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At least 1,369 records · Page 76

Design of protein-binding proteins from the target structure alone

The design of proteins that bind to a specific site on the surface of a target protein using no information other than the three-dimensional structure of the target remains a challenge. Here we describe a general solution to this problem that starts with a broad exploration of the vast space of possible binding modes to a selected region of a protein surface, and then intensifies the search in the vicinity of the most promising binding modes. We demonstrate the broad applicability of this approach through the de novo design of binding proteins to 12 diverse protein targets with different shapes and surface properties. Biophysical characterization shows that the binders, which are all smaller than 65 amino acids, are hyperstable and, following experimental optimization, bind their targets with nanomolar to picomolar affinities. We succeeded in solving crystal structures of five of the binder–target complexes, and all five closely match the corresponding computational design models. Experimental data on nearly half a million computational designs and hundreds of thousands of point mutants provide detailed feedback on the strengths and limitations of the method and of our current understanding of protein–protein interactions, and should guide improvements of both. Our approach enables the targeted design of binders to sites of interest on a wide variety of proteins for therapeutic and diagnostic applications.

59 BASIC BIOLOGICAL SCIENCES↗

Cryo-EM structure of the human neutral amino acid transporter ASCT2

Human ASCT2 belongs to the SLC1 family of secondary transporters and is specific for the transport of small neutral amino acids. ASCT2 is upregulated in cancer cells and serves as the receptor for many retroviruses; hence, it has importance as a potential drug target. Here we used single-particle cryo-EM to determine a structure of the functional and unmodified human ASCT2 at 3.85-Å resolution. ASCT2 forms a homotrimeric complex in which each subunit contains a transport and a scaffold domain. Prominent extracellular extensions on the scaffold domain form the predicted docking site for retroviruses. Relative to structures of other SLC1 members, ASCT2 is in the most extreme inward-oriented state, with the transport domain largely detached from the central scaffold domain on the cytoplasmic side. In conclusion, this domain detachment may be required for substrate binding and release on the intracellular side of the membrane.

59 BASIC BIOLOGICAL SCIENCES↗

Structural basis of amino acid surveillance by higher-order tRNA-mRNA interactions

Amino acid availability in Gram-positive bacteria is monitored by T-box riboswitches. T-boxes directly bind tRNAs, assess their aminoacylation state, and regulate the transcription or translation of downstream genes to maintain nutritional homeostasis. Here in this paper, we report cocrystal and cryo-EM structures of Geobacillus kaustophilus and Bacillus subtilis T-box–tRNA complexes, detailing their multivalent, exquisitely selective interactions. The T-box forms a U-shaped molecular vise that clamps the tRNA, captures its 3' end using an elaborate ‘discriminator’ structure, and interrogates its aminoacylation state using a steric filter fashioned from a wobble base pair. In the absence of aminoacylation, T-boxes clutch tRNAs and form a continuously stacked central spine, permitting transcriptional readthrough or translation initiation. A modeled aminoacyl disrupts tRNA-T-box stacking, severing the central spine and blocking gene expression. Our data establish a universal mechanism of amino acid sensing on tRNAs and gene regulation by T-box riboswitches and exemplify how higher-order RNA-RNA interactions achieve multivalency and specificity.

59 BASIC BIOLOGICAL SCIENCES↗

Structural Basis for the Bidirectional Activity of Bacillus nanoRNase NrnA

NanoRNAs are RNA fragments 2 to 5 nucleotides in length that are generated as byproducts of RNA degradation and abortive transcription initiation. Cells have specialized enzymes to degrade nanoRNAs, such as the DHH phosphoesterase family member NanoRNase A (NrnA). This enzyme was originally identifed as a 3'→5' exonuclease, but we show here that NrnA is bidirectional, degrading 2–5 nucleotide long RNA oligomers from the 3' end, and longer RNA substrates from the 5' end. The crystal structure of Bacillus subtilis NrnA reveals a dynamic bi-lobal architecture, with the catalytic N-terminal DHH domain linked to the substrate binding C-terminal DHHA1 domain via an extended linker. Whereas this arrangement is similar to the structure of RecJ, a 5'→3' DHH family DNase and other DHH family nanoRNases, Bacillus NrnA has gained an extended substrate-binding patch that we posit is responsible for its 3'→5' activity.

59 BASIC BIOLOGICAL SCIENCES↗

Structural and mechanistic basis for redox sensing by the cyanobacterial transcription regulator RexT

Abstract Organisms have a myriad of strategies for sensing, responding to, and combating reactive oxygen species, which are unavoidable consequences of aerobic life. In the heterocystous cyanobacterium Nostoc sp. PCC 7120, one such strategy is the use of an ArsR-SmtB transcriptional regulator RexT that senses H 2 O 2 and upregulates expression of thioredoxin to maintain cellular redox homeostasis. Different from many other members of the ArsR-SmtB family which bind metal ions, RexT has been proposed to use disulfide bond formation as a trigger to bind and release DNA. Here, we present high-resolution crystal structures of RexT in the reduced and H 2 O 2 -treated states. These structures reveal that RexT showcases the ArsR-SmtB winged-helix-turn-helix fold and forms a vicinal disulfide bond to orchestrate a response to H 2 O 2 . The importance of the disulfide-forming Cys residues was corroborated using site-directed mutagenesis, mass spectrometry, and H 2 O 2 -consumption assays. Furthermore, an entrance channel for H 2 O 2 was identified and key residues implicated in H 2 O 2 activation were pinpointed. Finally, bioinformatics analysis of the ArsR-SmtB family indicates that the vicinal disulfide “redox switch” is a unique feature of cyanobacteria in the Nostocales order, presenting an interesting case where an ArsR-SmtB protein scaffold has been evolved to showcase peroxidatic activity and facilitate redox-based regulation.

54 ENVIRONMENTAL SCIENCES↗

Structural Effects of Lanthanide Dopants on Alumina

Lanthanide (Ln 3+ ) doping in alumina has shown great promise for stabilizing and promoting desirable phase formation to achieve optimized physical and chemical properties. However, doping alumina with Ln elements is generally accompanied by formation of new phases (i.e. LnAlO3, Ln2O3), and therefore inclusion of Ln-doping mechanisms for phase stabilization of the alumina lattice is indispensable. In this study, Ln-doping (400 ppm) of the alumina lattice crucially delays the onset of phase transformation and enables phase population control, which is achieved without the formation of new phases. The delay in phase transition (θ → α), and alteration of powder morphology, particle dimensions, and composition ratios between α- and θ-alumina phases are studied using a combination of solid state nuclear magnetic resonance, electron microscopy, digital scanning calorimetry, and high resolution X-ray diffraction with refinement fitting. Loading alumina with a sparse concentration of Ln-dopants suggests that the dopants reside in the vacant octahedral locations within the alumina lattice, where complete conversion into the thermodynamically stable α-domain is shown in dysprosium (Dy)- and lutetium (Lu)-doped alumina. This study opens up the potential to control the structure and phase composition of Ln-doped alumina for emerging applications.

36 MATERIALS SCIENCE↗

Molecular Structures of Polymer/Sulfur Composites for Lithium-Sulfur Batteries with Long Cycle Life

Vulcanizedpolyaniline/sulfur (SPANI/S) nanostructures were investigated for Li-S battery applications, but the detailed molecular structures of such composites have not been fully illustrated. In this paper, we synthesize SPANI/S composites with different S content in a nanorod configuration. FTIR, Raman, XPS, XRD, SEM and elemental analysis methods are used to characterize the molecular structure of the materials. We provide clear evidence that a portion of S was grafted on PANI during heating and connected the PANI chains with disulfide bonds to form a crosslinked network and the rest of S was encapsulated within it.. Polysulfides and elementary sulfur nanoparticles are physically trapped inside the polymer network and are not chemically bound to the polymer. The performance of the composites is further improved by reducing the particle size. Even after 500 cycles a capacity retention rate of 68.8% is observed in the SPANI/S composite with 55% S content.

Environmental Molecular Sciences Laboratory↗

Structural phase transformation and Fe valence evolution in FeOxF2-x/C nanocomposite electrodes during lithiation and de-lithiation processes

In this study, the structural changes of FeOxF2-x/C during the first discharge and recharge cycles were studied by ex situ electron microscopy techniques including annular dark field scanning transmission electron microscopy (DF-STEM) imaging, selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) as well as by in situ X-ray absorption spectroscopy (XAS). The evolution of the valence state of Fe was determined by combined EELS using the Fe-L edge and XAS using the Fe-K edge. The results of this investigation show that the conversion reaction path during 1st lithiation is very different from the re-conversion path during 1st delithiation. During lithiation, intercalation is first observed followed by conversion into a lithiated rocksalt (Li–Fe–O–F) structure, and metallic Fe and LiF phases. During delithiation, the rocksalt phase does not disappear, but co-exists with an amorphous (rutile type) phase formed initially by the reaction of LiF and Fe. However, a de-intercalation stage is still observed at the end of reconversion similar to a single phase process despite the coexistence of these two (rocksalt and amorphous) phases.

36 MATERIALS SCIENCE↗

Electronic structure of cobalt doped CdSe quantum dots using soft X-ray spectroscopy

Here, the electronic structure and magnetic properties of cobalt doped CdSe quantum dots (QDs) are studied using electron microscopy, soft X-ray spectroscopy, and magnetometry. Magnetometry measurements suggest these QDs are superparamagnetic, contrary to a spin-glass state observed in the bulk analogue. Electron microscopy shows well formed QDs, but with cobalt existing as doped into the QD and as unreacted species not contained in the QD. X-ray absorption measurements at the Co L3-edge suggest that changes in spectra features as a function of particle size can be described considering combination of a cobalt ion in a tetrahedral crystal field and an octahedrally coordinated (impurity) phase. With decreasing particle sizes, the impurity phase increases, suggesting that small QDs can be difficult to dope.

36 MATERIALS SCIENCE↗

Electronic structure and characterization of a uranyl di-15-crown-5 complex with an unprecedented sandwich structure

Understanding of the nature and extent of chemical bonding in uranyl coordination complexes is crucial for the design of new ligands for nuclear waste separation, uranium extraction from seawater, and other applications. We report in this paper the synthesis, infrared spectroscopic characterization, and quantum chemical studies of a molecular uranyl–di-15-crown-5 complex. The structure and bonding of this unique complex featuring a distinctive 6-fold coplanar coordination staggered sandwich structure and an unusual non-perpendicular orientation of the uranyl moiety are evaluated using density functional theory and chemical bonding analyses. Finally, the results provide fundamental understanding of the coordination interaction of uranyl with oxygen-donor ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Examining the structural evolution of bicarbonate–water clusters: insights from photoelectron spectroscopy, basin-hopping structural search, and comparison with available IR spectral studies

Bicarbonate serves a crucial biochemical role in the physiological pH buffering system and also has important atmospheric implications. In the current study, HCO 3 $-$ (H 2 O) n (n = 0-13) clusters were successfully produced via electrospray ionization of corresponding bulk salt solution, and were characterized by combining negative ion photoelectron spectroscopy and theoretical calculations. The photoelectron spectra reveal that the electron binding energy monotonically increases with the cluster size up to n = 10 and remains largely the same after n > 10. The photo-detaching feature of the solute HCO3$-$itself, which dominates in the small clusters, diminishes with increase of water coverage. Based on the charge distribution and molecular orbital analyses, the universal high electron binding energy tail that dominates in the larger clusters can be attributed to ionization of water. Thus, the transition of ionization from solute to solvent at the size larger than n=10 has been observed. Extensive theoretical structural search based on the Basin-Hopping unbiased method was carried out, and a plethora of low energy isomers have been obtained for each medium and large size. By comparing the simulated photoelectron spectra and calculated electron binding energies with the experiments, as well as by comparing the simulated infrared spectra with previously reported IR spectra, the probable global minima and the structural evolutionary routes are presented. The nature of bicarbonate-water interactions are mainly electrostatic as implied by the electron localization function (ELF) analysis.

Environmental Molecular Sciences Laboratory↗

Flexible monomer-based covalent organic frameworks: design, structure and functions

The design and synthesis of flexible monomer-based covalent organic frameworks (COFs) have been considered a challenge. We describe the design and synthesis of a new flexible monomer-based COF, termed PPN-30 (PPN meaning porous polymer network), by the use of a flexible alkyl amine, 1,4-cyclohexanediamine, combined with 1,3,5-triformylbenzene. The structure and gas adsorption properties of PPN-30 were carefully investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High temperature hydrothermal synthesis of rare-earth titanates: synthesis and structure of RE 5 Ti 4 O 15 (OH) (RE = La, Er), Sm 3 TiO 5 (OH) 3 , RE 5 Ti 2 O 11 (OH) (RE = Tm–Lu) and Ce 2 Ti 4 O 11

Reactions of rare-earth oxides with TiO 2 were performed in high temperature (650–700 °C) hydrothermal fluids. Two different mineralizer fluids were examined, 20 M KOH and 30 M CsF, and their respective products analyzed. When concentrated KOH fluids were used, single crystals of a variety of new OH - containing species were isolated and structurally characterized: RE 5 Ti 4 O 15 (OH) (RE = La, Er) I, Sm 3 TiO 5 (OH) 3 II and RE 5 Ti 2 O 11 (OH) (RE = Tm–Lu) III. La 5 Ti 4 O 15 (OH) I crystallizes in the orthorhombic space group Pnnm with unit cell dimensions of a = 30.5152(12) Å, b = 5.5832(2) Å, c = 7.7590(3) Å and V = 1321.92(9) Å 3 , Z = 4. Sm 3 TiO 5 (OH) 3 II crystallizes in the monoclinic space group P21/m with unit cell parameters of a = 5.6066(2) Å, b = 10.4622(4) Å, c = 6.1258(2) Å and β = 104.7390(10)°, V = 347.50(2) Å3, Z = 2. Lu5Ti2O11(OH) III crystallizes in the monoclinic space group C2/m with unit cell dimensions of a = 12.1252(9) Å, b = 5.8243(4) Å, c = 7.0407(5) Å, β = 106.939(3)° and V = 475.65(6) Å3, Z = 2. When concentrated fluoride solutions are used, mostly RE 2 Ti 2 O 7 type compounds were isolated in either cubic or monoclinic phases. In the case of cerium, Ce2Ti4O11IV was isolated that crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 13.6875(7) Å, b = 5.0955(3) Å, c = 12.8592(7) Å, β = 108.964(2)° and V = 848.18(8) Å 3 , Z = 4. The synthesis, structural characterization, and supporting characterization are reported for all compounds. The work highlights the complementary nature of hydroxide and fluoride fluids in studying the reactivity of refractory oxides.

36 MATERIALS SCIENCE↗

The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3 BH 3 )(H 2 ) x (x = 1.5) compound

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3 BH 3 )(H 2 ) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3 BH 3 ) in an environment with an excess of molecular hydrogen (H 2 ). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weaving of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.

36 MATERIALS SCIENCE↗