Kinetic Measurements Research Articles

Bipolar Organic Cathodes for Stable and Sustainable Na‐Ion and Rechargeable Al Batteries

AbstractBipolar organic materials have emerged as promising cathode materials for rechargeable batteries because of their high voltage and high capacity. However, they suffer from poor cyclic stability and slow reaction kinetics. In this work, we designed and synthesized two bipolar organic cathode materials, containing carbonyl (n‐type) and amine (p‐type) functional groups, as well as extended conjugation structures, for Na‐ion batteries (NIBs) and rechargeable aluminum batteries (RABs). As universal electrode materials, bipolar organic materials exhibited exceptional electrochemical performance in terms of high capacity, high voltage, long cycle life, and fast rate capability. The extended conjugation structures in backbones of the bipolar organic materials facilitate the π–π stacking with graphene, playing a critical role in the high performance. Furthermore, the formation of a stable and robust NaF‐rich cathode electrolyte interphase was shown to stabilize the bipolar organic cathode in NIBs. Electrochemical kinetic measurements reveal that both functional groups undergo reversible redox reactions. Specifically, the electron transfer rate constant of the p‐type amine group is one order of magnitude higher than that of the n‐type carbonyl group. These results highlight the efficacy of developing bipolar organic materials for achieving high‐performance organic cathode in NIBs and RABs.

Real-Time Measurement of a Weak Interaction of a Transcription Factor Motif with a Protein Hub at Single-Molecule Precision.

Transcription factors often interact with other protein cofactors, regulating gene expression. Direct detection of these brief events using existing technologies remains challenging due to their transient nature. In addition, intrinsically disordered domains, intranuclear location, and lack of cofactor-dependent active sites of transcription factors further complicate the quantitative analysis of these critical processes. Here, we create a genetically encoded label-free sensor to identify the interaction between a motif of the MYC transcription factor, a primary cancer driver, and WDR5, a chromatin-associated protein hub. Using an engineered nanopore equipped with this motif, WDR5 is probed through reversible captures and releases in a one-by-one and time-resolved fashion. Our single-molecule kinetic measurements indicate a weak-affinity interaction arising from a relatively slow complex association and a fast dissociation of WDR5 from the tethered motif. Further, we validate this subtle interaction by determinations in an ensemble using single nanodisc-wrapped nanopores immobilized on a biolayer interferometry sensor. This study also provides the proof-of-concept for a sensor that reveals unique recognition signatures of different protein binding sites. Our foundational work may be further developed to produce sensing elements for analytical proteomics and cancer nanomedicine.

Thermometry with a dissipative heavy impurity

Improving the measurement precision of low temperature is significant in fundamental science and advanced quantum technology application. However, the measurement precision of temperature T usually diverges as T tends to zero. Here, by utilizing a heavy impurity to measure the temperature of a Bose gas, we obtain the Landau bound to precision δ2T∝T2 to avoid the divergence. When the initial momentum of the heavy impurity is close to be fixed and nonzero, the measurement precision can be δ2T∝T3 to break the Landau bound. We derive the momentum distribution of the heavy impurity at any moment and obtain the optimal measurement precision of the temperature by calculating the Fisher information. As a result, we find that increasing the expectation value P0 and reducing the variance Δ/2 of the initial momentum can help to improve the measurement precision. Moreover, under certain conditions, Δ/P0 is a relevant parameter, the smallness of which helps improve the thermometric precision of the probe. In addition, the momentum measurement is the optimal measurement of the temperature in the case that the initial momentum is close to be fixed and not equal to zero. The kinetic energy measurement is the optimal measurement in the case that the expectation value of the initial momentum is close to zero. Finally, we obtain that the temperatures of two Bose gases can be measured simultaneously. The simultaneous measurement precision is proportional to T2 when two temperatures are close to T. Published by the American Physical Society 2024

High-Throughput Determination of Infectious Virus Titers by Kinetic Measurement of Infection-Induced Changes in Cell Morphology.

Infectivity assays are the key analytical technology for the development and manufacturing of virus-based therapeutics. Here, we introduce a novel assay format that utilizes label-free bright-field images to determine the kinetics of infection-dependent changes in cell morphology. In particular, cell rounding is directly proportional to the amount of infectious virus applied, enabling rapid determination of viral titers in relation to a standard curve. Our kinetic infectious virus titer (KIT) assay is stability-indicating and, due to its sensitive readout method, provides results within 24 h post-infection. Compared to traditional infectivity assays, which depend on a single readout of an infection endpoint, cumulated analysis of kinetic data by a fit model results in precise results (CV < 20%) based on only three wells per sample. This approach allows for a high throughput with ~400 samples processed by a single operator per week. We demonstrate the applicability of the KIT assay for the genetically engineered oncolytic VSV-GP, Newcastle disease virus (NDV), and parapoxvirus ovis (ORFV), but it can potentially be extended to a wide range of viruses that induce morphological changes upon infection. The versatility of this assay, combined with its independence from specific instruments or software, makes it a promising solution to overcome the analytical bottleneck in infectivity assays within the pharmaceutical industry and as a routine method in academic research.

Azobenzene-Based Photoswitchable Substrates for Advanced Mechanistic Studies of Model Haloalkane Dehalogenase Enzyme Family.

The engineering of efficient enzymes for large-scale production of industrially relevant compounds is a challenging task. Utilizing rational protein design, which relies on a comprehensive understanding of mechanistic information, holds significant promise for achieving success in this endeavor. Pre-steady-state kinetic measurements, obtained either through fast-mixing techniques or photoswitchable substrates, provide crucial mechanistic insights. The latter approach not only furnishes mechanistic clarity but also affords real-time structural elucidation of reaction intermediates via time-resolved femtosecond crystallography. Unfortunately, only a limited number of such valuable mechanistic probes are available. To address this gap, we applied a multidisciplinary approach, including computational analysis, chemical synthesis, physicochemical property screening, and enzyme kinetics to identify promising candidates for photoswitchable probes. We demonstrate the approach by designing an azobenzene-based photoswitchable substrate tailored for haloalkane dehalogenases, a prototypic class of enzymes pivotal in developing computational tools for rational protein design. The probe was subjected to steady-state and pre-steady-state kinetic analysis, which revealed new insights about the catalytic behavior of the model biocatalysts. We employed laser-triggered Z-to-E azobenzene photoswitching to generate the productive isomer in situ, opening avenues for advanced mechanistic studies using time-resolved femtosecond crystallography. Our results not only pave the way for the mechanistic understanding of this model enzyme family, incorporating both kinetic and structural dimensions, but also propose a systematic approach to the rational design of photoswitchable enzymatic substrates.

The Effects of Mental Fatigue on Anaerobic Power and Power Endurance Performance.

Mental fatigue has been studied extensively in relation to its impact on aerobic-, strength-, and motor-based tasks, but anaerobic power-based tasks have received limited attention. Interdisciplinary research investigating the underlying mechanisms by which mental fatigue influences physical performance has been called for. In two studies, the effects of mental fatigue on maximal power jump and endurance jump performance as well as kinetics and kinematics during jump performance were examined. Samples of collegiate volleyball players (Study 1; N = 14) and recreationally active students (Study 2; N = 27) completed two 30 min experimental manipulations (high vs. low cognitive control exertion) before performing three maximal power squat jumps followed by 15 repeated countermovement jumps, with measurements of kinetics and kinematics. For Study 1, the maximal power performance was significantly lower under a mentally fatigued condition, but no differences were observed for repeated jump performance, which may have been attributable to alterations in jump mechanics. For Study 2, no between-condition differences were observed for the maximal power performance, although repeated jump performance was significantly lower under a mentally fatigued condition. Collectively, these findings suggest that the impacts of mental fatigue on power-based performance tasks may depend on the task demands as well as the training status of the individual.

Corrosion Resistance of Biodegradable Zinc Surfaces Enhanced by UV-Grafted Polydimethylsiloxane Coating.

Improved living conditions have led to an increase in life expectancy worldwide. However, as people age, the risk of vascular disease tends to increase due to the accumulation and buildup of plaque in arteries. Vascular stents are used to keep blood vessels open. Biodegradable stents are designed to provide a temporary support vessel that gradually degrades and is absorbed by the body, leaving behind healed blood vessels. However, biodegradable metals can suffer from reduced mechanical strength and/or inflammatory response, both of which can affect the rate of corrosion. Therefore, it is essential to achieve a controlled and predictable degradation rate. Here, we demonstrate that the corrosion resistance of biodegradable Zn surfaces is improved by electroless deposition of zinc hydroxystannate followed by UV-grafting with silicone oil (PDMS). Potentiodynamic polarization, electrochemical impedance spectroscopy, respiratory kinetic measurements, and long-term immersion in three simulated body fluids were applied. Although zinc hydroxystannate improves the corrosion resistance of Zn to some extent, it introduces a high surface area with hydroxyl units used to UV-graft PDMS molecules. Our results demonstrate that hydrophobic PDMS causes a 3-fold reduction in corrosion of Zn-based materials in biological environments and reduces cytotoxicity through the uncontrolled release of Zn ions.

Location Is Everything: Influence of His-Tag Fusion Site on Properties of Adenylosuccinate Synthetase from Helicobacter pylori.

The requirement for fast and dependable protein purification methods is constant, either for functional studies of natural proteins or for the production of biotechnological protein products. The original procedure has to be formulated for each individual protein, and this demanding task was significantly simplified by the introduction of affinity tags. Helicobacter pylori adenylosuccinate synthetase (AdSS) is present in solution in a dynamic equilibrium of monomers and biologically active homodimers. The addition of the His6-tag on the C-terminus (C-His-AdSS) was proven to have a negligible effect on the characteristics of this enzyme. This paper shows that the same enzyme with the His6-tag fused on its N-terminus (N-His-AdSS) has a high tendency to precipitate. Circular dichroism and X-ray diffraction studies do not detect any structural change that could explain this propensity. However, the dynamic light scattering, differential scanning fluorimetry, and analytical ultracentrifugation measurements indicate that the monomer of this construct is prone to aggregation, which shifts the equilibrium towards the insoluble precipitant. In agreement, enzyme kinetics measurements showed reduced enzyme activity, but preserved affinity for the substrates, in comparison with the wild-type and C-His-AdSS. The presented results reinforce the notion that testing the influence of the tag on protein properties should not be overlooked.

On-Demand Catalysed n-Doping of Organic Semiconductors.

A new approach to control the n-doping reaction of organic semiconductors is reported using surface-functionalized gold nanoparticles (f-AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n-type dopant precursor N-DMBI-H with several molecular and polymeric semiconductors at different temperatures with/without f-AuNPs, vis-à-vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f-AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10-140 S cm-1). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n-doped films in opto-electronic devices such as thin-film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts.

On‐Demand Catalysed n‐Doping of Organic Semiconductors

AbstractA new approach to control the n‐doping reaction of organic semiconductors is reported using surface‐functionalized gold nanoparticles (f‐AuNPs) with alkylthiols acting as the catalyst only upon mild thermal activation. To demonstrate the versatility of this methodology, the reaction of the n‐type dopant precursor N‐DMBI‐H with several molecular and polymeric semiconductors at different temperatures with/without f‐AuNPs, vis‐à‐vis the unfunctionalized catalyst AuNPs, was investigated by spectroscopic, morphological, charge transport, and kinetic measurements as well as, computationally, the thermodynamic of catalyst activation. The combined experimental and theoretical data demonstrate that while f‐AuNPs is inactive at room temperature both in solution and in the solid state, catalyst activation occurs rapidly at mild temperatures (~70 °C) and the doping reaction completes in few seconds affording large electrical conductivities (~10–140 S cm−1). The implementation of this methodology enables the use of semiconductor+dopant+catalyst solutions and will broaden the use of the corresponding n‐doped films in opto‐electronic devices such as thin‐film transistors, electrochemical transistors, solar cells, and thermoelectrics well as guide the design of new catalysts.

Marangoni flows triggered by cationic-anionic surfactant complexation

HypothesisThe gradients in surfactant distribution at a fluid-fluid interface can induce fluid flow known as the Marangoni flow. Fluid interfaces found in biological and environmental systems are seldom clean, where mixtures of various surfactants are present. The presence of multi-component surfactant mixtures introduces the possibility of interactions among constituents, which may impact Marangoni flows and alter flow dynamics. ExperimentsWe employed flow visualization, surface tension and reaction kinetic measurements, and numerical simulations to quantitatively investigate the Marangoni flows induced by the reacting surfactant mixtures. Different binary surfactant mixtures were utilized for comparative analysis. FindingsThe impact of surfactant interactions on Marangoni flows is confirmed through the observation of diverse complex flow patterns that result from the combination of oppositely charged surfactants in varying composition ratios and concentrations. Unique flow patterns originate from the composition-dependent interfacial phenomena upon mixing surfactants. Our findings provide vital insights that could be used to guide the development of effective oil remediation or the spreading of waterborne pathogens in contaminated regions.

H2-D2 Exchange Activity and Electronic Structure of Ag x Pd1-x Alloy Catalysts Spanning Composition Space.

Many computational studies of catalytic surface reaction kinetics have demonstrated the existence of linear scaling relationships between physical descriptors of catalysts and reaction barriers on their surfaces. In this work, the relationship between catalyst activity, electronic structure, and alloy composition was investigated experimentally using a Ag x Pd1-x Composition Spread Alloy Film (CSAF) and a multichannel reactor array that allows measurement of steady-state reaction kinetics at 100 alloy compositions simultaneously. Steady-state H2-D2 exchange kinetics were measured at atmospheric pressure on Ag x Pd1-x catalysts over a temperature range of 333-593 K and a range of inlet H2 and D2 partial pressures. X-ray photoelectron spectroscopy (XPS) was used to characterize the CSAF by determining the local surface compositions and the valence band electronic structure at each composition. The valence band photoemission spectra showed that the average energy of the valence band, ε̅v, shifts linearly with composition from -6.2 eV for pure Ag to -3.4 eV for pure Pd. At all reaction conditions, the H2-D2 exchange activity was found to be highest on pure Pd and gradually decreased as the alloy was diluted with Ag until no activity was observed for compositions with x Pd < 0.58. Measured H2-D2 exchange rates across the CSAF were fit using the Dual Subsurface Hydrogen (2H') mechanism to extract estimates for the activation energy barriers to dissociative adsorption, ΔE ads ‡, associative desorption, ΔE des ‡, and the surface-to-subsurface diffusion energy, ΔE ss, as a function of alloy composition, x Pd. The 2H' mechanism predicts ΔE ads ‡ = 0-10 kJ/mol, ΔE des ‡ = 30-65 kJ/mol, and ΔE ss = 20-30 kJ/mol for all alloy compositions with x Pd ≥ 0.64, including for the pure Pd catalyst (i.e., x Pd = 1). For these Pd-rich catalysts, ΔE des ‡ and ΔE ss appeared to increase by ∼5 kJ/mol with decreasing x Pd. However, due to the coupling of kinetic parameters in the 2H' mechanism, we are unable to exclude the possibility that the kinetic parameters predicted when x Pd ≥ 0.64 are identical to those predicted for pure Pd. This suggests that H2-D2 exchange occurs only on bulk-like Pd domains, presumably due to the strong interactions between H2 and Pd. In this case, the decrease in catalytic activity with decreasing x Pd can be explained by a reduction in the availability of surface Pd at high Ag compositions.

Harnessing ultrasound-derived hydroxyl radicals for the selective oxidation of aldehyde functions.

Ultrasonic irradiation holds potential for the selective oxidation of non-volatile organic substrates in the aqueous phase by harnessing hydroxyl radicals as chemical initiators. Here, a mechanistic description of hydroxyl radical-initiated glyoxal oxidation is constructed by gleaning insights from photolysis and radiation chemistry to explain the yields and kinetic trends for oxidation products. The mechanistic description and kinetic measurements reported herein reveal that increasing the formation rate of hydroxyl radicals by changing the ultrasound frequency increases both the rates of glyoxal consumption and the selectivity towards C2acid products over those from C-C cleavage. Glyoxal consumption also occurs more rapidly and with greater selectivity towards C2acids under acidic conditions, which favor the protonation of carboxylate intermediates into their less reactive acidic forms. Leveraging such pH and frequency effects is crucial to mitigating product degradation by secondary reactions with hydroxyl radicals and oxidation products (specifically hydrogen peroxide and superoxide). These findings demonstrate the potential of ultrasound as a driver forthe selective oxidation of aldehyde functions to carboxylic acids, offering a sustainable route for valorizing biomass-derived platform molecules.

Synergistic structure engineering and electrochemical activation modulating vanadium oxide cathode toward superior zinc-ion storage

Aqueous zinc-ion batteries (ZIBs) have emerged as competitive systems for grid-scale energy storage due to their high safety and low cost. However, the lack of suitable high-performance cathode composites limits the practical progress of ZIBs. Herein, a novel cathode material, ammonium cation-inserted and oxygen vacancy co-modulated VO2 (named NVE), was firstly synthesized through the ethylene glycol (EG) sacrificial solvent-assisted structure transformation with the ammonium vanadate (named NV) as the precursor. The sacrificial solvent promotes the structural transformation of ammonium vanadate to NH4+-intercalated vanadium oxide and enhances the number of oxygen vacancies in the resulting material. Moreover, the electrochemical activation process was performed for in-situ construction of NH4+-inserted hydrated vanadium oxide (V2O5·nH2O) material. The electrochemical activation process with high anodic voltage enables multiple electron reactions, increasing the utilization of vanadium elements and achieving high capacity. Additionally, the formed hydrogen bonds between the V-O host and inserted NH4+ ions can enhance the structural integrity, while the oxygen vacancies decrease the interaction between the V-O host and inserted Zn2+ ions to boost ion diffusion. Consequently, the resulting activated cathode demonstrates higher capacity (441 mAh/g at 0.1 A/g), superior cycling durability (85.6 % retention over 4000 cycles), and exceptional rate capability (205 mAh/g at 20 A/g). Besides, the fabricated devices based on the activated NVE cathode show decent capacity and excellent flexible stability. Furthermore, the reversible electrochemical Zn2+ storage mechanism upon battery cycling was evaluated by several kinetic measurements and in/ex-situ characterizations. This work provides novel perspectives for the fabrication of advanced cathode materials for superior aqueous ZIBs.

Complex evolutionary trajectories in vivo of two novel KPC variants conferring ceftazidime-avibactam resistance

More and more ceftazidime-avibactam-resistant KPC-producing Klebsiella pneumoniae have been reported with its widespread use, and the detection rate of KPC variants has increased dramatically. However, the evolutionary mechanism and fitness effects during KPC mutation remained unknown. Here, we report the complex in vivo evolutionary trajectories of two novel KPC variants, KPC-155 (L169P/GT242A) and KPC-185 (D179Y/GT242A), from K. pneumoniae in the same patient. The novel variants were shown to confer ceftazidime-avibactam resistance but restore carbapenem susceptibility based on the results of plasmid transformation assays, cloning experiments, and enzyme kinetic measurements. In vitro, competition experiments highlighted the adaptive advantage conferred by strains carrying these KPC variants, which could lead to the rapid spread of these ceftazidime-avibactam-resistant strains. The growth curve indicated that blaKPC-185 had better growth conditions at lower avibactam concentration compared to blaKPC-155, which was consistent with ceftazidime-avibactam use in vivo. In addition, replicative transposition of the IS26-flanked translocatable unit (IS26-ISKpn6-blaKPC-ISKpn27-IS26) also contributes to the blaKPC amplification and formation of two copies (blaKPC-2 and blaKPC-185), conferring both carbapenem and ceftazidime-avibactam resistance. However, strains with double copies showed reduced competitive advantage and configuration stability. The comparative plasmid analysis of IS26 group (IS26-blaKPC-IS26) and Tn1721 group (Tn1721-blaKPC-IS26) revealed that IS26-insertion could influence the distribution of resistance genes and ability of self-conjugation. The dynamic changes in blaKPC configuration highlight the need for consistent monitoring including antimicrobial susceptibility testing and determination of blaKPC subtypes – during clinical treatment, especially when ceftazidime-avibactam is administered.

Effects of Fatigue on Lower Limb Biomechanics and Kinetic Stabilization During the Tuck-Jump Assessment.

General and local muscular fatigue is postulated to negatively alter lower limb biomechanics; however, few prospective studies have been done to examine the effect of fatigue on tuck-jump performance. The tuck-jump assessment (TJA) is a criteria-based visual screening tool designed to identify neuromuscular deficits associated with anterior cruciate ligament (ACL) injury. Use of kinetics during the TJA after an intense sport-specific fatigue protocol may identify fatigue-induced neuromuscular deficits associated with ACL injury risk. To examine the effects of a sport-specific fatigue protocol on visually evidenced (2-dimensional) technical performance of repeated tuck jumps and lower limb kinetic stabilization. Cross-sectional study. Laboratory. Twelve female netball athletes (age = 20.8 ± 2.6 years, height = 170.0 ± 0.04 cm, mass = 67.5 ± 7.4 kg). Participants performed 1 set of a TJA before and after a sport-specific fatigue protocol. Paired t tests and effect sizes were used to evaluate differences and the magnitude of differences in TJA scoring criterion, kinetics, and kinetic stabilization prefatigue to postfatigue. A small increase was observed for vertical relative lower extremity stiffness postfatigue (P = .005; Hedges g = 0.45). Peak center-of-mass displacement, time of jump cycle, ground contact time, flight time, jump height, and vertical net impulse decreased with small to moderate effect sizes (P < .01; Hedges g range, 0.41-0.74). No differences were observed for TJA composite scores, peak vertical ground reaction force, and stabilization indices of kinetic variables after the fatigue protocol (P > .05). Kinetic analysis of repeated tuck jumps after a fatigue protocol identified an altered jumping strategy, which was not identifiable via visual 2-dimensional assessment. However, based on kinetic measures, fatigue induces a stiffer jumping strategy, and practitioners should consider assessing load attenuation strategies that may not be visually evident when evaluating ACL-injury risk factors in athletes who are fatigued.

Using interfacial behavior and adsorption kinetics measurements as a predictor of bulk hydrophobic development of paper supercritically impregnated with food-grade waxes

Supercritical Impregnation methods are becoming popular in the development of food packaging materials. Bulk functional improvements of cellulose substrates using this method may be influenced by interfacial interactions between the impregnated solutes and cellulose. Hence, an interfacial adsorption kinetics study of solute molecules onto the substrate can provide insight on bulk property development, leading to an optimized packaging material with improved functionality. Paper substrates were impregnated with two food-grade waxes: Alkyl Ketene Dimer (AKD) and Carnauba Wax (CW). Hydrophobic development was monitored over a 3-week period. A quartz crystal microbalance (QCM-D) was used to determine interfacial characteristics and behavior of each wax with cellulose, and adsorption kinetics were quantified to compare the mass transfer processes of each wax at the interface. AKD significantly contributed to the substrate’s hydrophobic development over time. CW generated mildly hydrophobic substrates only when heated. AKD strongly adhered to the cellulose fibers at the interface, and demonstrated a 3-stage kinetic adsorption process, tentatively assigned (i) diffusion through the solvent; (ii) diffusion through the substrate; and (iii) attachment onto the fibers. CW readily washed off the cellulose surface, demonstrating only the first adsorption process. The different chemical structures also impacted these behaviors, as did concentration and temperature.Graphical

Synthesis and characterization of a novel TiO2@chitosan/alginate nanocomposite sponge for highly efficient removal of As(V) ions from aqueous solutions: Adsorption isotherm, kinetics, experiment and adsorption mechanism optimization using Box-Behnken design

This research uses a novel TiO2@CSC.Alg composite sponge was created by encasing TiO2 nanoparticles in the natural polymers alginate and chitosan, resulting in a nanocomposite that is both ecologically friendly and biocompatible. Using the generated nanocomposite as a new environmentally friendly adsorbent, As(V) heavy metal ions were effectively removed from aqueous media. The following techniques were used to analyse the physicochemical properties of the obtained materials: pHZPC, FTIR, XRD, BET, SEM, and XPS. Utilizing nitrogen adsorption/desorption isotherms, the TiO2@CSC.Alg composite sponge's textural properties were identified. This revealed a BET surface area of 168.42 m2/g and a total pore volume of 1.18 cc/g, indicating its porous nature and potential for high adsorption capacity. Examine the effects of temperature, pH, dose, and beginning concentration on adsorption. The adsorption characteristics were determined based on equilibrium and adsorption kinetics measurements. The adsorption process was both pseudo-second-order (PSOE) and Langmuir isothermally fit. Chemisorption was the adsorption method since the adsorption energy was 25.45 kJ·mol−1. An endothermic and spontaneous adsorption process was indicated by more metal being absorbed as the temperature increased. The optimal conditions for adsorption were optimized via Box-Behnken design software to be pH of 5 in the solution, a dosage of 0.02 g of the TiO2@CSC.Alg composite sponge per 25 mL, and an arsenate (As(V)) solution the adsorption capacity was 202.27 mg/g are ideal for efficient adsorption. These parameters are critical in achieving the maximum adsorption capacity of the composite sponge for arsenate, which could be beneficial for water purification applications. Utilizing Design-Expert software's response surface methodology (RSM) and Box-Behnken design (BBD), the adsorption process was optimized with the fewest planned tests. After six successive cycles of adsorption and desorption, the adsorbent stability was confirmed by the adsorbent reusability test without any noticeable decrease in removal efficacy. Additionally, it displayed good efficiency, the same XRD and XPS data before and after reuse, and no change in chemical composition.

Fc engineering by monoclonal mammalian cell display for improved affinity and selectivity towards FcγRs.

Fc optimization can significantly enhance therapeutic efficacy of monoclonal antibodies. However, existing Fc engineering approaches are sub-optimal with noted limitations, such as inappropriate glycosylation, polyclonal libraries, and utilizing fragment but not full-length IgG display. Applying cell cycle arrested recombinase-mediated cassette exchange, this study constructed high-quality monoclonal Fc libraries in CHO cells, displayed full-length IgG on cell surface, and preformed ratiometric fluorescence activated cell sorting (FACS) with the antigen and individual FcγRs. Identified Fc variants were quantitatively evaluated by flow cytometry, ELISA, kinetic and steady-state binding affinity measurements, and cytotoxicity assays. An error-prone Fc library focusing on the hinge-CH2 region was constructed in CHO cells with a functional diversity of 7.5×106. Panels of novel Fc variants with enhanced affinity and selectivity for FcγRs were isolated. Particularly, clone 2a-10 (G236E/K288R/K290W/K320M) showed increased binding strength towards FcγRIIa-131R and 131H allotypes with kinetic dissociation constants (KD-K) of 140nM and 220nM, respectively, while reduced binding strength towards FcγRIIb compared to WT Fc; clone 2b-1 (K222I/V302E/L328F/K334E) had KD-K of 180nM towards FcγRIIb; clone 3a-2 (P247L/K248E/K334I) exhibited KD-K of 190nM and 100nM towards FcγRIIIa-176F and 176V allotypes, respectively, and improved potency of 2.0ng/ml in ADCC assays. Key mutation hotspots were identified, including P247 for FcγRIIIa, K290 for FcγRIIa, and K334 for FcγRIIb bindings. Discovery of Fc variants with enhanced affinity and selectivity towards individual FcγR and the identification of novel mutation hotspots provide valuable insights for further Fc optimization and serve as a foundation for advancing antibody therapeutics development.

Illuminating the nanostructure of diffuse interfaces: Recent advances and future directions in reflectometry techniques

Diffuse soft matter interfaces take many forms, from end-tethered polymer brushes or adsorbed surfactants to self-assembled layers of lipids. These interfaces play crucial roles across a multitude of fields, including materials science, biophysics, and nanotechnology. Understanding the nanostructure and properties of these interfaces is fundamental for optimising their performance and designing novel functional materials. In recent years, reflectometry techniques, in particular neutron reflectometry, have emerged as powerful tools for elucidating the intricate nanostructure of soft matter interfaces with remarkable precision and depth. This review provides an overview of selected recent developments in reflectometry and their applications for illuminating the nanostructure of diffuse interfaces. We explore various principles and methods of neutron and X-ray reflectometry, as well as ellipsometry, and discuss advances in their experimental setups and data analysis approaches. Improvements to experimental neutron reflectometry methods have enabled greater time resolution in kinetic measurements and elucidation of diffuse structure under shear or confinement, while innovation in analysis protocols has significantly reduced data processing times, facilitated co-refinement of reflectometry data from multiple instruments and provided greater-than-ever confidence in proposed structural models. Furthermore, we highlight some significant research findings enabled by these techniques, revealing the organisation, dynamics, and interfacial phenomena at the nanoscale. We also discuss future directions and potential advancements in reflectometry techniques. By shedding light on the nanostructure of diffuse interfaces, reflectometry techniques enable the rational design and tailoring of interfaces with enhanced properties and functionalities.