Chemical Exchange Processes Research Articles

Revealing the Solvation Structure and Dynamics of Carbonate Electrolytes in Lithium-Ion Batteries by Two-Dimensional Infrared Spectrum Modeling.

Carbonate electrolytes in lithium-ion batteries play a crucial role in conducting lithium ions between two electrodes. Mixed solvent electrolytes consisting of linear and cyclic carbonates are commonly used in commercial lithium-ion batteries. To understand how the linear and cyclic carbonates introduce different solvation structures and dynamics, we performed molecular dynamics simulations of two representative electrolyte systems containing either linear or cyclic carbonate solvents. We then modeled their two-dimensional infrared (2DIR) spectra of the carbonyl stretching mode of these carbonate molecules. We found that the chemical exchange process involving formation and dissociation of lithium-ion/carbonate complexes is responsible for the growth of 2DIR cross peaks with increasing waiting time. In addition, we also found that cyclic carbonates introduce faster dynamics of dissociation and formation of lithium-ion/carbonate complexes than linear carbonates. These findings provide new insights into understanding the lithium-ion mobility and its interplay with solvation structure and ultrafast dynamics in carbonate electrolytes used in lithium-ion batteries.

The dynamics of peptide-water interactions in dialanine: An ultrafast amide I 2D IR and computational spectroscopy study.

We present a joint experimental and computational study of the dynamic interactions of dialanine (Ala-Ala) with water, comparing the results of ultrafast 2D IR and infrared transient absorption spectroscopy of its amide I vibration with spectra modeled from molecular dynamics (MD) simulations. The experimental data are analyzed to describe vibrational frequency fluctuations, vibrational energy relaxation, and chemical exchange processes. The origin of these processes in the same underlying fluctuating forces allows a common description in terms of the fluctuations and conformational dynamics of the peptide and associated solvent. By comparing computational spectroscopy from MD simulations with multiple force fields and water models, we describe how the dynamics of water hydrogen bond fluctuations and switching processes act as a source of friction that governs the dephasing and vibrational relaxation, and provide a description of coupled water and peptide motions that give rise to spectroscopic exchange processes.

Synthesis and magnetic hyperthermia studies on high susceptible Fe1−xMgxFe2O4 superparamagnetic nanospheres

Majority studies on magnetic hyperthermia properties were carried out by modifying the saturation mass magnetization (Ms) of the samples. Here efforts were made to enhance the specific heat generation rate (SHGR) of single domain superparamagnetic (SP) material by modifying its magnetic susceptibility. Well crystallined, inverse spinel structured and close to monosize Fe1−xMgxFe2O4 (x=0, 0.1, 0.2, 0.3, 0.4, & 0.5) compounds with nanosphere geometry (diameter 10nm) were synthesized by solvothermal reflux method at ≈300°C. In the literature it is reported that magnesium ferrites synthesized at high temperatures yield mixed (normal & inverse) spinel structures. The inverse spinel structure was confirmed by X-ray powder diffraction (XRPD), lattice vibrations and magnetic characteristics of the compounds. The Ms of the compounds decrease with increase of substituent Mg2+ concentration. Under high excitation energy the inter-valance charge transfer whereas under low excitation energy the intra-valance charge transfer process were predominant. The as-synthesized nanospheres were encapsulated by hydrophobic oleic acid and were exchanged by hydrophilic poly(acrylic acid) by chemical exchange process. Estimated magnetic hyperthermia power or SHGR of the x=0, 0.3 & 0.5 were 11, 11.4 & 22.4W per gram of respective compounds, respectively, under 63.4kAm−1 field amplitude and 126kHz frequency. The SHGR enhances with Mg2+ concentration though its Ms reduces and is attributed to reduced spin-orbital coupling in the compounds with enhanced Mg2+ concentration. This may pave a new way to develop magnetic hyperthermia material by modifying magnetic susceptibility of the compounds against to the reported Ms modification approach. The obtained high SHGR of the biocompatible compounds could be used in magnetic hyperthermia applications in biomedical field.

Statistical design and kinetic and thermodynamic studies of Ni(II) adsorption on bentonite

The adsorption of the bentonite toward Ni(II) from aqueous solution was studied to obtain optimum conditions, equilibrium model, thermodynamic and kinetic parameters. Statistical method was used to evaluate maximum amount of adsorbed Ni (II). In this work, pH of solution during stirring, contact time, initial Ni (II) concentration, particle size of bentonite and amount of bentonite were considered as effective parameters which should be examined. The increase of temperature has negative effect on the Ni(II) adsorption. The equilibrium data were correlated well with Freundlich and Dubinin–Radushkevich isotherm models the correlation coefficients of which are (R 2) 0.994 and 0.971, respectively. This model indicates heterogeneous and chemical absorption or ion exchange process. The values of thermodynamic parameters such as ΔH°, ΔS° and ΔG° of nickel adsorption reveal that it is a spontaneous, exothermic and associative process. The experimental data fit the pseudo-second-order kinetic very well with correlation coefficient (R 2) more than 0.995.

Magnetizing Calixarene: Azo Dye Removal from Aqueous Media by Fe3O4 Nanoparticles Fabricated with Carboxylic-Substituted Calix[4]arene

Calix[4]arene was reacted with isonipecotic acid to synthesize the Mannich base derivative, and Fe3O4 magnetic nanoparticles were bonded to the lower rim of the calix[4]arene derivative through ether linkage to obtain carboxylic calix[4]arene magnetic nanoparticles (CCMN). After characterization with transmission electron microscopy and Fourier transform infrared spectroscopy, adsorption studies were carried out for the removal of azo dyes (Evans Blue and Chicago Sky Blue 6 B). Adsorption parameters such as effects of pH, dosage, concentration, temperature, and time were optimized. Results showed that adsorption equilibrium was achieved within 15 min, and maximum % adsorption was calculated as 95% for both dyes at pH 2.5. An equilibrium isotherm study suggests that the adsorption mechanism follows a chemical ion exchange process with an adsorption capacity value of 13.9 and 17.5 mmol g–1 for Evans Blue and Chicago Sky Blue 6 B, respectively. The adsorption kinetic follows pseudo-second-order kinetics as a...

Concentration Dependence of the Rate of Catalytic Isotopic Exchange of Hydrogen with Water Vapor on the Catalyst RKhTU-3SM

One method of separating hydrogen isotopes is chemical isotopic exchange of hydrogen with liquid water, combined with electrolysis of water. At present, different mathematical models are used to calculate the characteristics of newly developed setups. They all have the problem of inadequate data on the characteristics of the chemical isotopic exchange process occurring at medium and high deuterium concentrations. The present work is devoted to investigating one stage of chemical isotopic exchange – catalytic isotopic exchange between hydrogen and water vapor at high deuterium concentrations in application to the catalyst RKhTU-3SM. It is shown that the experimental rate constant of isotopic exchange for the pair protium – deuterium increases by almost a factor of two, while for exchange with tritium increasing the deuterium concentration from 5 to 95% does not change the experimentally observed rate constant to within the measurement error.

Longitudinal relaxation optimized amide 1H-CEST experiments for studying slow chemical exchange processes in fully protonated proteins.

Chemical Exchange Saturation Transfer (CEST) experiments are increasingly used to study slow timescale exchange processes in biomolecules. Although 15N- and 13C-CEST have been the approaches of choice, the development of spin state selective 1H-CEST pulse sequences that separate the effects of chemical and dipolar exchange [T. Yuwen, A. Sekhar and L. E. Kay, Angew Chem Int Ed Engl 2016 doi: 10.1002/anie.201610759 (Yuwen et al. 2017)] significantly increases the utility of 1H-based experiments. Pulse schemes have been described previously for studies of highly deuterated proteins. We present here longitudinal-relaxation optimized amide 1H-CEST experiments for probing chemical exchange in protonated proteins. Applications involving a pair of proteins are presented establishing that accurate 1H chemical shifts of sparsely populated conformers can be obtained from simple analyses of 1H-CEST profiles. A discussion of the inherent differences between 15N-/13C- and 1H-CEST experiments is presented, leading to an optimal strategy for recording 1H-CEST experiments.

Probing conformational dynamics in biomolecules via chemical exchange saturation transfer: a primer.

Although Chemical Exchange Saturation Transfer (CEST) type NMR experiments have been used to study chemical exchange processes in molecules since the early 1960s, there has been renewed interest in the past several years in using this approach to study biomolecular conformational dynamics. The methodology is particularly powerful for the study of sparsely populated, transiently formed conformers that are recalcitrant to investigation using traditional biophysical tools, and it is complementary to relaxation dispersion and magnetization transfer experiments that have traditionally been used to study chemical exchange processes. Here we discuss the concepts behind the CEST experiment, focusing on practical aspects as well, we review some of the pulse sequences that have been developed to characterize protein and RNA conformational dynamics, and we discuss a number of examples where the CEST methodology has provided important insights into the role of dynamics in biomolecular function.

Practical considerations for investigation of protein conformational dynamics by 15N R 1ρ relaxation dispersion.

It is becoming increasingly apparent that proteins are not static entities and that their function often critically depends on accurate sampling of multiple conformational states in aqueous solution. Accordingly, the development of methods to study conformational states in proteins beyond their ground-state structure ("excited states") has crucial biophysical importance. Here we investigate experimental schemes for optimally probing chemical exchange processes in proteins on the micro- to millisecond timescale by 15N R 1ρ relaxation dispersion. The schemes use selective Hartmann-Hahn cross-polarization (CP) transfer for excitation, and derive peak integrals from 1D NMR spectra (Korzhnev et al. in J Am Chem Soc 127:713-721, 2005; Hansen et al. in J Am Chem Soc 131:3818-3819, 2009). Simulation and experiment collectively show that in such CP-based schemes care has to be taken to achieve accurate suppression of undesired off-resonance coherences, when using weak spin-lock fields. This then (i) ensures that relaxation dispersion profiles in the absence of chemical exchange are flat, and (ii) facilitates extraction of relaxation dispersion profiles in crowded regions of the spectrum. Further improvement in the quality of the experimental data is achieved by recording the free-induction decays in an interleaved manner and including a heating-compensation element. The reported considerations will particularly benefit the use of CP-based R 1ρ relaxation dispersion to analyze conformational exchange processes in larger proteins, where resonance line overlap becomes the main limiting factor.

Revisiting Silicalite-1 Nucleation in Clear Solution by Electrochemical Impedance Spectroscopy.

Electrochemical impedance spectroscopy (EIS) was used to detect and investigate nucleation in silicalite-1 clear solutions. Although zeolite nucleation was previously assumed to be a step event, inducing a sharp discontinuity around a Si/OH- ratio of 1, complex bulk conductivity measurements at elevated temperatures reveal a gradual decay of conductivity with increased silicon concentrations. Inverse Laplace transformation of the complex conductivity allows the observation of the chemical exchange phenomena governing nanoaggregate formation. At low temperatures, the fast exchange between dissociated ions and ion pairs leads to a gradual decay of conductivity with an increasing silicon content. Upon heating, the exchange rate is slower and the residence time of ion pairs inside of the nanoaggregates is increasing, facilitating the crystallization process. This results in a bilinear chemical exchange and gives rise to the discontinuity at the Si/OH- ratio of 1, as observed by Fedeyko et al. EIS allows the observation of slow chemical exchange processes occurring in zeolite precursors. Until now, such processes could be observed only using techniques such as nuclear magnetic or electron paramagnetic resonance spectroscopy. In addition, EIS enables the quantification of interfacial processes via the double layer (DL) capacitance. The electrical DL thickness, derived from the DL capacitance, shows a similar gradual decay and confirms that the onset of nanoaggregate formation is indeed not narrowly defined.

Wet chemical preparation and isotope exchange process of H/D-terminated Si(111) and Si(110) studied by adsorbate vibrational analysis

A convenient procedure for preparing D-terminated Si(111)-(1×1) and Si(110)-(1×1) by wet chemical etching was developed and applied to the vibrational analysis of these surfaces by high-resolution electron-energy loss spectroscopy (HREELS). Fully H-terminated Si(111)/(110) was first prepared in regular 40% NH4F/H2O solution, followed by immersion in saturated KF/D2O solution. HREELS revealed partially D-terminated H:Si(111)/(110) with the amount of deuterium termination depending on the immersion time. A series of various immersion times revealed the H/D exchange reaction kinetics, which are associated with the Si substrate etching processes on Si(111) (step-flow etching) and Si(110) (zipper reaction). The H–Si and D–Si stretching vibration frequencies as functions of the surface D fraction did not appear to change on Si(111), but on Si(110) the H–Si signal red shifted at a high D fraction. This is due to the adsorbate–adsorbate interaction, which is more intense on Si(110) because of the short nearest-neighbor distance of the adsorbates.

Separating Dipolar and Chemical Exchange Magnetization Transfer Processes in 1H‐CEST

An amide 1 H-Chemical Exchange Saturation Transfer (CEST) experiment is presented for studies of conformational exchange in proteins. The approach, exploiting spin-state-selective magnetization transfer, completely suppresses undesired NOE-based dips in CEST profiles so that chemical exchange processes can be studied. The methodology is demonstrated with applications involving proteins that interconvert on the millisecond timescale between major and invisible minor states, and accurate amide 1 H chemical shifts of the minor conformer are obtained in each case. The spin-state-selective magnetization transfer approach offers unique possibilities for quantitative studies of protein exchange through 1 H-CEST.

Separating Dipolar and Chemical Exchange Magnetization Transfer Processes in 1H‐CEST

AbstractAn amide 1H‐Chemical Exchange Saturation Transfer (CEST) experiment is presented for studies of conformational exchange in proteins. The approach, exploiting spin‐state‐selective magnetization transfer, completely suppresses undesired NOE‐based dips in CEST profiles so that chemical exchange processes can be studied. The methodology is demonstrated with applications involving proteins that interconvert on the millisecond timescale between major and invisible minor states, and accurate amide 1H chemical shifts of the minor conformer are obtained in each case. The spin‐state‐selective magnetization transfer approach offers unique possibilities for quantitative studies of protein exchange through 1H‐CEST.

Comparison on efficiency of various techniques in treatment of waste and sewage water – A comprehensive review

In the present scenario, environmental laws have become stringent towards health, economy and reduction of pollution. The pollution is a result of discharge of various organic and inorganic substances into the environment. The sources of pollution include domestic agricultural and industrial water. Conventional techniques such as chemical precipitation, carbon adsorption, ion exchange, evaporations and membrane processes are found to be effective in treatment of waste and sewage water. Recently, biological treatments have gained popularity to remove toxic and other harmful substances. The objective of the paper is to make comprehensive review including the performance of each technique in treatment of waste and sewage water. The research directions are also suggested based on the review.

Probing Hydronium Ion Histidine NH Exchange Rate Constants in the M2 Channel via Indirect Observation of Dipolar-Dephased 15N Signals in Magic-Angle-Spinning NMR.

Water-protein chemical exchange in membrane-bound proteins is an important parameter for understanding how proteins interact with their aqueous environment, but has been difficult to observe in membrane-bound biological systems. Here, we demonstrate the feasibility of probing specific water-protein chemical exchange in membrane-bound proteins in solid-state MAS NMR. By spin-locking the 1H magnetization along the magic angle, the 1H spin diffusion is suppressed such that a water-protein chemical exchange process can be monitored indirectly by dipolar-dephased 15N signals through polarization transfer from 1H. In the example of the Influenza A full length M2 protein, the buildup of dipolar-dephased 15N signals from the tetrad of His37 side chains have been observed as a function of spin-lock time. This confirms that hydronium ions are in exchange with protons in the His37 NH bonds at the heart of the M2 proton conduction mechanism, with an exchange rate constant of ∼1750 s-1 for pH 6.2 at -10 °C.

Removal of dissolved sulfides in aqueous solution by activated sludge: mechanism and characteristics

Activated sludge recycling has been developed as a novel technique to directly prevent volatile sulfides emission from wastewater influents. In this study, mechanisms and characteristics of dissolved sulfides removal in aqueous solution by activated sludge were investigated. When DO content in water was 0.49mg/L, 70% of removed dissolved sulfides were released back from the activated sludge by lowering pH to 1. The SEM/EDS result revealed that removed sulfur was fixed in activated sludge and the XPS result showed that fixed sulfur had an oxidation state of −2. FTIR results showed that primary amine group (R-NH2) could be one of the radical groups bonding sulfides. All these results verified that sulfides removal by activated sludge is primarily attributed to adsorption, rather than biodegradation, under low DO conditions in 40min. The equilibrium isotherm data fit the Langmuir isotherm model well. The maximum adsorption capacity (q0) ranged in 25–38mg/g at temperatures of 10–40°C. The adsorption kinetic data fit the pseudo-second-order model well. The amounts of adsorbed sulfides at equilibrium (qe) were positively proportional to temperature, initial sulfides concentration and agitation speed. These results indicate that sulfides adsorption could be a chemical sorption or ion exchange process.

Spin Saturation Transfer Difference NMR (SSTD NMR): A New Tool to Obtain Kinetic Parameters of Chemical Exchange Processes

This detailed protocol describes the new Spin Saturation Transfer Difference Nuclear Magnetic Resonance protocol (SSTD NMR), recently developed in our group to study processes of mutual-site chemical exchange that are difficult to analyze by traditional methods. As the name suggests, this method combines the Spin Saturation Transfer method used for small molecules, with the Saturation Transfer Difference (STD) NMR method employed for the study of protein-ligand interactions, by measuring transient spin saturation transfer along increasing saturation times (build-up curves) in small organic and organometallic molecules undergoing chemical exchange.Advantages of this method over existing ones are: there is no need to reach coalescence of the exchanging signals; the method can be applied as long as one signal of the exchanging sites is isolated; there is no need to measure T1 or reach steady state saturation; rate constant values are measured directly, and T1 values are obtained in the same experiment, using only one set of experiments.To test the method, we have studied the dynamics of the hindered rotation of N,N-dimethylamides, for which much data is available for comparison. The thermodynamic parameters obtained using SSTD are very similar to the reported ones (spin-saturation transfer techniques and line-shape analysis). The method can be applied to more challenging substrates that cannot be studied by previous methods.We envisage that the simple experimental set up and the wide applicability of the method to a great variety of substrates will make this a common technique amongst organic and organometallic chemists without extensive expertise in NMR.

Aggregation‐induced changes in the chemical exchange saturation transfer (CEST) signals of proteins

Chemical exchange saturation transfer (CEST) is an MRI technique that allows mapping of biomolecules (small metabolites, proteins) with nearly the sensitivity of conventional water proton MRI. In living organisms, several tissue-specific CEST effects have been observed and successfully applied to diagnostic imaging. In these studies, particularly the signals of proteins showed a distinct correlation with pathological changes. However, as CEST effects depend on various properties that determine and affect the chemical exchange processes, the origins of the observed signal changes remain to be understood. In this study, protein aggregation was identified as an additional process that is encoded in the CEST signals of proteins. Investigation of distinct proteins that are involved in pathological disorders, namely amyloid beta and huntingtin, revealed a significant decrease of all protein CEST signals upon controlled aggregation. This finding is of particular interest with regard to diagnostic imaging of patients with neurodegenerative diseases that involve amyloidogenesis, such as Alzheimer's or Huntington's disease. To investigate whether the observed CEST signal decrease also occurs in heterogeneous mixtures of aggregated cellular proteins, and thus prospectively in tissue, heat-shocked yeast cell lysates were employed. Additionally, investigation of different cell compartments verified the assignment of the protein CEST signals to the soluble part of the proteome. The results of in vitro experiments demonstrate that aggregation affects the CEST signals of proteins. This observation can enable hypotheses for CEST imaging as a non-invasive diagnostic tool for monitoring pathological alterations of the proteome in vivo.

Solid‐state NMR studies of chemical exchange in ion conductors for alternative energy applications

AbstractHere we describe the selective inversion methodology for quantifying the rates of site‐specific ion exchange in materials such as lithium ion battery cathode frameworks. This strategy is shown to be robust in the presence of paramagnetic centers and viable and efficient for the evaluation of hopping rates, in spite of varying initial conditions for the NMR experiment. This is contrasted with 2D EXSY methodology, and selective inversion is shown to be preferable for a number of reasons articulated herein. Work in this area in our group was guided by insights into chemical exchange processes provide by our friend and colleague, Prof. Alex D. Bain. We dedicate this short review to him.

Comparison on efficiency of various techniques in treatment of waste and sewage water – A comprehensive review

In the present scenario, environmental laws have become stringent towards health, economy and reduction of pollution. The pollution is a result of discharge of various organic and inorganic substances into the environment. The sources of pollution include domestic agricultural and industrial water. Conventional techniques such as chemical precipitation, carbon adsorption, ion exchange, evaporations and membrane processes are found to be effective in treatment of waste and sewage water. Recently, biological treatments have gained popularity to remove toxic and other harmful substances. The objective of the paper is to make comprehensive review including the performance of each technique in treatment of waste and sewage water. The research directions are also suggested based on the review.