Multiple Proton Research Articles

Determination of concerted or stepwise mechanism of hydrogen tunneling from isotope effects: Departure between experiment and theory.

Isotope substitution is an important experimental technique that offers deep insight into reaction mechanisms, as the measured kinetic isotope effects (KIEs) can be directly compared with theory. For multiple proton transfer processes, there are two types of mechanisms: stepwise transfer and concerted transfer. The Bell-Limbach model provides a simple theory to determine whether the proton transfer mechanism is stepwise or concerted from KIEs. Recent scanning tunneling microscopy (STM) experiments have studied the proton switching process in water tetramers on NaCl(001). Theoretical studies predict that this process occurs via a concerted mechanism; however, the experimental KIEs resemble the Bell-Limbach model for stepwise tunneling, raising questions on the underlying mechanism or the validity of the model. We study this system using ab initio instanton theory, and in addition to thermal rates, we also considered microcanonical rates, as well as tunneling splittings. The instanton theory predicts a concerted mechanism, and the KIEs for tunneling rates (both thermal and microcanonical) upon deuteration are consistent with the Bell-Limbach model for concerted tunneling but could not explain the experiments. For tunneling splittings, partial and full deuteration change the size of it in a similar fashion to how they change the rates. We further examined the Bell-Limbach model in another system, porphycene, which has both stepwise and concerted tunneling pathways. The KIEs predicted by instanton theory are again consistent with the Bell-Limbach model. This study highlights differences between KIEs in stepwise and concerted tunneling and the discrepancy between theory and recent STM experiments. New theory/experiments are desired to settle this problem.

Recurrent Large‐Scale Solar Proton Events Before the Onset of the Wolf Grand Solar Minimum

AbstractCarbon‐14 in tree rings have suggested there had been multiple extreme solar proton events (SPEs) in the past. While the largest events such as in 774–775 CE can be significantly detected by the typical precision of accelerator mass spectrometry, smaller but possibly more frequent events have been difficult to be detected. Thus, the frequency or any characteristics of such relatively smaller events are still largely unknown. In this paper, we report that large SPEs had occurred in 1261–1262, 1268–1269, and 1279–1280 CE before the onset of the Wolf minimum based on high‐precision carbon‐14 analyses. It is suggested that they had occurred at the maximum and the declining phase of solar cycles, and that they had occurred during the transition time of solar activity into a deep minimum. We propose that this episode may provide a unique opportunity to elucidate a potential interaction between the solar dynamo and extreme solar flares.

Switchable two-color graphene quantum dot as a promising fluorescence probe to highly sensitive pH detection and bioimaging

Graphene quantum dots have been widely applied in biosensing, fluorescence imaging, biomedicine, energy storage and conversion and catalysis, but design and synthesis of polychromatic graphene quantum dot with high luminous efficiency still faces great challenges. The study reports synthesis of histidine, serine and pentaethylenehexamine-functionalized and boron-doped graphene quantum dot (HSPB-GQD) via one-step pyrolysis. The resulting HSPB-GQD consists of graphene sheets of 2–5 nm with carboxyl, hydroxyl, amino, imino and imidazole. Synergy of histidine, serine, pentaethylenehexamine and boron atoms improves the luminescence behavior. This realizes unique switchable two-color luminescence. UV excitation of 370 nm produces one strong blue fluorescence with the maximum emission wavelength of 455 nm and quantum yield of 72.34%. Vis. excitation of 480 nm produces one strong yellow fluorescence with the maximum emission wavelength of 560 nm and quantum yield of 72.59%. The multiple proton dissociation system constructed by nitrogen-containing and oxygen-containing groups makes yellow fluorescence sensitive to environmental pH value. The intensity linearly increases with increasing pH in the range of 4.5–10.0. Organic molecules and inorganic ions do not interfere pH detection. HSPB-GQD as a promising fluorescence probe with negligible effect on cell viability was successfully applied to pH detection in biological and environmental water samples and cell imaging.

A novel range telescope concept for proton CT

Proton beam therapy can potentially offer improved treatment for cancers of the head and neck and in paediatric patients. There has been a sharp uptake of proton beam therapy in recent years as improved delivery techniques and patient benefits are observed. However, treatments are currently planned using conventional x-ray CT images due to the absence of devices able to perform high quality proton computed tomography (pCT) under realistic clinical conditions. A new plastic-scintillator-based range telescope concept, named ASTRA, is proposed here to measure the proton’s energy loss in a pCT system. Simulations conducted using GEANT4 yield an expected energy resolution of 0.7%. If calorimetric information is used the energy resolution could be further improved to about 0.5%. In addition, the ability of ASTRA to track multiple protons simultaneously is presented. Due to its fast components, ASTRA is expected to reach unprecedented data collection rates, similar to 108 protons/s. The performance of ASTRA has also been tested by simulating the imaging of phantoms. The results show excellent image contrast and relative stopping power reconstruction.

Modulating the Structures and Magnetic Properties of Dy(III) Single-Molecule Magnets through Acid-Base Regulation.

Chemical modulation on the structures and physical properties of the coordination complexes is of great interest for the preparation of new functional materials. By changing the acidity or basicity of the reaction medium, the deprotonation degree of a multidentate ligand with multiple active protons, H4daps (H4daps = N',N'″-((1E,1'E)-pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(2-hydroxybenzohydrazide)), can be regulated on purpose. With this ligand of different deprotonation and charges, three new DyIII complexes ([Dy(H3daps)(CH3COO)2(EtOH)]·CH3COOH (1Dy), [Dy2(H2daps)2(EtOH)2(H2O)2(MeOH)2](CF3SO3)2·(H2O)2 (2Dy), and [Dy3(H1daps)2(H2daps)(μ3-OH)(EtOH)(H2O)] (3Dy)) of different nuclearities (mono-, di-, and trinuclear for 1Dy to 3Dy, respectively) have been synthesized and characterized structurally and magnetically. Analyses on the related bond lengths and resulting hydrogen bond modes in the complexes provide the details of the deprotonation position and the charge of the ligands, which can be in the form of H3daps-, H2daps2-, and H1daps3-. Interestingly, the more deprotonated ligand can act as a bridging ligand between the DyIII centers using the phenol and/or carbonyl oxygen atoms, which leads to the multinuclear structures. Magnetic studies on these complexes revealed that complex 1Dy is a field-induced single-molecule magnet (SMM), while complexes 2Dy and 3Dy show SMM behavior under a zero dc field.

Magnetic reconnection as a mechanism to produce multiple thermal proton populations and beams locally in the solar wind

Context.Spacecraft data revealed early on the frequent observation of multiple near-thermal proton populations in the solar wind. Decades of research on their origin have focused on processes such as magnetic reconnection in the low corona and wave-particle interactions in the corona and locally in the solar wind.Aims.This study aims to highlight the fact that such multiple thermal proton populations and beams are also produced by magnetic reconnection occurring locally in the solar wind.Methods.We used high-resolution Solar Orbiter proton velocity distribution function measurements, complemented by electron and magnetic field data, to analyze the association of multiple thermal proton populations and beams with magnetic reconnection during a period of slow Alfvénic solar wind on 16 July 2020.Results.At least six reconnecting current sheets with associated multiple thermal proton populations and beams, including a case of magnetic reconnection at a switchback boundary, were found on this day. This represents 2% of the measured distribution functions. We discuss how this proportion may be underestimated, and how it may depend on solar wind type and distance from the Sun.Conclusions.Although suggesting a likely small contribution, but which remains to be quantitatively assessed, Solar Orbiter observations show that magnetic reconnection must be considered as one of the mechanisms that produce multiple thermal proton populations and beams locally in the solar wind.

Realizing Diketopyrrolopyrrole Polymer‐Based Uniform Large‐Area Transistors for Active Circuit via Protonic Acid Mediated Molecular Self‐Assembly

AbstractThe solution‐handling characteristics of π‐conjugated polymer semiconductors make them promising candidates for low‐cost flexible electronics. Although homogeneous and stable nonchlorine solvent (NClS) processing is the only way that must be passed for future application, polymer semiconductors still meet the challenges of poor solubility and inhomogeneities in NClS. Here, the authors primp polymer molecules with protonic acid by multiple interactions, that is, proton exchange and hydrogen bond interaction, to achieve scale and model‐constrained PDVT‐10c assembly in NClS. As a result, a uniform near‐amorphous PDVT‐C10c film is developed for polymer thin‐film transistor (PTFT) array, which exhibits uniform performance with much narrower Gaussian standards deviation than pristine PDVT‐C10c one. Finally, a 5 cm × 5 cm PTFT as the active‐matrix circuit for blue organic light‐emitting diode is demonstrated. The results illustrate the great potential of protonic acid‐mediated molecular self‐assembly on homogeneous and stable NClS processing polymer semiconductors for next‐generation flexible electronics.

Dual-Silicon-Doped Graphitic Carbon Nitride Sheet: An Efficient Metal-Free Electrocatalyst for Urea Synthesis.

Searching for an alternative nonhazardous catalyst for direct urea synthesis that avoids the traditional route of NH3 synthesis followed by CO2 addition is a challenging field of research nowadays. Based on first-principles calculations, we herein propose a novel electrocatalyst comprising of totally nonmetal earth abundant elements (dual-Si doped g-C6N6 sheet) which is capable of activating N2 and making it susceptible toward direct insertion of CO into the N-N bond, producing *NCON* which is the precursor for urea production by direct coupling of N2 and CO2 followed by multiple proton coupled electron transfer processes. Remarkably, the calculated onset potential for urea production is much less than that of NH3 synthesis and hydrogen evolution reactions, and also the faradaic efficiency is nearly 100% for production urea over ammonia, which promotes exclusive electrocatalytic urea synthesis by suppressing the NH3 synthesis as well as hydrogen evolution reactions.

The current status of preclinical proton FLASH radiation and future directions.

We review the current status of proton FLASH experimental systems, including preclinical physical and biological results. Technological limitations on preclinical investigation of FLASH biological mechanisms and determination of clinically relevant parameters are discussed. A review of the biological data reveals no reproduced proton FLASH effect in vitro and a significant in vivo FLASH sparing effect of normal tissue toxicity observed with multiple proton FLASH irradiation systems. Importantly, multiple studies suggest little or no difference in tumor growth delay for proton FLASH when compared to conventional dose rate proton radiation. A discussion follows on future areas of development with a focus on the determination of the optimal parameters for maximizing the therapeutic ratio between tumor and normal tissue response and ultimately clinical translation of proton FLASH radiation.

Extra hydrogen-bonding and water chain altering water-mediated ground-state multiple proton transfer in 2-aminopyridine: a theoretical study

Extra hydrogen-bonding and water chain altering water-mediated ground-state multiple proton transfer in 2-aminopyridine: a theoretical study

Nitrogen-Containing Aromatic Radical Anions Perform Multiple Proton and Electron Transfers Near-Simultaneously with Multiply Protonated Cations.

Gas phase ion/ion reactions between singly charged radical reagent anions and multiply charged cation precursors primarily result in either proton or electron transfer. These ion/ion reactions have been extensively studied for bioanalysis, and many reagent anions have been tested and reported. Here, nitrogen-containing aromatic radical anions were tested for the ability to conduct proton or electron transfer by their reaction with the ubiquitin [M + 13H]+13 precursor. The singly charged anion of 2,2'-biquinoline was found to undergo charge inversion to singly protonated cations via near-simultaneous proton and electron transfers while reactants were bound in a single ion/ion reaction complex. Although the focus of this paper was 2,2'-biquinoline, all three nitrogen-containing aromatic compounds tested produced similar results.

Simultaneous determination of multiple coupling networks by high-resolution 2D J-edited NMR spectroscopy

J coupling constitutes an important NMR parameter for molecular-level composition analysis and conformation elucidation. Dozens of J-based approaches have been exploited for J coupling measurement and coupling network determination, however, they are generally imposed to insufficient spectral resolution to resolve crowded NMR resonances and low measurement efficiency that a single experiment records one J coupling network. Herein, we propose a general NMR method to collect high-resolution 2D J-edited NMR spectra, which are characterized with advantages of pure absorptive lineshapes, decoupled chemical shift dimension, as well as eliminated axial peaks, thus facilitating J coupling partner assignments and J coupling constant measurements. More meaningfully, this protocol allows simultaneous determination of multiple coupling networks for highly efficient multiplet analyses via addressing multiple protons within one single experiment. Additionally, another variant is proposed for high-resolution applications under adverse magnetic field conditions. Therefore, this study provides a useful NMR protocol for configurational and structural studies with extensive applications in chemistry, biology, and material science.

Reconstructing magnetic deflections from sets of proton images using differential evolution.

Proton imaging is a powerful technique for imaging electromagnetic fields within an experimental volume, in which spatial variations in proton fluence are a result of deflections to proton trajectories due to interaction with the fields. When deflections are large, proton trajectories can overlap, and this nonlinearity creates regions of greatly increased proton fluence on the image, known as caustics. The formation of caustics has been a persistent barrier to reconstructing the underlying fields from proton images. We have developed a new method for reconstructing the path-integrated magnetic fields, which begins to address the problem posed by caustics. Our method uses multiple proton images of the same object, each image at a different energy, to fill in the information gaps and provide some uniqueness when reconstructing caustic features. We use a differential evolution algorithm to iteratively estimate the underlying deflection function, which accurately reproduces the observed proton fluence at multiple proton energies simultaneously. We test this reconstruction method using synthetic proton images generated for three different, cylindrically symmetric field geometries at various field amplitudes and levels of proton statistics and present reconstruction results from a set of experimental images. The method we propose requires no assumption of deflection linearity and can reliably solve for fields underlying linear, nonlinear, and caustic proton image features for the selected geometries and is shown to be fairly robust to noise in the input proton intensity.

Ultrafast nonadiabatic excited-state intramolecular proton transfer in 3-hydroxychromone: A surface hopping approach.

We employ the ab initio molecular dynamics within the surface hopping method to explore the excited-state intramolecular proton transfer taking place on the coupled "bright" S1 (ππ*) and "dark" S2 (nπ*) states of 3-hydroxychromone. The nonadiabatic population transfer between these states via an accessible conical intersection would open up multiple proton transfer pathways. Our findings reveal the keto tautomer formation via S1 on a timescale similar to the O-H in-plane vibrational period (<100fs). Structural analysis indicates that a few parameters of the five-membered proton transfer geometry that constitute the donor (hydroxyl) and acceptor (carbonyl) groups would be adequate to drive the enol to keto transformation. We also investigate the role of O-H in-plane and out-of-plane vibrational motions in the excited-state dynamics of 3-hydroxychromone.

The Impact of Ligand Carboxylates on Electrocatalyzed Water Oxidation.

ConspectusFossil fuel shortage and severe climate changes due to global warming have prompted extensive research on carbon-neutral and renewable energy resources. Hydrogen gas (H2), a clean and high energy density fuel, has emerged as a potential solution for both fulfilling energy demands and diminishing the emission of greenhouse gases. Currently, water oxidation (WO) constitutes the bottleneck in the overall process of producing H2 from water. As a result, the design of efficient catalysts for WO has become an intensively pursued area of research in recent years. Among all the molecular catalysts reported to date, ruthenium-based catalysts have attracted particular attention due to their robust nature and higher activity compared to catalysts based on other transition metals.Over the past two decades, we and others have studied a wide range of ruthenium complexes displaying impressive catalytic performance for WO in terms of turnover number (TON) and turnover frequency (TOF). However, to produce practically applicable electrochemical, photochemical, or photo-electrochemical WO reactors, further improvement of the catalysts’ structure to decrease the overpotential and increase the WO rate is of utmost importance. WO reaction, that is, the production of molecular oxygen and protons from water, requires the formation of an O–O bond through the orchestration of multiple proton and electron transfers. Promotion of these processes using redox noninnocent ligand frameworks that can accept and transfer electrons has therefore attracted substantial attention. The strategic modifications of the ligand structure in ruthenium complexes to enable proton-coupled electron transfer (PCET) and atom proton transfer (APT; in the context of WO, it is the oxygen atom (metal oxo) transfer to the oxygen atom of a water molecule in concert with proton transfer to another water molecule) to facilitate the O–O bond formation have played a central role in these efforts.In particular, promising results have been obtained with ligand frameworks containing carboxylic acid groups that either are directly bonded to the metal center or reside in the close vicinity. The improvement of redox and chemical properties of the catalysts by introduction of carboxylate groups in the ligands has proven to be quite general as demonstrated for a range of mono- and dinuclear ruthenium complexes featuring ligand scaffolds based on pyridine, imidazole, and pyridazine cores. In the first coordination sphere, the carboxylate groups are firmly coordinated to the metal center as negatively charged ligands, improving the stability of the complexes and preventing metal leaching during catalysis. Another important phenomenon is the reduction of the potentials required for the formation of higher valent intermediates, especially metal-oxo species, which take active part in the key O–O bond formation step. Furthermore, the free carboxylic acid/carboxylate units in the proximity to the active center have shown exciting proton donor/acceptor properties (through PCET or APT, chemically noninnocent) that can dramatically improve the rate as well as the overpotential of the WO reaction.

PO-1561 In-vivo treatment verification by TOF-PET for multiple proton fields: a Monte Carlo simulation study

PO-1561 In-vivo treatment verification by TOF-PET for multiple proton fields: a Monte Carlo simulation study

Substituents effect on the methanol-assisted excited-state intermolecular proton transfer of 7-Aminoquinoline: A theoretical study

Studies have shown that changing the substituted groups applied to the amine can effectively affect the strength of the excited state hydrogen bond. However, it is not common to study the mechanism of how to effectively control the hydrogen bond strength of the excited state through the substituted group. Here, we have taken 7-Aminoquinoline and its various derivatives, the TDDFT method is used to study the influence of its R substitution on the hydrogen bond strength of the excited state and the mechanism of solvent-assisted excited-state multiple proton transfer (ESMPT) reaction. We have utilized bond length, IR vibrational spectra, atomic polar tensors (APT) charge analysis and potential energy curves to depict the relationship between hydrogen bond strength and substituted groups in excited state. We have modulated deliberately the number of methanol molecules involved in the ESMPT processes based on the site-specificity of hydrogen-bonding interactions, the potential energy curves indicate that the proton transfer process is more likely to happen in 7AQs·(MeOH)3 tetramer than in 7AQs·(MeOH)2 trimer, which is conflict with previous experimental conclusion. Meanwhile, the transition state structure during the ESMPT reaction indicates that the process is concerted. Our study demonstrates well the fluorescence behavior of 7AQs molecules regulated by different R substituents and extends the boundaries of site-specific hydrogen-bonding interactions research slightly.

Acceleration of Oxygen Ions In Dipolarization Events: 2. PSBL Distributions

AbstractThis paper represents the second part of an investigation of the acceleration of energetic oxygen ions from encounters with a dipolarization front (DF), based on test particle tracing in the fields of an MHD simulation. In this paper, we focus on distributions in the plasma sheet boundary layer (PSBL). O+ beams close to the plasma sheet boundary are found to be less pronounced and/or delayed against the H+ beams. The reason is that these particles are accelerated by nonadiabatic motion in the duskward electric field such that O+ ions gain the same amount of energy, but only 1/4 of the speed of protons. This causes a delay and larger equatorward displacement by the E × B drift. In contrast, the O+ beams somewhat deeper inside the plasma sheet, where previously multiple proton beams were found, are accelerated at an earthward propagating DF just like H+, forming a field‐aligned beam at a similar speed as the lowest‐energy H+ beam. We found that the source location depends on the adiabaticity of the orbit. For larger adiabaticity, the beam ions originate initially from the outer plasma sheet, but later from the opposite PSBL or lobe, but for low adiabaticity, sources are well inside the plasma sheet. The energy gained from a single encounter of a DF is comparable to the kinetic energy associated with the front speed. Assuming maximum speeds of 500–1,000 km/s, this yields a mass dependent acceleration of about 1–5 keV for protons and 20–80 keV for oxygen ions, independent of their charge state.

Theoretical Insights into Excited-State Intermolecular Proton Transfers of 2,7-Diazaindole in Water Using a Microsolvation Approach.

The detailed excited-state intermolecular proton transfer (ESInterPT) mechanism of 2,7-diazaindole with water wires consisting of either one or two shells [2,7-DAI(H2O)n; n = 1-5] has been theoretically explored by time-dependent density functional theory using microsolvation with an implicit solvent model. On the basis of the excited-state potential energy surfaces along the proton transfer (PT) coordinates, among all 2,7-DAI(H2O)n, the multiple ESInterPT of 2,7-DAI(H2O)2+3 through the first hydration shell (inner circuit) is the most easy process to occur with the lowest PT barrier and a highly exothermic reaction. The lowest PT barrier resulted from the outer three waters pushing the inner circuit waters to be much closer to 2,7-DAI, leading to the enhanced intermolecular hydrogen-bonding strength of the inner two waters. Moreover, on-the-fly dynamic simulations show that the multiple ESInterPT mechanism of 2,7-DAI(H2O)2+3 is the triple PT in a stepwise mechanism with the highest PT probability. This solvation effect using microsolvation and dynamic simulation is a cost-effect approach to reveal the solvent-assisted multiple proton relay of chromophores based on excited-state proton transfer.

Models to study photoinduced multiple proton coupled electron transfer processes

In water-oxidizing photosynthetic organisms, excitation of the reaction-center chlorophylls (P680) triggers a cascade of electron and proton transfer reactions that establish charge separation across the membrane and proton-motive force. An early oxidation step in this process involves proton-coupled electron transfer (PCET) via a tyrosine-histidine redox relay (Yz-H190). Herein, we report the synthesis and structural characterization of two isomeric dyads designed to model this PCET process. Both are based on the same high potential fluorinated porphyrin (model for P680), linked to isomeric pyridylbenzimidazole-phenols (models for Yz-H190). The two isomeric dyads have different hydrogen bond frameworks, which is expected to change the PCET photooxidation mechanism. In these dyads, 1H NMR evidence indicates that in one dyad the hydrogen bond network would support a Grotthuss-type proton transfer process, whereas in the other the hydrogen bond network is interrupted. Photoinduced one-electron, two-proton transfer is expected to occur in the fully hydrogen-bonded dyad upon oxidation of the phenol by the excited state of the porphyrin. In contrast for the isomer with the interrupted hydrogen bond network, an ultrafast photoinduced one-electron one-proton transfer process is anticipated, followed by a much slower proton transfer to the terminal proton acceptor. Understanding the nature of photoinduced PCET mechanisms in these biomimetic models will provide insights into the design of future generations of artificial constructs involved in energy conversion schemes.