Acid-base reactions proceed via direct proton transfer as well as through water-mediated steps.
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Scientific literature confirms that acid-base reactions can occur through direct proton transfer as well as through water-mediated pathways such as Grotthuss-type proton hopping.
The proton transfer mechanism between aqueous Brønsted acids and bases, forming an encounter pair, has been studied in real time with ultrafast infrared spectroscopy. The transient intermediacy of a hydrated proton, formed by ultrafast dissociation from an optically triggered photoacid proton donor ROH, is implicated by the appearance of an infrared absorption marker band before protonation of the base, B
–
. Thus, proton exchange between an acid and a base in aqueous solution is shown to proceed by a sequential, von Grotthuss–type, proton-hopping mechanism through water bridges. The spectra suggest a hydronium cation H
3
O
+
structure for the intermediate, stabilized in the Eigen configuration in the ionic complex RO
–
···H
3
O
+
···B
–
.
Proton channels exist in a wide variety of membrane proteins where they transport protons rapidly and efficiently. Usually the proton pathway is formed mainly by water molecules present in the protein, but its function is regulated by titratable groups on critical amino acid residues in the pathway. All proton channels conduct protons by a hydrogen-bonded chain mechanism in which the proton hops from one water or titratable group to the next. Voltage-gated proton channels represent a specific subset of proton channels that have voltage- and time-dependent gating like other ion channels. However, they differ from most ion channels in their extraordinarily high selectivity, tiny conductance, strong temperature and deuterium isotope effects on conductance and gating kinetics, and insensitivity to block by steric occlusion. Gating of H(+) channels is regulated tightly by pH and voltage, ensuring that they open only when the electrochemical gradient is outward. Thus they function to extrude acid from cells. H(+) channels are expressed in many cells. During the respiratory burst in phagocytes, H(+) current compensates for electron extrusion by NADPH oxidase. Most evidence indicates that the H(+) channel is not part of the NADPH oxidase complex, but rather is a distinct and as yet unidentified molecule.
We investigate one of the fundamental reactions in solutions, the neutralization of an acid by a base. We use a photoacid, 8-hydroxy-1,3,6-trisulfonate-pyrene (HPTS; pyranine), which upon photoexcitation reacts with acetate under transfer of a deuteron (solvent: deuterated water). We analyze in detail the resulting bimodal reaction dynamics between the photoacid and the base, the first report on which was recently published [M. Rini, B.-Z. Magnes, E. Pines, and E. T. J. Nibbering, Science 301, 349 (2003)]. We have ascribed the bimodal proton-transfer dynamics to contributions from preformed hydrogen bonding complexes and from initially uncomplexed acid and base. We report on the observation of an additional (6 ps)−1 contribution to the reaction rate constant. As before, we analyze the slower part of the reaction within the framework of the diffusion model and the fastest part by a static, sub-150 fs reaction rate. Adding the second static term considerably improves the overall modeling of the experimental results. It also allows to connect experimentally the diffusion controlled bimolecular reaction models as defined by Eigen-Weller and by Collins-Kimball [D. Shoup and A. Szabo, Biophys. J. 40, 33 (1982)]. Our findings are in agreement with a three-stage mechanism for liquid phase intermolecular proton transfer: mutual diffusion of acid and base to form a “loose” encounter complex, followed by reorganization of the solvent shells and by “tightening” of the acid-base encounter complex. These rearrangements last a few picoseconds and enable a prompt proton transfer along the reaction coordinate, which occurs faster than our time resolution of 150 fs. Alternative models for the explanation of the slower “on-contact” reaction time of the loose encounter complex in terms of proton transmission through a von Grotthuss mechanism are also discussed.
Hydrogen energy stands out as a zero‐carbon emission and high‐density energy carrier, with the hydrogen evolution reaction being central to water electrolysis. The hydrogen‐bond network in the electrical double layer (EDL) significantly affects the reaction kinetics, yet the dynamic interactions between interfacial water, proton transfer pathways, and electrode structures remain elusive. Here, inspired by the natural proton regulation behavior of tannic acid (TA) in plant cells, a biomimetic strategy is proposed to reconstruct the hydrogen bond network in the EDL using TA‐modified Ni(OH)2. Experimental and theoretical studies demonstrate that TA establishes a robust hydrogen bond network and reduces the proton‐electron coupled transfer barrier through the Grotthuss mechanism. In situ surface‐enhanced infrared spectroscopy and molecular dynamics simulations reveal TA‐mediated reorganization of Ni coordination and stabilization of interfacial water molecules. The optimized Ni(OH)2‐TA catalyst delivers 0.5 A cm−2 at 1.68 V in an anion exchange membrane electrolyzer, sustaining stable operation for 250 h (83% production efficiency@0.1 A cm−2). This work highlights organic ligand‐driven EDL hydrogen‐bond engineering as a universal strategy for high‐performance water electrolysis, bridging atomic‐level design with macroscopic performance.
Proton transfer underpins number of chemical and biochemical processes, yet its sub-100 fs dynamics have rarely been captured in real time. Here, we report direct and time-resolved observation of ionizing radiation-induced proton transfer in a heteroaromatic hydrate: the pyrrole-water complex. Both the electron-impact and strong-field laser experiments create a locally and doubly charged pyrrole unit (C4H5N2+), which immediately (within 60 fs) donates a proton to the adjacent H2O, generating deprotonated C4H4N+ and hydronium H3O+ cations that subsequently undergo Coulomb explosion. The electron-impact experiments directly revealed initial states and provided dynamical insights through fragment ions and electron coincidence momentum imaging. The strong-field femtosecond laser experiments tracked the ultrafast dynamics of proton transfer; complementary ab initio calculations unraveled the dynamical details. The 50-60 fs proton transfer qualifies as one of the fastest acid-base reactions observed to date. This study offers a novel perspective on radiation-induced proton transfer in hydrated biomolecules. Proton transfer plays a key role in nature, yet its ultrafast dynamics remain elusive. Here the authors use coincidence spectroscopy and theoretical simulations to show that radiolytic doubly-ionized pyrrole triggers proton transfer to water within 60 fs.
RNA polymerase II (RNA Pol II) is central to gene expression, but its catalytic mechanism remains elusive due to the absence of high-resolution structural data. The role of water molecules in RNA Pol II catalysis is unknown. Here, we present 3 high-resolution cryo-electron microscopy structures of active Saccharomyces cerevisiae RNA Pol II elongation complexes in distinct catalytic states: two pre-catalysis states at 1.96 Å and 2.26 Å resolution and a post-catalysis state at 2.33 Å resolution. Each structure contains over 700-1,350 ordered water molecules, many located at functionally critical positions. Comparative analysis shows that these waters play essential roles in proton-transfer steps during RNA Pol II catalysis, facilitating substrate recognition and trigger-loop folding during nucleotide addition. Strikingly, these waters are conserved between prokaryotic and eukaryotic transcription machineries (see Mueller and Darst). These findings provide unprecedented mechanistic insights into RNA Pol II catalysis and reveal vital and evolutionarily conserved roles of water molecules in transcription.
strength of an acid in solution expressed as an equilibrium constant for a chemical dissociation reaction in the context of acid-base reactions. It is often
This glossary of chemistry terms is a list of terms and definitions relevant to chemistry, including chemical laws, diagrams and formulae, laboratory tools, glassware, and equipment. Chemistry is a physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions; it features an extensive vocabulary and a significant
acid
1. (Brønsted–Lowry acid) Any chemical species or molecular entity that acts as a proton donor when reacting with another species, because it loses at least one proton (H+) which is then transferred or 'donated' to the other species, which by definition is a Brønsted–Lowry base. When dissolved in an aqueous solution, a proton donor which increases the concentration of hydronium ion (H3O+) by transferring protons to water molecules may also be called an Arrhenius acid. The term "acid", when not otherwise qualified, often refers implicitly to a Brønsted–Lowry acid.
2. (Lewis acid) Any chemical species or molecular entity that acts as an electron pair acceptor when reacting with another species, forming a covalent bond by accepting a lone pair of electrons donated by the other species, which is known as a Lewis base. This definition was intended as a generalization of the Brønsted–Lowry definition by proposing that acid-base reactions are best viewed as reorganizations of electrons rather than transfers of protons, with the acid being a species that accepts electron pairs from another species either directly or by releasing protons (H+) into the solution, which then accept electron pairs from the other species. The Lewis definition is inclusive of many Brønsted–Lowry acids, though not all: most Lewis acids are not Brønsted–Lowry acids, and most Brønsted–Lowry acids are not Lewis acids.
3. Colloquially, any compound which, when dissolved in water, yields a pH of less than 7.0. The term "acid" is commonly used to refer to the entire aqueous solution, whereas stricter definitions refer only to the acidic solute.
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