Chemical Exchange Model Research Articles

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.

Ultrafast CEST line scanning as a method to quantify mutarotation kinetics

The process of mutarotation of sugars caused by a balanced reaction between their corresponding α and β isomers, has been known for almost 200 years. Still, it remains essential in modern biochemical research, as enzymatic reactions catalyzed by mutarotases are crucial for various pathways in the energy metabolism.In our study a fast magnetic resonance technique based on chemical exchange saturation transfer (CEST) line scanning (LS) was implemented as a method to measure mutarotation kinetics on a 9.4 T small animal MRI scanner. As proof of concept, the isomeric conversion of two hexoses (glucose and galactose) and pentoses (xylose and arabinose) was investigated in an aqueous solution over time. The technique allowed for ultrafast data acquisition without the implementation of complicated encoding schemes and acceleration procedures. Thus, CEST LS provided complete CEST spectra with a frequency step size of 19.6 Hz in less than one minute.For the mutarotation analysis, CEST spectra were acquired over a time duration of four hours and analyzed with four established CEST quantification approaches - based on either asymmetry of CEST spectra or a multi-pool Lorentzian fit. The isomer ratios of the different sugars at equilibrium were determined with an overall accuracy of 94 %, using an adapted 2-side chemical exchange (CE) model. The estimated mutarotation rate constants at 22 °C were in good agreement with conventionally measured reference values, derived from optical and spectroscopic techniques.

Pertechnetate/Perrhenate Surface Complexation on Bamboo Engineered Biochar.

The work deals with the evaluation of biochar samples prepared from Phyllostachys Viridiglaucescens bamboo. This evaluation consists of the characterization of prepared materials’ structural properties, batch and dynamic sorption experiments, and potentiometric titrations. The batch technique was focused on obtaining basic sorption data of 99mTcO4− on biochar samples including influence of pH, contact time, and Freundlich isotherm. ReO4−, which has very similar chemical properties to 99mTcO4−, was used as a carrier in the experiments. Theoretical modeling of titration curves of biochar samples was based on the application of surface complexation models, namely, so called Chemical Equilibrium Model (CEM) and Ion Exchange Model (IExM). In this case it is assumed that there are two types of surface groups, namely, the so-called layer and edge sites. The dynamic experimental data of sorption curves were fitted by a model based on complementary error function erfc(x).

Lineshape analysis of concentrated perchlorate anion aqueous solution with coherence exchange model incorporating multiple bath modes

IR spectra of concentrated perchlorate aqueous ionic solutions were analysed using chemical exchange model with Fokker-Planck equation incorporating spectral diffusion bath mode. This spectral diffusion bath mode was further modelled using two kinds of regression methods incorporating multiple second bath modes. The overall regression residual errors of 6 M perchlorate solutions were reduced without much affecting main fitting parameters and features of main spectral diffusion bath mode, meaning that collective second bath mode having much greater motional strength seems to be quite isolated. Proposed two kinds of regression methods including multiple second bath modes reported similar overall features.

Infinite-order perturbative treatment for quantum evolution with exchange.

Many important applications in biochemistry, materials science, and catalysis sit squarely at the interface between quantum and statistical mechanics: Coherent evolution is interrupted by discrete events, such as binding of a substrate or isomerization. Theoretical models for such dynamics usually truncate the incorporation of these events to the linear response limit, thus requiring small step sizes. Here, we completely reassess the foundations of chemical exchange models and redesign a master equation treatment for exchange accurate to infinite order in perturbation theory. The net result is an astonishingly simple correction to the traditional picture, which vastly improves convergence with no increased computational cost. We demonstrate that this approach accurately and efficiently extracts physical parameters from complex experimental data, such as coherent hyperpolarization dynamics in magnetic resonance, and is applicable to a wide range of other systems.

Surface Complexation Models of Pertechnetate on Biochar/Montmorillonite Composite-Batch and Dynamic Sorption Study.

The study summarizes the results of monitoring the properties of two types of sorbents, BC1 (biochar sample 1) and BC2a (biochar sample 2), prepared by pyrolysis of bamboo biomass (BC1) and as its composite with montmorillonite K10 (BC2a). The main goal was to study their applicability to the Tc (VII) separation from liquid wastes, using NH4ReO4 as a carrier. The research was focused on determining the sorbents surface properties (by XRF (X-ray fluorescence) method and potentiometric titration in order to determine the properties of surface groups—Chemical Equilibrium Model (CEM) and Ion Exchange Model (IExM) models were applied here). As well as monitoring Tc (VII) (+Re(VII)) sorption, especially to determine equilibrium isotherm, the influence of pH and kinetics. The subject of research was also the dynamics of sorption, including its mathematical–physical modeling. Both sorbents have good properties against Tc (VII), however BC2a, due to the presence of montmorillonite, is more advantageous in this respect. It has a higher sorption capacity and faster kinetic investigation. An important finding is that the optimal pH is 2–3, which is related not only to the protonation of surface groups (they have a positive charge), but also to the negative form of the existence of Tc (VII) and Re (VII): TcO4− and ReO4−.

Lineshape analysis of perchlorate anions on manganese(III) porphyrin and observing nanoscopic water environments

Perchlorate IR lineshapes in ionic solutions, polymeric membrane, and perchlorate coordinated onto manganese(III) porphyrin were investigated using various model systems. The lineshape of perchlorate ligand is very sensitive to the nanoscopic aqueous environment. The observed asymmetric mode of ligated perchlorate has a smaller bandwidth and faster dynamics than that of 1M perchlorate aqueous solution. When we used chemical exchange models of coherence, the IR lineshapes of 6M-concentrated anionic solutions have better fit. The IR lineshape of 6M-concentrated anionic solution in the polymer matrix was best fitted by assuming the chemical exchange of coherence with spectral diffusion.

Approximated analytical characterization of the steady-state chemical exchange saturation transfer (CEST) signals.

CEST MRI can indirectly detect low-concentrated molecules via their proton exchange with the bulk water and is widely measured by a sensitivity index, the asymmetry of magnetization transfer ratio (MTRasym ). Because CEST applications are often limited by their low sensitivity or specificity, it is important to characterize MTRasym analytically to optimize its sensitivity or specifity. Approximated analytical solutions of the MTRasym spectrum were derived based on a 2-pool chemical exchange model for slow-to-intermediate exchanges. The optimal saturation pulse power for maximizing the MTRasym or tuning MTRasym to a specific exchange rate and the peak position and linewidth of a MTRasym spectrum were also derived. These approximated analytical solutions were compared with the solutions from the Bloch-McConnell equations using computer simulations. The approximated analytical solutions of the MTRasym spectra, the optimizing parameters, and the peak and linewidth of MTRasym matched well with the solutions of Bloch-McConnell equations in the slow or slow-to-intermediate exchange regimes. These approximate analytical solutions can provide insights to the understanding of CEST signal property and help the optimization of saturation parameters and the interpretation of CEST data.

Transfer of PCBs from Microplastics under Simulated Gut Fluid Conditions Is Biphasic and Reversible.

The role of plastic as a vector for bioaccumulation of toxic chemicals is central to the risk assessment of microplastic for human health and the environment. However, transfer kinetics of sorbed contaminants from ingested microplastics are poorly understood. We develop and parametrize a chemical exchange model on microplastics in a gut fluid mimic of aquatic biota, and also included food to provide a better representation of contaminant dynamics when plastic and food are ingested, as would occur in nature. The transfer kinetics of 14 polychlorinated biphenyls (PCBs) were measured in gut fluid mimic systems under three environmentally relevant exposure scenarios of plastic ingestion by organisms, for low-density polyethylene (LDPE) and polyvinyl chloride (PVC), and were evaluated with the model. Chemical transfer was demonstrated to be biphasic and fully reversible, with fast exchange within hours followed by a slow transfer lasting for weeks to months. In clean gut systems, the bioavailability of plastic-associated PCBs for lugworms and cod ranged from 14 to 42% and 45-83% respectively. However, in contaminated gut systems, clean microplastic was capable of rapidly extracting ("cleaning") PCBs from food inside the gut, thus demonstrating that the effect of microplastic is context dependent. Therefore, chemical contamination and cleaning are likely to occur simultaneously due to the ingestion of microplastic.

Drying process of pullulan edible films forming solutions studied by low-field NMR

The dynamics of water in pullulan film-forming solutions during drying were investigated by low-field nuclear magnetic resonance. At the begin of drying, two transverse relaxation times (T2) at around 32.77 and 2149ms were attributed to bound and free waters in pullulan samples, respectively. An additional T2 value, ascribed to the tightly bound water in entanglement zones of pullulan chains, appeared at around 3.51ms as the drying process continued (beyond 1080min of drying time). The observed three relaxation times revealed the multi-exponential relaxation behavior of water in pullulan. Moreover, the polymer exhibited spatial heterogeneity with increasing drying time from 1200 to 1920min. On the basis of diffusive and chemical exchange model, the dimension range of pullulan network decreased from 7.69-32.66 to 4.73-18.14µm as the pullulan films solidified. Furthermore, the rate of chemical exchange between water and pullulan significantly increased at the later stage of drying process.

Numerical Analysis of the Magnetization Behavior in Magnetic Resonance Imaging in the Presence of Multiple Chemical Exchange Pools

The purpose of this study was to demonstrate a simple and fast method for solving the time-dependent Bloch-McConnell equations describing the behavior of magnetization in magnetic resonance imaging (MRI) in the presence of multiple chemical exchange pools. First, the time-dependent Bloch- McConnell equations were reduced to a homogeneous linear differential equation, and then a simple equation was derived to solve it using a matrix operation and Kronecker tensor product. From these solutions, the longitudinal relaxation rate (R1ρ) and transverse relaxation rate in the rotating frame (R2ρ) and Z-spectra were obtained. As illustrative examples, the numerical solutions for linear and star-type three-pool chemical exchange models and linear, star- type, and kite-type four-pool chemical exchange models were presented. The effects of saturation time (ST) and radiofrequency irradiation power (ω1) on the chemical exchange saturation transfer (CEST) effect in these models were also investigated. Although R1ρ and R2ρ were not affected by the ST, the CEST effect observed in the Z-spectra increased and saturated with increasing ST. When ω1 was varied, the CEST effect increased with increasing ω1 in R1ρ, R2ρ, and Z-spectra. When ω1 was large, however, the spillover effect due to the direct saturation of bulk water protons also increased, suggesting that these parameters must be determined in consideration of both the CEST and spillover effects. Our method will be useful for analyzing the complex CEST contrast mechanism and for investigating the optimal conditions for CEST MRI in the presence of multiple chemical exchange pools.

Understanding the symmetric line shape in the 17O MAS spectra for hexagonal ice

Solid-state 17O Magic-Angle Spinning (MAS) nuclear magnetic resonance (NMR) spectra of 17O-enriched hexagonal ice, [17O]-Ih, between 173 and 253 K were presented. Marked changes in the line shape were clearly observed, indicating water molecular reorientation in the crystal structure. At 173 K, molecular motions were considered to be frozen and analysis of the 1D MAS spectrum yielded the following parameters: quadrupole coupling constant (CQ) = 6.6 ± 0.2 MHz and asymmetry parameter (ηQ) = 0.95 ± 0.05. At 232 K and above, contrary to the conventional explanation, pseudo-symmetric line shapes appeared in the 17O MAS NMR spectra arising from the contribution of second-order quadrupole interactions. As a chemical exchange model to describe these isotropic 17O MAS NMR spectra, a modified Ratcliffe model, which consider the effects of proton disorder, was proposed, and the resulting theoretical spectra could well reproduce the experimental spectra.

A theoretical and numerical consideration of the longitudinal and transverse relaxations in the rotating frame

We previously derived a simple equation for solving time-dependent Bloch equations by a matrix operation. The purpose of this study was to present a theoretical and numerical consideration of the longitudinal (R1ρ=1/T1ρ) and transverse relaxation rates in the rotating frame (R2ρ=1/T2ρ), based on this method. First, we derived an equation describing the time evolution of the magnetization vector (M(t)) by expanding the matrix exponential into the eigenvalues and the corresponding eigenvectors using diagonalization. Second, we obtained the longitudinal magnetization vector in the rotating frame (M1ρ(t)) by taking the inner product of M(t) and the eigenvector with the smallest eigenvalue in modulus, and then we obtained the transverse magnetization vector in the rotating frame (M2ρ(t)) by subtracting M1ρ(t) from M(t). For comparison, we also computed the spin-locked magnetization vector. We derived the exact solutions for R1ρ and R2ρ from the eigenvalues, and compared them with those obtained numerically from M1ρ(t) and M2ρ(t), respectively. There was excellent agreement between them. From the exact solutions for R1ρ and R2ρ, R2ρ was found to be given by R2ρ=(2R2+R1)/2−R1ρ/2, where R1 and R2 denote the conventional longitudinal and transverse relaxation rates, respectively. We also derived M1ρ(t) and M2ρ(t) for bulk water protons, in which the effect of chemical exchange was taken into account using a 2-pool chemical exchange model, and we compared the R1ρ and R2ρ values obtained from the eigenvalues and those obtained numerically from M1ρ(t) and M2ρ(t). There was also excellent agreement between them. In conclusion, this study will be useful for better understanding of the longitudinal and transverse relaxations in the rotating frame and for analyzing the contrast mechanisms in T1ρ- and T2ρ-weighted MRI.

Behavior of the magnetization in spin-locking magnetic resonance imaging using numerical solutions to the time-dependent Bloch equations

We present a simple method for calculating the magnetization in spin-locking (SL) magnetic resonance imaging (MRI), in which a simple matrix equation was derived for solving the time-dependent Bloch equations in the 2-pool chemical exchange model. We also present a method for visualizing the trajectory of a magnetization vector in a three-dimensional (3D) space. The longitudinal relaxation time in the rotating frame (T1ρ) was calculated by fitting the z component of magnetization for a duration of SL (tSL) (Mz(tSL)) to Mz(tSL) = (M0 − Mzss)exp ( − tSL/T1ρ) + Mzss, where M0 and Mzss denote the thermal equilibrium and steady-state z component of magnetization, respectively, and was compared with that calculated from the solution given by Trott and Palmer. Our 3D plots clearly visualized the effect of SL. When the population of the two pools was highly asymmetric, there was good agreement between the T1ρ values obtained by our method and Trott and Palmer's solutions. The difference between them increased with decreasing asymmetry in the population of the two pools. Our method will be useful for better understanding and optimization of SL MRI, because it allows us to calculate the magnetization vector and to visualize its trajectory simply and quickly.

Tissue-blood exchange of extravascular longitudinal magnetization with account of intracompartmental diffusion

The joint effect of both extravascular water diffusion and transcapillary water exchange on the longitudinal magnetisation is evaluated theoretically for tissues with sparse capillary networks (e.g., the brain and myocardium). The spatio-temporal profile of the extravascular longitudinal magnetisation is calculated for the limiting case of a high blood concentration of paramagnetic tracer resulting in negligible intravascular magnetisation, hence in a net flux of magnetisation from the extravascular tissue to its contained blood. A related parameter, termed the effective extravascular depolarised volume, is derived that quantifies the ensuing attenuation of the NMR signal and affords a taxonomy of exchange regimes. It is found that the spatio-temporal pattern of magnetisation decay may deviate strongly from that predicted by chemical exchange models when the rate of transcapillary exchange is limited by slow diffusive transport in the extravascular tissue but reproduces known results in the case of fast extravascular diffusion.

Control of Cross Relaxation of Multiple‐Quantum Coherences Induced by Fast Chemical Exchange under Heteronuclear Double‐Resonance Irradiation

A fully analytical description of the control of the cross-correlated cross relaxation of multiple-quantum coherences in the presence of local dynamics under heteronuclear double-resonance radio-frequency (RF) irradiation is presented. The contribution of chemical exchange to relaxation can be partly or fully quenched by RF fields. We assume a correlated two-site chemical exchange model with arbitrary populations, and show that in the limit of fast exchange the dependence of the effective multiple-quantum cross-relaxation rate on the applied RF amplitude can be described by a compact analytical expression. Numerical simulations and preliminary experiments support our theoretical results. The relaxation dispersion as a function of RF amplitude can provide accurate information on the kinetics of correlated processes.

Dependence of blood R2 relaxivity on CPMG echo‐spacing at 2.35 and 7 T

The transverse relaxation rate (R(2)) of fresh human blood has been investigated at high and ultrahigh field, to characterize the R(2) dependency on blood sample oxygenation, hematocrit, and Carr-Purcell Meiboom-Gill sequence inter-echo spacing. Data were fitted to chemical exchange and diffusion models to assess their performance at different field strengths. The diffusion model gave a slightly superior fit at both field strengths, but the difference is unlikely to be relevant for the signal to noise ratio achieved in most in vivo experiments. Fitted model parameters were similar to those found in literature.

A proton NMR relaxation study of water dynamics in bovine serum albumin nanoparticles

Water dynamics and compartmentation in glutaraldehyde cross-linked bovine serum albumin nanoparticles have been investigated by an integrated nuclear magnetic resonance (NMR) protocol based on water relaxation times and self-diffusion coefficients measurements. Multi-exponentially of water relaxation curves has been accounted for according to a diffusive and chemical exchange model (see B. P. Hills, S. F. Takacs and P. S. Belton, Mol. Phys., 1989, 67(4), 903, and Mol. Phys., 1989, 67(4), 913; E. Brosio, M. Belotti and R. Gianferri, in Food Science and Technology: New Research, ed. L. V. Greco and M. N. Bruno, Nova Science Publishers, Hauppauge (NY), 2008) that made it possible to single out water molecules in the molecular spaces in the interior of albumin nanoparticles, in the meso-cavities formed by packed nanoparticles and in the meniscus on top of the nanoparticles suspension. A quantitative rationalization of T(2) values of water different components allowed morphological information to be acquired as for the size of water filled compartments, while self-diffusion coefficient measurements of water excess or fluxed packed nanoparticles suspensions are describers of transport properties of soft biomaterials. The paper reports an NMR approach that can be seen as a general and relevant method to characterize excess-water-swollen soft biomaterials.

Characterization of Conformational Exchange of a Histidine Side Chain: Protonation, Rotamerization, and Tautomerization of His61 in Plastocyanin from Anabaena variabilis

A model describing conformational exchange of His 61 in plastocyanin from Anabaena variabilis is presented. A detailed picture of the exchange dynamics has been obtained using solution NMR relaxation measurements, chemical shift titrations, and structural information provided by a high-resolution crystal structure of the protein. A three-site model for chemical exchange that involves interconversion among the tautomeric and protonated forms of the histidine side chain with rates that are fast on the NMR chemical shift time scale can account for all of the data. In general, in the limit of fast exchange, it is not possible to obtain separate measures of chemical shift differences and populations of the participating states using NMR. However, we show here that when the data mentioned above are combined, it is possible to extract values of all of the parameters that characterize the exchange process, including rates, populations, and chemical shift changes, and to provide cross-validations that establish their accuracy. The methodology is generally applicable to the study of histidine side chain dynamics, which can play an important functional role in many protein systems.

Proton NMR relaxation study of swelling and gelatinisation process in rice starch–water samples

Proton transverse magnetization decay curves of rice flour starch–water samples were measured and analysed for the presence of four components in the relaxation curve. T2 values were interpreted on the basis of the diffusive and chemical exchange model that provided evidence for extra granular bulk water and three more water populations whose relaxation rate is governed by diffusive and chemical exchange with starch components. The analysis of relaxation data provided information on dynamics of water molecules as well as on the size and dispersion of diffusive domains. Furthermore, by measuring solid to liquid ratio, transverse and longitudinal relaxation curves of starch–water mixtures at increasing temperatures – from 20 to 77°C – swelling and gelatinisation processes were monitored.