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MAGE: Alleviating Uncertainty in Real-Time Decision-Making as a Function of Problem Complexity

In this paper, we discuss a critical aspect of uncertainty in the operation of complex systems, such as the future air traffic: the ability of agents in the system to arrive at satisfactory decisions and the attendant actions as a function of problem complexity. Intuitively, when the problem complexity is manageable, given an appropriate decision problem formulation and solution tools, an agent (computational or human) has no trouble arriving at a solution that yields good outcomes for the agent and the system. Growing problem complexity results in progressively larger computational problems that may yield suboptimal solutions or even be intractable within required time limits or at all. We propose a measurable representation of complexity in terms of problem tractability and quality of solutions. We also propose a computational scheme, MAGE (Monitor, Anticipate, Guide, Evolve), for detecting approaching transitions from efficient decision-making states to inefficient to unsafe ones, so that operations based on decision-making can be reconfigured to forestall unfavorable transitions, returning to efficient modes when complexity diminishes. Maintaining tractable complexity reduces the uncertainty in the outcomes of decision-making. We describe the general scheme, an outline of MAGE applied to managing airspace complexity, and initial examples of investigating the tractability of problem-solving schemes.

complexity management↗

DOE OSTI2022

Manganese(II) complexes of 1,1'-bis[(pyridin-2-yl)methyl)]-2,2'-bipiperidine (PYBP): Synthesis, structure, catalytic properties in alkene epoxidation with hydrogen peroxide, and related mechanistic studies

In this study, several manganese(II) complexes with the stereoisomers of ligand PYBP (1,1'-bis[(pyridin-2-yl)methyl]-2,2'-bipiperidine) and different anions were prepared and characterized by X-ray diffractometry. Complex [Mn II (rac-PYBP)] 2+ (1) was found to be an efficient catalyst of alkene epoxidation by hydrogen peroxide in the presence of acetic acid in acetonitrile at room temperature. Cyclooctene was converted to its epoxide with up to 91 % yield, 99.6 % selectivity, and the turnover number of 180 within 5 min. Fast epoxidations of cyclohexene, 1-decene, styrene, and cis-stilbene were also achieved. Isomeric complex [Mn II (meso-PYBP)] 2+ (2) was catalytically inactive under the same experimental conditions. Stopped-flow spectrophotometry and freeze-quenched EPR spectra show that complex 2 is not oxidized by H 2 O 2 in the presence of acetic acid (AcOH) but instead undergoes partial ligand protonation and liberation of the Mn 2+ cations due to the relatively poor chelating ability of ligand meso-PYBP. The rac-PYBP isomer acts as a better ligand and retains the coordinated Mn center when complex 1 is treated with the H 2 O 2 /AcOH mixture in acetonitrile solution yielding a mixture of intensely colored intermediates likely involving Mn III , Mn IV , and Mn V complexes. Magnetic susceptibility measurements, UV–vis and EPR spectra suggest that dinuclear complexes [Mn III 2 (μ-O)(μ-OAc)(rac-PYBP) 2 ] 3+ and [Mn III Mn IV (μ-O) 2 (rac-PYBP) 2 ] 3+ gradually accumulate in the reaction mixture as inactivated states of the catalyst. Complex 1 also causes fast decomposition of hydrogen peroxide into O 2 gas and H 2 O, which competes with the epoxidation of alkenes and requires gradual addition of H 2 O 2 for its efficient use. The catalytic activity of complex 1 is strongly influenced by its counterions and decreases in order ClO 4 - ≈ SbF 6 - > NO 3 – > Cl - indicating that labile ligands in the coordination sphere of Mn are required for the activation of H 2 O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Synthesis, structures and properties of a series of manganese coordination complexes constructed from dicarboxylic fluorene derivatives

Assembly reactions of 9,9-diethylfluorene-2,7-dicarboxylic acid (H{sub 2}DFDC) and Mn(CH{sub 3}COO){sub 2}{center_dot}4H{sub 2}O or MnCl{sub 2}{center_dot}4H{sub 2}O by tuning of various secondary ligands such as 2,2 Prime -bipyridine (2,2 Prime -bpy), 4,4 Prime -bipyridine (4,4 Prime -bpy) or 1,3-bis(4-pyridyl)propane) (bpp), gave rise to four complexes {l_brace} [Mn{sub 2}(DFDC){sub 2}(DMF){sub 2}]{center_dot}H{sub 2}O{r_brace} {sub n} (1), [Mn(DFDC)(2,2 Prime -bpy)]{sub n} (2), {l_brace} [Mn{sub 2}(DFDC){sub 2}(4,4 Prime -bpy){sub 2}]{center_dot}2CH{sub 3}OH{r_brace} {sub n} (3), and {l_brace} [Mn{sub 4}(DFDC){sub 4}(bpp){sub 2}(CH{sub 3}OH){sub 3} (H{sub 2}O){sub 3}]{center_dot}3(CH{sub 3}OH){center_dot}3(H{sub 2}O){r_brace} {sub n} (4). Single crystal X-ray diffraction analysis reveal that complex 1 is three dimensional structure with rhombic channels filled by guest water molecules; 2 presents a close-packed structure with high thermal stability; 3 exhibits a three dimensional framework with micro-porous channels filled by guest methanol molecules and 4 is a two-dimensional structure. The photoluminescent properties of 1-4 have been studied, respectively, showing that the Mn(II) ions, accessorial organic ligands or crystal structures exert important influences on the photoluminescence emissions of H{sub 2}DFDC ligands. Thermogravimetric analysis show that the complexes have remarkably high thermal stability. Magnetic susceptibility measurements have been finished and discussed for the complexes. - Graphical abstract: Assembly of 9,9-diethylfluorene-2,7-dicarboxylic acid and Mn(II) salts by tuning of various accessorial ligands resulted in four manganese complexes with different topological frameworks. Highlights: Black-Right-Pointing-Pointer Four manganese complexes based on 9,9-diethylfluorene-2,7-dicarboxylic acid were obtained. Black-Right-Pointing-Pointer The complexes were structurally characterized by single-crystal X-ray diffraction. Black-Right-Pointing-Pointer The complexes 1-4 display different topological structures. Black-Right-Pointing-Pointer Thermogravimetric analysis show the complexes have remarkably high thermal stability.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Double Intramolecular 1,2 C–H Addition of o -Methyl Groups To Form Ruthenium Pincer Double Tuck-In Complexes

Ruthenium pincer complexes have a rich history of coordination and reaction chemistries. In this work, we report our discoveries of previously unreported Ru pincer coordination geometries. We found that mono tuck-in κ 4 -ArPN H PRuLCl complexes react with NaN(SiMe 3 ) 2 producing double tuck-in mer-κ 5 -ArPN H PRuL complexes. Interestingly, when κ 4 -MesPN H PRuCl is dehydrohalogenated, the resulting double tuck-in complex binds N 2 , forming the nitrogen complex κ 5 -MesPN H PRuN 2 . Further, the mer-κ 5 -ArPN H PRuL complexes thermally isomerize to the fac-κ 5 -ArPN H PRuL isomers, which is an uncommon reaction for pincer complexes. The mer-κ 5 -ArPN H PRuL complexes react with CO and CO 2 to form amide κ 4 -ArPN H PRu(CO)L or carbamate κ 5 -ArPN(CO 2 )PRuL complexes, respectively, supporting the hypothesis that the κ 4 -ArPNPRuL amide intermediates are accessible and reactive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Thermodynamic Features of Benzene-1,2-Diphosphonic Acid Complexes with Several Metal Ions

Among his many contributions to the advancement of f-element chemistry and separation science, Professor Gregory R. Choppin’s research group completed numerous investigations featuring the application of distribution techniques to the determination of metal complexation equilibrium quotients. Most of these studies focused on the chemistry of lanthanide and actinide complexes. In keeping with that tradition, this report discusses the complex formation equilibrium constants for complexes of trivalent europium (Eu3+) with benzene-1,2-diphosphonic acid (H4BzDP) determined using solvent extraction distribution experiments in 0.2 M (Na,H)ClO4 media in the temperature range of 5 – 45 degrees C. Protonation constants for HnBzDP4-n and stoichiometry and stability of BzDP4- complexes with Zn2+, Ni2+, and Cu2+ have also been determined using potentiometric titration (at I = 0.1 M) and 31P NMR spectroscopy. Heats of protonation of HnBzDPn-4 species have been determined by titration calorimetry. From the temperature dependence of the complex Eu3+-HnBzDPn-4 equilibrium constant, a composite enthalpy (?H = -15.1 (+/-1.0) kJ mol-1) of complexation has been computed. Comparing these thermodynamic parameters with literature reports on other diphosphonic acids and structurally similar carboxylic acids indicates that exothermic heats of complexation are unique to the Eu-BzDP system. Comparisons with thermodynamic data from the literature indicate that the fixed geometry imposed by the benzene ring enhances complex stability.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2021

Feedback density and causal complexity of simulation model structure

Measures of simulation model complexity generally focus on outputs; we propose measuring the complexity of a model’s causal structure to gain insight into its fundamental character. This article introduces tools for measuring causal complexity. First, we introduce a method for developing a model’s causal structure diagram, which characterises the causal interactions present in the code. Causal structure diagrams facilitate comparison of simulation models, including those from different paradigms. Next, we develop metrics for evaluating a model’s causal complexity using its causal structure diagram. We discuss cyclomatic complexity as a measure of the intricacy of causal structure and introduce two new metrics that incorporate the concept of feedback, a fundamental component of causal structure. The first new metric introduced here is feedback density, a measure of the cycle-based interconnectedness of causal structure. The second metric combines cyclomatic complexity and feedback density into a comprehensive causal complexity measure. Finally, we demonstrate these complexity metrics on simulation models from multiple paradigms and discuss potential uses and interpretations. These tools enable direct comparison of models across paradigms and provide a mechanism for measuring and discussing complexity based on a model’s fundamental assumptions and design.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2011

The Enhancer of split complex arose prior to the diversification of schizophoran flies and is strongly conserved between Drosophila and stalk-eyed flies (Diopsidae)

Background: In Drosophila, the Enhancer of split complex (E(spl)-C) comprises 11 bHLH and Bearded genes that function during Notch signaling to repress proneural identity in the developing peripheral nervous system. Comparison with other insects indicates that the basal state for Diptera is a single bHLH and Bearded homolog and that the expansion of the gene complex occurred in the lineage leading to Drosophila. However, comparative genomic data from other fly species that would elucidate the origin and sequence of gene duplication for the complex is lacking. Therefore, in order to examine the evolutionary history of the complex within Diptera, we reconstructed, using several fosmid clones, the entire E(spl)-complex in the stalk-eyed fly, Teleopsis dalmanni and collected additional homologs of E(spl)-C genes from searches of dipteran EST databases and the Glossina morsitans genome assembly. Results: Comparison of the Teleopsis E(spl)-C gene organization with Drosophila indicates complete conservation in gene number and orientation between the species except that T. dalmanni contains a duplicated copy of E(spl)m5 that is not present in Drosophila. Phylogenetic analysis of E(spl)-complex bHLH and Bearded genes for several dipteran species clearly demonstrates that all members of the complex were present prior to the diversification of schizophoran flies. Comparison of upstream regulatory elements and 3’ UTR domains between the species also reveals strong conservation for many of the genes and identifies several novel characteristics of E(spl)-C regulatory evolution including the discovery of a previously unidentified, highly conserved SPS+A domain between E(spl)mg and E(spl)mb. Conclusion: Identifying the phylogenetic origin of E(spl)-C genes and their associated regulatory DNA is essential to understanding the functional significance of this well-studied gene complex. Results from this study provide numerous insights into the evolutionary history of the complex and will help refine the focus of studies examining the adaptive consequences of this gene expansion.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2015

Characterization of the host–guest complex of a curcumin analog with β-cyclodextrin and β-cyclodextrin–gemini surfactant and evaluation of its anticancer activity

Background: Curcumin analogs, including the novel compound NC 2067, are potent cytotoxic agents that suffer from poor solubility, and hence, low bioavailability. Cyclodextrin-based carriers can be used to encapsulate such agents. In order to understand the interaction between the two molecules, the physicochemical properties of the host–guest complexes of NC 2067 with β-cyclodextrin (CD) or β-cyclodextrin–gemini surfactant (CDgemini surfactant) were investigated for the first time. Moreover, possible supramolecular structures were examined in order to aid the development of new drug delivery systems. Furthermore, the in vitro anticancer activity of the complex of NC 2067 with CDgemini surfactant nanoparticles was demonstrated in the A375 melanoma cell line. Methods: Physicochemical properties of the complexes formed of NC 2067 with CD or CDgemini surfactant were investigated by synchrotron-based powder X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Synchrotron-based small- and wide-angle X-ray scattering and size measurements were employed to assess the supramolecular morphology of the complex formed by NC 2067 with CDgemini surfactant. Lastly, the in vitro cell toxicity of the formulations toward A375 melanoma cells at various drug-to-carrier mole ratios were measured by cell viability assay. Results: Physical mixtures of NC 2067 and CD or CDgemini surfactant showed characteristics of the individual components, whereas the complex of NC 2067 and CD or CDgemini surfactant presented new structural features, supporting the formation of the host–guest complexes. Complexes of NC 2067 with CDgemini surfactants formed nanoparticles having sizes of 100–200 nm. NC 2067 retained its anticancer activity in the complex with CDgemini surfactant for different drug-to-carrier mole ratios, with an IC 50 (half-maximal inhibitory concentration) value comparable to that for NC 2067 without the carrier. Conclusion: The formation of host–guest complexes of NC 2067 with CD or CDgemini surfactant has been confirmed and hence the CDgemini surfactant shows good potential to be used as a delivery system for anticancer agents.

60 APPLIED LIFE SCIENCES↗

NASA NTRS2019

Scenario Complexity for Unmanned Aircraft System Traffic

This work introduces an approach to estimate the complexity of a low-altitude air traffic scenario involving multiple UASs using mathematical programming. Given a set of multi-point UAS flight trajectories, vehicle dynamics, and a conflict resolution algorithm, an abstract model is developed such that it can be solved quickly using a mathematical programming optimization software without running high-fidelity simulations that can be computationally expensive and may not suit real-time apA quick and accurate assessment of complexity for a given traffic scenario can help plan and schedule flights to alleviate traffic bottleneck and mitigate operation risks, especially for unmanned aerial system traffic management where high traffic density or complexity is expected. This work introduces a traffic scenario complexity metric that was constructed based on the number of potential conflicts weighted by the conflict resolution cost associated. The cost associated with a conflict is calculated based on the corresponding conflict resolution maneuvers. To obtain the conflict resolution maneuvers, a MILP-based optimization was formulated with the vehicle model and conflict management parameters incorporated. To evaluate the complexity metrics, an approach of using measurements from high-fidelity simulations was proposed. The scenario complexity measurements for 920 random-generated scenarios were obtained through high-fidelity simulations and treated as the ground truth. Two statistics methods: Pearson and Alternative Conditional Expectations were applied for analysis. The results showed that the number of flights has low correlation with the scenario complexity according to the correlation coefficients calculated by both methods. The Alternative Conditional Expectations method shows that the proposed scenario complexity metric has better correlation with the ground truth than the number of potential conflicts.plications. In the abstract model, each vehicle is represented by a time-varied vector associated with position, speed, and heading information. The total extra distance that aircraft need to divert from their original routes to avoid collisions is computed and used to setup a quadratic programming formula. The metrics including the number of conflicts and extra distances travelled by all vehicles are then utilized to estimate the complexity of a given UAS flight scenario. Results and verification against high-fidelity simulations will be provided in the final draft.

traffic complexity↗

DOE OSTI2019

Subsystem complexity and holography

As a probe of circuit complexity in holographic field theories, we study sub-system analogues based on the entanglement wedge of the bulk quantities appearing in the “complexity = volume” and “complexity = action” conjectures. We calculate these quantities for one exterior region of an eternal static neutral or charged black hole in general dimensions, dual to a thermal state on one boundary with or without chemical potential respectively, as well as for a shock wave geometry. We then define several analogues of circuit complexity for mixed states, and use tensor networks to gain intuition about them. In the action approach, we find two possible cases depending on an ambiguity in the definition of the action associated with a counterterm. In one case, there is a promising qualitative match between the holographic action and what we call the purification complexity, the minimum number of gates required to prepare an arbitrary purification of the given mixed state. In the other case, the match is to what we call the basis complexity, the minimum number of gates required to prepare the given mixed state starting from a minimal complexity state with the same eigenvalue spectrum. One way to fix this ambiguity is to choose an action definition such that UV divergent part is positive, in which case the best match to the action result is the basis complexity. In contrast, the holographic volume does not appear to match any of our definitions of mixed-state complexity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2019

Probing the Dissociation of Protein Complexes by Means of Gas-Phase H/D Exchange Mass Spectrometry

Gas-phase hydrogen/deuterium exchange measured by mass spectrometry (gas-phase HDX-MS) is a fast method to probe the conformation of protein ions. The use of gas-phase HDX-MS to investigate the structure and interactions of protein complexes is however mostly unharnessed. Ionizing proteins under conditions that maximize preservation of their native structure (native MS) enables the study of solution-like conformation for milliseconds after electrospray ionization (ESI), which enables the use of ND{sub 3}-gas inside the mass spectrometer to rapidly deuterate heteroatom-bound non-amide hydrogens. Here, we explored the utility of gas-phase HDX-MS to examine protein-protein complexes and inform on their binding surface and the structural consequences of gas-phase dissociation. Protein complexes ranging from 24 kDa dimers to 395 kDa 24mers were analyzed by gas-phase HDX-MS with subsequent collision-induced dissociation (CID). The number of exchangeable sites involved in complex formation could, therefore, be estimated. For instance, dimers of cytochrome c or α-lactalbumin incorporated less deuterium/subunit than their unbound monomer counterparts, providing a measure of the number of heteroatom-bound side-chain hydrogens involved in complex formation. We furthermore studied if asymmetric charge-partitioning upon dissociation of protein complexes caused intermolecular H/D migration. In larger multimeric protein complexes, the dissociated monomer showed a significant increase in deuterium. This indicates that intermolecular H/D migration occurs as part of the asymmetric partitioning of charge during CID. We discuss several models that may explain this increase deuterium content and find that a model where only deuterium involved in migrating charge can account for most of the deuterium enrichment observed on the ejected monomer. In summary, the deuterium content of the ejected subunit can be used to estimate that of the intact complex with deviations observed for large complexes accounted for by charge migration. .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Dissipative quantum trajectories in complex space: Damped harmonic oscillator

Dissipative quantum trajectories in complex space are investigated in the framework of the logarithmic nonlinear Schrödinger equation. The logarithmic nonlinear Schrödinger equation provides a phenomenological description for dissipative quantum systems. Substituting the wave function expressed in terms of the complex action into the complex-extended logarithmic nonlinear Schrödinger equation, we derive the complex quantum Hamilton–Jacobi equation including the dissipative potential. It is shown that dissipative quantum trajectories satisfy a quantum Newtonian equation of motion in complex space with a friction force. Exact dissipative complex quantum trajectories are analyzed for the wave and solitonlike solutions to the logarithmic nonlinear Schrödinger equation for the damped harmonic oscillator. These trajectories converge to the equilibrium position as time evolves. It is indicated that dissipative complex quantum trajectories for the wave and solitonlike solutions are identical to dissipative complex classical trajectories for the damped harmonic oscillator. This study develops a theoretical framework for dissipative quantum trajectories in complex space.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2016

EM structure of a helicase-loader complex depicting a 6:2 binding sub-stoichiometry from Geobacillus kaustophilus HTA426

During DNA replication, bacterial helicase is recruited as a complex in association with loader proteins to unwind the parental duplex. Previous structural studies have reported saturated 6:6 helicase-loader complexes with different conformations. However, structural information on the sub-stoichiometric conformations of these previously-documented helicase-loader complexes remains elusive. Here, with the aid of single particle electron-microscopy (EM) image reconstruction, we present the Geobacillus kaustophilus HTA426 helicase-loader (DnaC-DnaI) complex with a 6:2 binding stoichiometry in the presence of ATPγS. In the 19 Å resolution EM map, the undistorted and unopened helicase ring holds a robust loader density above the C-terminal RecA-like domain. Meanwhile, the path of the central DNA binding channel appears to be obstructed by the reconstructed loader density, implying its potential role as a checkpoint conformation to prevent the loading of immature complex onto DNA. Our data also reveals that the bound nucleotides and the consequently induced conformational changes in the helicase hexamer are essential for active association with loader proteins. These observations provide fundamental insights into the formation of the helicase-loader complex in bacteria that regulates the DNA replication process. - Highlights: • Helicase-loader complex structure with 6:2 sub-stoichiometry is resolved by EM. • Helicase hexamer in 6:2 sub-stoichiometry is constricted and un-opened. • 6:2 binding ratio of helicase-loader complex could act as a DNA loading checkpoint. • Nucleotides stabilize helicase-loader complex at low protein concentrations.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2014

Syntheses, crystal structures, and characterization of three 1D, 2D and 3D complexes based on mixed multidentate N- and O-donor ligands

Three new 1D to 3D complexes, namely, ([Ni(btec)(Himb){sub 2}(H{sub 2}O){sub 2}]·6H{sub 2}O){sub n} (1), ([Cd(btec){sub 0.5}(imb)(H{sub 2}O)]·1.5H{sub 2}O){sub n} (2), and ([Zn(btec){sub 0.5}(imb)]·H{sub 2}O){sub n} (3) (H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, imb=2-(1H-imidazol-1-methyl)-1H-benzimidazole) have been synthesized by adjusting the central metal ions. Single-crystal X-ray diffraction analyses reveal that complex 1 possesses a 1D chain structure which is further extended into the 3D supramolecular architecture via hydrogen bonds. Complex 2 features a 2D network with Schla¨fli symbol (5{sup 3}·6{sup 2}·7)(5{sup 2}·6{sup 4}). Complex 3 presents a 3D framework with a point symbol of (4·6{sup 4}·8)(4{sup 2}·6{sup 2}·8{sup 2}). Moreover, their IR spectra, PXRD patterns, thermogravimetric curves, and luminescent emissions were studied at room temperature. - Graphical abstract: Three new 1D to 3D complexes with different structural and topological motifs have been obtained by modifying the central metal ions. Additionally, their IR, TG analyses and fluorescent properties are also investigated. - Highlights: • Three complexes based on mixed multidentate N- and O-donor ligands. • The complexes are characterized by IR, luminescence and TGA techniques. • Benzenetetracarboxylates display different coordination modes in complexes 1–3. • Changing the metal ions can result in complexes with completely different structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Ligand Many-Body Expansion as a General Approach for Accelerating Transition Metal Complex Discovery

Methods that accelerate the evaluation of molecular properties are essential for chemical discovery. While some degree of ligand additivity has been established for transition metal complexes, it is underutilized in asymmetric complexes, such as the square pyramidal coordination geometries highly relevant to catalysis. To develop predictive methods beyond simple additivity, we apply a many-body expansion to octahedral and square pyramidal complexes and introduce a correction based on adjacent ligands (i.e., the cis interaction model). We first test the cis interaction model on adiabatic spin-splitting energies of octahedral Fe(II) complexes, predicting DFT-calculated values of unseen binary complexes to within an average of 1.4 kcal/mol. Uncertainty analysis reveals the optimal basis, comprising the homoleptic and mer symmetric complexes. We next show that the cis model (i.e., the cis interaction model solved for the optimal basis) infers both DFT- and CCSD(T)-calculated model catalytic reaction energies to within 1 kcal/mol on average. The cis model predicts low-symmetry complexes with reaction energies outside the range of binary complex reaction energies. We observe that trans interactions are unnecessary for most monodentate systems but can be important for some combinations of ligands, such as complexes containing a mixture of bidentate and monodentate ligands. Lastly, we demonstrate that the cis model may be combined with Δ-learning to predict CCSD(T) reaction energies from exhaustively calculated DFT reaction energies and the same fraction of CCSD(T) reaction energies needed for the cis model, achieving around 30% of the error from using the CCSD(T) reaction energies in the cis model alone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Newly Synthesized Heteronuclear Ruthenium(II)/Ferrocene Complexes Suppress the Growth of Mammary Carcinoma in 4T1-Treated BALB/c Mice by Promoting Activation of Antitumor Immunity

The two new heterometallic Ru(II)-tpy/ferrocene complexes [Ru(tpy)Cl2(mtefc)] (1) and [Ru(tpy)Cl2(mtpfc)] (2) (where tpy = 2,2′:6′,2′′-terpyridine, mtefc = (2-(methylthio)ethyl)ferrocene, and mtpfc = (3-(methylthio)propyl)ferrocene) have been synthesized and then characterized through elemental analysis, followed by various spectroscopic (IR, UV-vis, 1D and 2D NMR) and mass spectrometric techniques (MALDI TOF and ESI Q-TOF MS). UV-vis and fluorescence spectroscopy and viscometry were employed to study the interactions of the complexes 1 and 2 with calf thymus DNA. Both 1 and 2 expelled ethidium bromide (EB) from the EB/DNA complex (Ksv = (1.5-1.8) × 104 M-1), which suggested that the complexes intercalated into the double helix of DNA. Both complexes strongly quenched the fluorescence of tryptophan residues in serum albumin through both static and dynamic quenching. Molecular docking confirmed the intercalative mode of complex interaction with DNA. The docking results implied that 1 and 2 interacted with hydrophobic residues of albumin, particularly with those lying in the proximity of Tyr 160. We here demonstrate the high cytotoxic potential of complexes 1 and 2 against the breast cancer cells that originated either from humans (MDA-MB-231) or from mice (4T1), with apoptosis being the main mechanism of complex-induced cell death. It is worth noting that both complexes promoted activation of innate and acquired antitumor immunity, which contributed to the reduced growth and progression of mammary carcinoma in vivo. Copyright © 2018 American Chemical Society.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2020

Discrete Open-Shell Tris(bipyridinium radical cationic) Inclusion Complexes in the Solid State

In the solid state the properties of organic radicals depend heavily on radical-radical interactions that are influenced by the superstructure of the crystalline phase. Here, we report the synthesis and characterization of a substituted tetracationic cyclophane, cyclobis(paraquat-p-1,4- dimethoxyphenylene), and outline how its bisradical dicationic redox state associates with the methyl viologen radical cation (MV •+ ) to give a trisradical tricationic inclusion complex. The (super)structures of the reduced cyclophane and this 1:1 complex in the solid-state deviate from the analogous (super)structures observed for the reduced state of cyclobis(paraquat-p-phenylene) and that of its trisradical tricationic complex. Titration experiments with a range of guests reveal that the methoxy substituents on the para-xylenyl do not influence significantly of the binding affinity of the cyclophane for small neutral guests, whereas the affinity decreases by an order of magnitude for larger radical cationic guests such as MV •+ . X-Ray diffraction reveals that the solid- state structures of the tricationic trisradical complexes to be a discrete entity with weak intermolecular orbital overlap between the neighboring complexes. Transient nutation EPR experiment and DFT calculations confirm that the complex has a doublet spin configuration in the ground state as a result of the strong orbital overlap within the complex, while the quartet-state spin configuration is higher in energy and so is inaccessible at ambient temperature. The superconducting quantum interference device (SQUID) measurement reveals that trisradical tricationic complexes interact antiferromagnetically (J/k = - 2.33 K) and form a 1D Heisenberg antiferromagnetic chain along the a-axis in the crystal. Furthermore, these results offer new insights into the design and synthesis of organic magnetic materials based on host-guest inclusion complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Tuning the reactivity of mononuclear nonheme manganese( iv )-oxo complexes by triflic acid

Triflic acid (HOTf)-bound nonheme Mn( IV )-oxo complexes, [(L)Mn IV (O)] 2+ –(HOTf) 2 (L = N4Py and Bn-TPEN; N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine and Bn-TPEN = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), were synthesized by adding HOTf to the solutions of the [(L)Mn IV (O)] 2+ complexes and were characterized by various spectroscopies. The one-electron reduction potentials of the Mn IV (O) complexes exhibited a significant positive shift upon binding of HOTf. The driving force dependences of electron transfer (ET) from electron donors to the Mn IV (O) and Mn IV (O)–(HOTf) 2 complexes were examined and evaluated in light of the Marcus theory of ET to determine the reorganization energies of ET. The smaller reorganization energies and much more positive reduction potentials of the [(L)Mn IV (O)] 2+ –(HOTf) 2 complexes resulted in greatly enhanced oxidation capacity towards one-electron reductants and para-X-substituted-thioanisoles. The reactivities of the Mn(IV)-oxo complexes were markedly enhanced by binding of HOTf, such as a 6.4 × 10 5 -fold increase in the oxygen atom transfer (OAT) reaction (i.e., sulfoxidation). Such a remarkable acceleration in the OAT reaction results from the enhancement of ET from para-X-substituted-thioanisoles to the MnIV(O) complexes as revealed by the unified ET driving force dependence of the rate constants of OAT and ET reactions of [(L)Mn IV (O)] 2+ –(HOTf) 2 . In contrast, deceleration was observed in the rate of H-atom transfer (HAT) reaction of [(L)Mn IV (O)] 2+ –(HOTf) 2 complexes with 1,4-cyclohexadiene as compared with those of the [(L)Mn IV (O)] 2+ complexes. Thus, the binding of two HOTf molecules to the Mn IV (O) moiety resulted in remarkable acceleration of the ET rate when the ET is thermodynamically feasible. When the ET reaction is highly endergonic, the rate of the HAT reaction is decelerated due to the steric effect of the counter anion of HOTf.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗