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At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Phenoxo bridged dinuclear Zn(II) Schiff base complex as new precursor for preparation zinc oxide nanoparticles: Synthesis, characterization, crystal structures and photoluminescence studies

Highlights: • A novel nano-scale Zn(II) complex was synthesized by solvothermal method. • Chemical structure of the nanostructures was characterized as well as bulk complex. • The photoluminescence property of the complex was investigated at room temperature. • The thermogravimetry and differential thermal analysis were carried out. • Thermal decomposition of the nanostructures was prepared zinc oxide nanoparticles. - Abstract: Nanoparticles of a novel Zn(II) Schiff base complex, [Zn(HL)NO{sub 3}]{sub 2} (1), (H{sub 2}L = 2-[(2-hydroxy-propylimino) methyl] phenol), was synthesized by using solvothermal method. Shape, morphology and chemical structure of the synthesized nanoparticles were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier Transform Infrared Spectoscopy (FT-IR) and UV–vis spectroscopy. Structural determination of compound 1 was determined by single-crystal X-ray diffraction. The results were revealed that the zinc complex is a centrosymmetric dimer in which deprotonated phenolates bridge the two five-coordinate metal atoms and link the two halves of the dimer. The thermal stability of compound 1 was analyzed by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of the initial substrates concentration and reaction time on size and morphology of compound 1 nanostructure was investigated as well. Furthermore, the luminescent properties of the complex 1 were examined. ZnO nanoparticles with diameter between 15 and 20 nm were simply synthesized by solid-state transformation of compound 1 at 700 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Compositionally-driven surface nanostructuring on refractory compositionally complex alloys under low energy helium bombardment

Additive manufacturing enables user-defined control of the compositional complexity, opening new design spaces for complex concentrated alloys (CCAs). Refractory CCAs may offer enhanced performance in the divertor region of a fusion reactor environment where plasma-facing materials will be subject to high temperatures, low energy He and D particles, and 14 MeV neutrons. In this work, specimens with the nominal composition of NbTaMoTi, NbTaMo, NbTaTi, and NbTa were fabricated via directed energy deposition (DED) then bombarded with 40 eV He ions to a fluence of 2x10 26 m −2 at ∼ 1000 K. Post irradiation, the surface morphology and composition were examined with electron microscopy and x-ray photoelectron spectroscopy to offer information on the spatial distribution of surface nano-structuring. Sub-surface He bubbles driving the nano-structuring were examined with electron microscopy techniques. Analysis indicates the local composition directly influences the He bubble and tendril size, while the region with the highest complexity showed the shortest nano-structuring. Molecular Dynamics simulations complement the experimental results, showing comparable helium bubble growth and migration as a function of compositional complexity. This work demonstrates the compositional dependence of surface nanostructure formation of compositionally complex alloys, important for future design of complex plasma facing materials in fusion reactors.

Complex concentrated alloys↗
DOE OSTI2013

Lethal synergism between organic and inorganic wood preservatives via formation of an unusual lipophilic ternary complex

We have shown previously that exposing bacteria to wood preservatives pentachlorophenol (PCP) and copper-containing compounds together causes synergistic toxicity. However, it is not clear whether these findings also hold true in mammalian cells; and if so, what is the underlying molecular mechanism? Here we show that PCP and a model copper complex bis-(1,10-phenanthroline) cupric (Cu(OP){sub 2}), could also induce synergistic cytotoxicity in human liver cells. By the single crystal X-ray diffraction and atomic absorption spectroscopy assay, the synergism was found to be mainly due to the formation of a lipophilic ternary complex with unusual structural and composition characteristics and subsequent enhanced cellular copper uptake, which markedly promoted cellular reactive oxygen species (ROS) production, leading to apoptosis by decreasing mitochondrial membrane potential, increasing pro-apoptotic protein expression, releasing cytochrome c from mitochondria and activating caspase-3, and -9. Analogous results were observed with other polychlorinated phenols (PCPs) and Cu(OP){sub 2}. Synergistic cytotoxicity could be induced by PCP/Cu(OP){sub 2} via formation of an unusual lipophilic complex in HepG2 cells. The formation of ternary complexes with similar lipophilic character could be of relevance as a general mechanism of toxicity, which should be taken into consideration especially when evaluating the toxicity of environmental pollutants found at currently-considered non- or sub-toxic concentrations. -- Highlights: ► The combination of PCP/Cu(OP){sub 2} induces synergistic cytotoxicity in HepG2 cells. ► The synergism is mainly due to forming a lipophilic ternary complex between them. ► The formation of lipophilic ternary complex enhances cellular copper uptake. ► PCP/Cu(OP){sub 2} stimulates the cellular ROS production. ► The ROS promoted by PCP/Cu(OP){sub 2} induces mitochondria-dependent apoptosis.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2012

GSK3 inactivation is involved in mitochondrial complex IV defect in transforming growth factor (TGF) {beta}1-induced senescence

Transforming growth factor {beta}1 (TGF {beta}1) induces Mv1Lu cell senescence by persistently producing mitochondrial reactive oxygen species (ROS) through decreased complex IV activity. Here, we investigated the molecular mechanism underlying the effect of TGF {beta}1 on mitochondrial complex IV activity. TGF {beta}1 progressively phosphorylated the negative regulatory sites of both glycogen synthase kinase 3 (GSK3) {alpha} and {beta}, corresponding well to the intracellular ROS generation profile. Pre-treatment of N-acetyl cysteine, an antioxidant, did not alter this GSK3 phosphorylation (inactivation), whereas pharmacological inhibition of GSK3 by SB415286 significantly increased mitochondrial ROS, implying that GSK3 phosphorylation is an upstream event of the ROS generation. GSK3 inhibition by SB415286 decreased complex IV activity and cellular O{sub 2} consumption rate and eventually induced senescence of Mv1Lu cell. Similar results were obtained with siRNA-mediated knockdown of GSK3. Moreover, we found that GSK3 not only exists in cytosol but also in mitochondria of Mv1Lu cell and the mitochondrial GSK3 binds complex IV subunit 6b which has no electron carrier and is topologically located in the mitochondrial intermembrane space. Involvement of subunit 6b in controlling complex IV activity and overall respiration rate was proved with siRNA-mediated knockdown of subunit 6b. Finally, TGF {beta}1 treatment decreased the binding of the subunit 6b to GSK3 and subunit 6b phosphorylation. Taken together, our results suggest that GSK3 inactivation is importantly involved in TGF {beta}1-induced complex IV defects through decreasing phosphorylation of the subunit 6b, thereby contributing to senescence-associated mitochondrial ROS generation.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Complexation of NpO 2 + with Amine-Functionalized Diacetamide Ligands in Aqueous Solution: Thermodynamic, Structural, and Computational Studies

Complexation of Np(V) with three structurally related amine-functionalized diacetamide ligands, including 2,2'-azanediylbis( N, N'-dimethylacetamide) (ABDMA), 2,2'-(methylazanediyl)bis( N, N'-dimethylacetamide) (MABDMA), and 2,2'-(benzylazanediyl)bis( N, N'-dimethylacetamide) (BnABDMA), in aqueous solutions was investigated. The stability constants of two successive complexes, namely, NpO 2 L + and NpO 2 L 2 + , where L stands for the ligands, were determined by absorption spectrophotometry. The results suggest that the stability constants of corresponding Np(V) complexes follow the trend: MABDMA > ABDMA ≈ BnABDMA. The data are discussed in terms of the basicity of the ligands and compared with those for the complexation of Np(V) with an ether oxygen-linked diacetamide ligand. Extended X-ray absorption fine structure data indicate that, similar to the complexation with Nd 3+ and UO 2 2+ , the ligands coordinate to NpO 2 + in a tridentate mode through the amine nitrogen and two oxygen atoms of the amide groups. Furthermore, computational results, in conjunction with spectrophotometric data, verify that the 1:2 complexes (NpO 2 (L) 2 + ) in aqueous solutions are highly symmetric with Np at the inversion center, so that the f-f transition of Np(V) is forbidden and NpO 2 (L) 2 + does not display significant absorption in the near-IR region.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The Complexation Properties of Self-Defensive Microgel-Modified Antimicrobial Surfaces

The complexation of cationic antimicrobials with polyanionic microgels on a biomaterial surface can render that surface self-defensive against bacteria by killing those bacteria which physically contact the antimicrobial-loaded microgels. This killing has been attributed to the contact-driven transfer of antimicrobial from a microgel to a challenging bacterium, though much remains unknown about this process. Here, in this study, we use a combination of experiments and computational modeling to identify key aspects of the complexation phenomena which influence the self-defensive properties. We synthesize poly(acrylic acid) (PAA) microgels (∼2–5 μm diameter) via membrane emulsification and electrostatically deposit them onto polycaprolactone (PCL) coupons or onto glass to form a discontinuous submonolayer. Subsequent microgel loading with colistin or with Sub5 antimicrobial peptide (AMP) causes microgel deswelling. Under physiological conditions Sub5 remains stably sequestered whereas colistin is quickly released. Coarse-grained molecular dynamics (CGMD) simulations confirm stronger Sub5/PAA complexation. CGMD calculations also indicate that Sub5 forms dimers and higher-order structures, a prediction confirmed experimentally by Small-Angle X-ray Scattering (SAXS). Supramolecular structure entropically enhances the complexation strength because of enhanced counterion release per complexation event, and this finding can help identify other antimicrobials well suited for such a nonelutive yet self-defensive strategy. CGMD simulations also show that Sub5 has a higher complexation strength with the Staphylococcus aureus membrane than it does with PAA, confirming that there is a thermodynamic driving force for antimicrobial transfer. Such self-defensive surfaces significantly reduce S. aureus colonization (over 90% reduction relative to unmodified controls) in an in vitro hematogenous contamination model and remain cyto-compatible as evidenced by mesenchymal stem cell spreading and proliferation.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Surface Complexation of Neptunium(V) onto Whole Cells and Cell Components of Shewanella alga: Modeling and Experimental Study

We systematically quantified surface complexation of Np(V) onto whole cells, cell wall, and extracellular polymeric substances (EPS) of Shewanella alga strain BrY. We first performed acid and base titrations and used the mathematical model FITEQL to estimate the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl group not associated with amino acids (pK{sub a} {approx} 5), a phosphoryl site (pK{sub a} {approx} 7.2), and an amine site (pK{sub a} > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components as a function of pH. Since significant Np(V) sorption was observed on S. alga whole cells and its components in the pH range 2-5, we assumed the existence of a fourth site: a low-pK{sub a} carboxyl site (pK{sub a} {approx} 2.4) that is associated with amino acids. We used the SPECIATE submodel of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, the aquo NpO{sub 2}{sup +} species was the dominant form of Np(V), and its log K values for the low-pK{sub a} carboxyl, mid-pK{sub a} carboxyl, and phosphoryl groups were 1.8, 1.8, and 2.5-3.1, respectively. For pH greater than 8, the key surface ligand was amine > XNH{sub 3}{sup +}, which complexed with NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-}. The log K for NpO{sub 2}(CO{sub 3}){sub 3}{sup 5-} complexed onto the amine groups was 3.1-3.9. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results help quantify the role of surface complexation in defining actinide-microbiological interactions in the subsurface.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Ruthenium Bis-diimine Complexes with a Chelating Thioether Ligand: Delineating 1,10-Phenanthrolinyl and 2,2'-Bipyridyl Ligand Substituent Effects

A new series of ruthenium(II) bis-diimine complexes with a chelating thioether donor ligand has been prepared: Ru(diimine)2(dpte)2+ (diimine=1,10-phenanthroline (phen) (1); 5-CH3-phen (2), 5-Cl-phen (3); 5-Br-phen (4); 5-NO2-phen (5); 3,4,7,8-tetramethyl-phen (6); 4,7-diphenyl-phen (7); 5,5'-dimethyl-2,2'-bipyridine (8); 4,4'-di-tert-butyl-2,2'-bipyridine (9)). Crystal structures of 2, 5, 7 and 9 show that the complexes form 2 of the 12 possible conformational/configurational isomers, adopting compact C2-symmetric structures with short intramolecular transannular interactions between the diimine ligands and dpte phenyl groups; crystals of 2 and 5 contain non-statistical distributions of geometric isomers. In keeping with the π-acidity of the dpte, the Ru(III/II) couple, E°'(Ru3+/2+), occurs at relatively high potentials (1.4-1.7 V vs Ag/AgCl), and the lowest spin-allowed MLCT absorption band occurs near 400 nm. Surprisingly, the complexes also exhibit fluid-solution luminescence originating from a lowest MLCT excited state with lifetimes in the 140-750 ns time range; in acetonitrile, compound 8 undergoes photo-induced solvolysis. Variations in the MLCT energies and redox potentials are quantitatively described using a summative Hammett parameter (σT), as well as using Lever's electrochemical parameters (EL). Recommended parameterizations for 2,2'-bipyridyl and 1,10-phenanthrolinyl ligands were derived from analysis of correlations based on 199 measurements of E°'(Ru3+/2+) for 99 homo- and heteroleptic ruthenium(II) tris-diimine complexes. Variations in E°'(Ru3+/2+) due to substituents at the 4- and 4'-positions of bipyridyl ligands and 4- and 7-positions of phenanthrolinyl ligands are significantly more strongly correlated with σp+ than either σm or σp. Substituents at the 5- and 6-positions of phenanthrolinyl ligands are best described by σm and have effects comparable to those of substituents at the 3- and 8-positions. Correlations of EL with σT for 20 1,10-phenanthrolinyl ligands and for 35 2,2'-bipyridyl ligands show similar results, except that σp and σp+ are almost equally effective in describing the influence of substituents at the 4- and 4'-positions of bipyridyl ligands. For complexes 1-5 having an X-substituent at the 5-position of the phenanthrolinyl ligand, the MLCT absorption and emission energies, as well as the d5/d6-electron redox couple, are correlated with values for several other series of d6-electron metal complexes and give slopes that can be rationalized in terms of the relative number of diimine ligands and X-substituents.

1,10-Phenanthroline derivatives↗
DOE OSTI2024

EF-Hand Battle Royale: Hetero-ion Complexation in Lanmodulin

The lanmodulin (LanM) protein has emerged as an effective means for rare earth element (REE) extraction and separation from complex feedstocks without the use of organic solvents. Whereas the binding of LanM to individual REEs has been well characterized, little is known about the thermodynamics of mixed metal binding complexes (i.e., heterogeneous ion complexes), which limits the ability to accurately predict separation performance for a given metal ion mixture. In this paper, we employ the law of mass action to establish a theory of perfect cooperativity for LanM-REE complexation at the two highest-affinity binding sites. The theory is then used to derive an equation that explains the nonintuitive REE binding behavior of LanM, where separation factors for binary pairs of ions vary widely based on the ratio of ions in the aqueous phase, a phenomenon that is distinct from single-ion-binding chemical chelators. We then experimentally validate this theory and perform the first quantitative characterization of LanM complexation with heterogeneous ion pairs using resin-immobilized LanM. Importantly, the resulting homogeneous and heterogeneous constants enable accurate prediction of the equilibrium state of LanM in the presence of mixtures of up to 10 REEs, confirming that the perfect cooperativity model is an accurate mechanistic description of REE complexation by LanM. We further employ the model to simulate separation performance over a range of homogeneous and heterogeneous binding constants, revealing important insights into how mixed binding differentially impacts REE separations based on the relative positioning of the ion pairs within the lanthanide series. In addition to informing REE separation process optimization, these results provide mathematical and experimental insight into competition dynamics in other ubiquitous and medically relevant, cooperative binding proteins, such as calmodulin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A nanobody suite for yeast scaffold nucleoporins provides details of the nuclear pore complex structure

Nuclear pore complexes (NPCs) are the main conduits for molecular exchange across the nuclear envelope. The NPC is a modular assembly of ~500 individual proteins, called nucleoporins or nups. Most scaffolding nups are organized in two multimeric subcomplexes, the Nup84 or Y complex and the Nic96 or inner ring complex. Working in S. cerevisiae, and to study the assembly of these two essential subcomplexes, we here develop a set of twelve nanobodies that recognize seven constituent nucleoporins of the Y and Nic96 complexes. These nanobodies all bind specifically and with high affinity. We present structures of several nup-nanobody complexes, revealing their binding sites. Additionally, constitutive expression of the nanobody suite in S. cerevisiae detect accessible and obstructed surfaces of the Y complex and Nic96 within the NPC. Overall, this suite of nanobodies provides a unique and versatile toolkit for the study of the NPC.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Spectroscopic characterization of a new Re(i) tricarbonyl complex with a thiosemicarbazone derivative: towards sensing and electrocatalytic applications

This work describes the preparation of a new thiosemicarbazone derivative, (Z)- N -ethyl-2-(6-oxo-1,10-phenanthrolin-5(6 H )-ylidene)hydrazinecarbothioamide (phet) and its respective Re( I ) tricarbonyl chloro complex, fac -[ReCl(CO) 3 (phet)]. The spectroscopic, photophysical and electrochemical properties of the new complex were fully investigated through steady state and time-resolved techniques along with computational calculations. In fac -[ReCl(CO) 3 (phet)], the new ligand is coordinated to the metal center through the pyridyl rings of the phenanthroline moiety. The unbound electron pairs in the S atom of the bending thiosemicarbazone group induce new low energy lying electronic transitions. Consequently, enhanced visible light absorption up to 550 nm is observed in acetonitrile due to the overlap between MLCT Re→phet and IL phet(n→π*) transitions. The absorption bands and emission quantum yields of fac -[ReCl(CO) 3 (phet)] are sensitive to proton concentration due to an acid-basic equilibrium in the N atoms of the thiosemicarbazone. Proton dissociation constants of 10.0 ± 0.1 and 11.4 ± 0.2 were determined respectively for the ground and excited states of the new complex. Spectral changes could also be observed in the presence of Zn 2+ cations which can be further explored for sensing applications. The electrochemical behavior of the new complex was studied in detail, revealing up to four one electron reduction processes in the range from 0 to -2.4 V vs. Fc + /Fc. With support of DFT calculations, the first three processes are ascribed to the reduction of the coordinated phet ligand followed by the Re I/0 reduction and consequent Cl - release. Furthermore, the new complex was able to act as an electrocatalyst for CO 2 reduction into CO ( E onset = -1.92 V vs. Fc + /Fc), with a turnover frequency of 2.81 s -1 and turnover number of 24 ± 1 in anhydrous acetonitrile, being the first Re( I ) tricarbonyl complex with a thiosemicarbazone derivative described for this goal. The detailed characterization carried out here can drive the development of new Re( I )-thiosemicarbazone derivatives for different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Ion-specific clustering of metal-amphiphile complexes in rare earth separations

The nanoscale structure of a complex fluid can play a major role in the selective adsorption of ions at the nanometric interfaces, which is crucial in industrial and technological applications. Here we study the effect of anions and lanthanide ions on the nanoscale structure of a complex fluid formed by metal-amphiphile complexes, using small angle X-ray scattering. The nano- and mesoscale structures we observed can be directly connected to the preferential transfer of light (La and Nd) or heavy (Er and Lu) lanthanides into the complex fluid from an aqueous solution. While toluene-based complex fluids containing trioctylmethylammonium-nitrate (TOMA-nitrate) always show the same mesoscale hierarchical structure regardless of lanthanide loading and prefer light lanthanides, those containing TOMA-thiocyanate show an evolution of the mesoscale structure as a function of the lanthanide loading and prefer heavy lanthanides. The hierarchical structure indicates the presence of attractive interactions between ion-amphiphile aggregates, causing them to form clusters. A clustering model that accounts for the hard sphere repulsions and short-range attractions between the aggregates has been adapted to model the X-ray scattering results. The new model successfully describes the nanoscale structure and helps in understanding the mechanisms responsible for amphiphile assisted ion transport between immiscible liquids. Accordingly, our results imply different mechanisms of lanthanide transport depending on the anion present in the complex fluid and correspond with anion-dependent trends in rare earth separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Communication: Photoactivation of nucleobase bound platinum{sup II} metal complexes: Probing the influence of the nucleobase

We present UV laser action spectra (220-300 nm) of isolated nucleobase-bound Pt{sup II}(CN){sub 4}{sup 2−} complexes, i.e., Pt(CN){sub 4}{sup 2−}⋅M, where M = uracil, thymine, cytosine, and adenine. These metal complex-nucleobase clusters represent model systems for identifying the fundamental photophysical and photochemical processes occurring in photodynamic platinum (II) drug therapies that target DNA. This is the first study to explore the specific role of the nucleobase in the photophysics of the aggregate complex. Each of the complexes studied displays a broadly similar absorption spectra, with a strong λ{sub max} ∼ 4.7 eV absorption band (nucleobase localized chromophore) and a subsequent increase in the absorption intensity towards higher spectral-energy (Pt(CN){sub 4}{sup 2−} localized chromophore). However, strikingly different band widths are observed across the series of complexes, decreasing in the order Pt(CN){sub 4}{sup 2−}⋅Thymine > Pt(CN){sub 4}{sup 2−}⋅Uracil > Pt(CN){sub 4}{sup 2−}⋅Adenine > Pt(CN){sub 4}{sup 2−}⋅Cytosine. Changes in the bandwidth of the ∼4.7 eV band are accompanied by distinctive changes in the photofragment product ions observed following photoexcitation, with the narrower-bandwidth complexes showing a greater propensity to decay via electron detachment decay. We discuss these observations in the context of the distinctive nucleobase-dependent excited state lifetimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural insights into the assembly of the histone deacetylase-associated Sin3L/Rpd3L corepressor complex

Acetylation is correlated with chromatin decondensation and transcriptional activation, but its regulation by histone deacetylase (HDAC)-bearing corepressor complexes is poorly understood. Here, we describe the mechanism of assembly of the mammalian Sin3L/Rpd3L complex facilitated by Sds3, a conserved subunit deemed critical for proper assembly. Sds3 engages a globular, helical region of the HDAC interaction domain (HID) of the scaffolding protein Sin3A through a bipartite motif comprising a helix and an adjacent extended segment. Sds3 dimerizes through not only one of the predicted coiled-coil motifs but also, the segment preceding it, forming an ~150-Å-long antiparallel dimer. Contrary to previous findings in yeast, Sin3A rather than Sds3 functions in recruiting HDAC1 into the complex by engaging the latter through a highly conserved segment adjacent to the helical HID subdomain. In the resulting model for the ternary complex, the two copies of the HDACs are situated distally and dynamically because of a natively unstructured linker connecting the dimerization domain and the Sin3A interaction domain of Sds3; these features contrast with the static organization described previously for the NuRD (nucleosome remodeling and deacetylase) complex. Finally, the Sds3 linker features several conserved basic residues that could potentially maintain the complex on chromatin by nonspecific interactions with DNA after initial recruitment by sequence-specific DNA-binding repressors.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

Purification and SAXS Analysis of the Integrin Linked Kinase, PINCH, Parvin (IPP) Heterotrimeric Complex

The heterotrimeric protein complex containing the integrin linked kinase (ILK), parvin, and PINCH proteins, termed the IPP complex, is an essential component of focal adhesions, where it interacts with many proteins to mediate signaling from integrin adhesion receptors. Here we conduct a biochemical and structural analysis of the minimal IPP complex, comprising full-length human ILK, the LIM1 domain of PINCH1, and the CH2 domain of α-parvin. We provide a detailed purification protocol for IPP and show that the purified IPP complex is stable and monodisperse in solution. Using small-angle X-ray scattering (SAXS), we also conduct the first structural characterization of IPP, which reveals an elongated shape with dimensions 120×60×40 Å. Flexibility analysis using the ensemble optimization method (EOM) is consistent with an IPP complex structure with limited flexibility, raising the possibility that inter-domain interactions exist. However, our studies suggest that the inter-domain linker in ILK is accessible and we detect no inter-domain contacts by gel filtration analysis. This study provides a structural foundation to understand the conformational restraints that govern the IPP complex.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Eu(III) and Cm(III) Complexation by the Aminocarboxylates NTA, EDTA, and EGTA Studied with NMR, TRLFS, and ITC—An Improved Approach to More Robust Thermodynamics

The complex formation of Eu(III) and Cm(III) was studied via tetradentate, hexadentate, and octadentate coordinating ligands of the aminopolycarboxylate family, viz., nitrilotriacetate (NTA 3- ), ethylenediaminetetraacetate (EDTA 4- ), and ethylene glycol-bis(2-aminoethyl ether)-N,N,N',N'-tetraacetate (EGTA 4- ), respectively. Based on the complexones’ pK a values obtained from 1 H nuclear magnetic resonance (NMR) spectroscopic pH titration, complex formation constants were determined by means of the parallel-factor-analysis-assisted evaluation of Eu(III) and Cm(III) time-resolved laser-induced fluorescence spectroscopy (TRLFS). This was complemented by isothermal titration calorimetry (ITC), providing the enthalpy and entropy of the complex formation. This allowed us to obtain genuine species along with their molecular structures and corresponding reliable thermodynamic data. The three investigated complexones formed 1:1 complexes with both Eu(III) and Cm(III). Besides the established Eu(III)–NTA 1:1 and 1:2 complexes, we observed, for the first time, the existence of a Eu(III)–NTA 2:2 complex of millimolar metal and ligand concentrations. Demonstrated for thermodynamic studies on Eu(III) and Cm(III) interaction with complexones, the utilized approach is commonly applicable to many other metal–ligand systems, even to high-affinity ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Polyelectrolyte Complexation of Oligonucleotides by Charged Hydrophobic—Neutral Hydrophilic Block Copolymers

Polyelectrolyte complex micelles (PCMs, core-shell nanoparticles formed by complexation of a polyelectrolyte with a polyelectrolyte-hydrophilic neutral block copolymer) offer a solution to the critical problem of delivering therapeutic nucleic acids, Despite this, few systematic studies have been conducted on how parameters such as polycation charge density, hydrophobicity, and choice of charged group influence PCM properties, despite evidence that these strongly influence the complexation behavior of polyelectrolyte homopolymers. In this article, we report a comparison of oligonucleotide PCMs and polyelectrolyte complexes formed by poly(lysine) and poly((vinylbenzyl) trimethylammonium) (PVBTMA), a styrenic polycation with comparatively higher charge density, increased hydrophobicity, and a permanent positive charge. All of these differences have been individually suggested to provide increased complex stability, but we find that PVBTMA in fact complexes oligonucleotides more weakly than does poly(lysine), as measured by stability versus added salt. Using small angle X-ray scattering and electron microscopy, we find that PCMs formed from both cationic blocks exhibit very similar structure-property relationships, with PCM radius determined by the cationic block size and shape controlled by the hybridization state of the oligonucleotides. These observations narrow the design space for optimizing therapeutic PCMs and provide new insights into the rich polymer physics of polyelectrolyte self-assembly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The Straightening of a River Meander Leads to Extensive Losses in Flow Complexity and Ecosystem Services

To assist river restoration efforts we need to slow the rate of river degradation. This study provides a detailed explanation of the hydraulic complexity loss when a meandering river is straightened in order to motivate the protection of river channel curvature. We used computational fluid dynamics (CFD) modeling to document the difference in flow dynamics in nine simulations with channel curvature (C) degrading from a well-established tight meander bend (C = 0.77) to a straight channel without curvature (C = 0). To control for covariates and slow the rate of loss to hydraulic complexity, each of the nine-channel realizations had equivalent bedform topography. The analyzed hydraulic variables included the flow surface elevation, streamwise and transverse unit discharge, flow velocity at streamwise, transverse, and vertical directions, bed shear stress, stream function, and the vertical hyporheic flux rates at the channel bed. The loss of hydraulic complexity occurred gradually when initially straightening the channel from C = 0.77 to C = 0.33 (i.e., the radius of the channel is three-times the channel width), and additional straightening incurred rapid losses to hydraulic complexity. Other studies have shown hydraulic complexity provides important riverine habitat and is positively correlated with biodiversity. This study demonstrates how hydraulic complexity can be gradually and then rapidly lost when unwinding a river, and hopefully will serve as a cautionary tale.

54 ENVIRONMENTAL SCIENCES↗