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DOE OSTI2024

The structural OFF and ON states of myosin can be decoupled from the biochemical super- and disordered-relaxed states

Abstract There is a growing awareness that both thick-filament and classical thin-filament regulations play central roles in modulating muscle contraction. Myosin ATPase assays have demonstrated that under relaxed conditions, myosin may reside either in a high-energy-consuming disordered-relaxed (DRX) state available for binding actin to generate force or in an energy-sparing super-relaxed (SRX) state unavailable for actin binding. X-ray diffraction studies have shown that the majority of myosin heads are in a quasi-helically ordered OFF state in a resting muscle and that this helical ordering is lost when myosin heads are turned ON for contraction. It has been assumed that myosin heads in SRX and DRX states are equivalent to the OFF and ON states, respectively, and the terms have been used interchangeably. In this study, we use X-ray diffraction and ATP turnover assays to track the structural and biochemical transitions of myosin heads, respectively, induced with either omecamtiv mecarbil (OM) or piperine in relaxed porcine myocardium. We find that while OM and piperine induce dramatic shifts of myosin heads from the OFF to the ON state, there are no appreciable changes in the population of myosin heads in the SRX and DRX states in both unloaded and loaded preparations. Our results show that biochemically defined SRX and DRX can be decoupled from structurally defined OFF and ON states. In summary, while SRX/DRX and OFF/ON transitions can be correlated in some cases, these two phenomena are measured using different approaches, reflect different properties of the thick filament, and should be investigated and interpreted separately.

Jani, Vivek P. (ORCID:0000000238114973)↗

DOE OSTI2020

The potential application of VS 2 as an electrode material for Mg ion battery: A DFT study

Herein, by means of first-principle calculations based on density functional theory (DFT), the electrochemical properties of monolayer VS 2 (M-VS 2 ), double-layer VS 2 (D-VS 2 ) and bulk VS 2 (B-VS 2 ) as electrode materials for Mg-ion batteries (MIBs) were comprehensively explored. The computation results reveal that Mg atom can strongly bind with the three different forms of VS 2 . All of the Mg adsorbed VS 2 systems demonstrate metallic characteristics, which indicates a good electronic conductivity. In addition, crystal orbital hamiltonian population shows that the stability of V-S bond is weakened after adsorption of Mg atom. The low diffusion barriers of Mg give rise to the high rate performance of VS 2 in MIBs. More interestingly, the three types of VS 2 display same storage ability for Mg cations, which can adsorb 0.5 Mg atoms for VS 2 , producing maximum theoretical capacity 233 mA h g -1 for MIBs. Furthermore, the average working voltages results suggest that M-VS 2 can be employed as anode materials, while D-VS 2 , B-VS 2 can be used as cathode materials for MIBs.

25 ENERGY STORAGE↗

DOE OSTI2021

Experimental and calculated infrared spectra of disubstituted naphthoquinones

In recent years there has been interest in incorporating substituted 1,4-naphthoquinones (NQs) into the A 1 binding site in photosystem I (PSI) photosynthetic protein complexes. This interest in part stems from the considerably altered bioenergetics of electron transfer that occur in PSI with such substitutions. Time resolved FTIR studies of PSI complexes with disubstituted NQs incorporated have and currently are being undertaken, and with this in mind it is worth considering FTIR absorption spectra of these disubstituted NQs in solution. Here we present FTIR absorbance spectra for 2-bromo-3-methyl-1,4-naphthoquinone (BrMeNQ), 2-chloromethyl-3-methyl-1,4-naphthoquinone (CMMeNQ) and 2-ethylthio-3-methyl-1,4-naphthoquinone (ETMeNQ) in tetrahydrofuran (THF). The FTIR spectra of these di-substituted naphthoquinones (NQs) were compared to FTIR spectra of 2-methyl-3-phytyl-1,4-naphthoquinone [phylloquinone (PhQ)], 2,3-dimethyl-1,4-naphthoquinone (DMNQ), and 2-methyl-1,4-naphthoquinone (2MNQ). To aid in the assignment of bands in the experimental spectra, density functional theory (DFT) based vibrational frequency calculations for all the substituted NQs in solution were undertaken. The calculated and experimental spectra agree well. By calculating normal mode potential energy distributions, unambiguous quantitative band assignments were made. The calculated and experimental spectra together make predictions about what may be observable in time resolved FTIR difference spectra obtained using PSI with the different NQs incorporated. As a result, time resolved FTIR difference spectra are presented that support these predictions.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2020

Binding of Formic Acid on Anatase TiO2(101)

The adsorption of formic acid (FA) and the formation of formate species on metal oxide surfaces are of great interest in catalysis. Formic acid is used to probe the adsorption properties of surface sites and formates are common intermediates in many catalytic reactions. Here we focus on the interaction of FA with a prototypical anatase TiO2(101) surface by using a combination of scanning tunneling microscopy (STM), infrared reflection absorption spectroscopy (IRAS), electron stimulated desorption (ESD), and density functional theory (DFT) to assess the coverage dependent evolution of different FA-derived surface species at low temperatures (80–240 K). We find that isolated FA adsorbs at 80 K in both monodentate (MD) and bidentate (BD) configurations on top of undercoordinated Ti sites (Ti5c). The MD form is likely deprotonated and readily converts upon annealing to bridging BD on two neighboring Ti5c sites. DFT calculations show that molecularly-bound MD FA is metastable and readily converts into a deprotonated state in the proximity of subsurface oxygen vacancy. The stability of the MD species increases as the availability of the paired Ti5c sites for BD formation diminishes at high coverages. Upon surface saturation, a mixed configuration of alternating bidentate and monodentate species with coverage of 2/3 FA/Ti5c represents the most favorable configuration. This is in contrast with the adsorption of FA on rutile TiO2(110) and many other oxides, where bidentate formate species dominate. Y.W., A.D., G.A.K., R.R., N.G.P., and Z.D. were supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (CSGB) under FWP 47319. B.W. and A.S. acknowledge the support of DOE BES, CSGB Division under Award DESC0007347. The experimental studies were performed in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle. The authors also acknowledge computational resources from the TIGRESS high-performance computer center at Princeton University.

Wang, Yang↗

DOE OSTI2022

Density matrix renormalization group description of the island of inversion isotopes F 28 – 33

Recent experiments have confirmed that the neutron-rich isotopes 28,29 F belong to the so-called island of inversion (IOI), a region of the nuclear chart around Z = 10 and N = 20 where nuclear structure deviates from the standard shell model predictions due to deformation and continuum effects. However, while the general principles leading to the IOI are relatively well understood, the details of the low-lying structure of the exotic fluorine isotopes 28–33 F are basically unknown. In this study, we perform large-scale shell model calculations including continuum states to investigate the properties of the neutron-rich isotopes 25–33 F, from a core of 24 O and using an effective two-body interaction with a small number of adjustable parameters in the central and tensor channels. We develop two models adjusted on experimentally confirmed states in 25,26 O and 25–27 F based on different assumptions concerning the positions of the neutron 0d 3/2 and 1p 3/2 shells, and solve the many-body problem using the density matrix renormalization group (DMRG) method for open quantum systems in an sd–fp model space. We obtain the first detailed spectroscopy of 25–33F in the continuum and show how the interplay between continuum effects and deformation explains the recent data on 28,29 F. Several deformed one- and two-neutron halo states are predicted in 29,31 F, and we provide some information about the possible structure of the heaviest fluorine isotopes. We also suggest several experimental studies of interest to constraint models and test the present predictions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRSDate not supplied

REACTER 2.0: Quantum-Informed Reaction Constraints and Automated Interaction Typing

REACTER is a heuristic method for modeling chemical reactions in classical molecular dynamics simulations, implemented in LAMMPS as fix bond/react. The authors recently extended LAMMPS to support alphanumeric labels for atom types, bond types etc., which enables the pre- and post-reaction templates required by the REACTER protocol to be portable between different simulations and greatly simplifies the task of creating simulation-ready reaction templates. To further increase the generality of reaction templates, support for wildcard characters within atom types has been added, along with the automatic assignment of interaction types for new bonds, angles, etc. based on the involved atom types. In some cases, this feature can express a class of reactions with one pair of reaction templates, where previously dozens may have been required. Advanced reaction constraints have also been added, including an Arrhenius constraint to enforce an effective activation energy, a root-mean-square-deviation option for complex geometrical constraints, as well as a custom constraint that leverages LAMMPS’ powerful built-in variable framework. Other new features include variable support for various inputs (e.g., to allow reaction rates or cutoffs to be dependent on overall conversion), on-the-fly update of molecule IDs, and the ability to create new atoms positioned with respect to the reaction site. The new features are applied to modeling polymeric, thermosetting and composite materials, and advanced applications of the new reaction constraints are demonstrated. For example, REACTER is shown to accurately reproduce mechanically-induced bond breaking, as characterized by third-order DFT-based tight-binding (DFTB3) simulations, via a constraint on the total potential energy of the involved atoms.

polymer simulations↗

DOE OSTI2021

Complexation of Lanthanides and Heavy Actinides with Aqueous Sulfur-Donating Ligands

The separation of trivalent lanthanides and actinides is challenging because of their similar sizes and charge densities. S-donating extractants have shown significant selectivity for trivalent actinides over lanthanides, with single-stage americium/ lanthanide separation efficiencies for some thiol-based extractants reported at >99.999%. While such separations could transform the nuclear waste management landscape, these systems are often limited by the hydrolytic and radiolytic stability of the extractant. Progress away from thiol-based systems is limited by the poorly understood and complex interactions of these extractants in organic phases, where molecular aggregation and micelle formation obfuscates assessment of the metal–extractant coordination environment. Because S-donating thioethers are generally more resistant to hydrolysis and oxidation and the aqueous phase coordination chemistry is anticipated to lack complications brought on by micelle formation, we have considered three thioethers, 2,2'-thiodiacetic acid (TDA), (2R,5S)- tetrahydrothiophene-2,5-dicarboxylic acid, and 2,5-thiophenedicarboxylic acid (TPA), as possible trivalent actinide selective reagents. Formation constants, extended X-ray absorption fine structure spectroscopy, and computational studies were completed for thioether complexes with a variety of trivalent lanthanides and actinides including Nd, Eu, Tb, Am, Cm, Bk, and Cf. TPA was found to have moderately higher selectivity for the actinides because of its ability to bind actinides in a different manner than lanthanides, but the utility of TPA is limited by poor water solubility and high rigidity. While significant competition with water for the metal center limits the efficacy of aqueous-based thioethers for separations, the characterization of these solution-phase, S-containing lanthanide and actinide complexes is the most comprehensively available in the literature to date. Here, this is due to the breadth of lanthanides and actinides considered as well as the techniques deployed and serves as a platform for the further development of Scontaining reagents for actinide separations. Additionally, this paper reports on the first bond lengths for Cf and Bk with a neutral S donor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Gas-phase stability of large lanthanide:diglycolamide clusters evaluated using collision-induced dissociation

Efficient utilization of long-term deep geologic storage repositories is critical for the large-scale deployment of nuclear energy. As the minor actinides (americium and curium) are the largest contributor to the decay heat of used nuclear fuel after a few hundred years, their removal from used fuel prior to disposal can significantly increase the amount of waste that can be stored in a given volume. The development of ligands that can effectively separate the minor actinides from other components of used nuclear fuel are crucial to efficient utilization of geological storage repositories. N,N,N’,N’-tetraoctyl diglycolamide (TODGA) is a promising extractant for the separation of lanthanides and the minor actinides from other components of used nuclear fuel. While the use of TODGA in f-element separations has been investigated in process-based formulations, gas-phase metal ion cluster experiments enable the study of covalent interactions in reprocessing systems absent from solvent effects. Exploring fundamental differences in lanthanide-ligand covalent interactions can impact the development and implementation of actinide-lanthanide separation systems in nuclear fuels reprocessing. In this study, lanthanide-TODGA clusters were synthesized in the gas-phase and identified using mass spectrometry fragmentation experiments. Large europium and samarium clusters were identified that contained up to 8 and 10 bound TODGA ligands, respectively; this was surprising due to the size and multidentate binding that is normal for TODGA. In addition, while smaller clusters showed evidence of sequential ligand fragmentation, larger clusters displayed the loss of neutral TODGA with applied collision voltage. Interestingly, the voltage required for this removal decreased as more TODGA ligands were bound to the metal, suggesting that the metal coordination sphere was becoming more saturated and TODGA ligands were more weakly bound as the clusters got larger.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

NASA NTRS1991

Structure and functions of water-membrane interfaces and their role in proto-biological evolution

Among the most important developments in proto-biological evolution was the emergence of membrane-like structures. These are formed by spontaneous association of relatively simple amphiphilic molecules that would have been readily available in the primordial environment. The resulting interfacial regions between water and nonpolar interior of the membrane have several properties which made them uniquely suitable for promoting subsequent evolution. They can (1) selectively attract organic material and mediate its transport, (2) serve as simple catalysts for chemical reactions, and (3) promote the formation of trans-membrane electrical and chemical gradients which could provide energy sources for proto-cells. Understanding the structure of interfaces, their interactions with organic molecules and molecular mechanisms of their functions is an essential step to understanding proto-biological evolution. In our computer simulation studies, we showed that the structure of water at interfaces with nonpolar media is significantly different from that in the bulk. In particular, the average surface dipole density points from the vapor to the liquid. As a result, negative ions can approach the interface more easily than positive ions. Amphiphilic molecules composed of hydrocarbon conjugated rings and polar substituents (e.g., phenol) assume at the interface rigid orientations in which polar groups are buried in water while hydrocarbon parts are located in the nonpolar environment. These orientational differences are of special interest in connection with the ability of some of these molecules to efficiently absorb photons. Flexible molecules with polar substituents often adopt at interfaces conformations different from those in the bulk aquaeous solution and in the gas phase. As a result, in many instances both specificity and kinetics of chemical reactions in which these molecules can participate is modified by the presence of surfaces. Of special interest is the mechanism by which polar molecules are transferred across interface between water and a nonpolar medium. Our recent study showed that simple ionophores bind ions by the same mechanisms as ion channels and carriers from modern cells.

Pohorille, A.↗

DOE OSTI2020

Adhesive Polymers as Efficient Binders for High-Capacity Silicon Electrodes

The major cause for capacity fading of silicon nanoparticle (SiNP)-based electrodes is the immense pressure applied toward the conductive networks during the charge/discharge process. While numerous efforts have been devoted to investigating different types of polymer binders, the rational design of an adhesive binder with pressure sensitivity has rarely been reported. Herein, a series of pressure-sensitive adhesives (PSAs) synthesized via copolymerization of 2-ethylhexyl acrylate (2-EHA) and acrylic acid (AA) are evaluated as polymer binders for SiNP-based electrodes. The balance between the density of interaction groups and viscoelastic properties is systematically investigated for efficient binding performance. The SiNP-based electrode using PSA with 20 mol % of 2-EHA (Si-PSA-20%) exhibits excellent electrochemical performance, achieving a capacity retention of 83% at the 100th cycle compared with 54% for Si-PAA after activation. Si-PSA-20% also delivers a superior cycling performance at a high current density (1731 mAh g –1 after 350 cycles vs 719 mAh g –1 after 150 cycles for Si-PAA, 1.8 A g –1 ) and at high mass loading of active materials (capacity retention of 74 vs 38% for Si-PAA after 100 cycles, SiNP content ~1.2 mg cm –2 ). Atomic force microscopy (AFM), peel tests, and Car–Parrinello molecular dynamics (CPMD) simulations are employed to understand their binder performance. The novel design and systematical investigation of PSAs as binders will definitely be appealing for not only the Si electrode but also for other high-energy-density electrode materials.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Quantum Monte Carlo Approaches to Na Intercalation on Bilayer Graphene

We have performed Quantum Monte Carlo (QMC) simulations on Na-intercalated bilayer graphene to study the evolution of electronic and optical properties upon Na intercalation into hard carbon layers. The objective was to model the optimal configuration of Na intercalation into a hard carbon matrix containing graphene regions. Our study showed that Na intercalation can be energetically stabilized at large interlayer distances (over 6 Å) in both AA- and AB-stacked bilayer graphene. In the QMC results, we found a significant band gap opening at the equilibrium interlayer distance of Na-intercalated bilayer graphene, while corresponding density functional theory (DFT) results showed no gap. This difference between DFT and QMC results indicates that the gap opening induced by Na intercalation into a hard carbon is underestimated within the DFT framework. In addition, a zigzag configuration of Na atoms was found to be energetically stable at interlayer distances up to 10 Å, leading us to predict the existence of a local minimum of Na intercalation at large interlayer distance. These computation and modeling results can provide guidance on how to synthesize and optimize hard carbon with bilayer graphene regions that permit a zigzag intercalation configuration that will maximize and stabilize sodium hosting.

Binding energy↗

DOE OSTI2024

Investigating Cu-Site Doped Cu–Sb–S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy

Tetrahedrite (Cu 12 Sb 4 S 13 ) and famatinite (Cu 3 SbS 4 ) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu–Cu spin exchange or spin–lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Twisted symmetric trilayer graphene: Single-particle and many-body Hamiltonians and hidden nonlocal symmetries of trilayer moiré systems with and without displacement field

Here, we derive the Hamiltonian for trilayer moiré systems with the Coulomb interaction projected onto the bands near the charge neutrality point. Motivated by the latest experimental results, we focus on the twisted symmetric trilayer graphene (TSTG) with a mirror symmetry with respect to the middle layer. We provide a full symmetry analysis of the noninteracting Hamiltonian with a perpendicular displacement field coupling the band structure made otherwise of the twisted bilayer graphene (TBG) and the high-velocity Dirac fermions, and we identify a hidden nonlocal symmetry of the problem. In the presence of this displacement field, we construct an approximate single-particle model, akin to the tripod model for TBG, capturing the essence of noninteracting TSTG. We also derive more quantitative perturbation schemes for the low-energy physics of TSTG with displacement field, obtaining the corresponding eigenstates. This allows us to obtain the Coulomb interaction Hamiltonian projected in the active band TSTG wave functions and derive the full many-body Hamiltonian of the system. We also provide an efficient parametrization of the interacting Hamiltonian. Finally, we show that the discrete symmetries at the single-particle level promote the U (2) × U (2) spin-valley symmetry to enlarged symmetry groups of the interacting problem under different limits. The interacting part of the Hamiltonian exhibits a large U (4) × U (4) × U (4) × U (4) symmetry in the chiral limit. Moreover, by identifying a symmetry which we dub spatial many-body charge conjugation, we show that the physics of TSTG is symmetric around charge neutrality.

2-dimensional systems↗

DOE OSTI2022

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗

DOE OSTI2021

Rationalization of promoted reverse water gas shift reaction by Pt 3 Ni alloy: Essential contribution from ensemble effect

Bimetallic alloys have attracted considerable attention due to the tunable catalytic activity and selectivity that can be different from those of pure metals. Here, we study the superior catalytic behaviors of the Pt 3 Ni nanowire (NW) over each individual, Pt and Ni NWs during the reverse Water Gas Shift (rWGS) reaction, using density functional theory. The results show that the promoted rWGS activity by Pt3Ni strongly depends on the ensemble effect (a particular arrangement of active sites introduced by alloying), while the contributions from ligand and strain effects, which are of great importance in electrocatalysis, are rather subtle. As a result, a unique Ni–Pt hybrid ensemble is observed at the 110/111 edge of the Pt 3 Ni NW, where the synergy between Ni and Pt sites is active enough to stabilize carbon dioxide on the surface readily for the rWGS reaction but moderate enough to allow for the facile removal of carbon monoxide and hydrogenation of hydroxyl species. Furthermore, our study highlights the importance of the ensemble effect in heterogeneous catalysis of metal alloys, enabling selective binding–tuning and promotion of catalytic activity.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2025

Pd–Methyl Bond Energy─Property Correlations, Noncorrelations, Machine Learning Models, and Application to Polymerization Catalysis

Metal–carbon bonds are a key intermediate in a variety of homogeneous organometallic transformations and often determine the critical thermodynamics and kinetics of catalytic processes. Surprisingly, the influence of different ligands on metal–carbon bond strengths has been largely overlooked. Here, in this study, we evaluated nearly 700 experimental Pd–methyl complexes by calculating their bond dissociation energies using density functional theory (DFT) and compared these bond strengths to several fundamental molecular properties, and this revealed several surprising correlations and noncorrelations. Most surprising was that several fundamental properties, such as the bond length, bond force constant, and bond electron density, have no correlation with bond strength, despite these correlations often holding for main-group compounds. We were indeed able to identify key ligand-dependent chemical features/descriptors that provided a highly accurate machine learning model and provided insight into the general factors that control the Pd–carbon bond strength, such as radical delocalization and nucleophilicity. Insights gained from the Pd–Me bond energy analysis were then applied to CO migratory insertion steps that are part of copolymerization reactions.

binding energy↗

NASA NTRS2002

Assembly of Colloidal Materials Using Bioadhesive Interactions

We have pursued the use of biological crosslinking molecules of several types to make colloidal materials at relatively low volume fraction of colloidal particles. The objective is to make binary alloys of colloidal particles, made of two different colloidal particles coated with complementary biological lock-and-key binding molecules, which assemble due to the biological specificity. The long-term goal is to use low affinity lock-and-key biological interactions, so that the can anneal to form crystalline states. We have used a variety of different surface chemistries in order to make colloidal materials. Our first system involved using selectin-carbohydrate (sialyl-Lewis) interactions; this chemistry is derived from immune system. This chemical interaction is of relatively low affinity, with timescales for dissociation of several seconds. Furthermore, the adhesion mediated by these molecules can be reversed by the chelation of calcium atoms; thus assembled structures can be disassembled reversibly. Our second system employed avidin-biotin chemistry. This well-studied system is of high affinity, and is generally irreversible on a laboratory time-scale. Thus, we would expect selectin-carbohydrate interactions at high molecular density and avidin-biotin interactions to give kinetically-trapped structures; however, at low densities, we would expect significant differences in the structure and dynamics of the two materials, owing to their very different release rates. We have also begun to use a third chemistry - DNA hybridization. By attaching single stranded DNA oligonucleotide chains to beads, we can drive the assembly of colloidal materials by hybridization of complementary DNA chains. It is well known that DNA adenosine-thymine (A-T) and guanine-cytosine (G-C) bases hybridize pairwise with a Gibbs free energy change of 1.7 kcal/mol per base; thus, the energy of the assembly can be modulated by altering the number of complementary bases in the DNA chains. Using these different crosslinking molecules, we have assembled colloidal materials from different-sized colloidal particles, A and B. In the first sets of experiment, we used high densities of adhesion molecules, and 0.96 micron (A) and 5.5 micron (B) diameter particles. The high density of adhesion molecules means that the structures are kinetically trapped in nonequilibrium configurations. The structure of the suspension can be varied by changing the number ratio of the two types of colloidal particles, NA and NB, where A is the smaller particle. With carbohydrate-selectin or avidin-biotin interactions, large NA/NB leads to the formation of colloidal micelles, with the large center B particle surrounded by many smaller A particles. As the ratio NA/NB decreases, the structures become more extended, approaching the formation of macro-Rouse polymers - extended linear chains where A beads are connected with intervening small B linkers.

Hammer, Daniel A.↗

DOE OSTI2026

Electrolyte-Dependent, “Microscopically Irreversible” H-Atom Transfer Kinetics of Ce-Based Metal–Organic Framework, Ce-MOF-808

Redox reactions at the interface of metal oxides and protic electrolytes almost always involve protons and electrons in equal amounts. Given the stoichiometry, these proton-coupled electron transfer (PCET) reactions are thermochemically equivalent to net H-atom transfer (HAT) reactions. The correlation between the chemical nature of solid catalysts and HAT kinetics has been employed for decades as the design principle for energy-relevant reactions (e.g., reactions of 2H + /H 2 ). More recently, chemists have experimentally determined that a change in liquid electrolytes that alters the microenvironment at the redox-active sites has an equally profound impact on electrocatalysis involving PCET/HAT. Yet, precise correlations between the chemical nature of electrolytes and the PCET kinetics are, to date, rare in the literature. Herein, we report our findings using the Ce-based metal−organic framework, Ce-MOF-808, as a model system. Each Ce 6 (μ 3 −O) 4 (μ 3 − OH) 4 (OH) 6 (H 2 O) 6 node of this MOF undergoes a 1H + /1e − redox reaction. Using chronoamperometry and the Cottrell analysis, we have determined that the PCET hopping kinetics within the pores of Ce-MOF-808 can change by orders of magnitude by altering the buffer species and the proton activity of the electrolyte. Furthermore, in all buffers, reductive reactions were ∼3−10 times faster in kinetics than the reverse oxidative reaction with the same electrochemical driving force, suggesting that the system, at first glance, violates the principle of microscopic reversibility. Isothermal titration calorimetry (ITC) and computational simulations corroborated that the buffer-node binding thermodynamics are quite distinct, depending on the chemical nature of the buffer and the oxidation state of the node. Together, these results suggest that the substrate and the product during the oxidative vs reductive reaction of Ce-MOF-808 are chemically different species, which explains the apparent ‘microscopic irreversibility.’ Thus, the rational modulation of electrolytes can dramatically enhance PCET kinetics, even though the solid electrodes remain identical. Implications of these findings are contrasted with the electrochemical/electrocatalytic behavior of other redox-active MOFs, heterogeneous catalysts, and enzymatic systems at the solid−liquid interface.

Ce-based MOF↗