-day precision values were below 9.5% and 10.8%, respectively. The developed method was applied to determine chloroanilines in real waters, yielding acceptable recoveries ranging from 80% to 109% for spiked tap, rain, and stream waters. Additionally, the method was successfully employed for on-site extraction of target contaminants, demonstrating no statistically significant differences compared to laboratory results.

KRAS4b:RAF-1 Homogenous Time-Resolved Fluorescence Resonance Energy Transfer Assay for Drug Discovery.

Homogenous time-resolved FRET (HTRF) assays have become one of the most popular tools for pharmaceutical drug screening efforts over the last two decades. Large Stokes shifts and long fluorescent lifetimes of lanthanide chelates lead to robust signal to noise, as well as decreased false positive rates compared to traditional assay techniques. In this chapter, we describe an HTRF protein-protein interaction (PPI) assay for the KRAS4b G-domain in the GppNHp-bound state and the RAF-1-RBD currently used for drug screens. Application of this assay contributes to the identification of lead compounds targeting the GTP-bound active state of K-RAS.

Prandtl and Ohnesorge numbers dependent of ultrasonic horn energy in Newtonian liquid under batch and continuous flow.

The level of knowledge on the non-thermal contribution of ultrasonic wave's energy to perform physico-chemical phenomena is one of the bottlenecks for the commercialization purposes. Under constant nominal power of transducer (Pn), the input electrical power (Pin) is less and sensitive to the medium's physical properties. This study attempts to assess the conversion of acoustic to thermal power experimentally and numerically using COMSOL Multiphysis@ for a 24 kHz horn-type sonicator through a medium without any sono-chemical effect. Single- and homogeneous two-phase Newtonian mixtures of sunflower oil and water (o/w) with a relatively wide range of density (914-998 kg/m3) and viscosity (0.5-63.5 mPa.s) were irradiated in a lab-scale vessel (1 L) under batch and continuous flow configuration. The direct influence of Pn (80-400 W) and o/w ratio (0-1) on temperature rise and subsequent thermo-physical properties of liquid and the indirect influence on Pin and thermal energy conversion (TEC) were investigated employing calorimetric method. A new engineering concept including a power factor correlation was proposed and validated for prediction of Pin as a function of liquid space velocity (ϑ), temperature, Prandtl (Pr) and Ohnesorge (Oh) dimensionless groups. The results showed that under constant temperature and Pn, increasing Pr and Oh increased Pin with a similar trend for both modes of operation. An increase in temperature directly led to a decrease in Pin with a power factor closed to "-1". The Pin in continuous flow was higher compared to batch configuration at similar temperature, liquid properties, and Pn. This effect was more significant with increasing ϑ. An increase in ϑ at constant Pn led to a decrease in the inlet/outlet temperature difference in continuous flow and an increase in Pin. Increasing Pn resulted in higher TEC for both configurations; however, TEC was relatively lower in continuous flow than batch configuration indicating more efficient sonication in continuous flow.

Bronchoscopic lung volume reduction by instillation of fibrinogen and thrombin in COPD patients with homogenous emphysema.

BACKGROUND: The new endobronchial therapy called biological lung volume reduction (BioLVR) involves using a rapid polymerizing sealant to block off the most emphysematous portions of the lungs. The primary mechanism of action is resorption atelectasis, which is then followed by inflammation and remodeling of the airspace. The remodeling process will result in the formation of scars, leading to the contraction of the lung tissue. As a result, a decrease in functional lung volume is anticipated for a period of 6-8 weeks. OBJECTIVE: Assessing the safety and effectiveness of bronchoscopic installation of (fibrinogen and thrombin) in COPD patients with homogeneous emphysema in terms of radiological, physiological, and quality of life outcomes. METHODS: Between December 2017 and December 2019, 40 COPD patients with homogeneous emphysema were studied using a fiber optic bronchoscope while they were awake but sedated. Tanta University Hospitals' chest medicine department collaborated with the diagnostic radiology department of the Faculty of Medicine. RESULTS: All the following parameters were reduced from their initial values: HRCT volumetry, RV/TLC, mMRC dyspnea scale, CAT score, 6MWT, FEV1, and the FEV1/FVC ratio at the first, third, and sixth months from the beginning (p = 0.001). One individual (0.025%) had pneumonia, whereas three individuals had COPD (0.075%). Using fibrin glue produced locally, biological lung volume reduction (Bio LVR) may be an effective treatment for advanced homogenous emphysema. CONCLUSION: By using locally prepared fibrin glue the biologic lung volume reduction (Bio LVR) may be a convenient method to treat advanced homogenous emphysema.

UHPLC-MS/MS for plasma lamotrigine analysis and comparison with a homogenous enzyme immunoassay.

Aims: To develop and validate a UHPLC-MS/MS method for lamotrigine (LTG) analysis in human plasma and evaluate its agreement with a homogenous enzyme immunoassay (HEIA). Materials & methods: The UHPLC-MS/MS method was developed and validated according to the USFDA/EMA guidelines. A Bland-Altman plot was used to evaluate the agreement between UHPLC-MS/MS and HEIA. Results: Samples were pretreated with one-step protein precipitation and separated in 2.6 min. The intra- and inter-day bias and imprecisions were -15.8 to 15.0% and less than 11.17%, respectively. The recovery and matrix factor were 98.30 to 111.97%. The mean overestimation of UHPLC-MS/MS compared with HEIA was 21.57%. Conclusion: A rapid, sensitive and robust UHPLC-MS/MS method for plasma LTG analysis was developed and validated and was a 21.57% overestimation compared with HEIA.

Algal carbohydrate polymers: Catalytic innovations for sustainable development.

Algal polysaccharides, harnessed for their catalytic potential, embody a compelling narrative in sustainable chemistry. This review explores the complex domains of algal carbohydrate-based catalysis, revealing its diverse trajectory. Starting with algal polysaccharide synthesis and characterization methods as catalysts, the investigation includes sophisticated techniques like NMR spectroscopy that provide deep insights into the structural variety of these materials. Algal polysaccharides undergo various preparation and modification techniques to enhance their catalytic activity such as immobilization. Homogeneous catalysis, revealing its significance in practical applications like crafting organic compounds and facilitating chemical transformations. Recent studies showcase how algal-derived catalysts prove to be remarkably versatile, showcasing their ability to customise reactions for specific substances. Heterogeneous catalysis, it highlights the significance of immobilization techniques, playing a central role in ensuring stability and the ability to reuse catalysts. The practical applications of heterogeneous algal catalysts in converting biomass and breaking down contaminants, supported by real-life case studies, emphasize their effectiveness. In sustainable chemistry, algal polysaccharides emerge as compelling catalysts, offering a unique intersection of eco-friendliness, structural diversity, and versatile catalytic properties. Tackling challenges such as dealing with complex structural variations, ensuring the stability of the catalyst, and addressing economic considerations calls for out-of-the-box and inventive solutions. Embracing the circular economy mindset not only assures sustainable catalyst design but also promotes efficient recycling practices. The use of algal carbohydrates in catalysis stands out as a source of optimism, paving the way for a future where chemistry aligns seamlessly with nature, guiding us toward a sustainable, eco-friendly, and thriving tomorrow. This review encapsulates-structural insights, catalytic applications, challenges, and future perspectives-invoking a call for collective commitment to catalyze a sustainable scientific revolution.

Determination of bisphenols in beeswax based on sugaring out-assisted liquid-liquid extraction: Method development and application in survey, recycling and degradation studies.

The methodology of sugaring out-assisted liquid-liquid extraction (SULLE) coupled with high-performance liquid chromatography-fluorescence detection was devised for quantifying bisphenol A (BPA) and bisphenol B (BPB) in beeswax. The effectiveness of SULLE was methodically explored and proved superior to the salting out-assisted liquid-liquid extraction approach for beeswax sample preparation. The analytical performance underwent comprehensive validation, revealing detection limits of 10 µg/kg for BPA and 20 µg/kg for BPB. The method developed was employed to analyse commercial beeswax (n = 15), beeswax foundation (n = 15) and wild-build comb wax (n = 26) samples. The analysis revealed BPA presence in four commercial beeswax samples and three beeswax foundation samples, with the highest detected residue content being 88 ± 7 µg/kg. For BPB, two beeswax foundation samples were positive, with concentrations below the limits of quantification and 85 ± 4 µg/kg, respectively. No bisphenols were detected in wild-build comb wax. Furthermore, the bisphenol removal efficacy of two recycling methods-boiling in water and methanol extraction-was assessed. The findings indicated that after four recycling cycles using water boiling, 9.6% of BPA and 29.2% of BPB remained in the beeswax. Whereas methanol extraction resulted in approximately 7% residual after one recycling process. A long-term study over 210 days revealed the slow degradation of bisphenols in comb beeswax. This degradation fitted well with a first-order model, indicating half-lives (DT50) of 139 days for BPA and 151 days for BPB, respectively. This research provides the first report on bisphenol contamination in beeswax. The low removal rate during the recycling process and the gradual degradation in beeswax underscore the significance of bisphenol contamination and migration in bee hives along with their potential risk to pollinators warranting concern. Furthermore, the developed SULLE method shows promise in preparing beeswax samples to analyse other analytes.

Counterion Effect in Cobaltate-Catalyzed Alkene Hydrogenation.

We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(η4 -cod)2 ] (Cat=K (1), Na (2), Li (3), (Dep nacnac)Mg (4), and N(n Bu)4 (5); cod=1,5-cyclooctadiene, Dep nacnac={2,6-Et2 C6 H3 NC(CH3 )}2 CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover-limiting migratory insertion step. The results of these studies suggest an active co-catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates.

Stereoselective Copper-Catalyzed Olefination of Imines.

Alkenes are an important class of organic molecules found among synthetic intermediates and bioactive compounds. They are commonly synthesized through stoichiometric Wittig-type olefination of carbonyls and imines, using ylides or their equivalents. Despite the importance of Wittig-type olefination reactions, their catalytic variants remain underdeveloped. We explored the use of transition metal catalysis to form ylide equivalents from readily available starting materials. Our investigation led to a new copper-catalyzed olefination of imines with alkenyl boronate esters as coupling partners. We identified a heterobimetallic complex, obtained by hydrocupration of the alkenyl boronate esters, as the key catalytic intermediate that serves as an ylide equivalent. The high E-selectivity observed in the reaction is due to the stereoselective addition of this intermediate to an imine, followed by stereospecific anti-elimination.

The Role of Indirect Immunofluorescence (IIF) and Line Immunoassay (LIA) in the Diagnosis of Autoimmune Diseases and Their Clinical Correlation: An Observational Study From a Tertiary Care Center in Bihar.

Background and aim The presence of distinct sets of autoantigens and autoantibodies bestow these autoimmune diseases (ADs) with specific immune profiles or fingerprints, which has cleared the diagnostic dilemma associated with these ADs. This study was planned to collate and compare the reporting of indirect immunofluorescence (IIF) with line immunoassay (LIA) and their clinical correlations. This study was conducted to investigate the association between the reporting of anti-nuclear antibody (ANA) screening by IIF and ANA profile reporting by LIA. Additionally, it aimed to explore the association of ANA pattern detection by IIF with the detection of autoantibodies against nuclear antigens by LIA and the association of autoantibody detection by LIA with clinical diagnosis. Methodology A total of 98 samples from patients suspected of having ADs were subjected to both IIF and LIA, and results were correlated with clinical diagnosis. Results In the homogenous pattern noted by IIF, the clustered antigens identified by LIA included dsDNA, Nucleosome, Histone, and Mi-2. In the speckled pattern, the identified antigens were SS-A/Ro52, P0, SS-A/Ro60, SS-B/La, and U1-snRNP. On the other hand, the nucleolar pattern revealed antigens AMA M2, PCNA, and CENP-B. The centromere pattern was mostly associated with CENP-B. The speckled pattern was found to be most commonly associated with systemic lupus erythematosus (SLE). The most common autoantibody found in total ANA profile-positive samples was anti-U1-snRNP followed by anti-SS-A/Ro60 and anti-SS-B/La, and all three were found to be associated with SLE. Conclusions SLE was the most common AD identified in our study samples, with the speckled pattern being the most common pattern on IIF and anti-U1-snRNP being the most common ANA identified by LIA. The fluorescence pattern of IIF predicts the presence of specific antibodies. LIA should be reserved for IIF-positive but dubious cases and whose signs and symptoms are nebulous and do not match the disease dictated by IIF.