Proton Transfer Pathways Research Articles

Probing the Influence of the Protein Scaffold on H-Cluster Reactivity via Gain-of-Function Studies─Improved H2 Evolution and O2 Tolerance through Rational Design of [FeFe] Hydrogenase.

[FeFe] hydrogenases make up a structurally diverse family of metalloenzymes that catalyze proton/dihydrogen interconversion. They can be classified into phylogenetically distinct groups denoted A-G, which differ in structure and reactivity. Prototypical Group A hydrogenases have high turnover rates and remarkable energy efficiency. As compared to Group A enzymes, the putatively sensory Group D hydrogenase from Thermoanaerobacter mathranii (TamHydS) has a thousand-fold lower H2 evolution rate and a high overpotential requirement to drive catalysis (irreversible) but shows increased inhibitor tolerance. This divergence in structure and activity between hydrogenases makes them ideal models for studying second (active-site environment) and outer (e.g., substrate transport) coordination sphere effects on metal cofactors. Herein, we generated three TamHydS-based variants, each mimicking proposed key structural features of Group A hydrogenase: the "active site" (AS), "proton-transfer pathway" (PTP), and "combined" (CM = AS + PTP) variant. A fourth single-point variant, A137C, which introduces a proposed critical cysteine in the active site, was characterized as a reference. No change in isolation resulted in Group A-like behavior; i.e., no positive impact on catalytic performance was observed. The CM variant, however, showed increased H2 evolution activity but retained the overpotential requirement. Additionally, the CM variant improved the already relatively high stability of TamHydS against O2 and CO inhibition. These findings show that activity rates, (ir)reversibility, and susceptibility to gaseous inhibitors are decoupled. Moreover, the results highlight the importance of exploring hydrogenase diversity as a path toward understanding the structural factors that enable the outstanding catalytic properties of [FeFe] hydrogenases.

Side-On Bound Beryllium Dinitrogen Complex: A Precursor for Complete Conversion of Dinitrogen to Ammonia Mediated by N-Heterocyclic Carbene.

The complete conversion of dinitrogen to ammonia mediated by a side-on N2-bound carbene-beryllium complex, [NHC-Be(η2-N2)] has been studied considering both the symmetric and unsymmetric pathways. N-heterocyclic carbenes complexed with Be(η2-N2) moieties were considered substrates in our study. We found that two mechanistic pathways were possible for the reduction of dinitrogen to form ammonia. Our calculations revealed that the symmetric pathway is more favorable compared to the unsymmetric one. The interconversion of the complex from the symmetric product to the unsymmetric one involves a large activation energy barrier for the proton transfer pathway. Both of these pathways were associated with high exergonicity, and the N-N bond is observed to be elongated, which indicates that the NHC-Be(η2-N2) complex is a promising candidate for dinitrogen activation and subsequent reduction, resulting in the formation of ammonia. The bonding scenario of the NHC-Be(η2-N2) complex can be explained well by the famous Dewar-Chatt-Duncanson (DCD) model. Our calculations reveal that the symmetric pathway is found to be more suitable due to more negative values of change in Gibbs free energy. Solvent phase calculations have identified the viability of the NHC-Be(η2-N2) complex, indicating that the complex is sustainable in low-polar organic solvents, such as toluene and diethyl ether.

Solvent‐Assisted Prototopic Switching of Norharmane Along Hydrogen‐Bonded Network: Assessing the Precise Length of Network

ABSTRACTIn this article, the proton transfer dynamics along a stable norharmane•(H2O)n (n = 2–4) hydrogen‐bonded cluster on conversion from the neutral to cationic form of norharmane (NHM) in water medium was demonstrated experimentally and theoretically. The distinct absorption and emission bands of different prototropic forms of NHM are well‐known in the literature. Initially, the conversion from neutral to cationic form of NHM on moving from a polar aprotic (acetonitrile) to a polar protic (water) solvent was ensured by steady‐state absorption and fluorescence studies. The analysis of IR spectra and steady‐state anisotropy data of NHM confirmed the possibility of the formation of a hydrogen‐bonded network in the presence of water. The length of the network was explored and assumed by extensive Density Functional Theory (DFT) calculations. Then, by time‐dependent density functional theory (TD‐DFT), the excited state proton transfer (ESPT) pathway was established interrogating the NHM‐water cluster with different numbers of water molecules. The theoretical analysis assured that the NHM•(H2O)2 cluster was incapable of maintaining the stable hydrogen bonding wire in the course of the ESPT mechanism. Rather, NHM•(H2O)3 and NHM•(H2O)4 clusters were simultaneously involved in operating the ESPT mechanism. The NHM•(H2O)4 cluster was more feasible to carry out the proton transfer than the NHM•(H2O)3 cluster. To the best of our knowledge, this was possibly the first theoretical evidence behind the conversion from neutral to cationic form of NHM via the formation of a hydrogen‐bonded network.

Effective Proton Conduction in Quasi‐Solid Zinc‐Manganese Batteries via Constructing Highly Connected Transfer Pathways

AbstractElusive ion behaviors in aqueous electrolyte remain a challenge to break through the practicality of aqueous zinc‐manganese batteries (AZMBs), a promising candidate for safe grid‐scale energy storage systems. The proposed electrolyte strategies for this issue most ignore the prominent role of proton conduction, which greatly affects the operation stability of AZMBs. Here we report a water‐poor quasi‐solid electrolyte with efficient proton transfer pathways based on the large‐space interlayer of montmorillonite and strong‐hydration Pr3+ additive in AZMBs. Proton conduction is deeply understood in this quasi‐solid electrolyte. Pr3+ additive not only dominates the proton conduction kinetics, but also regulates the reversible manganese interfacial deposition. As a result, the Cu@Zn||α‐MnO2 cell could achieve a high specific capacity of 433 mAh g−1 at 0.4 mA cm−2 and an excellent stability up to 800 cycles with a capacity retention of 92.2 % at 0.8 mA cm−2 in such water‐poor quasi‐solid electrolyte for the first time. Ah‐scale pouch cell with mass loading of 15.19 mg cm−2 sustains 100 cycles after initial activation, which is much better than its counterparts. Our work provides a new path for the development of zinc metal batteries with good sustainability and practicality.

Unconventional Pathways in Nitrogen-Centered SN2 Reactions: From Roundabout to Hydride Transfer.

The mechanisms and dynamics of bimolecular nucleophilic substitution (SN2) reactions are complex and influenced by the nature of the central atom. In this study, we explore SN2 at a nitrogen center (SN2@N) by investigating the reaction of chloramine (NH2Cl) with methoxide ion (CH3O-) using ab initio classical trajectory simulations at the MP2(fc)/aug-cc-pVDZ level of theory. We observe that, in addition to the expected SN2 product formation (CH3ONH2 + Cl-), a high-energy proton-transfer pathway leading to CH3OH and NHCl- dominates, with near-quantitative agreement between simulations and experimental data. Notably, we identify a novel hydride-transfer pathway yielding NH3, H2CO, and Cl-, revealing alternative reactivity channels previously uncharacterized in nitrogen-centered SN2 reactions. Mechanistic analysis uncovers unconventional roaming-mediated and roundabout pathways alongside the traditional direct rebound and indirect mechanisms. Additionally, an umbrella inversion of the NH2 group resulting in retention of configuration in the CH3ONH2 product was observed in a fraction of trajectories.

Effective Proton Conduction in Quasi-Solid Zinc-Manganese Batteries via Constructing Highly Connected Transfer Pathways.

Elusive ion behaviors in aqueous electrolyte remain a challenge to break through the practicality of aqueous zinc-manganese batteries (AZMBs), a promising candidate for safe grid-scale energy storage systems. The proposed electrolyte strategies for this issue most ignore the prominent role of proton conduction, which greatly affects the operation stability of AZMBs. Here we report a water-poor quasi-solid electrolyte with efficient proton transfer pathways based on the large-space interlayer of montmorillonite and strong-hydration Pr3+ additive in AZMBs. Proton conduction is deeply understood in this quasi-solid electrolyte. Pr3+ additive not only dominates the proton conduction kinetics, but also regulates the reversible manganese interfacial deposition. As a result, the Cu@Zn||α-MnO2 cell could achieve a high specific capacity of 433 mAh g-1 at 0.4 mA cm-2 and an excellent stability up to 800 cycles with a capacity retention of 92.2% at 0.8 mA cm-2 in such water-poor quasi-solid electrolyte for the first time. Ah-scale pouch cell with mass loading of 15.19 mg cm-2 sustains 100 cycles after initial activation, which is much better than its counterparts. Our work provides a new path for the development of zinc metal batteries with good sustainability and practicality.

Balancing Brightness and Photobasicity: Modulating Excited-State Proton Transfer Pathways in Push-Pull Fluorophores for Biological Two-Photon Imaging.

Push-pull fluorophores with donor-π-acceptor architectures are attractive scaffolds for the design of probes and labels for two-photon microscopy. Such fluorophores undergo a significant charge-delocalization in the excited state, which is essential for achieving a large two-photon absorption cross-section and brightness. The polarized excited state may, however, also facilitate excited-state proton transfer (ESPT) pathways that can interfere with the probe response. Herein, we employed steady-state and time-resolved spectroscopic studies to elucidate whether ESPT is responsible for the pH-dependent emission response of the Zn(II)-selective fluorescent probe chromis-1. Composed of a push-pull architecture with a pyridine ring as the acceptor, the chromis-1 fluorophore core acts as a photobase that promotes ESPT upon acidification. Although the pKa of the pyridine acceptor increases more than six orders of magnitude upon excitation, the photobasicity is not sufficient to deprotonate solvent water molecules under neutral conditions. Rather, the pH-dependent emission response is caused by the pendant bis-isonicotinic acid chelating group which upon protonation facilitates an excited-state intramolecular proton transfer to the pyridine acceptor. A simple permutation of the core pyridine nitrogen from the para- to the ortho-position relative to the thiazole substituent was sufficient to reduce the excited-state basicity by two orders of magnitude without compromising the two-photon excited brightness. These results highlight the importance of choosing the appropriate fluorophore core and chelating moiety for minimizing pH-dependent responses in the design of fluorescent probes for biological imaging.

Role of H2O2 as Oxidant and H2O as Co-Catalyst Over Anatase-TiO2(101) for Conversion of Methane to Methanol.

Computations based on density functional theory are carried out to examine the mechanism of photocatalytic oxidation of methane to methanol with H2O2 as oxidant and water as co-catalyst over anatase TiO2(101) surface. The reaction proceeds with hydrogen abstraction from methane followed by the formation of surface methoxy species, which is reduced to methanol. We compare the reaction energetics for C-H dissociation in the presence and absence of surface defect, but find no discernible impact of O-vacancy on methane oxidation. In comparison, hydroxyl produced as a result of H2O2 or H2O photo-decomposition dramatically reduces the barrier for CH3-H bond cleavage. The reaction proceeds further by the reduction of surface methoxy group and is the rate-limiting step for methanol formation. Additionally, we find that methyl can also react with water to form methanol with a considerably lower barrier, suggesting an active involvement of water for methanol formation. We also study the role of water as a co-catalyst and observe significant reduction in barriers, facilitated by alternate pathway for proton transfer. The reaction pathways presented provide valuable insights into the mechanism of methane oxidation in the presence of H2O2 as oxidant and demonstrate the rate-enhancing role of water for these steps.

Computational Studies of Nucleophilic Substitution at Nitrogen Center: Reactions of NH2Cl with HO-, CH3O- and C2H5O.

The atomic-level mechanisms of the nucleophilic substitution reactions at the nitrogen center (SN2@N) were investigated for the reactions of chloramine (NH2Cl) with the alkoxide ions (RO-, where R=H, CH3, and C2H5) using DFT and MP2 methods. The computed potential energy profiles for the SN2@N pathways involving the back-side attack of the nucleophiles show the typical double-well potential with submerged barriers similar to the SN2 reactions at the carbon center (SN2@C). However, the pre-reaction and post-reaction complexes are, respectively, the N-H⋅⋅⋅O and N-H⋅⋅⋅Cl hydrogen-bonded intermediates, which are different from those generally seen in SN2@C reactions. The SN2@N pathways involving front-side attack of the nucleophiles have high-energy barriers. The potential energy surfaces (PESs) along the proton-transfer pathways were flat. In addition to the proton-transfer and SN2 pathways, we also observed a new path for the methoxide and ethoxide nucleophiles where a hydride-transfer from the nucleophile to chloramine resulted in the products Cl-+R'CHO+NH3, (R'=H, CH3), and was the most exoergic. A comparison of the energetics obtained used different DFT and MP2 methods with that of the benchmark coupled-cluster methods reveals that CAM-B3LYP best describes the PESs.

Regulating Local Electron Distribution of Cu Electrocatalyst via Boron Doping for Boosting Rapid Absorption and Conversion of Nitrate to Ammonia

AbstractThe electrochemical reduction of nitrate to ammonia (NO3RR) is an effective route to ammonia synthesis with the characteristics of low energy input. However, the complex multi‐electron/proton transfer pathways associated with this reaction may trigger the accumulation of competitive by‐products. Herein, boron (B)‐doped Cu electrode (denoted as B–Cu2O/Cu/CP) as “all‐in‐one” catalyst is prepared by one‐step electrodeposition strategy. Caused by the B doping, the charge redistribution and local coordination environment of Cu2O/Cu species are modulated, resulting in the exposure of active sites on the Cu2O/Cu/CP catalyst. In‐situ Fourier transform infrared spectroscopy and theoretical investigations demonstrate that both Cu2O and Cu sites modulated by B can effectively enhance the adsorption of NO3− and facilitate the conversion of intermediate by‐products, thus promoting the direct reduction of NO3− to NH3. Consequently, a remarkable Faradaic efficiency of 92.74% can be obtained on B–Cu2O/Cu/CP catalyst with minimal accumulation of by‐products. It is expected that this work, based on the heterogeneous B doping, will open a maneuverable and versatile way for the design of effective catalysts.

Intermolecular Proton Transfer Enabled Reactive CO2 Capture by the Malononitrile Anion.

Task-specific ionic liquids (ILs) employing carbanions represent a new class of ILs for carbon capture. The deprotonated malononitrile carbanion, [CH(CN)2]-, has shown close to equimolar capacity for reactive CO2 capture. Although the formation of the [C(CN)2COOH]- carboxylic acid was found to be the final product, how the hydrogen atom on the [CH(CN)2]- carbanion transfers to the carboxylate group as a proton has not been fully understood. In this work, we employ density functional theory calculations with an implicit solvation model to investigate the proton transfer mechanisms in forming carboxylic acid from the reaction of the [CH(CN)2]- carbanion with CO2. We find that the intramolecular proton-transfer pathway in [CH(CN)2COO]- to form [C(CN)2COOH]- is unlikely due to the high energy barrier of 152 kJ/mol. Instead, the intermolecular proton transfer pathway between two [CH(CN)2COO]- anions is more feasible to form two molecules of [C(CN)2COOH]-, with a significantly lower activation energy of 50 kJ/mol. Moreover, the [C(CN)2COOH]- dimer is further stabilized by the intermolecular hydrogen bonds of the two -COOH groups in the Z-configuration of the π-conjugated planar geometry. This insight of reactive CO2 capture enabled by intermolecular proton transfer will be useful in designing novel carbanions and ILs for carbon capture and conversion.

Modulating the Leverage Relationship in Nitrogen Fixation Through Hydrogen‐Bond‐Regulated Proton Transfer

In the electrochemical nitrogen reduction reaction (NRR), a leverage relationship exists between NH3‐producing activity and selectivity because of the competing hydrogen evolution reaction (HER), which means that high activity with strong protons adsorption causes low product selectivity. Herein, we design a novel metal‐organic hydrogen bonding framework (MOHBF) material to modulate this leverage relationship by a hydrogen‐bond‐regulated proton transfer pathway. The MOHBF material was composited with reduced graphene oxide (rGO) to form a Ni‐N2O2 molecular catalyst (Ni‐N2O2/rGO). The unique structure of O atoms in Ni‐O‐C and N‐O‐H could form hydrogen bonds with H2O molecules to interfere with protons being directly adsorbed onto Ni active sites, thus regulating the proton transfer mechanism and slowing the HER kinetics, thereby modulating the leverage relationship. Moreover, this catalyst has abundant Ni‐single‐atom sites enriched with Ni‐N/O coordination, conducive to the adsorption and activation of N2. The Ni‐N2O2/rGO exhibits simultaneously enhanced activity and selectivity of NH3 production with a maximum NH3 yield rate of 209.7 μg h−1 mgcat.−1 and a Faradaic efficiency of 45.7%, outperforming other reported single‐atom NRR catalysts.

Tandem Proton Transfer in Carboxylated Supramolecular Polymer for Highly Efficient Overall Photosynthesis of Hydrogen Peroxide.

Proton supply is as critical as O2 activation for artificial photosynthesis of hydrogen peroxide (H2O2) via two-electron oxygen reduction reaction (2e- ORR). However, proton release via water dissociation is frequently hindered because of the sluggish water oxidation reaction (WOR), extremely limiting the efficiency of photocatalytic H2O2 production. To tackle this challenge, carboxyl-enriched supramolecular polymer (perylene tetracarboxylic acid-PTCA) is elaborately prepared by molecular self-assembly for overall photosynthesis of H2O2. Interestingly, the interconversion between carboxyl as Brønsted acid and its conjugated base realizes rapid proton circulation. Through this efficient tandem proton transfer process, the spatial effect of photocatalytic reduction and oxidation reaction is greatly enhanced with reduced reaction barrier. This significantly facilitates 2e- photocatalytic ORR to synthesize H2O2 and in the meanwhile promotes 4e- photocatalytic WOR to evolve O2. Consequently, the as-developed PTCA exhibits a remarkable H2O2 yield of 185.6 μM h-1 in pure water and air atmosphere under visible light illumination. More impressively, an appreciable H2O2 yield of 78.6 μM h-1 can be well maintained in an anaerobic system owing to in situ O2 generation by 4e- photocatalytic WOR. Our study presents a novel concept for artificial photosynthesis of H2O2 via constructing efficient proton transfer pathway to enable rapid proton circulation.

Tandem Proton Transfer in Carboxylated Supramolecular Polymer for Highly Efficient Overall Photosynthesis of Hydrogen Peroxide

AbstractProton supply is as critical as O2 activation for artificial photosynthesis of hydrogen peroxide (H2O2) via two‐electron oxygen reduction reaction (2e− ORR). However, proton release via water dissociation is frequently hindered because of the sluggish water oxidation reaction (WOR), extremely limiting the efficiency of photocatalytic H2O2 production. To tackle this challenge, carboxyl‐enriched supramolecular polymer (perylene tetracarboxylic acid—PTCA) is elaborately prepared by molecular self‐assembly for overall photosynthesis of H2O2. Interestingly, the interconversion between carboxyl as Brønsted acid and its conjugated base realizes rapid proton circulation. Through this efficient tandem proton transfer process, the spatial effect of photocatalytic reduction and oxidation reaction is greatly enhanced with reduced reaction barrier. This significantly facilitates 2e− photocatalytic ORR to synthesize H2O2 and in the meanwhile promotes 4e− photocatalytic WOR to evolve O2. Consequently, the as‐developed PTCA exhibits a remarkable H2O2 yield of 185.6 μM h−1 in pure water and air atmosphere under visible light illumination. More impressively, an appreciable H2O2 yield of 78.6 μM h−1 can be well maintained in an anaerobic system owing to in situ O2 generation by 4e− photocatalytic WOR. Our study presents a novel concept for artificial photosynthesis of H2O2 via constructing efficient proton transfer pathway to enable rapid proton circulation.

A Competition among Three Ultrafast Photoinduced Events in Thiotropolone: Internal Conversion vs Intersystem Crossing vs ESIPT.

Gas phase excited-state quantum wavepacket dynamics simulations of the thiotropolone demonstrate the ultrafast triplet formation upon photoexcitation to the dipole-allowed S2 state. The dominant relaxation pathway of the S2-T4 intersystem crossing, facilitated by the strong spin-orbit coupling and narrow energy gap, competes with the S2 to S1/S3 internal conversion. The wavepacket populated in T4 via the former pathway decays to lower triplet states. Computed potential energy profiles suggest proton transfer via S2, which might compete with internal conversion and intersystem crossing. The nonadiabatic population transfer from the S2 to S1/S3 states enables proton transfer via the latter states, resulting in multiple proton transfer pathways. Experimental investigations are necessary to shed light on the complex ultrafast photodynamics of thiotropolone.

Searching for proton transfer channels in respiratory complex I

We have explored a strategy to identify potential proton transfer channels using computational analysis of a protein structure based on Voronoi partitioning and applied it for the analysis of proton transfer pathways in redox-driven proton-pumping respiratory complex I. The analysis results in a network of connected voids/channels, which represent the dual structure of the protein; we then hydrated the identified channels using our water placement program Dowser++. Many theoretical water molecules found in the channels perfectly match the observed experimental water molecules in the structure; some other predicted water molecules have not been resolved in the experiments. The channels are of varying cross sections. Some channels are big enough to accommodate water molecules that are suitable to conduct protons; others are too narrow to hold water but require only minor conformational changes to accommodate proton transfer. We provide a preliminary analysis of the proton conductivity of the network channels, classifying the proton transfer channels as open, closed, and partially open, and discuss possible conformational changes that can modulate, i.e., open and close, the channels.

CdS Quantum Dot Gels as a Direct Hydrogen Atom Transfer Photocatalyst for C-H Activation.

Here, we report CdS quantum dot (QD) gels, a three-dimensional network of interconnected CdS QDs, as a new type of direct hydrogen atom transfer (d-HAT) photocatalyst for C-H activation. We discovered that the photoexcited CdS QD gel could generate various neutral radicals, including α-amido, heterocyclic, acyl, and benzylic radicals, from their corresponding stable molecular substrates, including amides, thio/ethers, aldehydes, and benzylic compounds. Its C-H activation ability imparts a broad substrate and reaction scope. The mechanistic study reveals that this reactivity is intrinsic to CdS materials, and the neutral radical generation did not proceed via the conventional sequential electron transfer and proton transfer pathway. Instead, the C-H bonds are activated by the photoexcited CdS QD gel via a d-HAT mechanism. This d-HAT mechanism is supported by the linear correlation between the logarithm of the C-H bond activation rate constant and the C-H bond dissociation energy (BDE) with a Brønsted slope α=0.5. Our findings expand the currently limited direct hydrogen atom transfer photocatalysis toolbox and provide new possibilities for photocatalytic C-H activation.

CdS Quantum Dot Gels as a Direct Hydrogen Atom Transfer Photocatalyst for C−H Activation

AbstractHere, we report CdS quantum dot (QD) gels, a three‐dimensional network of interconnected CdS QDs, as a new type of direct hydrogen atom transfer (d‐HAT) photocatalyst for C−H activation. We discovered that the photoexcited CdS QD gel could generate various neutral radicals, including α‐amido, heterocyclic, acyl, and benzylic radicals, from their corresponding stable molecular substrates, including amides, thio/ethers, aldehydes, and benzylic compounds. Its C−H activation ability imparts a broad substrate and reaction scope. The mechanistic study reveals that this reactivity is intrinsic to CdS materials, and the neutral radical generation did not proceed via the conventional sequential electron transfer and proton transfer pathway. Instead, the C−H bonds are activated by the photoexcited CdS QD gel via a d‐HAT mechanism. This d‐HAT mechanism is supported by the linear correlation between the logarithm of the C−H bond activation rate constant and the C−H bond dissociation energy (BDE) with a Brønsted slope α=0.5. Our findings expand the currently limited direct hydrogen atom transfer photocatalysis toolbox and provide new possibilities for photocatalytic C−H activation.

Elucidation of the stereochemical mechanism of cystathionine γ-lyase reveals how substrate specificity constrains catalysis.

Pyridoxal phosphate (PLP)-dependent enzymes play essential roles in metabolism and have found applications for organic synthesis and as enzyme therapeutics. The vinylglycine ketimine (VGK) subfamily hosts a growing set of enzymes that play diverse roles in primary and secondary metabolism. However, the molecular determinates of substrate specificity and the complex acid-base chemistry that enables VGK catalysis remain enigmatic. We use a recently discovered amino acid γ-lyase as a model system to probe catalysis in this enzyme family. We discovered that two stereochemically distinct proton transfer pathways occur. Combined kinetic and spectroscopic analysis revealed that progression through the catalytic cycle is correlated with the presence of an H-bond donor after Cγ of an amino acid substrate, suggesting substrate binding is kinetically coupled to a conformational change. High-resolution X-ray crystallography shows that cystathionine-γ-lyases generate an s-trans intermediate and that this geometry is likely conserved throughout the VGK family. An H-bond acceptor in the active site templates substrate binding but does so by pre-organizing substrates away from catalytically productive orientations. Mutagenesis eliminates this pre-organization, such that there is a relaxation of the substrate specificity, but an increase in k cat for diverse substrates. We exploit this information to perform preparative scale α,β,β-tri-deuteration of polar amino acids. Together, these data untangle a complex mode of substrate specificity and provide a foundation for the future study and applications of VGK enzymes.

An affordable convertible: Engineering proton transfer pathways in microbial rhodopsins

An affordable convertible: Engineering proton transfer pathways in microbial rhodopsins