Exchange Kinetics Research Articles

Investigation of atomic-scale decorations on mixed conducting oxides via time-of-flight secondary ion mass spectrometry (ToF-SIMS)

Sub-nanometer modifications of mixed ionic electronic conducting (MIEC) materials, like the perovskite La0.6Sr0.4CoO3-δ (LSC), represent a promising approach to improving their oxygen exchange kinetics and degradation stability. The complex interactions between decoration layers and the host material are still not fully understood and are a subject of current research. Under these circumstances, a novel approach using time-of-flight secondary ion mass spectrometry (ToF-SIMS) was developed to gain deeper insight into the electronic and chemical interactions of LSC with different oxidic decorations. The investigated samples were prepared by pulsed laser deposition (PLD) on YSZ single crystals, starting with a 100 nm thin LSC layer, which was then modified by sub-nm decorations of CaO, TiO2, and SnO2 (nominally 0.05–0.5 nm) on top. By using ToF-SIMS with a sampling depth of 1–2 nm, it was possible to extract information simultaneously on the decoration layer and the host oxide. Significant differences in secondary ion (SI) intensities of the host material LSC were found that can be attributed to the formation of surface-near dipoles as a consequence of the acidic or basic nature of the decoration oxide. Further, relative stoichiometric variations of the La+, Sr+, and Co+ signals depending on the decoration oxide were observed, suggesting different preferential decoration sites on the LSC surface.

HDX-MS Reveals Substrate-Dependent, Localized EX1 Conformational Dynamics in the Retaining GT-B Glycosyltransferase, MshA.

Glycosyltransferases (GTs) are well-characterized with respect to static 3D structures and molecular dynamics simulations, but there is a lack of reports on in-solution dynamics on time scales relevant to turnover. Here, backbone amide hydrogen/deuterium exchange followed by mass spectrometry (HDX-MS) was used to investigate the in-solution dynamics of the model retaining GT MshA from Corynebacterium glutamicum (CgMshA). CgMshA has a GT-B fold and catalyzes the transfer of N-acetyl-glucosamine (GlcNAc) from UDP-GlcNAc to l-myo-inositol-1-phosphate in the first step in mycothiol biosynthesis. HDX-MS results identify several key regions of conformational changes in response to UDP-GlcNAc binding, including residues 159-198 in the N-terminal domain and residues 323-354 in the C-terminal domain. These regions also exhibited substrate-dependent EX1 exchange kinetics consistent with conformational tension on the milliseconds to seconds time scale. A potential source of this conformational change is the flexible β4/α5 loop in the C-terminal domain, which sits at the interface of the two domains and likely interacts with the GlcNAc ring of UDP-GlcNAc. In contrast to UDP-GlcNAc, the UDP-CgMshA product complex exhibited severe decreases in deuterium incorporation, suggesting a less dynamic conformation. The HDX-MS results are complemented by solvent viscosity effects of 1.8-2.3 on the CgMshA kcat value, which are consistent with product release as a rate-determining step and possibly a direct role for protein dynamics in catalysis. The identification of in-solution dynamics that are sensitive to substrate binding allows for the proposal of a more detailed mechanism in CgMshA including conformation tension between the donor sugar and the flexible C-terminal domain β4/α5 loop providing sufficient conformational sampling for substrate-assisted catalysis to occur.

Transient conformations in the unliganded FK506 binding domain of FKBP51 correspond to two distinct inhibitor-bound states

Members of the FK506-binding protein (FKBP) family regulate a range of important physiological processes. Unfortunately, current therapeutics such as FK506 and rapamycin exhibit only modest selectivity among these functionally distinct proteins. Recent progress in developing selective inhibitors has been reported for FKBP51 and FKBP52, which act as mutual antagonists in the regulation of steroid hormone signaling. Two structurally similar inhibitors yield distinct protein conformations at the binding site. Localized conformational transition in the binding site of the unliganded FK1 domain of FKBP51 is suppressed by a K58T mutation that also suppresses the binding of these inhibitors. Here, it is shown that the changes in amide hydrogen exchange kinetics arising from this K58T substitution are largely localized to this structural region. Accurate determination of the hydroxide-catalyzed exchange rate constants in both the wildtype and K58T variant proteins impose strong constraints upon the pattern of amide exchange reactivities within either a single or a pair of transient conformations that could give rise to the differences between these two sets of measured rate constants. Poisson-Boltzmann continuum dielectric calculations provide moderately accurate predictions of the structure-dependent hydrogen exchange reactivity for solvent-exposed protein backbone amides. Applying such calculations to the local protein conformations observed in the two inhibitor-bound FKBP51 domains demonstrated that the experimentally determined exchange rate constants for the wildtype domain are robustly predicted by a population-weighted sum of the experimental hydrogen exchange reactivity of the K58T variant and the predicted exchange reactivities in model conformations derived from the two inhibitor-bound protein structures.

In Situ Observation of Solvent Exchange Kinetics in a MOF with Coordinatively Unsaturated Sites.

Solvent exchange of synthesis solvent within metal-organic frameworks (MOFs) is an essential process for the activation of coordinatively unsaturated sites (CUS) to achieve an optimal surface area; activation of the CUS is required to exploit the versatile applications of MOFs. However, it is challenging to replace CUS-bound synthesis solvent prior to MOF activation, which can lead to a structural collapse and reduced surface area post-evacuation. Herein, we quantify the exchange behavior of a copper paddlewheel-based CUS-MOF (HKUST-1) in the presence of three different solvents: ethanol (EtOH), dichloromethane (DCM), and N,N-dimethylformamide (DMF). The DMF release profiles are monitored via in situ observation of the exchange solvent composition via 1H NMR and Raman spectroscopy at the macroscopic scale. Furthermore, the change in solvent within a single crystal is measured to directly elucidate the exchange behavior. We demonstrate the DMF release profile from HKUST-1 exhibits different rate laws depending on whether the solvent exchange occurs at the CUS or is purely diffusive through the pores. This contribution represents the first characterization of release from a CUS-MOF as a function exchange solvent and reveals that solvent exchange in a CUS-MOF is not diffusion-limited, but rather is limited by the solvent exchange kinetics at the metal center. Insights from this study can be generalized to the variety of copper-paddlewheel-based MOFs, informing best practices for solvent exchange.

Phenoxy resin-based vinylogous urethane covalent adaptable networks

This work presents a post-polymerization approach to the preparation of vitrimers, exploiting the transamination of vinylogous urethane in linear phenoxy resins. Phenoxy vitrimers are obtained by a two-steps synthesis from a commercial phenoxy resin via partial conversion of hydroxyl groups to acetoacetates (AcAc), followed by network formation by reaction with m-xylylendiamine as crosslinker. Three different vitrimers with variable crosslinking density are obtained by tuning the density of AcAc moieties along the phenoxy resin scaffold (5%, 10% and 15% conversion of hydroxyl groups). The conversion of linear polymers to dynamic crosslinked networks is confirmed by dynamic mechanical thermal analyzer and rheology measurements, followed by stress relaxation tests to investigate the kinetics of bond exchanges. Tensile tests as a function of reprocessing cycles reveal an increase of the maximum elongation and stress at break and prove the good recyclability of the vitrimers. Enhanced adhesive properties compared to pristine phenoxy resins are demonstrated, including the possibility to thermally re-join the assembly after its mechanical failure. Finally, the solvent-free preparation of vitrimers is explored at 5% crosslinking density via melt reactive blending, providing a valuable alternative to the less environmentally sustainable synthesis in solution.

How Digestive Processes Can Affect the Bioavailability of PCBs Associated with Microplastics: A Modeling Study Supported by Empirical Data.

The transfer kinetics of plastic-associated chemicals during intestinal digestive processes is unknown. Here, we assessed whether digestive processes affect chemical exchange kinetics on microplastics, using an in vitro gut fluid digestive model mimicking the human upper intestinal tract. Chemical exchange kinetics of microplastics were measured for 10 polychlorinated biphenyls (PCBs) as proxies for the broad class of hydrophobic organic chemicals. Following earlier studies, olive oil was used as a proxy for digestible food, under high and low digestive enzyme activities. The micelle-water and oil-water partition coefficients of the 10 PCBs were also determined to evaluate the relative contribution of each gut component to sorb PCBs. A new biphasic and reversible chemical exchange model, which included the digestion process, fitted well to the empirical data. We demonstrate that the digestive processes that break down contaminated food can lead to a substantial increase in chemical concentration in microplastics by a factor of 10-20, thereby reducing the overall chemical bioavailability in the gastrointestinal tract when compared to a scenario without microplastics. Higher enzyme activities result in more chemicals being released by the digested food, thereby resulting in higher chemical concentrations in the microplastics. While the model-calibrated kinetic parameters are specific to the studied scenario, we argue that the mechanism of the reduced bioavailability of chemicals and the modeling tool developed have generic relevance. These digestive processes should be considered when assessing the risks of microplastics to humans and also biomagnification in aquatic food webs.

Sorption of Lead, Zinc and Copper from Simulated Wastewater by Amberlite Ir-120 Resin

The presence of heavy metals in the environment is major concern due to their toxicity. In the present study a strong acid cation exchange resin, Amberlite IR 120 was used for the removal of lead, zinc and copper from simulated wastewater. The optimum conditions were determined in a batch system of concentration 100 mg/L, pH range between 1 and 8, contact time between 5 and 120 minutes, and amount of adsorbent was from 0.05 to 0.45 g/100 ml. A constant stirring speed, 180 rpm, was chosen during all of the experiments. The optimum conditions were found to be pH of 4 for copper and lead and pH 6 for zinc, contact time of 60 min and 0.35 g of adsorbent. Three different temperatures (25, 40 and 60°C) were selected to investigate the effect of adsorption temperature on heavy metals adsorption onto Amberlite IR. The equilibrium data were analyzed by the Langmuir and Freundlich isotherms. The thermodynamic parameters such as Gibbs free energy, enthalpy and entropy changes were calculated. Moreover, in order to understand the heavy metal extraction kinetics in the presence of Amberlite IR 120, the ion exchange kinetics was also studied. The ion exchange kinetics data were regressed by the pseudo first-order, second-order models. The results obtained show that the Amberlite IR 120 strong acid cation exchange resin performed well for the removal of lead, zinc and copper.

FRET-based analysis on the structural stability of polymeric micelles: Another key attribute beyond PEG coverage and particle size affecting the blood clearance

Various attributes of micelles, such as PEG density and particle size, are considered to be related to blood clearance. The structural stability of micelles is another key attribute that will affect the in vivo fate. This study employed fluorescence resonance energy transfer (FRET) analysis to guide the preparation of polymeric micelles with different structural stability. Micelles prepared using copolymers with longer hydrophobic blocks showed higher structural stability; emulsification was a better method than nanoprecipitation to prepare stable micelles. The fast chain exchange kinetics and the high-water content of micellar cores explained the low structural stability of those micelles. Moreover, this study highlighted the importance of structural stability that affected blood clearance in concert with PEG length and particle size. One-third of the small and stable micelles were detected in the blood 24 h after injection. While unstable micelles would be cleared from the circulation within 4 h. Notably, there would be a threshold of structural stability. Micelles with structural stability below this threshold were quickly cleared even if they possessed a longer PEG length and a smaller size. In contrast, higher structural stability allowed polymeric micelles to maintain higher integrity in vivo and enhance tumor accumulation and anti-tumor efficacy. In conclusion, this study systematically analyzed the importance of the structural stability of micelles on the in vivo fate.

Metal exchange kinetics of asymmetrically substituted cd(II)- tetraarylporphyrins with cobalt and zinc chlorides in dmf

The metal exchange reactions of Cd(II)-5-(4-nitrophenyl)-10,15,20-triphenylporphyrin and Cd(II)-5,10,15-tri-(4-nitrophenyl)-20-phenylporphyrin with cobalt and zinc chlorides in dimethylformamide were studied by the spectrophotometric method. The kinetic parameters of metal exchange were calculated and a possible stoichiometric mechanism of the process is established. The influence of the nature of the solvate salt and the chemical modification of the tetrapyrrole macrocycle on the kinetic parameters of the metal exchange reaction was revealed.

Downward Band Bending as an Efficient Strategy to Accelerate Oxygen Exchange Kinetics in Mixed Conducting Oxides─Studies on Different Oriented LSCF Thin Films

Downward Band Bending as an Efficient Strategy to Accelerate Oxygen Exchange Kinetics in Mixed Conducting Oxides─Studies on Different Oriented LSCF Thin Films

Fast in vivo assay of creatine kinase activity in the human brain by 31 P magnetic resonance fingerprinting.

A new and efficient magnetisation transfer 31 P magnetic resonance fingerprinting (MT-31 P-MRF) approach is introduced to measure the creatine kinase metabolic rate between phosphocreatine (PCr) and adenosine triphosphate (ATP) in human brain. The MRF framework is extended to overcome challenges in conventional 31 P measurement methods in the human brain, enabling reduced acquisition time and specific absorption rate (SAR). To address the challenge of creating and matching large multiparametric dictionaries in an MRF scheme, a nested iteration interpolation method (NIIM) is introduced. As the number of parameters to estimate increases, the size of the dictionary grows exponentially. NIIM can reduce the computational load by breaking dictionary matching into subsolutions of linear computational order. MT-31 P-MRF combined with NIIM provides , and estimates in good agreement with those obtained by the exchange kinetics by band inversion transfer (EBIT) method and literature values. Furthermore, the test-retest reproducibility results showed that MT-31 P-MRF achieves a similar or better coefficient of variation (<12%) for and measurements in 4 min 15 s, than EBIT with 17 min 4 s scan time, enabling a fourfold reduction in scan time. We conclude that MT-31 P-MRF in combination with NIIM is a fast, accurate, and reproducible approach for in vivo assays in the human brain, which enables the potential to investigate energy metabolism in a clinical setting.

Characterization of molecular environments and chemical exchange in acrylic paints via single-sided NMR

Both oil and acrylic paints consist of pigments bound within a polymeric network; however, acrylic paints dry by evaporation of aqueous solvent, rather than curing chemically like oil paints. In this study, we used single-sided 1H NMR relaxometry to characterize the molecular environments in both dry and wet acrylic paints by their molecular mobilities. We measured the transverse relaxation behaviors of paints with various pigment concentrations and conducted T2–T2 correlation measurements on wet paint to monitor exchange. In dry paint, we identified two transverse relaxation behaviors, indicating regions of greater and lesser mobility, which we attributed to amorphous and crystalline domains of the semi-crystalline acrylic polymer in the film. These polymer domains were not affected by pigment concentration. In wet paint, we characterized two different relaxation behaviors, which we hypothesize to originate from unique molecular environments in the acrylic binding medium. Additionally, we characterized two simultaneous exchange processes involving aqueous solvent in wet paint and showed the effects of pigment concentration on the exchange kinetics. Through non-invasive, non-destructive relaxometry measurements, we characterized the unique molecular environments in both dry and wet acrylic paints, which can be compared to molecular environments characterized by others in oil paints and can provide new insights into the physical properties of acrylics relevant to art conservation.

Size-dependent miscibility controls the kinetics of anion exchange in cesium lead halide nanocrystals.

Anion exchange is a facile, post-synthetic method to tune the emission wavelength of colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) perovskite nanocrystals. While colloidal nanocrystals can exhibit size-dependent phase stability and chemical reactivity, the role of size in the mechanism of anion exchange in CsPbX3 nanocrystals has not been elucidated. We used single-particle fluorescence microscopy to monitor the transformation of individual CsPbBr3 nanocrystals to CsPbI3. By systematically varying the size of the nanocrystals and the concentration of substitutional iodide, we observed that smaller nanocrystals exhibit longer transition times in their fluorescence trajectories, while larger nanocrystals undergo a more abrupt transition during anion exchange. Monte Carlo simulations were used to rationalize the size-dependent reactivity, in which we varied how each exchange event affects the probability for further exchange. Greater cooperativity for simulated ion exchange leads to shorter transition times to complete the exchange. We propose that size-dependent miscibility between CsPbBr3 and CsPbI3 at the nanoscale controls the reaction kinetics. Smaller nanocrystals maintain a homogeneous composition during anion exchange. As the nanocrystal size increases, variations in the octahedral tilting patterns of the perovskite crystals lead to different structures for CsPbBr3 and CsPbI3. Thus, an iodide-rich region must first nucleate within larger CsPbBr3 nanocrystals, which is followed by rapid transformation to CsPbI3. While higher concentrations of substitutional anions can suppress this size-dependent reactivity, the inherent differences in reactivity between nanocrystals of different sizes are important to consider when scaling up this reaction for applications in solid-state lighting and biological imaging.

Kinetics of CO[formula omitted] dissolution for underground applications

In the current energy transition context, underground storage of carbon dioxide (CO2) in salt caverns and aquifers has emerged as a promising solution for the Power-to-Gas process complications. However, mass exchange between the CO2 and the aqueous phase present in the storage site remains a major problem. This paper addresses the question of the kinetics of this mass exchange by performing both experimental and numerical investigations. A series of experiments under storage conditions were carried out in a PVT (Pressure–Volume–Temperature) cell, exposing a volume of CO2 to pure water or brine at low and high pressure values ranging between 10 and 16.8 MPa and at constant temperatures of 30 and 40 °C. In order to interpret the obtained experimental results and to characterize the transient mass exchange, two modeling approaches were developed: a simplified one based on pure diffusion, and a second combining pure diffusion with density-driven natural convection. Both modeling approaches have proven accurate in predicting the kinetics of CO2 dissolution. The scope of this study is limited to the laboratory scale but it can be used to quantify the CO2 dissolution on the storage site scale.

Loosely Adsorbed Chains Expedite the Desorption of Flattened Polystyrene Chains on Flat Silicon Surface.

Herein, the desorption of the adsorbed chains (including two regions of flattened chains and loosely adsorbed chains) was examined by monitoring the chain exchange kinetics between the adsorbed chains and the top-free chains in a bilayer system by using fluorine-labeled polystyrene (PS). The results indicated that the exchange behavior of PS-flattened chains with the top-free chains is much slower than that of PS-loose chains and has a strong molecular weight (MW) dependence. Interestingly, in the presence of loosely adsorbed chains, the desorption of flattened chains was accelerated greatly and had weaker MW dependency. We attribute the MW-dependent desorption phenomena to the average number of contact sites between polymer adsorbed chains and the substrate, which rapidly increased with increasing MW. Likewise, the desorption of loosely adsorbed chains may provide extra conformational energy to accelerate the desorption of flattened chains.

Two-Dimensional Covalent Organic Framework with Synergistic Active Centers for Efficient Electrochemical Sodium Storage

Benefiting from the adjustable molecule structures, abundant functional units, large specific surface areas, and ordered pores, covalent organic frameworks (COFs) are highly desirable for electrochemical energy storage. Herein, a two-dimensional COF (denoted as HHTP-TABQ) with a fully π-conjugated framework and C═N and C═O dual-active sites has been synthesized and applied as the anode in organic rechargeable sodium-ion batteries (SIBs). During the sodium-storage process, it delivered remarkable rate capability, satisfactory ultra-long cycle stability (84.5% capacity retention ratio after 1000 cycles at 5000 mA g–1), and facile charge exchange kinetics (2.49 × 10–7 cm2 s–1), which is superior among most reported COF-based electrodes. Furthermore, the sodiation mechanism was investigated by density functional theory calculations and ex situ characterizations, which confirms that the electrochemical reaction is dominated by the synergistic reaction of C═N and C═O groups. These results suggest that COFs with stable π-conjugated structures, insoluble characteristics, and abundant active sites would have great potential for practical applications in rechargeable SIBs.

Crystal-Orientation-Dependent Oxygen Exchange Kinetics on Mixed Conducting Thin-Film Surfaces Investigated by In Situ Studies.

The oxygen exchange kinetics and the surface chemistry of epitaxially grown, dense La0.6Sr0.4CoO3-δ (LSC) thin films in three different orientations, (001), (110), and (111), were investigated by means of in situ impedance spectroscopy during pulsed laser deposition (i-PLD) and near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS). i-PLD measurements showed that pristine LSC surfaces exhibit very fast surface exchange kinetics but revealed no significant differences between the specific orientations. However, as soon as the surfaces were in contact with acidic, gaseous impurities, such as S-containing compounds in nominally pure measurement atmospheres, NAP-XPS measurements revealed that the (001) orientation is substantially more susceptible to the formation of sulfate adsorbates and a concomitant performance decrease. This result is further substantiated by a stronger increase of the work function on (001)-oriented LSC surfaces upon sulfate adsorbate formation and by a faster performance degradation of these surfaces in ex situ measurement setups. This phenomenon has potentially gone unnoticed in the discussion of the interplay between the crystal orientation and the oxygen exchange kinetics and might have far-reaching implications for real solid oxide cell electrodes, where porous materials exhibit a wide variety of differently oriented and reconstructed surfaces.

Stabilization of pre-existing neurotensin receptor conformational states by β-arrestin-1 and the biased allosteric modulator ML314

The neurotensin receptor 1 (NTS1) is a G protein-coupled receptor (GPCR) with promise as a drug target for the treatment of pain, schizophrenia, obesity, addiction, and various cancers. A detailed picture of the NTS1 structural landscape has been established by X-ray crystallography and cryo-EM and yet, the molecular determinants for why a receptor couples to G protein versus arrestin transducers remain poorly defined. We used 13CεH3-methionine NMR spectroscopy to show that binding of phosphatidylinositol-4,5-bisphosphate (PIP2) to the receptor’s intracellular surface allosterically tunes the timescale of motions at the orthosteric pocket and conserved activation motifs – without dramatically altering the structural ensemble. β-arrestin-1 further remodels the receptor ensemble by reducing conformational exchange kinetics for a subset of resonances, whereas G protein coupling has little to no effect on exchange rates. A β-arrestin biased allosteric modulator transforms the NTS1:G protein complex into a concatenation of substates, without triggering transducer dissociation, suggesting that it may function by stabilizing signaling incompetent G protein conformations such as the non-canonical state. Together, our work demonstrates the importance of kinetic information to a complete picture of the GPCR activation landscape.

Designing highly active core/shell cathode materials for low-temperature PCFCs

Designing a cathode with exceptional oxygen reduction reaction (ORR) activity and durability at intermediate-to-low temperatures is vital to increase the improvement of solid oxide fuel cells (SOFCs), a captivating energy conversion technology with reduced environmental impact and high performance. Cathodes made of perovskite oxides have been developed extensively. Doping is a crucial method for modifying perovskites' lattice diffusion and surface exchange properties to achieve desired catalytic performances in a wide range of redox reactions, including oxygen reduction reactions (ORRs) for ceramic fuel cells (CFCs). The reported BaCo0.4Fe0.4Zr0.1Y0.1O3-δ (BCFZY) is a potential cathode in CFCs. Here, we systematically explore the partial doping of B-sites with Al of varied content (from 5% to 30%) to further enhance the performance of BCFZY at lower temperatures. The polarization impedance of proton ion conducting fuel cells is lowest in Ba(Co0.4Fe0.4Zr0.1Y0.1)0.90Al0.1O3-δ (BCFZYA). The oxygen mobility, surface exchange kinetics, and bulk oxygen ion conductivity are all enhanced by 10%Al doping, as determined by EIS and performance tests.Moreover, Al doping led to the formation of the core-shell structure during the rearrangement of atoms. This results in an oxygen reduction reaction (ORR) of up to 0.157 cm2 at 520 oC on proton ion conducting electrolytes. As a result, BCFZYA appears to be a strong candidate for use in the cathode of advanced PCFCs (proton ceramic fuel cells).

Pr0.7Ba0.3Co0.8-xFe0.2NixO3−δ perovskite: High activity and durable cathode for intermediate-to-low-temperature proton-conducting solid oxide fuel cells

The development of triple-conductivity (H+/O2−/e−) durable cathode with effective oxygen reduction reaction (ORR) activity is significant to boost the application of proton-conducting solid oxide fuel cell (H–SOFC) at intermediate-to-low-temperature. Herein, we developed the Pr0.7Ba0.3Co0.8-xFe0.2NixO3−δ (x = 0, 0.1, 0.2, 0.3) cathode material with triple-conductivity. Based on the distribution of relaxation time results, it is found that nickel doping enhanced the surface exchange kinetics and boosted bulk charge transfer. As a result, Pr0.7Ba0.3Co0.6Fe0.2Ni0.2O3−δ (PBCFN2) shows better ORR activity with lower polarization resistance (0.043 Ω cm2) and higher power output (1.61 W cm−2) for H–SOFC at 700 °C. Meanwhile, PBCFN2 also shows suitable durability at 600 °C (0.919 A cm−2 for ∼105 h). In general, this research may provide a beneficial instruction for further research and optimization for triple-conducting cathodes in intermediate-to-low-temperature H–SOFC.