Supramolecular "Big Bang" in a Single-Ionic Surfactant/Water System Driven by Electrostatic Repulsion: From Vesicles to Micelles.

PubMed

Leclercq, Loïc; Bauduin, Pierre; Nardello-Rataj, Véronique

2017-04-11

In aqueous solution, dimethyldi-n-octylammonium chloride, [DiC 8 ][Cl], spontaneously forms dimers at low concentrations (1-10 mM) to decrease the strength of the hydrophobic-water contact. Dimers represent ideal building blocks for the abrupt edification of vesicles at 10 mM. These vesicles are fully characterized by dynamic and static light scattering, self-diffusion nuclear magnetic resonance, and freeze-fracture transmission electron microscopy. An increase in concentration leads to electrostatic repulsion between vesicles that explode into small micelles at 30 mM. These transitions are detected by means of surface tension, conductivity, and solubility of hydrophobic solutes as well as by isothermal titration microcalorimetry. These unusual supramolecular transitions emerge from the surfactant chemical structure that combines two contradictory features: (i) the double-chain structure tending to form low planar aggregates with low water solubility and (ii) the relatively short chains giving high hydrophilicity. The well-balanced hydrophilic-hydrophobic character of [DiC 8 ][Cl] is then believed to be at the origin of the unusual supramolecular sequence offering new opportunities for drug delivery systems.

Unusual Crystallization Behavior Close to the Glass Transition

NASA Astrophysics Data System (ADS)

Desgranges, Caroline; Delhommelle, Jerome

2018-03-01

Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, Ag6 Cu4 , which has a positive heat of mixing, and CuZr, characterized by a large negative heat of mixing. Our results allow us to identify this unusual behavior as directly correlated with a nonmonotonic temperature dependence for the formation energy of connected icosahedral structures, which are incompatible with crystalline order and impede the development of the crystal nucleus, leading to an unexpectedly larger free energy barrier at low temperature. This, in turn, promotes the formation of a predominantly closed-packed critical nucleus, with fewer defects, thereby suggesting a new way to control the structure of the crystal nucleus, which is of key importance in catalysis.

Rauvomines A and B, Two Monoterpenoid Indole Alkaloids from Rauvolfia vomitoria.

PubMed

Zeng, Jun; Zhang, Dong-Bo; Zhou, Pan-Pan; Zhang, Qi-Li; Zhao, Lei; Chen, Jian-Jun; Gao, Kun

2017-08-04

Two unusual normonoterpenoid indole alkaloids rauvomine A (1) and rauvomine B (2), together with two known compounds peraksine (3) and alstoyunine A (4), were isolated from the aerial parts of Rauvolfia vomitoria. The structures with absolute configurations of 1 and 2 were elucidated by spectroscopic analysis, single-crystal X-ray diffraction, and electronic circular dichroism (ECD) calculations. Compound 2 is a novel C 18 normonoterpenoid indole alkaloid with a substituted cyclopropane ring that forms an unusual 6/5/6/6/3/5 hexcyclic rearranged ring system. The plausible biogenetic pathways of 1 and 2 were proposed. Compound 2 exhibited significant anti-inflammatory activity.

Self-organized minimum-energy structures for dielectric elastomer actuators

NASA Astrophysics Data System (ADS)

Kofod, G.; Paajanen, M.; Bauer, S.

2006-11-01

When a stretched elastomer is laminated to a flat plastic frame, a complex shape is formed, which is termed a minimum-energy structure. It is shown how self-organized structures can be applied in the development of actuators with complex, out-of-plane actuationmodes. This unusual concept is then demonstrated in the case of dielectric elastomer actuators. Among advantages of this approach are the simplicity in manufacturing, the potential complexity and sophistication of the manufactured structures, and the general benefits of the concept when applied to other electro-mechanically active materials.

Architecture of a Diels-Alderase ribozyme with a preformed catalytic pocket.

PubMed

Keiper, Sonja; Bebenroth, Dirk; Seelig, Burckhard; Westhof, Eric; Jäschke, Andres

2004-09-01

Artificial ribozymes catalyze a variety of chemical reactions. Their structures and reaction mechanisms are largely unknown. We have analyzed a ribozyme catalyzing Diels-Alder cycloaddition reactions by comprehensive mutation analysis and a variety of probing techniques. New tertiary interactions involving base pairs between nucleotides of the 5' terminus and a large internal loop forming a pseudoknot fold were identified. The probing data indicate a preformed tertiary structure that shows no major changes on substrate or product binding. Based on these observations, a molecular architecture featuring a Y-shaped arrangement is proposed. The tertiary structure is formed in a rather unusual way; that is, the opposite sides of the asymmetric internal loop are clamped by the four 5'-terminal nucleotides, forming two adjacent two base-pair helices. It is proposed that the catalytic pocket is formed by a wedge within one of these helices.

Sequence-specific unusual (1-->2)-type helical turns in alpha/beta-hybrid peptides.

PubMed

Prabhakaran, Panchami; Kale, Sangram S; Puranik, Vedavati G; Rajamohanan, P R; Chetina, Olga; Howard, Judith A K; Hofmann, Hans-Jörg; Sanjayan, Gangadhar J

2008-12-31

This article describes novel conformationally ordered alpha/beta-hybrid peptides consisting of repeating l-proline-anthranilic acid building blocks. These oligomers adopt a compact, right-handed helical architecture determined by the intrinsic conformational preferences of the individual amino acid residues. The striking feature of these oligomers is their ability to display an unusual periodic pseudo beta-turn network of nine-membered hydrogen-bonded rings formed in the forward direction of the sequence by 1-->2 amino acid interactions both in solid-state and in solution. Conformational investigations of several of these oligomers by single-crystal X-ray diffraction, solution-state NMR, and ab initio MO theory suggest that the characteristic steric and dihedral angle restraints exerted by proline are essential for stabilizing the unusual pseudo beta-turn network found in these oligomers. Replacing proline by the conformationally flexible analogue alanine (Ala) or by the conformationally more constrained alpha-amino isobutyric acid (Aib) had an adverse effect on the stabilization of this structural architecture. These findings increase the potential to design novel secondary structure elements profiting from the steric and dihedral angle constraints of the amino acid constituents and help to augment the conformational space available for synthetic oligomer design with diverse backbone structures.

Study of an Unusual Advanced Glycation End-Product (AGE) Derived from Glyoxal Using Mass Spectrometry

NASA Astrophysics Data System (ADS)

Lopez-Clavijo, Andrea F.; Duque-Daza, Carlos A.; Romero Canelon, Isolda; Barrow, Mark P.; Kilgour, David; Rabbani, Naila; Thornalley, Paul J.; O'Connor, Peter B.

2014-04-01

Glycation is a post-translational modification (PTM) that affects the physiological properties of peptides and proteins. In particular, during hyperglycaemia, glycation by α-dicarbonyl compounds generate α-dicarbonyl-derived glycation products also called α-dicarbonyl-derived advanced glycation end products. Glycation by the α-dicarbonyl compound known as glyoxal was studied in model peptides by MS/MS using a Fourier transform ion cyclotron resonance mass spectrometer. An unusual type of glyoxal-derived AGE with a mass addition of 21.98436 Da is reported in peptides containing combinations of two arginine-two lysine, and one arginine-three lysine amino acid residues. Electron capture dissociation and collisionally activated dissociation results supported that the unusual glyoxal-derived AGE is formed at the guanidino group of arginine, and a possible structure is proposed to illustrate the 21.9843 Da mass addition.

Dual Catalytic Activity of a Cytochrome P450 Controls Bifurcation at a Metabolic Branch Point of Alkaloid Biosynthesis in Rauwolfia serpentina

PubMed Central

Dang, Thu‐Thuy T.; Franke, Jakob; Tatsis, Evangelos

2017-01-01

Abstract Plants create tremendous chemical diversity from a single biosynthetic intermediate. In plant‐derived ajmalan alkaloid pathways, the biosynthetic intermediate vomilenine can be transformed into the anti‐arrhythmic compound ajmaline, or alternatively, can isomerize to form perakine, an alkaloid with a structurally distinct scaffold. Here we report the discovery and characterization of vinorine hydroxylase, a cytochrome P450 enzyme that hydroxylates vinorine to form vomilenine, which was found to exist as a mixture of rapidly interconverting epimers. Surprisingly, this cytochrome P450 also catalyzes the non‐oxidative isomerization of the ajmaline precursor vomilenine to perakine. This unusual dual catalytic activity of vinorine hydroxylase thereby provides a control mechanism for the bifurcation of these alkaloid pathway branches. This discovery highlights the unusual catalytic functionality that has evolved in plant pathways. PMID:28654178

Dual Catalytic Activity of a Cytochrome P450 Controls Bifurcation at a Metabolic Branch Point of Alkaloid Biosynthesis in Rauwolfia serpentina.

PubMed

Dang, Thu-Thuy T; Franke, Jakob; Tatsis, Evangelos; O'Connor, Sarah E

2017-08-01

Plants create tremendous chemical diversity from a single biosynthetic intermediate. In plant-derived ajmalan alkaloid pathways, the biosynthetic intermediate vomilenine can be transformed into the anti-arrhythmic compound ajmaline, or alternatively, can isomerize to form perakine, an alkaloid with a structurally distinct scaffold. Here we report the discovery and characterization of vinorine hydroxylase, a cytochrome P450 enzyme that hydroxylates vinorine to form vomilenine, which was found to exist as a mixture of rapidly interconverting epimers. Surprisingly, this cytochrome P450 also catalyzes the non-oxidative isomerization of the ajmaline precursor vomilenine to perakine. This unusual dual catalytic activity of vinorine hydroxylase thereby provides a control mechanism for the bifurcation of these alkaloid pathway branches. This discovery highlights the unusual catalytic functionality that has evolved in plant pathways. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Anatomical Analysis of Saccharomyces cerevisiae Stalk-Like Structures Reveals Spatial Organization and Cell Specialization

PubMed Central

Scherz, Ruth; Shinder, Vera; Engelberg, David

2001-01-01

Recently we reported an unusual multicellular organization in yeast that we termed stalk-like structures. These structures are tall (0.5 to 3 cm long) and narrow (1 to 3 mm in diameter). They are formed in response to UV radiation of cultures spread on high agar concentrations. Here we present an anatomical analysis of the stalks. Microscopic inspection of cross sections taken from stalks revealed that stalks are composed of an inner core in which cells are dense and vital and a layer of cells (four to six rows) that surrounds the core. This outer layer is physically separated from the core and contains many dead cells. The outer layer may form a protective shell for the core cells. Through electron microscopy analysis we observed three types of cells within the stalk population: (i) cells containing many unusual vesicles, which might be undergoing some kind of cell death; (ii) cells containing spores (usually one or two spores only); and (iii) familiar rounded cells. We suggest that stalk cells are not only spatially organized but may undergo processes that induce a certain degree of cell specialization. We also show that high agar concentration alone, although not sufficient to induce stalk formation, induces dramatic changes in a colony's morphology. Most striking among the agar effects is the induction of growth into the agar, forming peg-like structures. Colonies grown on 4% agar or higher are reminiscent of stalks in some aspects. The agar concentration effects are mediated in part by the Ras pathway and are related to the invasive-growth phenomenon. PMID:11514526

An Unusual Fatty Acyl:Adenylate Ligase (FAAL)-Acyl Carrier Protein (ACP) Didomain in Ambruticin Biosynthesis.

PubMed

Hemmerling, Franziska; Lebe, Karen E; Wunderlich, Johannes; Hahn, Frank

2018-03-08

The divinylcyclopropane (DVC) fragment of the ambruticins is proposed to be formed by a unique polyene cyclisation mechanism, in which the unusual didomain AmbG plays a key role. It is proposed to activate the branched thioester carboxylic acid resulting from polyene cyclisation and to transfer it to its associated acyl carrier protein (ACP). After oxidative decarboxylation, the intermediate is channelled back into polyketide synthase (PKS) processing. AmbG was previously annotated as an adenylation-thiolation didomain with a very unusual substrate selectivity code but has not yet been biochemically studied. On the basis of sequence and homology model analysis, we reannotate AmbG as a fatty acyl:adenylate ligase (FAAL)-acyl carrier protein didomain with unusual substrate specificity. The expected adenylate-forming activity on fatty acids was confirmed by in vitro studies. AmbG also adenylates a number of structurally diverse carboxylic acids, including functionalised fatty acids and unsaturated and aromatic carboxylic acids. HPLC-MS analysis and competition experiments show that AmbG preferentially acylates its ACP with long-chain hydrophobic acids and tolerates a π system and a branch near the carboxylic acid. AmbG is the first characterised example of a FAAL-ACP didomain that is centrally located in a PKS and apparently activates a polyketidic intermediate. This is an important step towards deeper biosynthetic studies such as partial reconstitution of the ambruticin pathway to elucidate DVC formation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structure of granzyme C reveals an unusual mechanism of protease autoinhibition

PubMed Central

Kaiserman, Dion; Buckle, Ashley M.; Van Damme, Petra; Irving, James A.; Law, Ruby H. P.; Matthews, Antony Y.; Bashtannyk-Puhalovich, Tanya; Langendorf, Chris; Thompson, Philip; Vandekerckhove, Joël; Gevaert, Kris; Whisstock, James C.; Bird, Phillip I.

2009-01-01

Proteases act in important homeostatic pathways and are tightly regulated. Here, we report an unusual structural mechanism of regulation observed by the 2.5-Å X-ray crystal structure of the serine protease, granzyme C. Although the active-site triad residues adopt canonical conformations, the oxyanion hole is improperly formed, and access to the primary specificity (S1) pocket is blocked through a reversible rearrangement involving Phe-191. Specifically, a register shift in the 190-strand preceding the active-site serine leads to Phe-191 filling the S1 pocket. Mutation of a unique Glu–Glu motif at positions 192–193 unlocks the enzyme, which displays chymase activity, and proteomic analysis confirms that activity of the wild-type protease can be released through interactions with an appropriate substrate. The 2.5-Å structure of the unlocked enzyme reveals unprecedented flexibility in the 190-strand preceding the active-site serine that results in Phe-191 vacating the S1 pocket. Overall, these observations describe a broadly applicable mechanism of protease regulation that cannot be predicted by template-based modeling or bioinformatic approaches alone. PMID:19299505

Mars Life? - Microscopic Tube-like Structures

NASA Technical Reports Server (NTRS)

1996-01-01

This high-resolution scanning electron microscope image shows an unusual tube-like structural form that is less than 1/100th the width of a human hair in size found in meteorite ALH84001, a meteorite believed to be of Martian origin. Although this structure is not part of the research published in the Aug. 16 issue of the journal Science, it is located in a similar carbonate glob in the meteorite. This structure will be the subject of future investigations that could confirm whether or not it is fossil evidence of primitive life on Mars 3.6 billion years ago.

Crystal structure of metallo DNA duplex containing consecutive Watson-Crick-like T-Hg(II)-T base pairs.

PubMed

Kondo, Jiro; Yamada, Tom; Hirose, Chika; Okamoto, Itaru; Tanaka, Yoshiyuki; Ono, Akira

2014-02-24

The metallo DNA duplex containing mercury-mediated T-T base pairs is an attractive biomacromolecular nanomaterial which can be applied to nanodevices such as ion sensors. Reported herein is the first crystal structure of a B-form DNA duplex containing two consecutive T-Hg(II)-T base pairs. The Hg(II) ion occupies the center between two T residues. The N3-Hg(II) bond distance is 2.0 Å. The relatively short Hg(II)-Hg(II) distance (3.3 Å) observed in consecutive T-Hg(II)-T base pairs suggests that the metallophilic attraction could exist between them and may stabilize the B-form double helix. To support this, the DNA duplex is largely distorted and adopts an unusual nonhelical conformation in the absence of Hg(II). The structure of the metallo DNA duplex itself and the Hg(II)-induced structural switching from the nonhelical form to the B-form provide the basis for structure-based design of metal-conjugated nucleic acid nanomaterials. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural and magnetic properties of two- and three-dimensional molecule-based magnets (cat) +[M IIM III(C 2O 4) 3] -

NASA Astrophysics Data System (ADS)

Ovanesyan, Nikolai S.; Shilov, Gena V.; Pyalling, Alex A.; Train, Cyrille; Gredin, Patrick; Gruselle, Michel; Kiss, László F.; Bottyán, László

2004-05-01

We discuss the different structural arrangements of NBu 4[Fe IICr III(C 2O 4) 3] layered compounds in their racemic and enantiomeric forms and related magnetic properties. For [Mn IIFe III(C 2O 4) 3] networks of dimensionalities 2 and 3 Mössbauer spectroscopy was applied to study the Fe III sublattice magnetization. Unusual magnetic relaxation phenomena below TN were observed for both 2D and 3D networks.

The Crystal Structure of Thorium and Zirconium Dihydrides by X-ray and Neutron Diffraction

DOE R&D Accomplishments Database

Rundle, R.E.; Shull, C.G.; Wollan, E.O.

1951-04-20

Thorium forms a tetragonal lower hydride of composition ThH{sub 2}. The hydrides ThH{sub 2}, ThD{sub 2}, and ZrD{sub 2} have been studied by neutron diffraction in order that hydrogen positions could be determined. The hydrides are isomorphous, and have a deformed fluorite structure. Metal-hydrogen distances in thorium hydride are unusually large, as in UH{sub 3}. Thorium and zirconium scattering amplitudes and a revised scattering amplitude for deuterium are reported.

Coexpression of an unusual form of the EWS-WT1 fusion transcript and interleukin 2/15 receptor betamRNA in a desmoplastic small round cell tumour.

PubMed

Nakanishi, Y; Oinuma, T; Sano, M; Fuchinoue, F; Komatsu, K; Seki, T; Obana, Y; Tabata, M; Kikuchi, K; Shimamura, M; Ohmori, K; Nemoto, N

2006-10-01

The beta chain of the interleukin 2/15 receptor (IL-2/15Rbeta) is induced by the expression of the EWS-WT1. A case of desmoplastic small round cell tumour (DSRCT) expressing only an unusual EWS-WT1 treated by us is reported here. To characterise an unusual form of EWS-WT1. Frozen tissue sections of the axillary tumour were examined using a laser-assisted microdissection technique and reverse transcriptase polymerase chain reaction. The novel fusion of exon 8 of EWS and the defective exon 10 of WT1 (-KTS) was detected. Although it was an unusual form, the coexpression of the present EWS-WT1, IL-2/15Rbeta and Janus kinase (JAK1) mRNA was detected in the tumour cells. IL-2 and signal transducers and activators of transcription (STAT5) mRNA were detected in both tumour and stromal cells. The induction of the IL-2/15 receptor signalling pathway may contribute to tumorigenesis in DSRCT through a paracrine or an autocrine system, even though the EWS-WT1 was an unusual form.

An anencephalic monocephalus diprosopus "headed twin": postmortem and CT findings with emphasis on the cranial bones.

PubMed

Ekinci, Gazanfer; Balci, Sevim; Erzen, Canan

2005-01-01

Monocephalus diprosopus is a form of conjoined twinning characterized by a single body, one unusual head and two faces or a spectrum of duplication of the craniofacial structures. Such cases have been mainly described according to postmortem pathologic examination. This presented case is a 26-week-stillborn female fetus, with unusual facial appearance with four eyes, two mouths, two noses, two ears and a defective cranial vault. To our knowledge, a detailed computerized tomography (CT) examination of the aberrant facial and cranial bones of such a case has not been reported to date. In this reported case, we present an anencephalic monocephalus diprosopus "headed twin", and describe the CT findings with emphasis on the cranial bones.

Synthesis and characterization of two crystallographic forms of Ag{sub 0.79}VS{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ali, Mazhar N., E-mail: maz@berkeley.edu; Ji, Huiwen; Hirai, Daigorou

2013-06-15

A previously unreported compound, Ag{sub 0.79}VS{sub 2}, has been synthesized; its structure and elementary properties are reported. Ag{sub 0.79}VS{sub 2} crystallizes in two forms, designated as the α and β, related to the 1s-InTaS{sub 2} structure. Single crystal x-ray diffraction shows the α form to have a single layer hexagonal structure with a unit cell of 3.213(3) Å×7.809(6) Å, consisting of layers of edge-shared VS{sub 6} triangular prisms separated by layers of Ag. The β form is similar but has an a{sub o}√((3)) supercell in the basal plane, yielding a unit cell of 5.573(5) Å×7.822(6) Å. Both forms have disorderedmore » and displaced silver in the basal plane, but the β form has partial ordering of its silver sublattice and in-plane vanadium trimers. Resistivity measurements show metallic temperature dependence with an unusual hysteresis between 210 K and 130 K. Magnetic susceptibility measurements show Pauli Paramagnetic behavior. The Seebeck coefficient at 300 K is 42 µV/K. - Graphical abstract: Red=Vanadium, Gray=Silver, Yellow=Sulfur. Top left is α-Ag{sub 0.79}VS{sub 2} in the 1s-InTaS{sub 2} structure type. Top right: 2a×2b projection down the c-axis with displacement ellipsoids (50% probability) of atoms drawn to illustrate the split silver model. Bottom left is β-Ag{sub 0.79}VS{sub 2} having the a{sub o}√((3)) supercell. Bottom right: projection along the c-axis, displacement ellipsoids of atoms drawn. - Highlights: • Two crystallographic forms of Ag{sub 0.79}VS{sub 2}, designated α and β, are reported. • They are found to crystallize in the 1s-InTaS{sub 2} structure type. • β-Ag{sub 0.79}VS{sub 2} has partial ordering of the Ag sublattice and vanadium trimers. • Ag{sub 0.79}VS{sub 2} shows Pauli Paramagnetic behavior, a Seebeck coefficient of 42 µV/K at 300 K. • Ag{sub 0.79}VS{sub 2} shows metallic resistivity with an unusual hysteresis between 210 K and 130 K.« less

Structure and Function of the Unusual Tungsten Enzymes Acetylene Hydratase and Class II Benzoyl-Coenzyme A Reductase.

PubMed

Boll, Matthias; Einsle, Oliver; Ermler, Ulrich; Kroneck, Peter M H; Ullmann, G Matthias

2016-01-01

In biology, tungsten (W) is exclusively found in microbial enzymes bound to a bis-pyranopterin cofactor (bis-WPT). Previously known W enzymes catalyze redox oxo/hydroxyl transfer reactions by directly coordinating their substrates or products to the metal. They comprise the W-containing formate/formylmethanofuran dehydrogenases belonging to the dimethyl sulfoxide reductase (DMSOR) family and the aldehyde:ferredoxin oxidoreductase (AOR) families, which form a separate enzyme family within the Mo/W enzymes. In the last decade, initial insights into the structure and function of two unprecedented W enzymes were obtained: the acetaldehyde forming acetylene hydratase (ACH) belongs to the DMSOR and the class II benzoyl-coenzyme A (CoA) reductase (BCR) to the AOR family. The latter catalyzes the reductive dearomatization of benzoyl-CoA to a cyclic diene. Both are key enzymes in the degradation of acetylene (ACH) or aromatic compounds (BCR) in strictly anaerobic bacteria. They are unusual in either catalyzing a nonredox reaction (ACH) or a redox reaction without coordinating the substrate or product to the metal (BCR). In organic chemical synthesis, analogous reactions require totally nonphysiological conditions depending on Hg2+ (acetylene hydration) or alkali metals (benzene ring reduction). The structural insights obtained pave the way for biological or biomimetic approaches to basic reactions in organic chemistry. © 2016 S. Karger AG, Basel.

B38: an all-boron fullerene analogue

NASA Astrophysics Data System (ADS)

Lv, Jian; Wang, Yanchao; Zhu, Li; Ma, Yanming

2014-09-01

Fullerene-like structures formed by elements other than carbon have long been sought. Finding all-boron (B) fullerene-like structures is challenging due to the geometrical frustration arising from competitions among various structural motifs. We report here the prediction of a B38 fullerene analogue found through first-principles swarm structure searching calculations. The structure is highly symmetric and consists of 56 triangles and four hexagons, which provide an optimal void in the center of the cage. Energetically, it is more favorable than the planar and tubular structures, and possesses an unusually high chemical stability: a large energy gap (~2.25 eV) and a high double aromaticity, superior to those of most aromatic quasi-planar B12 and double-ring B20 clusters. Our findings represent a key step forward towards to the understanding of structures of medium-sized B clusters and map out the experimental direction of the synthesis of an all-B fullerene analogue.Fullerene-like structures formed by elements other than carbon have long been sought. Finding all-boron (B) fullerene-like structures is challenging due to the geometrical frustration arising from competitions among various structural motifs. We report here the prediction of a B38 fullerene analogue found through first-principles swarm structure searching calculations. The structure is highly symmetric and consists of 56 triangles and four hexagons, which provide an optimal void in the center of the cage. Energetically, it is more favorable than the planar and tubular structures, and possesses an unusually high chemical stability: a large energy gap (~2.25 eV) and a high double aromaticity, superior to those of most aromatic quasi-planar B12 and double-ring B20 clusters. Our findings represent a key step forward towards to the understanding of structures of medium-sized B clusters and map out the experimental direction of the synthesis of an all-B fullerene analogue. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01846j

Structural analysis of the nurse shark (new) antigen receptor (NAR): molecular convergence of NAR and unusual mammalian immunoglobulins.

PubMed

Roux, K H; Greenberg, A S; Greene, L; Strelets, L; Avila, D; McKinney, E C; Flajnik, M F

1998-09-29

We recently have identified an antigen receptor in sharks called NAR (new or nurse shark antigen receptor) that is secreted by splenocytes but does not associate with Ig light (L) chains. The NAR variable (V) region undergoes high levels of somatic mutation and is equally divergent from both Ig and T cell receptors (TCR). Here we show by electron microscopy that NAR V regions, unlike those of conventional Ig and TCR, do not form dimers but rather are independent, flexible domains. This unusual feature is analogous to bona fide camelid IgG in which modifications of Ig heavy chain V (VH) sequences prevent dimer formation with L chains. NAR also displays a uniquely flexible constant (C) region. Sequence analysis and modeling show that there are only two types of expressed NAR genes, each having different combinations of noncanonical cysteine (Cys) residues in the V domains that likely form disulfide bonds to stabilize the single antigen-recognition unit. In one NAR class, rearrangement events result in mature genes encoding an even number of Cys (two or four) in complementarity-determining region 3 (CDR3), which is analogous to Cys codon expression in an unusual human diversity (D) segment family. The NAR CDR3 Cys generally are encoded by preferred reading frames of rearranging D segments, providing a clear design for use of preferred reading frame in antigen receptor D regions. These unusual characteristics shared by NAR and unconventional mammalian Ig are most likely the result of convergent evolution at the molecular level.

46 CFR 170.173 - Criterion for vessels of unusual proportion and form.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 46 Shipping 7 2010-10-01 2010-10-01 false Criterion for vessels of unusual proportion and form. 170.173 Section 170.173 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) SUBDIVISION AND STABILITY STABILITY REQUIREMENTS FOR ALL INSPECTED VESSELS Weather Criteria § 170.173 Criterion...

The Structure of the Protonated Serine Octamer.

PubMed

Scutelnic, Valeriu; Perez, Marta A S; Marianski, Mateusz; Warnke, Stephan; Gregor, Aurelien; Rothlisberger, Ursula; Bowers, Michael T; Baldauf, Carsten; von Helden, Gert; Rizzo, Thomas R; Seo, Jongcheol

2018-06-20

The amino acid serine has long been known to form a protonated "magic-number" cluster containing eight monomer units that shows an unusually high abundance in mass spectra and has a remarkable homochiral preference. Despite many experimental and theoretical studies, there is no consensus on a Ser 8 H + structure that is in agreement with all experimental observations. Here, we present the structure of Ser 8 H + determined by a combination of infrared spectroscopy and ab initio molecular dynamics simulations. The three-dimensional structure that we determine is ∼25 kcal mol -1 more stable than the previous most stable published structure and explains both the homochiral preference and the experimentally observed facile replacement of two serine units.

From Phosphorous to Arsenic: Changing the Classic Paradigm for the Structure of Biomolecules

PubMed Central

Knodle, Ryan; Agarwal, Pratima; Brown, Mark

2012-01-01

Biomolecules are composed primarily of the elements carbon, nitrogen, hydrogen, oxygen, sulfur, and phosphorus. The structured assembly of these elements forms the basis for proteins, nucleic acids and lipids. However, the recent discovery of a new bacterium, strain GFAJ-1 of the Halomonadaceae, has shaken the classic paradigms for the architecture of life. Mounting evidence supports the claim that these bacteria substitute arsenic for phosphorus in macromolecules. Herein, we provide a brief commentary and fuel the debate related to what may be a most unusual organism. PMID:24970138

From phosphorous to arsenic: changing the classic paradigm for the structure of biomolecules.

PubMed

Knodle, Ryan; Agarwal, Pratima; Brown, Mark

2012-05-30

Biomolecules are composed primarily of the elements carbon, nitrogen, hydrogen, oxygen, sulfur, and phosphorus. The structured assembly of these elements forms the basis for proteins, nucleic acids and lipids. However, the recent discovery of a new bacterium, strain GFAJ-1 of the Halomonadaceae, has shaken the classic paradigms for the architecture of life. Mounting evidence supports the claim that these bacteria substitute arsenic for phosphorus in macromolecules. Herein, we provide a brief commentary and fuel the debate related to what may be a most unusual organism.

Iridoids and sesquiterpenoids from the roots of Valeriana officinalis.

PubMed

Wang, Peng-Cheng; Hu, Jiang-Miao; Ran, Xin-Hui; Chen, Zhong-Quan; Jiang, He-Zhong; Liu, Yu-Qing; Zhou, Jun; Zhao, You-Xing

2009-09-01

Two new iridoids, volvaltrates A and B (1 and 2), and three new sesquiterpenoids, E-(-)-3beta,4beta-epoxyvalerenal (3), E-(-)-3beta,4beta-epoxyvalerenyl acetate (4), and mononorvalerenone (5), together with five known iridoids and two known sesquiterpenoids were isolated from the roots of Valeriana officinalis. The structures and relative configurations of 1-5 were elucidated by spectroscopic evidence. Compound 1 was an unusual iridoid with an oxygen bridge connecting C-3 and C-10, forming a cage-like structure, and compound 5 was a mononorsesquiterpenoid.

An unusual type of polymorphism in a liquid crystal

DOE PAGES

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan; ...

2018-02-19

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

An unusual type of polymorphism in a liquid crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Lin; Salamonczyk, Miroslaw; Shadpour, Sasan

Polymorphism is a remarkable concept in chemistry, materials science, computer science, and biology. Whether it is the ability of a material to exist in two or more crystal structures, a single interface connecting to two different entities, or alternative phenotypes of an organism, polymorphism determines function and properties. In materials science, polymorphism can be found in an impressively wide range of materials, including crystalline materials, minerals, metals, alloys, and polymers. Here in this paper we report on polymorphism in a liquid crystal. A bent-core liquid crystal with a single chiral side chain forms two structurally and morphologically significantly different liquidmore » crystal phases solely depending on the cooling rate from the isotropic liquid state. On slow cooling, the thermodynamically more stable oblique columnar phase forms, and on rapid cooling, a not heretofore reported helical microfilament phase. Since structure determines function and properties, the structural color for these phases also differs.« less

Hydatid cyst of parotid: Report of unusual cytological findings extending the cytomorphological spectrum.

PubMed

Arora, Vinod Kumar; Chopra, Neha; Singh, Poorva; Venugopal, Vasantha Kumar; Narang, Salil

2016-09-01

Hydatid disease is a zoonotic infestation caused by larval cestode of genus Echinococcus. Cystic form of this infection mostly involves liver and lung. Hydatid disease of the parotid gland is very rare even in endemic areas and is often clinically mistaken for parotid tumors or cysts. The presence of protoscolices, laminated membranes, and isolated hooklets are characteristic cytological features observed on fine-needle aspirate from hydatid cysts. We report unusual cytological features from a hydatid cyst of parotid in a 13-year-old girl. She presented with a slowly enlarging hard mass in left parotid. Fine-needle aspiration yielded slightly turbid fluid. Smears from the sediment revealed naked parasitic micronuclei, fragments of germinative layer (endocyst), and abortive brood capsules (buds from endocyst) seen as spherical structures with multiple parasitic nuclei. Some of these spherical structures were degenerated with recognizable nuclei and others were completely necrotic. Diagn. Cytopathol. 2016;44:770-773. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Crystallization and preliminary X-ray crystallographic analysis of a highly specific serpin from the beetle Tenebrio molitor

PubMed Central

Park, Sun Hee; Piao, Shunfu; Kwon, Hyun-Mi; Kim, Eun-Hye; Lee, Bok Luel; Ha, Nam-Chul

2010-01-01

The Toll signalling pathway, which is crucial for innate immunity, is transduced in insect haemolymph via a proteolytic cascade consisting of three serine proteases. The proteolytic cascade is downregulated by a specific serine protease inhibitor (serpin). Recently, the serpin SPN48 was found to show an unusual specific reactivity towards the terminal serine protease, Spätzle-processing enzyme, in the beetle Tenebrio molitor. In this study, the mature form of SPN48 was overexpressed in Escherichia coli and purified. The purified SPN48 protein was crystallized using 14% polyethylene glycol 8000 and 0.1 M 2-(N-morpho­lino)ethanesulfonic acid pH 6.0 as the precipitant. The crystals diffracted X-rays to 2.1 Å resolution and were suitable for structure determination. The crystals belonged to space group P21. The crystal structure will provide information regarding how SPN48 achieves its unusual specificity for its target protease. PMID:20124722

Generation of and Retraction from Cross-Linguistically Motivated Structures in Bilingual First Language Acquisition.

ERIC Educational Resources Information Center

Dopke, Susanne

2000-01-01

Focuses on unusual developmental structures during the simultaneous acquisition of German and English in early childhood, which were evident parallel to a majority of target structures. Explains the cognitive motivation for unusual acquisition structures as well as the eventual retraction from them. (Author/VWL)

Modelling the development of defects during composite reinforcements and prepreg forming

PubMed Central

Hamila, N.; Madeo, A.

2016-01-01

Defects in composite materials are created during manufacture to a large extent. To avoid them as much as possible, it is important that process simulations model the onset and the development of these defects. It is then possible to determine the manufacturing conditions that lead to the absence or to the controlled presence of such defects. Three types of defects that may appear during textile composite reinforcement or prepreg forming are analysed and modelled in this paper. Wrinkling is one of the most common flaws that occur during textile composite reinforcement forming processes. The influence of the different rigidities of the textile reinforcement is studied. The concept of ‘locking angle’ is questioned. A second type of unusual behaviour of fibrous composite reinforcements that can be seen as a flaw during their forming process is the onset of peculiar ‘transition zones’ that are directly related to the bending stiffness of the fibres. The ‘transition zones’ are due to the bending stiffness of fibres. The standard continuum mechanics of Cauchy is not sufficient to model these defects. A second gradient approach is presented that allows one to account for such unusual behaviours and to master their onset and development during forming process simulations. Finally, the large slippages that may occur during a preform forming are discussed and simulated with meso finite-element models used for macroscopic forming. This article is part of the themed issue ‘Multiscale modelling of the structural integrity of composite materials’. PMID:27242300

Modelling the development of defects during composite reinforcements and prepreg forming.

PubMed

Boisse, P; Hamila, N; Madeo, A

2016-07-13

Defects in composite materials are created during manufacture to a large extent. To avoid them as much as possible, it is important that process simulations model the onset and the development of these defects. It is then possible to determine the manufacturing conditions that lead to the absence or to the controlled presence of such defects. Three types of defects that may appear during textile composite reinforcement or prepreg forming are analysed and modelled in this paper. Wrinkling is one of the most common flaws that occur during textile composite reinforcement forming processes. The influence of the different rigidities of the textile reinforcement is studied. The concept of 'locking angle' is questioned. A second type of unusual behaviour of fibrous composite reinforcements that can be seen as a flaw during their forming process is the onset of peculiar 'transition zones' that are directly related to the bending stiffness of the fibres. The 'transition zones' are due to the bending stiffness of fibres. The standard continuum mechanics of Cauchy is not sufficient to model these defects. A second gradient approach is presented that allows one to account for such unusual behaviours and to master their onset and development during forming process simulations. Finally, the large slippages that may occur during a preform forming are discussed and simulated with meso finite-element models used for macroscopic forming. This article is part of the themed issue 'Multiscale modelling of the structural integrity of composite materials'. © 2016 The Author(s).

A previously unreported association between Nance-Horan syndrome and spontaneous dental abscesses.

PubMed

Hibbert, Sally

2005-02-01

Atypical dentofacial structures may be the first indicator of other anomalies linked to a syndrome. This case describes the management of a 9-year-old girl referred for the routine management of supernumerary teeth. The anomalous form of her teeth, together with multiple supernumerary units and a history of congenital cataracts, were suggestive of a diagnosis of Nance-Horan syndrome. This is an X-linked disorder, in which females usually demonstrate mild expression; this case was unusual in respect to the marked phenotype expressed. Unusually, the girl developed 2 spontaneous abscesses of her noncarious upper incisor teeth; a feature never previously described in this syndrome. This report details the patient's dental management and discusses the possible pathogenesis of the dental abscesses, together with the genetic implications of this syndrome.

Unusual Configurations of Personality Traits Indicate Multiple Patterns of Their Coalescence

PubMed Central

Allik, Jüri; Hřebíčková, Martina; Realo, Anu

2018-01-01

It is widely accepted that the Five Factor Model (FFM) is a satisfactory description of the pattern of covariations among personality traits, which supposedly fits, more or less adequately, every individual. As an amendment to the FFM, we propose that the customary five-factor structure is only a near-universal, because it does not fit all individuals but only a large majority of them. Evidences reveal a small minority of participants who have an unusual configuration of personality traits, which is clearly recognizable, both in self- and observer-ratings. We identified three types of atypical configurations of personality traits, characterized mainly by a scatter of subscale scores within each of the FFM factors. How different configurations of personality traits are formed, persist, and function needs further investigation. PMID:29515499

Synthesis and structural characterisation of iron(II) and copper(II) diphosphates containing flattened metal oxotetrahedra

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keates, Adam C.; Wang, Qianlong; Weller, Mark T., E-mail: m.t.weller@bath.ac.uk

2014-02-15

Single crystal and bulk polycrystalline forms of K{sub 2}MP{sub 2}O{sub 7} (M=Fe(II), Cu(II)) have been synthesised and their structures determined from single crystal X-ray diffraction data. Both compounds crystallize in the tetragonal system, space group P-42{sub 1}m. Their structures are formed from infinite sheets of linked oxopolyhedra of the stoichiometry [MP{sub 2}O{sub 7}]{sup 2−} with potassium cations situated between the layers. The MO{sub 4} tetrahedra share oxygen atoms with [P{sub 2}O{sub 7}]{sup 4−} diphosphate groups and the potassium ions have KO{sub 8} square prismatic geometry. In both compounds the M(II) centre has an unusual strongly flattened, tetrahedral coordination to oxygen,more » as a result of the Jahn–Teller (JT) effect for the high spin d{sup 6} Fe(II) and p-orbital mixing or a second order JT effect for d{sup 9} Cu(II) centres in four fold coordination. The uncommon transition metal ion environments found in these materials are reflected in their optical absorption spectra and magnetism data. - Graphical abstract: The structures of the tetragonal polymorphs of K{sub 2}MP{sub 2}O{sub 7}, M=Cu(II), Fe(II), consist of infinite sheets of stoichiometry [MP{sub 2}O{sub 7}]{sup 2−}, formed from linked pyrophosphate groups and MO{sub 4} tetrahedra, separated by potassium ions. In both compounds the unusual tetrahedral coordination of the M(II) centre is strongly flattened as a result of Jahn–Teller (JT) effects for high spin, d{sup 6} Fe(II) and p-orbital mixing and second-order JT effects for d{sup 9} Cu(II). Display Omitted - Highlights: • Tetrahedral copper and iron(II) coordinated by oxygen. • New layered phosphate structure. • Jahn–Teller and d{sup 10} distorted coordinations.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maaloum, M.; Muller, P.; Beker, A-F.

Almost two decades ago, measurements of force versus extension on isolated double-stranded DNA molecules revealed a force plateau. This unusual stretching phenomenon in DNA suggests that the long molecules may be extended from the usual B form into a new conformation. Different models have been proposed to describe the nature of DNA in its stretched form, S-DNA. Using atomic force microscopy combined with a molecular combing method, we identified the structure of {lambda}-phage DNA for different stretching values. We provide strong evidence for the existence of a first-order transition between B form and S form. Beyond a certain extension ofmore » the natural length, DNA molecules adopt a new double-helix conformation characterized by a diameter of 1.2 nm and a helical pitch of18 nm.« less

Tetra-ammine-(carbonato-κ(2) O,O')cobalt(III) nitrate: a powder X-ray diffraction study.

PubMed

Le Bail, Armel

2013-01-01

Practical chemistry courses at universities very frequently propose the synthesis and characterization of [Co(CO3)(NH3)4]NO3, but this goal is never achieved since students only obtain the hemihydrated form. The anhydrous form can be prepared, however, and its structure is presented here. Similar to the hemihydrate form, the anhydrous phase contains the Co(III) ion in an octahedral O2N4 coordination by a chelating carbonate group and four ammine ligands. The structure reveals an intricate array of N-H⋯O hydrogen bonds involving both the chelating and the non-chelating O atoms of the carbonate ligand as hydrogen-bond acceptors of the amine H atoms, which are also involved in hydrogen-bonding inter-actions with the nitrate O atoms. The structure of the anhydrous form is close to that of the hemihydrate phase, suggesting a probable topotactic reaction with relatively small rotations and translations of the [Co(CO3)(NH3)4](+) and NO3 (-) groups during the dehydration process, which produces an unusual volume increase of 4.3%.

Tetra­ammine­(carbonato-κ2 O,O′)cobalt(III) nitrate: a powder X-ray diffraction study

PubMed Central

Le Bail, Armel

2013-01-01

Practical chemistry courses at universities very frequently propose the synthesis and characterization of [Co(CO3)(NH3)4]NO3, but this goal is never achieved since students only obtain the hemihydrated form. The anhydrous form can be prepared, however, and its structure is presented here. Similar to the hemihydrate form, the anhydrous phase contains the CoIII ion in an octahedral O2N4 coordination by a chelating carbonate group and four ammine ligands. The structure reveals an intricate array of N—H⋯O hydrogen bonds involving both the chelating and the non-chelating O atoms of the carbonate ligand as hydrogen-bond acceptors of the amine H atoms, which are also involved in hydrogen-bonding inter­actions with the nitrate O atoms. The structure of the anhydrous form is close to that of the hemihydrate phase, suggesting a probable topotactic reaction with relatively small rotations and translations of the [Co(CO3)(NH3)4]+ and NO3 − groups during the dehydration process, which produces an unusual volume increase of 4.3%. PMID:24046543

Unusual spacecraft materials

NASA Technical Reports Server (NTRS)

Post, Jonathan V.

1990-01-01

For particularly innovative space exploration missions, unusual requirements are levied on the structural components of the spacecraft. In many cases, the preferred solution is the utilization of unusual materials. This trend is forecast to continue. Several hypothetic examples are discussed.

The homo-oligomerisation of both Sas-6 and Ana2 is required for efficient centriole assembly in flies

PubMed Central

Cottee, Matthew A; Muschalik, Nadine; Johnson, Steven; Leveson, Joanna; Raff, Jordan W; Lea, Susan M

2015-01-01

Sas-6 and Ana2/STIL proteins are required for centriole duplication and the homo-oligomerisation properties of Sas-6 help establish the ninefold symmetry of the central cartwheel that initiates centriole assembly. Ana2/STIL proteins are poorly conserved, but they all contain a predicted Central Coiled-Coil Domain (CCCD). Here we show that the Drosophila Ana2 CCCD forms a tetramer, and we solve its structure to 0.8 Å, revealing that it adopts an unusual parallel-coil topology. We also solve the structure of the Drosophila Sas-6 N-terminal domain to 2.9 Å revealing that it forms higher-order oligomers through canonical interactions. Point mutations that perturb Sas-6 or Ana2 homo-oligomerisation in vitro strongly perturb centriole assembly in vivo. Thus, efficient centriole duplication in flies requires the homo-oligomerisation of both Sas-6 and Ana2, and the Ana2 CCCD tetramer structure provides important information on how these proteins might cooperate to form a cartwheel structure. DOI: http://dx.doi.org/10.7554/eLife.07236.001 PMID:26002084

Molecular Cloning of Human Gene(s) Directing the Synthesis of Nervous System Cholinesterases

DTIC Science & Technology

1987-09-01

and shed light on the unknown physiological function of these serine hydrolases in proliferating and differentiating cells. In pheochromocytoma cells...Reiness, C.G., Reichardt, L.F. and Hall, Z.W. (1981) Cellular localization of the molecular forms of acetylcholinesterase in rat pheochromocytoma PC12...melanogaster: Structural gene for acetylcholinesterase with an unusual 5’ leader. The EMBO J., 2949-2954. 99. Merken, L., Simons, M.J., Swillens, S

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

DOE PAGES

Snyder, Benjamin E. R.; Bottger, Lars H.; Bols, Max L.; ...

2018-04-02

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify howmore » the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.« less

Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snyder, Benjamin E. R.; Bottger, Lars H.; Bols, Max L.

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify howmore » the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.« less

Biosynthesis of t-Butyl in Apratoxin A: Functional Analysis and Architecture of a PKS Loading Module.

PubMed

Skiba, Meredith A; Sikkema, Andrew P; Moss, Nathan A; Lowell, Andrew N; Su, Min; Sturgis, Rebecca M; Gerwick, Lena; Gerwick, William H; Sherman, David H; Smith, Janet L

2018-05-08

The unusual feature of a t-butyl group is found in several marine-derived natural products including apratoxin A, a Sec61 inhibitor produced by the cyanobacterium Moorea bouillonii PNG 5-198. Here, we determine that the apratoxin A t-butyl group is formed as a pivaloyl acyl carrier protein (ACP) by AprA, the polyketide synthase (PKS) loading module of the apratoxin A biosynthetic pathway. AprA contains an inactive "pseudo" GCN5-related N-acetyltransferase domain (ΨGNAT) flanked by two methyltransferase domains (MT1 and MT2) that differ distinctly in sequence. Structural, biochemical, and precursor incorporation studies reveal that MT2 catalyzes unusually coupled decarboxylation and methylation reactions to transform dimethylmalonyl-ACP, the product of MT1, to pivaloyl-ACP. Further, pivaloyl-ACP synthesis is primed by the fatty acid synthase malonyl acyltransferase (FabD), which compensates for the ΨGNAT and provides the initial acyl-transfer step to form AprA malonyl-ACP. Additionally, images of AprA from negative stain electron microscopy reveal multiple conformations that may facilitate the individual catalytic steps of the multienzyme module.

The effect of high-pressure torsion on the microstructure and properties of magnesium

NASA Astrophysics Data System (ADS)

Figueiredo, Roberto B.; Sabbaghianrad, Shima; Langdon, Terence G.

2017-05-01

High-pressure torsion provides the opportunity to introduce significant plastic strain at room temperature in magnesium and its alloys. It is now established that this processing operation produces ultrafine-grained structures and changes the properties of these materials. The present paper shows that the mechanism of grain refinement differs from f.c.c. and b.c.c. materials. It is shown that fine grains are formed at the grain boundaries of coarse grains and gradually consume the whole structure. Also, the processed material exhibits unusual mechanical properties due to the activation of grain boundary sliding at room temperature.

Dysmorphometrics: the modelling of morphological abnormalities.

PubMed

Claes, Peter; Daniels, Katleen; Walters, Mark; Clement, John; Vandermeulen, Dirk; Suetens, Paul

2012-02-06

The study of typical morphological variations using quantitative, morphometric descriptors has always interested biologists in general. However, unusual examples of form, such as abnormalities are often encountered in biomedical sciences. Despite the long history of morphometrics, the means to identify and quantify such unusual form differences remains limited. A theoretical concept, called dysmorphometrics, is introduced augmenting current geometric morphometrics with a focus on identifying and modelling form abnormalities. Dysmorphometrics applies the paradigm of detecting form differences as outliers compared to an appropriate norm. To achieve this, the likelihood formulation of landmark superimpositions is extended with outlier processes explicitly introducing a latent variable coding for abnormalities. A tractable solution to this augmented superimposition problem is obtained using Expectation-Maximization. The topography of detected abnormalities is encoded in a dysmorphogram. We demonstrate the use of dysmorphometrics to measure abrupt changes in time, asymmetry and discordancy in a set of human faces presenting with facial abnormalities. The results clearly illustrate the unique power to reveal unusual form differences given only normative data with clear applications in both biomedical practice & research.

Third wave of African swine fever infection in Armenia: Virus demonstrates the reduction of pathogenicity

PubMed Central

Sargsyan, M. A.; Voskanyan, H. E.; Karalova, E. M.; Hakobyan, L. H.; Karalyan, Z. A.

2018-01-01

Aim: First cases of clinically uncommon African swine fever (ASF), caused by virus genotype II are described in this article. These cases occurred in Armenia, Tavush region, Dilijan municipality in 2011. The aim of this study was to identify and describe the new pathogenic forms of ASF in Armenia. Materials and Methods: The isolation and identification of ASF virus (ASFV) were carried out using conventional techniques. Clinical signs of infection were recorded daily. Gross anatomical pathology characteristics were observed during routine postmortem examinations. Blood and serum were obtained by puncture of the jugular vein using a vacutainer system. Results: The presence of ASFV DNA in the spleens was confirmed by polymerase chain reaction. Sequenced sections of p72 showed phylogenetic identity to genotype 2. The pathology exhibits unusual manifestations of the main disease. The unusual form of ASF demonstrates characteristics of a subacute form of the disease, with the possibility of conversion to a chronic form. Decreased lethality, low level of hemorrhages, and absence of severe pancytopenia in smears from spleen, lymph nodes, and blood are common features of the new form of ASF. Unlike severe thrombocytopenia in the typical ASF, the unusual form exhibited moderate or minor decrease of this feature. Despite a moderate decrease in hemadsorption titers, the unusual pattern of the disease was characterized by viremia and the presence of the virus in the visceral organs, including the brain. Conclusion: Our data allow assuming that new nosological form of ASF (genotype II) may present as a transitional form of the disease with the possibility of chronization. PMID:29479149

Effects of proline cis-trans isomerization on TB domain secondary structure.

PubMed Central

Yuan, X.; Werner, J. M.; Knott, V.; Handford, P. A.; Campbell, I. D.; Downing, K.

1998-01-01

The transforming growth factor beta (TGF-beta) binding protein-like (TB) domain is found principally in proteins localized to extracellular matrix fibrils, including human fibrillin-1, the defective protein in the Marfan syndrome. Analysis of the nuclear magnetic resonance (NMR) data for the sixth TB module from human fibrillin-1 has revealed the existence of two stable conformers that differ in the isomerization states of two proline residues. Unusually, the two isoforms do not readily interconvert and are stable on the time scale of milliseconds. We have computed independent structures of the major and minor conformers of TB6 to assess how the domain fold adjusts to incorporate alternatively cis- or trans-prolines. Based on previous observations, it has been suggested that multiple conformers can only be accommodated in flexible regions of protein structure. In contrast, P22, which exists in trans in the major form and cis in the minor form of TB6, is in a rigid region of the domain, which is confirmed by backbone dynamics measurements. Overall, the structures of the major and minor conformers are similar. However, the secondary structure topologies of the two forms differ as a direct consequence of the changes in proline conformation. PMID:9792099

Alotamide A, a Novel Neuropharmacological Agent From the Marine Cyanobacterium Lyngbya bouillonii

PubMed Central

Soria-Mercado, Irma E.; Pereira, Alban; Cao, Zhengyu; Murray, Thomas F.; Gerwick, William H.

2009-01-01

Alotamide A (1), a structurally intriguing cyclic depsipeptide, was isolated from the marine mat-forming cyanobacterium Lyngbya bouillonii collected in Papua New Guinea. It features three contiguous peptidic residues and an unsaturated heptaketide with oxidations and methylations unlike those found in any other marine cyanobacterial metabolite. Pure alotamide A (1) displays an unusual calcium influx activation profile in murine cerebrocortical neurons with an EC50 of 4.18 μM. PMID:19754100

Photosynthetic microorganism-mediated synthesis of akaganeite (beta-FeOOH) nanorods.

PubMed

Brayner, Roberta; Yéprémian, Claude; Djediat, Chakib; Coradin, Thibaud; Herbst, Fréderic; Livage, Jacques; Fiévet, Fernand; Couté, Alain

2009-09-01

Common Anabaena and Calothrix cyanobacteria and Klebsormidium green algae are shown to form intracellularly akaganeite beta-FeOOH nanorods of well-controlled size and unusual morphology at room temperature. X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy X-ray energy dispersive spectrometry (SEM-EDS) analyses are used to investigate particle structure, size, and morphology. A mechanism involving iron-siderophore complex formation is proposed and compared with iron biomineralization in magnetotactic bacteria.

Locally Aggressive Fibrous Dysplasia Mimicking Malign Calvarial Lesion.

PubMed

Ogul, Hayri; Keskin, Emine

2018-05-01

Fibrous dysplasia is an unusual benign bone tumor. It is divided into 3 groups as monostotic, polyostotic, and craniofacial form. The authors reported an unusual patient with fibrous dysplasia with an aggressive radiologic appearance.

Unusual Domain Structure and Filamentary Superfluidity for 2D Hard-Core Bosons in Insulating Charge-Ordered Phase

NASA Astrophysics Data System (ADS)

Panov, Yu. D.; Moskvin, A. S.; Rybakov, F. N.; Borisov, A. B.

2016-12-01

We made use of a special algorithm for compute unified device architecture for NVIDIA graphics cards, a nonlinear conjugate-gradient method to minimize energy functional, and Monte-Carlo technique to directly observe the forming of the ground state configuration for the 2D hard-core bosons by lowering the temperature and its evolution with deviation away from half-filling. The novel technique allowed us to examine earlier implications and uncover novel features of the phase transitions, in particular, look upon the nucleation of the odd domain structure, emergence of filamentary superfluidity nucleated at the antiphase domain walls of the charge-ordered phase, and nucleation and evolution of different topological structures.

Structural basis for IL-1α recognition by a modified DNA aptamer that specifically inhibits IL-1α signaling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ren, Xiaoming; Gelinas, Amy D.; von Carlowitz, Ira

IL-1α is an essential cytokine that contributes to inflammatory responses and is implicated in various forms of pathogenesis and cancer. Here we report a naphthyl modified DNA aptamer that specifically binds IL-1α and inhibits its signaling pathway. By solving the crystal structure of the IL-1α/aptamer, we provide a high-resolution structure of this critical cytokine and we reveal its functional interaction interface with high-affinity ligands. The non-helical aptamer, which represents a highly compact nucleic acid structure, contains a wealth of new conformational features, including an unknown form of G-quadruplex. The IL-1α/aptamer interface is composed of unusual polar and hydrophobic elements, alongmore » with an elaborate hydrogen bonding network that is mediated by sodium ion. IL-1α uses the same interface to interact with both the aptamer and its cognate receptor IL-1RI, thereby suggesting a novel route to immunomodulatory therapeutics.« less

Structural transformations of heat treated Co-less high entropy alloys

NASA Astrophysics Data System (ADS)

Mitrica, D.; Tudor, A.; Rinaldi, A.; Soare, V.; Predescu, C.; Berbecaru, A.; Stoiciu, F.; Badilita, V.

2018-03-01

Co is considered to be one of the main ingredients in superalloys. Co is considered a critical element and its substitution is difficult due to its unique ability to form high temperature stable structures with high mechanical and corrosion/oxidation resistance. High entropy alloys (HEA) represent a relatively new concept in material design. HEA are characterised by a high number of alloying elements, in unusually high proportion. Due to their specific particularities, high entropy alloys tend to form predominant solid solution structures that develop potentially high chemical, physical and mechanical properties. Present paper is studying Co-less high entropy alloys with high potential in severe environment applications. The high entropy alloys based on Al-Cr-Fe-Mn-Ni system were prepared by induction melting and casting under protective atmosphere. The as-cast specimens were heat treated at various temperatures to determine the structure and property behaviour. Samples taken before and after heat treatment were investigated for chemical, physical, structural and mechanical characteristics. Sigma phase composition and heat treatment parameters had major influence over the resulted alloy structure and properties.

Packing C60 in Boron Nitride Nanotubes

NASA Astrophysics Data System (ADS)

Mickelson, W.; Aloni, S.; Han, Wei-Qiang; Cumings, John; Zettl, A.

2003-04-01

We have created insulated C60 nanowire by packing C60 molecules into the interior of insulating boron nitride nanotubes (BNNTs). For small-diameter BNNTs, the wire consists of a linear chain of C60 molecules. With increasing BNNT inner diameter, unusual C60 stacking configurations are obtained (including helical, hollow core, and incommensurate) that are unknown for bulk or thin-film forms of C60. C60 in BNNTs thus presents a model system for studying the properties of dimensionally constrained ``silo'' crystal structures. For the linear-chain case, we have fused the C60 molecules to form a single-walled carbon nanotube inside the insulating BNNT.

Unconventional field induced phases in a quantum magnet formed by free radical tetramers

NASA Astrophysics Data System (ADS)

Saúl, Andrés; Gauthier, Nicolas; Askari, Reza Moosavi; Côté, Michel; Maris, Thierry; Reber, Christian; Lannes, Anthony; Luneau, Dominique; Nicklas, Michael; Law, Joseph M.; Green, Elizabeth Lauren; Wosnitza, Jochen; Bianchi, Andrea Daniele; Feiguin, Adrian

2018-02-01

We report experimental and theoretical studies on the magnetic and thermodynamic properties of NIT-2Py, a free radical based organic magnet. From magnetization and specific-heat measurements we establish the temperature versus magnetic field phase diagram which includes two Bose-Einstein condensates (BEC) and an infrequent half-magnetization plateau. Calculations based on density functional theory demonstrate that magnetically this system can be mapped to a quasi-two-dimensional structure of weakly coupled tetramers. Density matrix renormalization group calculations show the unusual characteristics of the BECs where the spins forming the low-field condensate are different than those participating in the high-field one.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maiti, Tushar K.; Permaul, Michelle; Boudreaux, David A.

Ubiquitin carboxy-terminal hydrolase L5 (UCHL5) is a proteasome-associated deubiquitinating enzyme, which, along with RPN11 and USP14, is known to carry out deubiquitination on proteasome. As a member of the ubiquitin carboxy-terminal hydrolase (UCH) family, UCHL5 is unusual because, unlike UCHL1 and UCHL3, it can process polyubiquitin chain. However, it does so only when it is bound to the proteasome; in its free form, it is capable of releasing only relatively small leaving groups from the C-terminus of ubiquitin. Such a behavior might suggest at least two catalytically distinct forms of the enzyme, an apo form incapable of chain processing activity,more » and a proteasome-induced activated form capable of cleaving polyubiquitin chain. Through the crystal structure analysis of two truncated constructs representing the catalytic domain (UCH domain) of this enzyme, we were able to visualize a state of this enzyme that we interpret as its inactive form, because the catalytic cysteine appears to be in an unproductive orientation. While this work was in progress, the structure of a different construct representing the UCH domain was reported; however, in that work the structure reported was that of an inactive mutant [catalytic Cys to Ala; Nishio K et al. (2009) Biochem Biophys Res Commun390, 855-860], which precluded the observation that we are reporting here. Additionally, our structures reveal conformationally dynamic parts of the enzyme that may play a role in the structural transition to the more active form.« less

Self-assembly of three-dimensional open structures using patchy colloidal particles.

PubMed

Rocklin, D Zeb; Mao, Xiaoming

2014-10-14

Open structures can display a number of unusual properties, including a negative Poisson's ratio, negative thermal expansion, and holographic elasticity, and have many interesting applications in engineering. However, it is a grand challenge to self-assemble open structures at the colloidal scale, where short-range interactions and low coordination number can leave them mechanically unstable. In this paper we discuss the self-assembly of three-dimensional open structures using triblock Janus particles, which have two large attractive patches that can form multiple bonds, separated by a band with purely hard-sphere repulsion. Such surface patterning leads to open structures that are stabilized by orientational entropy (in an order-by-disorder effect) and selected over close-packed structures by vibrational entropy. For different patch sizes the particles can form into either tetrahedral or octahedral structural motifs which then compose open lattices, including the pyrochlore, the hexagonal tetrastack and the perovskite lattices. Using an analytic theory, we examine the phase diagrams of these possible open and close-packed structures for triblock Janus particles and characterize the mechanical properties of these structures. Our theory leads to rational designs of particles for the self-assembly of three-dimensional colloidal structures that are possible using current experimental techniques.

Sulfolobus turreted icosahedral virus c92 protein responsible for the formation of pyramid-like cellular lysis structures.

PubMed

Snyder, Jamie C; Brumfield, Susan K; Peng, Nan; She, Qunxin; Young, Mark J

2011-07-01

Host cells infected by Sulfolobus turreted icosahedral virus (STIV) have been shown to produce unusual pyramid-like structures on the cell surface. These structures represent a virus-induced lysis mechanism that is present in Archaea and appears to be distinct from the holin/endolysin system described for DNA bacteriophages. This study investigated the STIV gene products required for pyramid formation in its host Sulfolobus solfataricus. Overexpression of STIV open reading frame (ORF) c92 in S. solfataricus alone is sufficient to produce the pyramid-like lysis structures in cells. Gene disruption of c92 within STIV demonstrates that c92 is an essential protein for virus replication. Immunolocalization of c92 shows that the protein is localized to the cellular membranes forming the pyramid-like structures.

Crystal structure of the human 4-1BB/4-1BBL complex.

PubMed

Gilbreth, Ryan N; Oganesyan, Vaheh Y; Amdouni, Hamza; Novarra, Shabazz; Grinberg, Luba; Barnes, Arnita; Baca, Manuel

2018-05-02

4-1BBL is a member of the TNF superfamily and is the ligand for the TNFRsuperfamily receptor, 4-1BB. 4-1BB plays an immunomodulatory role in T cells and NK cells and agonists of this receptor have garnered strong attention as potentialimmunotherapy agents. Broadly speaking, the structural features of TNF superfamilymembers, their receptors and ligand/receptor complexes are similar. However, apublished crystal structure of human 4-1BBL suggests that it may be unique in thisregard, exhibiting a three-bladed propeller-like trimer assembly that is distinctly different from that observed in other family members. This unusual structure also suggests that the human 4-1BB/4-1BBL complex may be structurally unique within the TNF/TNFR superfamily, but to date no structural data have been reported. Here we report the crystal structure of the human 4-1BB/4-1BBL complex at 2.4 Å resolution. In this structure, 4-1BBL does not adopt the unusual trimer assembly previously reported, but instead forms a canonical bell-shaped trimer typical of other TNF superfamily members. The structure of 4-1BB is also largely canonical as is the 4-1BB/4-1BBL complex. Mutational data support the 4-1BBL structure reported here as being biologically relevant, suggesting that the previously reported structure is not. Together, the data presented here offer insight into structure/function relationships in the 4-1BB/4-1BBL system and improve our structural understanding of the TNF/TNFR superfamily more broadly. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

Acoustic Levitation Containerless Processing

NASA Technical Reports Server (NTRS)

Whymark, R. R.; Rey, C. A.

1985-01-01

This research program consists of the development of acoustic containerless processing systems with applications in the areas of research in material sciences, as well as the production of new materials, solid forms with novel and unusual microstructures, fusion target spheres, and improved optical fibers. Efforts have been focused on the containerless processing at high temperatures for producing new kinds of glasses. Also, some development has occurred in the areas of containerlessly supporting liquids at room temperature, with applications in studies of fluid dynamics, potential undercooling of liquids, etc. The high temperature area holds the greatest promise for producing new kinds of glasses and ceramics, new alloys, and possibly unusual structural shapes, such as very uniform hollow glass shells for fusion target applications. High temperature acoustic levitation required for containerless processing has been demonstrated in low-g environments as well as in ground-based experiments. Future activities include continued development of the signals axis acoustic levitator.

Unusual Passivation Ability of Superconcentrated Electrolytes toward Hard Carbon Negative Electrodes in Sodium-Ion Batteries.

PubMed

Takada, Koji; Yamada, Yuki; Watanabe, Eriko; Wang, Jianhui; Sodeyama, Keitaro; Tateyama, Yoshitaka; Hirata, Kazuhisa; Kawase, Takeo; Yamada, Atsuo

2017-10-04

The passivation of negative electrodes is key to achieving prolonged charge-discharge cycling with Na-ion batteries. Here, we report the unusual passivation ability of superconcentrated Na-salt electrolytes. For example, a 50 mol % sodium bis(fluorosulfonyl)amide (NaFSA)/succinonitrile (SN) electrolyte enables highly reversible Na + insertion into a hard carbon negative electrode without any electrolyte additive, functional binder, or electrode pretreatment. Importantly, an anion-derived passivation film is formed via preferential reduction of the anion upon charging, which can effectively suppress further electrolyte reduction. As a structural characteristic of the electrolyte, most anions are coordinated to multiple Na + cations at high concentration, which shifts the lowest unoccupied molecular orbitals of the anions downward, resulting in preferential anion reduction. The present work provides a new understanding of the passivation mechanism with respect to the coordination state of the anion.

Structure of the inositol-1-phosphate cytidylyltransferase from Thermotoga maritima.

PubMed

Kurnasov, Oleg V; Luk, Hung-Jie Daniel; Roberts, Mary F; Stec, Boguslaw

2013-09-01

The unique steps in the synthesis of an unusual osmolyte in hyperthermophiles, di-myo-inositol-1,1'-phosphate (DIP), involve the production of CDP-inositol and its condensation with an inositol-1-phosphate molecule to form phosphorylated DIP. While many organisms fuse both activities into a single enzyme, the two are separate in Thermotoga maritima. The crystal structure of the T. maritima inositol-1-phosphate cytidylyltransferase, which as a soluble protein may transiently associate with its membrane-embedded partner phospho-DIP synthase (P-DIPS), has now been obtained. The structure shows a conserved motif of sugar nucleotide transferases (COG1213) with a structurally reinforced C-terminal Cys bonded to the core of the protein. A bound arsenosugar identifies the location of the active site for inositol 1-phosphate. Based on homologous structures from several species and the identification of the crucial conserved aspartate residue, a catalytic mechanism for this enzyme is proposed as well as a mode for its association with P-DIPS. This structure imposes constraints on the mode of association, communication and temperature activation of two separate enzymes in T. maritima. For the first time, a working model for the membrane-bound P-DIPS unit has been constructed. This sheds light on the functioning of the phosphatidylserine and phosphatidylinositol synthases involved in many physiological processes that are homologous to P-DIPS. This work provides fresh insights into the synthesis of the unusual thermoprotective compound DIP in hyperthermophiles.

Neutrino Background from Population III Stars

NASA Astrophysics Data System (ADS)

Iocco, Fabio

2011-12-01

Population III Stars (PopIII) are the first generation of stars formed from the collapse of the very first structures in the Universe. Their peculiar chemical composition (metal-free, resembling the Primordial Nucleosynthesis yields) affects their formation and evolution and makes them unusually big and hot stars. They are good candidates for the engines of Reionization of the Universe although their direct observation is extremely difficult. Here we summarize a study of their expected diffuse low-energy neutrino background flux at Earth.

Substrate specificity in enzymatic fluorination. The fluorinase from Streptomyces cattleya accepts 2′-deoxyadenosine substrates†

PubMed Central

Cobb, Steven L.; Deng, Hai; McEwan, Andrew R.; Naismith, James H.; O’Hagan, David; Robinson, David A.

2012-01-01

The fluorinase enzyme from Streptomyces cattleya displays an unusual ability in biocatalysis in that it forms a C–F bond. We now report that the enzyme will accept 2′-deoxyadenosine in place of adenosine substrates, and structural evidence reveals a reorganisation in hydrogen bonding to accommodate this substrate series. It emerges from this study that the enzyme does not require a planar ribose conformation of the substrate to catalyse C–F bond formation. PMID:16604208

The Unusual Genetics and Biochemistry of Bovine Immunoglobulins.

PubMed

Stanfield, Robyn L; Haakenson, Jeremy; Deiss, Thaddeus C; Criscitiello, Michael F; Wilson, Ian A; Smider, Vaughn V

2018-01-01

Antibodies are the key circulating molecules that have evolved to fight infection by the adaptive immune system of vertebrates. Typical antibodies of most species contain six complementarity-determining regions (CDRs), where the third CDR of the heavy chain (CDR H3) has the greatest diversity and often makes the most significant contact with antigen. Generally, the process of V(D)J recombination produces a vast repertoire of antibodies; multiple V, D, and J gene segments recombine with additional junctional diversity at the V-D and D-J joints, and additional combinatorial possibilities occur through heavy- and light-chain pairing. Despite these processes, the overall structure of the resulting antibody is largely conserved, and binding to antigen occurs predominantly through the CDR loops of the immunoglobulin V domains. Bovines have deviated from this general paradigm by having few VH regions and thus little germline combinatorial diversity, but their antibodies contain long CDR H3 regions, with substantial diversity generated through somatic hypermutation. A subset of the repertoire comprises antibodies with ultralong CDR H3s, which can reach over 70 amino acids in length. Structurally, these unusual antibodies form a β-ribbon "stalk" and disulfide-bonded "knob" that protrude far from the antibody surface. These long CDR H3s allow cows to mount a particularly robust immune response when immunized with viral antigens, particularly to broadly neutralizing epitopes on a stabilized HIV gp140 trimer, which has been a challenge for other species. The unusual genetics and structural biology of cows provide for a unique paradigm for creation of immune diversity and could enable generation of antibodies against especially challenging targets and epitopes. © 2018 Elsevier Inc. All rights reserved.

Extremely strong self-assembly of a bimetallic salen complex visualized at the single-molecule level.

PubMed

Salassa, Giovanni; Coenen, Michiel J J; Wezenberg, Sander J; Hendriksen, Bas L M; Speller, Sylvia; Elemans, Johannes A A W; Kleij, Arjan W

2012-04-25

A bis-Zn(salphen) structure shows extremely strong self-assembly both in solution as well as at the solid-liquid interface as evidenced by scanning tunneling microscopy, competitive UV-vis and fluorescence titrations, dynamic light scattering, and transmission electron microscopy. Density functional theory analysis on the Zn(2) complex rationalizes the very high stability of the self-assembled structures provoked by unusual oligomeric (Zn-O)(n) coordination motifs within the assembly. This coordination mode is strikingly different when compared with mononuclear Zn(salphen) analogues that form dimeric structures having a typical Zn(2)O(2) central unit. The high stability of the multinuclear structure therefore holds great promise for the development of stable self-assembled monolayers with potential for new opto-electronic materials.

Development of solar flares and features of the fine structure of solar radio emission

NASA Astrophysics Data System (ADS)

Chernov, G. P.; Fomichev, V. V.; Yan, Y.; Tan, B.; Tan, Ch.; Fu, Q.

2017-11-01

The reason for the occurrence of different elements of the fine structure of solar radio bursts in the decimeter and centimeter wavelength ranges has been determined based on all available data from terrestrial and satellite observations. In some phenomena, fast pulsations, a zebra structre, fiber bursts, and spikes have been observed almost simultaneously. Two phenomena have been selected to show that the pulsations of radio emission are caused by particles accelerated in the magnetic reconnection region and that the zebra structure is excited in a source, such as a magnetic trap for fast particles. The complex combination of unusual fiber bursts, zebra structure, and spikes in the phenomenon on December 1, 2004, is associated with a single source, a magnetic island formed after a coronal mass ejection.

Structure of colicin I receptor bound to the R-domain of colicin Ia: implications for protein import

PubMed Central

Buchanan, Susan K; Lukacik, Petra; Grizot, Sylvestre; Ghirlando, Rodolfo; Ali, Maruf M U; Barnard, Travis J; Jakes, Karen S; Kienker, Paul K; Esser, Lothar

2007-01-01

Colicin Ia is a 69 kDa protein that kills susceptible Escherichia coli cells by binding to a specific receptor in the outer membrane, colicin I receptor (70 kDa), and subsequently translocating its channel forming domain across the periplasmic space, where it inserts into the inner membrane and forms a voltage-dependent ion channel. We determined crystal structures of colicin I receptor alone and in complex with the receptor binding domain of colicin Ia. The receptor undergoes large and unusual conformational changes upon colicin binding, opening at the cell surface and positioning the receptor binding domain of colicin Ia directly above it. We modelled the interaction with full-length colicin Ia to show that the channel forming domain is initially positioned 150 Å above the cell surface. Functional data using full-length colicin Ia show that colicin I receptor is necessary for cell surface binding, and suggest that the receptor participates in translocation of colicin Ia across the outer membrane. PMID:17464289

DOE Office of Scientific and Technical Information (OSTI.GOV)

Faucher, Frédérick; Robey-Bond, Susan M.; Wallace, Susan S.

DNA is subject to a multitude of oxidative damages generated by oxidizing agents from metabolism and exogenous sources and by ionizing radiation. Guanine is particularly vulnerable to oxidation, and the most common oxidative product 8-oxoguanine (8-oxoG) is the most prevalent lesion observed in DNA molecules. 8-OxoG can form a normal Watson-Crick pair with cytosine (8-oxoG:C), but it can also form a stable Hoogsteen pair with adenine (8-oxoG:A), leading to a G:C {yields} T:A transversion after replication. Fortunately, 8-oxoG is recognized and excised by either of two DNA glycosylases of the base excision repair pathway: formamidopyrimidine-DNA glycosylase and 8-oxoguanine DNA glycosylasemore » (Ogg). While Clostridium acetobutylicum Ogg (CacOgg) DNA glycosylase can specifically recognize and remove 8-oxoG, it displays little preference for the base opposite the lesion, which is unusual for a member of the Ogg1 family. This work describes the crystal structures of CacOgg in its apo form and in complex with 8-oxo-2'-deoxyguanosine. A structural comparison between the apo form and the liganded form of the enzyme reveals a structural reorganization of the C-terminal domain upon binding of 8-oxoG, similar to that reported for human OGG1. A structural comparison of CacOgg with human OGG1, in complex with 8-oxoG containing DNA, provides a structural rationale for the lack of opposite base specificity displayed by CacOgg.« less

An amyloid-forming peptide from the yeast prion Sup35 reveals a dehydrated β-sheet structure for amyloid

PubMed Central

Balbirnie, Melinda; Grothe, Robert; Eisenberg, David S.

2001-01-01

X-ray diffraction and other biophysical tools reveal features of the atomic structure of an amyloid-like crystal. Sup35, a prion-like protein in yeast, forms fibrillar amyloid assemblies intrinsic to its prion function. We have identified a polar peptide from the N-terminal prion-determining domain of Sup35 that exhibits the amyloid properties of full-length Sup35, including cooperative kinetics of aggregation, fibril formation, binding of the dye Congo red, and the characteristic cross-β x-ray diffraction pattern. Microcrystals of this peptide also share the principal properties of the fibrillar amyloid, including a highly stable, β-sheet-rich structure and the binding of Congo red. The x-ray powder pattern of the microcrystals, extending to 0.9-Å resolution, yields the unit cell dimensions of the well-ordered structure. These dimensions restrict possible atomic models of this amyloid-like structure and demonstrate that it forms packed, parallel-stranded β-sheets. The unusually high density of the crystals shows that the packed β-sheets are dehydrated, despite the polar character of the side chains. These results suggest that amyloid is a highly intermolecularly bonded, dehydrated array of densely packed β-sheets. This dry β-sheet could form as Sup35 partially unfolds to expose the peptide, permitting it to hydrogen-bond to the same peptide of other Sup35 molecules. The implication is that amyloid-forming units may be short segments of proteins, exposed for interactions by partial unfolding. PMID:11226247

Modeling Temporal Behavior in Large Networks: A Dynamic Mixed-Membership Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rossi, R; Gallagher, B; Neville, J

Given a large time-evolving network, how can we model and characterize the temporal behaviors of individual nodes (and network states)? How can we model the behavioral transition patterns of nodes? We propose a temporal behavior model that captures the 'roles' of nodes in the graph and how they evolve over time. The proposed dynamic behavioral mixed-membership model (DBMM) is scalable, fully automatic (no user-defined parameters), non-parametric/data-driven (no specific functional form or parameterization), interpretable (identifies explainable patterns), and flexible (applicable to dynamic and streaming networks). Moreover, the interpretable behavioral roles are generalizable, computationally efficient, and natively supports attributes. We applied ourmore » model for (a) identifying patterns and trends of nodes and network states based on the temporal behavior, (b) predicting future structural changes, and (c) detecting unusual temporal behavior transitions. We use eight large real-world datasets from different time-evolving settings (dynamic and streaming). In particular, we model the evolving mixed-memberships and the corresponding behavioral transitions of Twitter, Facebook, IP-Traces, Email (University), Internet AS, Enron, Reality, and IMDB. The experiments demonstrate the scalability, flexibility, and effectiveness of our model for identifying interesting patterns, detecting unusual structural transitions, and predicting the future structural changes of the network and individual nodes.« less

B38: an all-boron fullerene analogue.

PubMed

Lv, Jian; Wang, Yanchao; Zhu, Li; Ma, Yanming

2014-10-21

Fullerene-like structures formed by elements other than carbon have long been sought. Finding all-boron (B) fullerene-like structures is challenging due to the geometrical frustration arising from competitions among various structural motifs. We report here the prediction of a B38 fullerene analogue found through first-principles swarm structure searching calculations. The structure is highly symmetric and consists of 56 triangles and four hexagons, which provide an optimal void in the center of the cage. Energetically, it is more favorable than the planar and tubular structures, and possesses an unusually high chemical stability: a large energy gap (∼2.25 eV) and a high double aromaticity, superior to those of most aromatic quasi-planar B12 and double-ring B20 clusters. Our findings represent a key step forward towards to the understanding of structures of medium-sized B clusters and map out the experimental direction of the synthesis of an all-B fullerene analogue.

High-Resolution X-Ray Structures of Two Functionally Distinct Members of the Cyclic Amide Hydrolase Family of Toblerone Fold Enzymes

PubMed Central

Peat, Thomas S.; Balotra, Sahil; Wilding, Matthew; Hartley, Carol J.; Newman, Janet

2017-01-01

ABSTRACT The Toblerone fold was discovered recently when the first structure of the cyclic amide hydrolase, AtzD (a cyanuric acid hydrolase), was elucidated. We surveyed the cyclic amide hydrolase family, finding a strong correlation between phylogenetic distribution and specificity for either cyanuric acid or barbituric acid. One of six classes (IV) could not be tested due to a lack of expression of the proteins from it, and another class (V) had neither cyanuric acid nor barbituric acid hydrolase activity. High-resolution X-ray structures were obtained for a class VI barbituric acid hydrolase (1.7 Å) from a Rhodococcus species and a class V cyclic amide hydrolase (2.4 Å) from a Frankia species for which we were unable to identify a substrate. Both structures were homologous with the tetrameric Toblerone fold enzyme AtzD, demonstrating a high degree of structural conservation within the cyclic amide hydrolase family. The barbituric acid hydrolase structure did not contain zinc, in contrast with early reports of zinc-dependent activity for this enzyme. Instead, each barbituric acid hydrolase monomer contained either Na+ or Mg2+, analogous to the structural metal found in cyanuric acid hydrolase. The Frankia cyclic amide hydrolase contained no metal but instead formed unusual, reversible, intermolecular vicinal disulfide bonds that contributed to the thermal stability of the protein. The active sites were largely conserved between the three enzymes, differing at six positions, which likely determine substrate specificity. IMPORTANCE The Toblerone fold enzymes catalyze an unusual ring-opening hydrolysis with cyclic amide substrates. A survey of these enzymes shows that there is a good correlation between physiological function and phylogenetic distribution within this family of enzymes and provide insights into the evolutionary relationships between the cyanuric acid and barbituric acid hydrolases. This family of enzymes is structurally and mechanistically distinct from other enzyme families; however, to date the structure of just two, physiologically identical, enzymes from this family has been described. We present two new structures: a barbituric acid hydrolase and an enzyme of unknown function. These structures confirm that members of the CyAH family have the unusual Toblerone fold, albeit with some significant differences. PMID:28235873

Solid-state structure of a Li/F carbenoid: pentafluoroethyllithium.

PubMed

Waerder, Benedikt; Steinhauer, Simon; Neumann, Beate; Stammler, Hans-Georg; Mix, Andreas; Vishnevskiy, Yury V; Hoge, Berthold; Mitzel, Norbert W

2014-10-20

Lithium carbenoids are versatile compounds for synthesis owing to their intriguing ambiphilic behavior. Although this class of compounds has been known for several years, few solid-state structures exist because of their high reactivity and often low thermal stability. Using cryo X-ray techniques, we were now able to elucidate the first solid-state structure of a Li/F alkyl carbenoid, pentafluoroethyllithium (LiC2F5), finally yielding a prototype for investigating structure-reactivity relationships for this class of molecules. The compound forms a diethyl ether-solvated dimer bridged by a rare C-F-Li link. Complementary NMR spectroscopy studies in solution show dynamic processes and indicate rapid exchange of starting material and product. Theoretical investigations help to understand the formation of the observed unusual structural motif. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mutational analysis of the folding transition state of the C-terminal domain of ribosomal protein L9: a protein with an unusual beta-sheet topology.

PubMed

Li, Ying; Gupta, Ruchi; Cho, Jae-Hyun; Raleigh, Daniel P

2007-01-30

The C-terminal domain of ribosomal protein L9 (CTL9) is a 92-residue alpha-beta protein which contains an unusual three-stranded mixed parallel and antiparallel beta-sheet. The protein folds in a two-state fashion, and the folding rate is slow. It is thought that the slow folding may be caused by the necessity of forming this unusual beta-sheet architecture in the transition state for folding. This hypothesis makes CTL9 an interesting target for folding studies. The transition state for the folding of CTL9 was characterized by phi-value analysis. The folding of a set of hydrophobic core mutants was analyzed together with a set of truncation mutants. The results revealed a few positions with high phi-values (> or = 0.5), notably, V131, L133, H134, V137, and L141. All of these residues were found in the beta-hairpin region, indicating that the formation of this structure is likely to be the rate-limiting step in the folding of CTL9. One face of the beta-hairpin docks against the N-terminal helix. Analysis of truncation mutants of this helix confirmed its importance in folding. Mutations at other sites in the protein gave small phi-values, despite the fact that some of them had major effects on stability. The analysis indicates that formation of the antiparallel hairpin is critical and its interactions with the first helix are also important. Thus, the slow folding is not a consequence of the need to fully form the unusual three-stranded beta-sheet in the transition state. Analysis of the urea dependence of the folding rates indicates that mutations modulate the unfolded state. The folding of CTL9 is broadly consistent with the nucleation-condensation model of protein folding.

Electric Field Effects on the Intermolecular Interactions in Water Whiskers: Insight from Structures, Energetics, and Properties

DOE PAGES

Bai, Yang; He, Hui-Min; Li, Ying; ...

2015-02-19

Modulation of intermolecular interactions in response to external electric fields could be fundamental to the formation of unusual forms of water, such as water whiskers. However, a detailed understanding of the nature of intermolecular interactions in such systems is lacking. In this study, we present novel theoretical results based on electron correlation calculations regarding the nature of H-bonds in water whiskers, which is revealed by studying their evolution under external electric fields with various field strengths. We find that the water whiskers consisting of 2-7 water molecules all have a chain-length dependent critical electric field. Under the critical electric field,more » the most compact chain structures are obtained, featuring very strong H-bonds, herein referred to as covalent H-bonds. In the case of a water dimer whisker, the bond length of the novel covalent H-bond shortens by 25%, the covalent bond order increases by 9 times, and accordingly the H-bond energy is strengthened by 5 times compared to the normal H-bond in a (H 2O) 2 cluster. Below the critical electric field, it is observed that with increasing field strength, H-bonding orbitals display gradual evolutions in the orbital energy, orbital ordering, and orbital nature (i.e., from typical -style orbital to unusual -style double H-bonding orbital). We also show that beyond the critical electric field, a single water whisker may disintegrate to form a loosely bound zwitterionic chain due to a relay-style proton transfer, whereas two water whiskers may undergo intermolecular cross-linking to form a quasi-two-dimensional water network. In conclusion, these results help shed new insight on the effects of electric fields on water whisker formation.« less

Texture related unusual phenomena in electrodeposition and vapor deposition

NASA Astrophysics Data System (ADS)

Lee, D. N.; Han, H. N.

2015-04-01

The tensile strength of electrodeposits generally decreases with increasing bath temperature because the grain size increases and the dislocation density decreases with increasing bath temperature. Therefore, discontinuities observed in the tensile strength vs. bath temperature curves in electrodeposition of copper are unusual. The tensile strength of electrodeposits generally increases with increasing cathode current density because the rate of nucleation in electrodeposits increases with increasing current density, which in turn gives rise to a decrease in the grain size and in turn an increase in the strength. Therefore, a decrease in the tensile strength of copper electrodeposits at a high current density is unusual. The grain size of vapor deposits is expected to decrease with decreasing substrate temperature. However, rf sputtered Co-Cr deposits showed that deposits formed on water-cooled polyimide substrates had a larger grain size than deposits formed on polyimide substrates at 200 °C. These unusual phenomena can be explained by the preferred growth model for deposition texture evolution.

A fluorophosphate-based inverse Keggin structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fielden, John; Quasdorf, Kyle; Cronin, Leroy

An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

A fluorophosphate-based inverse Keggin structure.

PubMed

Fielden, John; Quasdorf, Kyle; Cronin, Leroy; Kögerler, Paul

2012-09-07

An unusual PFO(3)(2-)-templated "inverse Keggin" polyanion, [Mo(12)O(46)(PF)(4)](4-), has been isolated from the degradation reaction of an {Mo(132)}-type Keplerate to [PMo(12)O(40)](3-) by [Cu(MeCN)(4)](PF(6)) in acetonitrile. (31)P-NMR studies suggest a structure-directing role for [Cu(MeCN)(4)](+) in the formation of the highly unusual all-inorganic inverse Keggin structure.

Structure of the bacteriophage T4 long tail fiber receptor-binding tip

PubMed Central

Bartual, Sergio G.; Otero, José M.; Garcia-Doval, Carmela; Llamas-Saiz, Antonio L.; Kahn, Richard; Fox, Gavin C.; van Raaij, Mark J.

2010-01-01

Bacteriophages are the most numerous organisms in the biosphere. In spite of their biological significance and the spectrum of potential applications, little high-resolution structural detail is available on their receptor-binding fibers. Here we present the crystal structure of the receptor-binding tip of the bacteriophage T4 long tail fiber, which is highly homologous to the tip of the bacteriophage lambda side tail fibers. This structure reveals an unusual elongated six-stranded antiparallel beta-strand needle domain containing seven iron ions coordinated by histidine residues arranged colinearly along the core of the biological unit. At the end of the tip, the three chains intertwine forming a broader head domain, which contains the putative receptor interaction site. The structure reveals a previously unknown beta-structured fibrous fold, provides insights into the remarkable stability of the fiber, and suggests a framework for mutations to expand or modulate receptor-binding specificity. PMID:21041684

Assembly of Reconfigurable Colloidal Structures by Multidirectional Field-Induced Interactions.

PubMed

Bharti, Bhuvnesh; Velev, Orlin D

2015-07-28

Field-directed colloidal assembly has shown remarkable recent progress in increasing the complexity, degree of control, and multiscale organization of the structures. This has largely been achieved by using particles of complex shapes and polarizabilites (Janus, patchy, shaped, and faceted). We review the fundamentals of the interactions leading to the directed assembly of such structures, the ways to simulate the dynamics of the process, and the effect of particle size, shape, and properties on the type of structure obtained. We discuss how directional polarization interactions induced by external electric and magnetic fields can be used to assemble complex particles or particle mixtures into lattices of tailored structure. Examples of such systems include isotropic and anisotropic shaped particles with surface patches, which form networks and crystals of unusual symmetry by dipolar, quadrupolar, and multipolar interactions in external fields. The emerging trends in making reconfigurable and dynamic structures are discussed.

78 FR 76980 - Special Conditions: Airbus, A350-900 Series Airplane; Interaction of Systems and Structures

Federal Register 2010, 2011, 2012, 2013, 2014

2013-12-20

... series airplanes. These airplanes will have novel or unusual design features when compared to the state...-900 series because of a novel or unusual design feature, special conditions are prescribed under Sec...)(2). Novel or Unusual Design Features The Airbus Model A350-900 series will incorporate the following...

Toxoplasma gondii: Biochemical and biophysical characterization of recombinant soluble dense granule proteins GRA2 and GRA6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bittame, Amina; Université Grenoble Alpes, 38042 Grenoble; Effantin, Grégory

2015-03-27

The most prominent structural feature of the parasitophorous vacuole (PV) in which the intracellular parasite Toxoplasma gondii proliferates is a membranous nanotubular network (MNN), which interconnects the parasites and the PV membrane. The MNN function remains unclear. The GRA2 and GRA6 proteins secreted from the parasite dense granules into the PV have been implicated in the MNN biogenesis. Amphipathic alpha-helices (AAHs) predicted in GRA2 and an alpha-helical hydrophobic domain predicted in GRA6 have been proposed to be responsible for their membrane association, thereby potentially molding the MMN in its structure. Here we report an analysis of the recombinant proteins (expressedmore » in detergent-free conditions) by circular dichroism, which showed that full length GRA2 displays an alpha-helical secondary structure while recombinant GRA6 and GRA2 truncated of its AAHs are mainly random coiled. Dynamic light scattering and transmission electron microscopy showed that recombinant GRA6 and truncated GRA2 constitute a homogenous population of small particles (6–8 nm in diameter) while recombinant GRA2 corresponds to 2 populations of particles (∼8–15 nm and up to 40 nm in diameter, respectively). The unusual properties of GRA2 due to its AAHs are discussed. - Highlights: • Toxoplasma gondii: soluble GRA2 forms 2 populations of particles. • T. gondii: the dense granule protein GRA2 folds intrinsically as an alpha-helix. • T. gondii: monomeric soluble GRA6 forms particles of 6–8 nm in diameter. • T. gondii: monomeric soluble GRA6 is random coiled. • Unusual biophysical properties of the dense granule protein GRA2 from T. gondii.« less

Structures of Staphylococcus aureus D-tagatose-6-phosphate kinase implicate domain motions in specificity and mechanism.

PubMed

Miallau, Linda; Hunter, William N; McSweeney, Sean M; Leonard, Gordon A

2007-07-06

High resolution structures of Staphylococcus aureus d-tagatose-6-phosphate kinase (LacC) in two crystal forms are herein reported. The structures define LacC in apoform, in binary complexes with ADP or the co-factor analogue AMP-PNP, and in a ternary complex with AMP-PNP and D-tagatose-6-phosphate. The tertiary structure of the LacC monomer, which is closely related to other members of the pfkB subfamily of carbohydrate kinases, is composed of a large alpha/beta core domain and a smaller, largely beta "lid." Four extended polypeptide segments connect these two domains. Dimerization of LacC occurs via interactions between lid domains, which come together to form a beta-clasp structure. Residues from both subunits contribute to substrate binding. LacC adopts a closed structure required for phosphoryl transfer only when both substrate and co-factor are bound. A reaction mechanism similar to that used by other phosphoryl transferases is proposed, although unusually, when both substrate and co-factor are bound to the enzyme two Mg(2+) ions are observed in the active site. A new motif of amino acid sequence conservation common to the pfkB subfamily of carbohydrate kinases is identified.

NMR structure of the 101-nucleotide core encapsidation signal of the Moloney murine leukemia virus.

PubMed

D'Souza, Victoria; Dey, Anwesha; Habib, Dina; Summers, Michael F

2004-03-19

The full length, positive-strand genome of the Moloney Murine Leukemia Virus contains a "core encapsidation signal" that is essential for efficient genome packaging during virus assembly. We have determined the structure of a 101-nucleotide RNA that contains this signal (called mPsi) using a novel isotope-edited NMR approach. The method is robust and should be generally applicable to larger RNAs. mPsi folds into three stem loops, two of which (SL-C and SL-D) co-stack to form an extended helix. The third stem loop (SL-B) is connected to SL-C by a flexible, four-nucleotide linker. The structure contains five mismatched base-pairs, an unusual C.CG base-triple platform, and a novel "A-minor K-turn," in which unpaired adenosine bases A340 and A341 of a GGAA bulge pack in the minor groove of a proximal stem, and a bulged distal uridine (U319) forms a hydrogen bond with the phosphodiester of A341. Phylogenetic analyses indicate that these essential structural elements are conserved among the murine C-type retroviruses.

[Clinical aspects of witchcraft delusions].

PubMed

Pashkovskiĭ, V E

2005-01-01

To distinguish clinical variants and to specify nosologic entity of witchcraft delusions, 69 patients (10 males, aged 15-72 years) have been examined. It was found that witchcraft delusions exist in passive and active forms. In a passive form, the patient is sure that unknown (mystic) power damaged him/her; in an active form the patient, possessing a gift for unusual abilities, can influence the others (bewitches, heals, etc). Five clinical syndromes, in the structure of which the above delusions were found, namely, paranoiac-hypochondriac, hallucination-paranoid, depressive-paranoid, paraphrenic and delirious, were identified. Psychoses of schizophrenia spectrum were diagnosed in 52 patients, organic--in 8, alcoholic--in 7 and recurrent depressive disorder--in 2. Clinical significance of witchcraft delusions is closely related to its social aspect. Being combined with ideas of persecution, poisoning and damage, it results in the brutal forms of delusions defense and may be considered as an unfavorable prognostic trait.

Correlations of Life Form, Pollination Mode and Sexual System in Aquatic Angiosperms

PubMed Central

Du, Zhi-Yuan; Wang, Qing-Feng

2014-01-01

Aquatic plants are phylogenetically well dispersed across the angiosperms. Reproductive and other life-history traits of aquatic angiosperms are closely associated with specific growth forms. Hydrophilous pollination exhibits notable examples of convergent evolution in angiosperm reproductive structures, and hydrophiles exhibit great diversity in sexual system. In this study, we reconstructed ancestral characters of aquatic lineages based on the phylogeny of aquatic angiosperms. Our aim is to find the correlations of life form, pollination mode and sexual system in aquatic angiosperms. Hydrophily is the adaptive evolution of completely submersed angiosperms to aquatic habitats. Hydroautogamy and maleflower-ephydrophily are the transitional stages from anemophily and entomophily to hydrophily. True hydrophily occurs in 18 submersed angiosperm genera, which is associated with an unusually high incidence of unisexual flowers. All marine angiosperms are submersed, hydrophilous species. This study would help us understand the evolution of hydrophilous pollination and its correlations with life form and sexual system. PMID:25525810

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holt, Allison M; Standaert, Robert F; Jubb, Aaron M

Biological membranes, formed primarily by the self-assembly of complex mixtures of phospholipids, provide a structured scaffold for compartmentalization and structural processes in living cells. The specific physical properties of phospholipid species present in a given membrane play a key role in mediating these processes. Phosphatidylethanolamine (PE), a zwitterionic lipid present in bacterial, yeast, and mammalian cell membranes, is exceptional. In addition to undergoing the standard lipid polymorphic transition between the gel and liquid-crystalline phase, it can also assume an unusual polymorphic state, the inverse hexagonal phase (HII). Divalent cations are among the factors that drive the formation of the HIImore » phase, wherein the lipid molecules form stacked tubular structures by burying the hydrophilic head groups and exposing the hydrophobic tails to the bulk solvent. Most biological membranes contain a lipid species capable of forming the HII state suggesting that such lipid polymorphic structural states play an important role in structural biological processes such as membrane fusion. In this study, the interactions between Mg2+ and biomimetic bacterial cell membranes composed of PE and phosphatidylglycerol (PG) were probed using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), and fluorescence spectroscopy. The lipid phase transitions were examined at varying ratios of PE to PG and upon exposure to physiologically relevant concentrations of Mg2+. An understanding of these basic interactions enhances our understanding of membrane dynamics and how membrane-mediated structural changes may occur in vivo.« less

A novel Sulfolobus virus with an exceptional capsid architecture.

PubMed

Wang, Haina; Guo, Zhenqian; Feng, Hongli; Chen, Yufei; Chen, Xiuqiang; Li, Zhimeng; Hernández-Ascencio, Walter; Dai, Xin; Zhang, Zhenfeng; Zheng, Xiaowei; Mora-López, Marielos; Fu, Yu; Zhang, Chuanlun; Zhu, Ping; Huang, Li

2017-12-06

A novel archaeal virus, denoted Sulfolobus ellipsoid virus 1 (SEV1), was isolated from an acidic hot spring in Costa Rica. The morphologically unique virion of SEV1 contains a protein capsid with 16 regularly spaced striations and an 11-nm-thick envelope. The capsid exhibits an unusual architecture in which the viral DNA, probably in the form of a nucleoprotein filament, wraps around the longitudinal axis of the virion in a plane to form a multilayered disk-like structure with a central hole, and 16 of these structures are stacked to generate a spool-like capsid. SEV1 harbors a linear double-stranded DNA genome of ∼23 kb, which encodes 38 predicted open reading frames (ORFs). Among the few ORFs with a putative function is a gene encoding a protein-primed DNA polymerase. Six-fold symmetrical virus-associated pyramids (VAPs) appear on the surface of the SEV1-infected cells, which are ruptured to allow the formation of a hexagonal opening and subsequent release of the progeny virus particles. Notably, the SEV1 virions acquire the lipid membrane in the cytoplasm of the host cell. The lipid composition of the viral envelope correlates with that of the cell membrane. These results suggest the use of a unique mechanism by SEV1 in membrane biogenesis. IMPORTANCE Investigation of archaeal viruses has greatly expanded our knowledge of the virosphere and its role in the evolution of life. Here we show that Sulfolobus ellipsoid virus 1 (SEV1), an archaeal virus isolated from a hot spring in Costa Rica, exhibits a novel viral shape and an unusual capsid architecture. The SEV1 DNA wraps multiple times in a plane around the longitudinal axis of the virion to form a disk-like structure, and 16 of these structures are stacked to generate a spool-like capsid. The virus acquires its envelope intracellularly and exits the host cell by creating a hexagonal hole on the host cell surface. These results shed significant light on the diversity of viral morphogenesis. Copyright © 2017 American Society for Microbiology.

Domain swapping dissection in Thermotoga maritima arginine binding protein: How structural flexibility may compensate destabilization.

PubMed

Smaldone, Giovanni; Berisio, Rita; Balasco, Nicole; D'Auria, Sabato; Vitagliano, Luigi; Ruggiero, Alessia

2018-05-31

Thermotoga maritima Arginine Binding Protein (TmArgBP) is a valuable candidate for arginine biosensing in diagnostics. This protein is endowed with unusual structural properties that include an extraordinary thermal/chemical stability, a domain swapped structure that undergoes large tertiary and quaternary structural transition, and the ability to form non-canonical oligomeric species. As the intrinsic stability of TmArgBP allows for extensive protein manipulations, we here dissected its structure in two parts: its main body deprived of the swapping fragment (TmArgBP 20-233 ) and the C-terminal peptide corresponding to the helical swapping element. Both elements have been characterized independently or in combination using a repertoire of biophysical/structural techniques. Present investigations clearly indicate that TmArgBP 20-233 represents a better scaffold for arginine sensing compared to the wild-type protein. Moreover, our data demonstrate that the ligand-free and the ligand-bound forms respond very differently to this helix deletion. This drastic perturbation has an important impact on the ligand-bound form of TmArgBP 20-233 stability whereas it barely affects its ligand-free state. The crystallographic structures of these forms provide a rationale to this puzzling observation. Indeed, the arginine-bound state is very rigid and virtually unchanged upon protein truncation. On the other hand, the flexible ligand-free TmArgBP 20-233 is able to adopt a novel state as a consequence of the helix deletion. Therefore, the flexibility of the ligand-free form endows this state with a remarkable robustness upon severe perturbations. In this scenario, TmArgBP dissection highlights an intriguing connection between destabilizing/stabilizing effects and the overall flexibility that could operate also in other proteins. Copyright © 2018 Elsevier B.V. All rights reserved.

High-resolution molecular structure of a peptide in an amyloid fibril determined by magic angle spinning NMR spectroscopy

NASA Astrophysics Data System (ADS)

Jaroniec, Christopher P.; Macphee, Cait E.; Bajaj, Vikram S.; McMahon, Michael T.; Dobson, Christopher M.; Griffin, Robert G.

2004-01-01

Amyloid fibrils are self-assembled filamentous structures associated with protein deposition conditions including Alzheimer's disease and the transmissible spongiform encephalopathies. Despite the immense medical importance of amyloid fibrils, no atomic-resolution structures are available for these materials, because the intact fibrils are insoluble and do not form diffraction-quality 3D crystals. Here we report the high-resolution structure of a peptide fragment of the amyloidogenic protein transthyretin, TTR(105-115), in its fibrillar form, determined by magic angle spinning NMR spectroscopy. The structure resolves not only the backbone fold but also the precise conformation of the side chains. Nearly complete 13C and 15N resonance assignments for TTR(105-115) formed the basis for the extraction of a set of distance and dihedral angle restraints. A total of 76 self-consistent experimental measurements, including 41 restraints on 19 backbone dihedral angles and 35 13C-15N distances between 3 and 6 Å were obtained from 2D and 3D NMR spectra recorded on three fibril samples uniformly 13C, 15N-labeled in consecutive stretches of four amino acids and used to calculate an ensemble of peptide structures. Our results indicate that TTR(105-115) adopts an extended -strand conformation in the amyloid fibrils such that both the main- and side-chain torsion angles are close to their optimal values. Moreover, the structure of this peptide in the fibrillar form has a degree of long-range order that is generally associated only with crystalline materials. These findings provide an explanation of the unusual stability and characteristic properties of this form of polypeptide assembly.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asubay, Sezai; Durap, Feyyaz; Aydemir, Murat

An organic-inorganic junction was fabricated by forming [Ru(Cy{sub 2}PNHCH{sub 2}-C{sub 4}H{sub 3}O)(η{sup 6}-p-cymene)Cl{sub 2}] complex thin film using spin coating technique on n-Si and evaporating Au metal on the film. It was seen that the structure had perfect rectification property. Current-voltage (I-V) measurements were carried out in dark and under various illumination conditions (between 50-100 mW/cm{sup 2}) and with the temperature range from 303 to 380 K. The structure showed unusually forward and reverse bias temperature and light sensing behaviors. It was seen that the current both in forward and reverse bias increased with the increase in light intensity and temperature.

The structure of drug-deoxydinucleoside phosphate complex; generalized conformational behavior of intercalation complexes with RNA and DNA fragments.

PubMed Central

Shieh, H S; Berman, H M; Dabrow, M; Neidle, S

1980-01-01

A 2:2 complex of proflavine and deoxycytidylyl-3', 5'-guanosine has been crystallized and its structure determined by x-ray crystallography. The two dinucleoside phosphate strands form self complementary duplexes with Watson Crick hydrogen bonds. One proflavin is asymmetrically intercalated between the base pairs and the other is stacked above them. The conformations of the nucleotides are unusual in that one strand has C3',C2'endomixed sugar puckering and the other has C3',C3' endo deoxyribose sugars. These results show that the conformation of the 3'sugar is of secondary importance to the intercalated geometry. PMID:7355129

Dirac Fermions in Borophene

NASA Astrophysics Data System (ADS)

Feng, Baojie; Sugino, Osamu; Liu, Ro-Ya; Zhang, Jin; Yukawa, Ryu; Kawamura, Mitsuaki; Iimori, Takushi; Kim, Howon; Hasegawa, Yukio; Li, Hui; Chen, Lan; Wu, Kehui; Kumigashira, Hiroshi; Komori, Fumio; Chiang, Tai-Chang; Meng, Sheng; Matsuda, Iwao

2017-03-01

Honeycomb structures of group IV elements can host massless Dirac fermions with nontrivial Berry phases. Their potential for electronic applications has attracted great interest and spurred a broad search for new Dirac materials especially in monolayer structures. We present a detailed investigation of the β12 sheet, which is a borophene structure that can form spontaneously on a Ag(111) surface. Our tight-binding analysis revealed that the lattice of the β12 sheet could be decomposed into two triangular sublattices in a way similar to that for a honeycomb lattice, thereby hosting Dirac cones. Furthermore, each Dirac cone could be split by introducing periodic perturbations representing overlayer-substrate interactions. These unusual electronic structures were confirmed by angle-resolved photoemission spectroscopy and validated by first-principles calculations. Our results suggest monolayer boron as a new platform for realizing novel high-speed low-dissipation devices.

Direct observation of a single nanoparticle-ubiquitin corona formation

NASA Astrophysics Data System (ADS)

Ding, Feng; Radic, Slaven; Chen, Ran; Chen, Pengyu; Geitner, Nicholas K.; Brown, Jared M.; Ke, Pu Chun

2013-09-01

The advancement of nanomedicine and the increasing applications of nanoparticles in consumer products have led to administered biological exposure and unintentional environmental accumulation of nanoparticles, causing concerns over the biocompatibility and sustainability of nanotechnology. Upon entering physiological environments, nanoparticles readily assume the form of a nanoparticle-protein corona that dictates their biological identity. Consequently, understanding the structure and dynamics of a nanoparticle-protein corona is essential for predicting the fate, transport, and toxicity of nanomaterials in living systems and for enabling the vast applications of nanomedicine. Here we combined multiscale molecular dynamics simulations and complementary experiments to characterize the silver nanoparticle-ubiquitin corona formation. Notably, ubiquitins competed with citrates for the nanoparticle surface, governed by specific electrostatic interactions. Under a high protein/nanoparticle stoichiometry, ubiquitins formed a multi-layer corona on the particle surface. The binding exhibited an unusual stretched-exponential behavior, suggesting a rich binding kinetics. Furthermore, the binding destabilized the α-helices while increasing the β-sheet content of the proteins. This study revealed the atomic and molecular details of the structural and dynamic characteristics of nanoparticle-protein corona formation.The advancement of nanomedicine and the increasing applications of nanoparticles in consumer products have led to administered biological exposure and unintentional environmental accumulation of nanoparticles, causing concerns over the biocompatibility and sustainability of nanotechnology. Upon entering physiological environments, nanoparticles readily assume the form of a nanoparticle-protein corona that dictates their biological identity. Consequently, understanding the structure and dynamics of a nanoparticle-protein corona is essential for predicting the fate, transport, and toxicity of nanomaterials in living systems and for enabling the vast applications of nanomedicine. Here we combined multiscale molecular dynamics simulations and complementary experiments to characterize the silver nanoparticle-ubiquitin corona formation. Notably, ubiquitins competed with citrates for the nanoparticle surface, governed by specific electrostatic interactions. Under a high protein/nanoparticle stoichiometry, ubiquitins formed a multi-layer corona on the particle surface. The binding exhibited an unusual stretched-exponential behavior, suggesting a rich binding kinetics. Furthermore, the binding destabilized the α-helices while increasing the β-sheet content of the proteins. This study revealed the atomic and molecular details of the structural and dynamic characteristics of nanoparticle-protein corona formation. Electronic supplementary information (ESI) available: Experimental and computational methods as well as supporting figures. See DOI: 10.1039/c3nr02147e

Stepwise Elastic Behavior in a Model Elastomer

NASA Astrophysics Data System (ADS)

Bhawe, Dhananjay M.; Cohen, Claude; Escobedo, Fernando A.

2004-12-01

MonteCarlo simulations of an entanglement-free cross-linked polymer network of semiflexible chains reveal a peculiar stepwise elastic response. For increasing stress, step jumps in strain are observed that do not correlate with changes in the number of aligned chains. We show that this unusual behavior stems from the ability of the system to form multiple ordered chain domains that exclude the cross-linking species. This novel elastomer shows a toughening behavior similar to that observed in biological structural materials, such as muscle proteins and abalone shell adhesive.

A possible Harappan astronomical observatory at Dholavira

NASA Astrophysics Data System (ADS)

Vahia, Mayank; Menon, Srikumar M.

2013-11-01

Astronomy arises very early in a civilisation and evolves as the civilisation advances. It is therefore reasonable to assume that a vibrant knowledge of astronomy would have been a feature of a civilisation the size of the Harappan Civilisation. We suggest that structures dedicated to astronomy existed in every major Harappan city. One such city was Dholavira, an important trading port that was located on an island in what is now the Rann of Kutch during the peak of the Harappan Civilisation. We have analysed an unusual structure at Dholavira that includes two circular rooms. Upon assuming strategically-placed holes in their ceilings we examine the internal movement of sunlight within these rooms and suggest that the larger structure of which they formed a part could have functioned as an astronomical observatory.

Twisting Right to Left: A…A Mismatch in a CAG Trinucleotide Repeat Overexpansion Provokes Left-Handed Z-DNA Conformation

PubMed Central

2015-01-01

Conformational polymorphism of DNA is a major causative factor behind several incurable trinucleotide repeat expansion disorders that arise from overexpansion of trinucleotide repeats located in coding/non-coding regions of specific genes. Hairpin DNA structures that are formed due to overexpansion of CAG repeat lead to Huntington’s disorder and spinocerebellar ataxias. Nonetheless, DNA hairpin stem structure that generally embraces B-form with canonical base pairs is poorly understood in the context of periodic noncanonical A…A mismatch as found in CAG repeat overexpansion. Molecular dynamics simulations on DNA hairpin stems containing A…A mismatches in a CAG repeat overexpansion show that A…A dictates local Z-form irrespective of starting glycosyl conformation, in sharp contrast to canonical DNA duplex. Transition from B-to-Z is due to the mechanistic effect that originates from its pronounced nonisostericity with flanking canonical base pairs facilitated by base extrusion, backbone and/or base flipping. Based on these structural insights we envisage that such an unusual DNA structure of the CAG hairpin stem may have a role in disease pathogenesis. As this is the first study that delineates the influence of a single A…A mismatch in reversing DNA helicity, it would further have an impact on understanding DNA mismatch repair. PMID:25876062

Synthesis of two-dimensional TlxBi1−x compounds and Archimedean encoding of their atomic structure

PubMed Central

Gruznev, Dimitry V.; Bondarenko, Leonid V.; Matetskiy, Andrey V.; Mihalyuk, Alexey N.; Tupchaya, Alexandra Y.; Utas, Oleg A.; Eremeev, Sergey V.; Hsing, Cheng-Rong; Chou, Jyh-Pin; Wei, Ching-Ming; Zotov, Andrey V.; Saranin, Alexander A.

2016-01-01

Crystalline atomic layers on solid surfaces are composed of a single building block, unit cell, that is copied and stacked together to form the entire two-dimensional crystal structure. However, it appears that this is not an unique possibility. We report here on synthesis and characterization of the one-atomic-layer-thick TlxBi1−x compounds which display quite a different arrangement. It represents a quasi-periodic tiling structures that are built by a set of tiling elements as building blocks. Though the layer is lacking strict periodicity, it shows up as an ideally-packed tiling of basic elements without any skips or halting. The two-dimensional TlxBi1−x compounds were formed by depositing Bi onto the Tl-covered Si(111) surface where Bi atoms substitute appropriate amount of Tl atoms. Atomic structure of each tiling element as well as arrangement of TlxBi1−x compounds were established in a detail. Electronic properties and spin texture of the selected compounds having periodic structures were characterized. The shown example demonstrates possibility for the formation of the exotic low-dimensional materials via unusual growth mechanisms. PMID:26781340

A 1:2 crystalline complex of ApA:proflavine: a model for binding to single-stranded regions in RNA.

PubMed Central

Neidle, S; Taylor, G; Sanderson, M

1978-01-01

The structure of a 1"2 complex of adenylyl-(3',5')-adenosine phosphate and proflavine hemisulfate has been determined using the methods of x-ray crystallography. Since the ApA does not form a mini double helix, it may serve as a model for the interaction of planar molecules with single stranded nucleic acids. The dinucleotide adopts an extended conformation with the adenines in adjacent molecules forming base pairs. A most unusual feature of the molecule is that it does not obey the "rigid nucleotide" concept although none of the torsion angles occur in energetically unfavourable regions. This is most probably due to the strong interactions between the proflavine and the oligonucleotide. PMID:724521

Imido-pyridine Ti(IV) compounds: synthesis of unusual imido-amido heterobimetallic derivatives.

PubMed

Pedrosa, Sergio; Vidal, Fernando; Lee, Lucia Myongwon; Vargas-Baca, Ignacio; Gómez-Sal, Pilar; Mosquera, Marta E G

2015-06-28

The reaction of lithiated picolines and [TiCl3(η(5)-C5Me5)] leads to several bridging or terminal imido compounds, each of which can be selectively formed by controlling the stoichiometry and temperature. Specifically, the dinuclear imido-bridged [TiCl(η(5)-C5Me5)(μ-NR)]2 (1a, NR = 2-imido-3-picoline; 1b, NR = 2-imido-5-picoline) species and the unusual Ti-Li imido-amido heterobimetallic complex [{Li(THF)}{Ti(η(5)-C5Me5)(NR)(NHR)2}] (2a, NR = 2-imido-3-picoline; 2b, NR = 2-imido-5-picoline) were isolated. Compounds 2 are in effect the first structurally characterized examples of titanium(IV) coordinated to terminal imido-pyridines. DFT-D calculations for 2a denote a multiple bond character between titanium and the imido ligand and a strong polarization of the electron density by the alkali cation in spite of the lack of intermetallic bonding.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Lin -Lin; Johnson, Duane D.; Tringides, Michael C.

Density functional theory is used to study structural energetics of Pb vacancy cluster formation on C 60/Pb/Si(111) to explain the unusually fast and error-free transformations between the “Devil's Staircase” (DS) phases on the Pb/Si(111) wetting layer at low temperature (~110K). The formation energies of vacancy clusters are calculated in C 60/Pb/Si(111) as Pb atoms are progressively ejected from the initial dense Pb wetting layer. Vacancy clusters larger than five Pb atoms are found to be stable with seven being the most stable, while vacancy clusters smaller than five are highly unstable, which agrees well with the observed ejection rate ofmore » ~5 Pb atoms per C 60. Furthermore, the high energy cost (~0.8 eV) for the small vacancy clusters to form indicates convincingly that the unusually fast transformation observed experimentally between the DS phases, upon C 60 adsorption at low temperature, cannot be the result of single-atom random walk diffusion but of correlated multi-atom processes.« less

The biosynthesis of nitrogen-, sulfur-, and high-carbon chain-containing sugars.

PubMed

Lin, Chia-I; McCarty, Reid M; Liu, Hung-wen

2013-05-21

Carbohydrates serve many structural and functional roles in biology. While the majority of monosaccharides are characterized by the chemical composition (CH2O)n, modifications including deoxygenation, C-alkylation, amination, O- and N-methylation, which are characteristic of many sugar appendages of secondary metabolites, are not uncommon. Interestingly, some sugar molecules are formed via modifications including amine oxidation, sulfur incorporation, and "high-carbon" chain attachment. Most of these unusual sugars have been identified over the past several decades as components of microbially produced natural products, although a few high-carbon sugars are also found in the lipooligosaccharides of the outer cell walls of Gram-negative bacteria. Despite their broad distribution in nature, these sugars are considered "rare" due to their relative scarcity. The biosynthetic steps that underlie their formation continue to perplex researchers to this day and many questions regarding key transformations remain unanswered. This review will focus on our current understanding of the biosynthesis of unusual sugars bearing oxidized amine substituents, thio-functional groups, and high-carbon chains.

Linear Chains of Magnetic Ions Stacked with Variable Distance: Ferromagnetic Ordering with a Curie Temperature above 20 K.

PubMed

Friedländer, Stefan; Liu, Jinxuan; Addicoat, Matt; Petkov, Petko; Vankova, Nina; Rüger, Robert; Kuc, Agnieszka; Guo, Wei; Zhou, Wencai; Lukose, Binit; Wang, Zhengbang; Weidler, Peter G; Pöppl, Andreas; Ziese, Michael; Heine, Thomas; Wöll, Christof

2016-10-04

We have studied the magnetic properties of the SURMOF-2 series of metal-organic frameworks (MOFs). Contrary to bulk MOF-2 crystals, where Cu(2+) ions form paddlewheels and are antiferromagnetically coupled, in this case the Cu(2+) ions are connected via carboxylate groups in a zipper-like fashion. This unusual coupling of the spin 1/2 ions within the resulting one-dimensional chains is found to stabilize a low-temperature, ferromagnetic (FM) phase. In contrast to other ordered 1D systems, no strong magnetic fields are needed to induce the ferromagnetism. The magnetic coupling constants describing the interaction between the individual metal ions have been determined in SQUID experiments. They are fully consistent with the results of ab initio DFT electronic structure calculations. The theoretical results allow the unusual magnetic behavior of this exotic, yet easy-to-fabricate, material to be described in a detailed fashion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Large PAMAM Dendron Induces Formation of Unusual P4332 Mesophase in Monoolein/Water system.

PubMed

Kumar, Manoj; Patil, Naganath G; Ambade, Ashootosh V; Kumaraswamy, Guruswamy

2018-05-18

Compact macromolecular dendrons have been shown to induce the formation of discontinuous inverse micellar assemblies with Fd3m symmetry in monoolein/water systems. Here, we demonstrate that a large PAMAM dendron (G5: fifth generation) induces the formation a very unusual mesophase with P4332 symmetry. This mesophase had previously been observed in monoolein/water systems only on addition of cytochrome C. The P4332 mesophase can be considered an intermediate phase between the bicontinuous Ia3d and discontinuous micellar mesophases. In this unusual phase, every third rod junction of the Ia3d mesophase is replaced with a spherical micelle. We present a detailed investigation of the phase behaviour of monoolein/water as a function of G5 concentration and temperature. Addition of 1% G5 in 85/15 monoolein/water system induces a transition from the L to Ia3d phase. Further increase in G5 concentration to above 2% induces the formation of the P4332 phase. Thus, incorporation of G5 yields a qualitatively different phase diagram when compared with incorporation of lower generation PAMAM dendrons (G2 - G4) in monoolein/water, where the reverse micellar Fd3m phase forms. PAMAM dendrons of all generations, G2 - G5, bear terminal amine groups that interact with the monoolein head group. The compact molecular architecture of the dendrons and these attractive interactions induce bending of the monoolein bilayer structure. For smaller dendrons, G2 - G4, this results in the formation of the Fd3m phase. However, the large size of the G5 dendron precludes this and a rare intermediate phase between the Ia3d and discontinuous micellar phase, the P4332 mesophase forms instead.

Differential structural status of the RNA counterpart of an undecamer quasi-palindromic DNA sequence present in LCR of human β-globin gene cluster.

PubMed

Kaushik, Mahima; Kukreti, Shrikant

2015-01-01

Our previous work on structural polymorphism shown at a single nucleotide polymorphism (SNP) (A → G) site located on HS4 region of locus control region (LCR) of β-globin gene has established a hairpin → duplex equilibrium corresponding to A → B like DNA transition (Kaushik M, Kukreti, R., Grover, D., Brahmachari, S.K. and Kukreti S. Nucleic Acids Res. 2003; Kaushik M, Kukreti S. Nucleic Acids Res. 2006). The G-allele of A → G SNP has been shown to be significantly associated with the occurrence of β-thalassemia. Considering the significance of this 11-nt long quasi-palindromic sequence [5'-TGGGG(G/A)CCCCA; HP(G/A)11] of β-globin gene LCR, we further explored the differential behavior of the same DNA sequence with its RNA counterpart, using various biophysical and biochemical techniques. In contrast to its DNA counterpart exhibiting a A → B structural transition and an equilibrium between duplex and hairpin forms, the studied RNA oligonucleotide sequence [5'-UGGGG(G/A)CCCCA; RHP(G/A)11] existed only in duplex form (A-conformation) and did not form hairpin. The single residue difference from A to G led to the unusual thermal stability of the RNA structure formed by the studied sequence. Since, naturally occurring mutations and various SNP sites may stabilize or destabilize the local DNA/RNA secondary structures, these structural transitions may affect the gene expression by a change in the protein-DNA recognition patterns.

Elemental Fluorine Based Syntheses of Pentafluoro Phenly and other Aromatic Perfluoropolyether Polymers

DTIC Science & Technology

1994-01-31

ECM 300 PA. 13.8 Pe: -1.0 SCALE $000 00 MZ/o• 14.7171 Pe•/CM 50 0 -50 -100 -150 -200 PPM 3 Very unusual perfluoro polyketone structures have beeni...11PIA C14 LI) LL. L)V LLL cim C45 We think the zeolitic solid state structure of this very interesting perfluoro polyketone is most unusual and there

Observation of unusual topological surface states in half-Heusler compounds LnPtBi (Ln=Lu, Y)

DOE PAGES

Liu, Z. K.; Yang, L. X.; Wu, S. -C.; ...

2016-09-27

Topological quantum materials represent a new class of matter with both exotic physical phenomena and novel application potentials. Many Heusler compounds, which exhibit rich emergent properties such as unusual magnetism, superconductivity and heavy fermion behaviour, have been predicted to host non-trivial topological electronic structures. The coexistence of topological order and other unusual properties makes Heusler materials ideal platform to search for new topological quantum phases (such as quantum anomalous Hall insulator and topological superconductor). By carrying out angle-resolved photoemission spectroscopy and ab initio calculations on rare-earth half-Heusler compounds LnPtBi (Ln=Lu, Y), we directly observe the unusual topological surface states onmore » these materials, establishing them as first members with non-trivial topological electronic structure in this class of materials. Moreover, as LnPtBi compounds are non-centrosymmetric superconductors, our discovery further highlights them as promising candidates of topological superconductors.« less

Observation of unusual topological surface states in half-Heusler compounds LnPtBi (Ln=Lu, Y)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Z. K.; Yang, L. X.; Wu, S. -C.

Topological quantum materials represent a new class of matter with both exotic physical phenomena and novel application potentials. Many Heusler compounds, which exhibit rich emergent properties such as unusual magnetism, superconductivity and heavy fermion behaviour, have been predicted to host non-trivial topological electronic structures. The coexistence of topological order and other unusual properties makes Heusler materials ideal platform to search for new topological quantum phases (such as quantum anomalous Hall insulator and topological superconductor). By carrying out angle-resolved photoemission spectroscopy and ab initio calculations on rare-earth half-Heusler compounds LnPtBi (Ln=Lu, Y), we directly observe the unusual topological surface states onmore » these materials, establishing them as first members with non-trivial topological electronic structure in this class of materials. Moreover, as LnPtBi compounds are non-centrosymmetric superconductors, our discovery further highlights them as promising candidates of topological superconductors.« less

Crystal structure of a β-aminopeptidase from an Australian Burkholderia sp.

PubMed

John-White, Marietta; Dumsday, Geoff J; Johanesen, Priscilla; Lyras, Dena; Drinkwater, Nyssa; McGowan, Sheena

2017-07-01

β-Aminopeptidases are a unique group of enzymes that have the unusual capability to hydrolyze N-terminal β-amino acids from synthetic β-peptides. β-Peptides can form secondary structures mimicking α-peptide-like structures that are resistant to degradation by most known proteases and peptidases. These characteristics of β-peptides give them great potential as peptidomimetics. Here, the X-ray crystal structure of BcA5-BapA, a β-aminopeptidase from a Gram-negative Burkholderia sp. that was isolated from activated sludge from a wastewater-treatment plant in Australia, is reported. The crystal structure of BcA5-BapA was determined to a resolution of 2.0 Å and showed a tetrameric assembly typical of the β-aminopeptidases. Each monomer consists of an α-subunit (residues 1-238) and a β-subunit (residues 239-367). Comparison of the structure of BcA5-BapA with those of other known β-aminopeptidases shows a highly conserved structure and suggests a similar proteolytic mechanism of action.

Probing the crystal structure landscape by doping: 4-bromo, 4-chloro and 4-methylcinnamic acids.

PubMed

Desiraju, Gautam R; Chakraborty, Shaunak; Joseph, Sumy

2018-06-11

Accessing the data points in the crystal structure landscape of a molecule is a challenging task, either experimentally or computationally. We have charted the crystal structure landscape of 4-bromocinnamic acid (4BCA) experimentally and computationally: experimental doping is achieved with 4-methylcinnamic acid (4MCA) to obtain new crystal structures; computational doping is performed with 4-chlorocinnamic acid (4CCA) as a model system, because of the difficulties associated in parameterizing the Br-atom. The landscape of 4CCA is explored experimentally in turn, also by doping it with 4MCA, and is found to bear a close resemblance to the landscape of 4BCA, justifying the ready miscibility of these two halogenated cinnamic acids to form solid solutions without any change in crystal structure. In effect, 4MCA, 4CCA and 4BCA form a commutable group of crystal structures, which may be realized experimentally or computationally, and constitute the landscape. Unlike the results obtained by Kitaigorodskii and others, all but two of the multiple solid solutions obtained in the methyl-doping experiments take structures that are different from the hitherto observed crystal forms of the parent compounds. Even granted that the latter might be inherently polymorphic, this unusual observation provokes the suggestion that solid solution formation may be used to probe the crystal structure landscape. The influence of pi...pi interactions, weak hydrogen bonds and halogen bonds in directing the formation of these new structures is also seen. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bottom-up formation of robust gold carbide

PubMed Central

Westenfelder, Benedikt; Biskupek, Johannes; Meyer, Jannik C.; Kurasch, Simon; Lin, Xiaohang; Scholz, Ferdinand; Gross, Axel; Kaiser, Ute

2015-01-01

A new phenomenon of structural reorganization is discovered and characterized for a gold-carbon system by in-situ atomic-resolution imaging at temperatures up to 1300 K. Here, a graphene sheet serves in three ways, as a quasi transparent substrate for aberration-corrected high-resolution transmission electron microscopy, as an in-situ heater, and as carbon supplier. The sheet has been decorated with gold nanoislands beforehand. During electron irradiation at 80 kV and at elevated temperatures, the accumulation of gold atoms has been observed on defective graphene sites or edges as well as at the facets of gold nanocrystals. Both resulted in clustering, forming unusual crystalline structures. Their lattice parameters and surface termination differ significantly from standard gold nanocrystals. The experimental data, supported by electron energy loss spectroscopy and density-functional theory calculations, suggests that isolated gold and carbon atoms form – under conditions of heat and electron irradiation – a novel type of compound crystal, Au-C in zincblende structure. The novel material is metastable, but surprisingly robust, even under annealing condition. PMID:25772348

A study on an unusual SN2 mechanism in the methylation of benzyne through nickel-complexation.

PubMed

Hatakeyama, Makoto; Sakamoto, Yuki; Ogata, Koji; Sumida, Yuto; Sumida, Tomoe; Hosoya, Takamitsu; Nakamura, Shinichiro

2017-10-11

In this study, three reaction mechanisms of a benzyne-nickel (Ni) complex ([Ni(C 6 H 4 )(dcpe)]) with iodomethane during the methylation process were investigated, namely (a) S N 2 reaction of the benzyne-Ni complex with iodomethane, (b) concerted σ-bond metathesis during the bond breaking/forming processes, and (c) oxidative addition of iodomethane to the Ni-center and the subsequent reductive elimination process. DFT calculations revealed that the reaction barrier of the S N 2 reaction is slightly lower than those of the other mechanisms. The results of orbital analyses suggest that [Ni(C 6 H 4 )(dcpe)] forms a metallacycle structure between benzyne and the Ni II (3d 8 ) center instead of the η 2 -structure with the Ni 0 (3d 10 ) center. The metallacycle structures became inappropriate as the intermediates of oxidative addition in the formation of the Ni II -Me bond, avoiding further oxidation to the high-valent Ni IV . The high free energy along σ-bond metathesis was generated from the steric hindrance, thus invoking methylation and Ni-I bond formation concertedly.

An unusual foreign body in the preputial sac.

PubMed Central

Jaiswal, A K

1992-01-01

A 28 year old Indian male presented with an unusual foreign body, a penicillin bottle containing tincture of iodine, in the preputial sac. The purpose of introducing the bottle was to tickle his glans penis as a form of masturbation. The bottle was so firmly impacted that it could be removed only under general anaesthesia. Images PMID:1427809

Congenital uni-leaflet mitral valve with severe stenosis: A case report with literature review.

PubMed

Zhang, Weixin; Wang, Yonghuai; Ma, Chunyan; Zhang, Zhiwei; Yang, Jun

2017-03-01

Numerical abnormalities of mitral leaflets is a special entity in congenital mitral malformations. Previously reported cases of uni-leaflet mitral valve were primarily related to absence or dysplasia of certain leaflets. We present a case here with mitral leaflets that were not divided into anterior and posterior as usual, but developed as an integral structure instead, which is different from previously documented cases of uni-leaflet mitral valves. Real time three-dimensional echocardiography (RT3DE) provides a visual presentation of the abnormal mitral structure which was confirmed by surgical operation. To the best of our knowledge, this unusual form of uni-leaflet mitral valve has not been reported yet. © 2017, Wiley Periodicals, Inc.

Polymyxins and quinazolines are LSD1/KDM1A inhibitors with unusual structural features.

PubMed

Speranzini, Valentina; Rotili, Dante; Ciossani, Giuseppe; Pilotto, Simona; Marrocco, Biagina; Forgione, Mariantonietta; Lucidi, Alessia; Forneris, Federico; Mehdipour, Parinaz; Velankar, Sameer; Mai, Antonello; Mattevi, Andrea

2016-09-01

Because of its involvement in the progression of several malignant tumors, the histone lysine-specific demethylase 1 (LSD1) has become a prominent drug target in modern medicinal chemistry research. We report on the discovery of two classes of noncovalent inhibitors displaying unique structural features. The antibiotics polymyxins bind at the entrance of the substrate cleft, where their highly charged cyclic moiety interacts with a cluster of positively charged amino acids. The same site is occupied by quinazoline-based compounds, which were found to inhibit the enzyme through a most peculiar mode because they form a pile of five to seven molecules that obstruct access to the active center. These data significantly indicate unpredictable strategies for the development of epigenetic inhibitors.

Active site residues critical for flavin binding and 5,6-dimethylbenzimidazole biosynthesis in the flavin destructase enzyme BluB.

PubMed

Yu, Ta-Yi; Mok, Kenny C; Kennedy, Kristopher J; Valton, Julien; Anderson, Karen S; Walker, Graham C; Taga, Michiko E

2012-06-01

The "flavin destructase" enzyme BluB catalyzes the unprecedented conversion of flavin mononucleotide (FMN) to 5,6-dimethylbenzimidazole (DMB), a component of vitamin B(12). Because of its unusual chemistry, the mechanism of this transformation has remained elusive. This study reports the identification of 12 mutant forms of BluB that have severely reduced catalytic function, though most retain the ability to bind flavin. The "flavin destructase" BluB is an unusual enzyme that fragments the flavin cofactor FMNH(2) in the presence of oxygen to produce 5,6-dimethylbenzimidazole (DMB), the lower axial ligand of vitamin B(12) (cobalamin). Despite the similarities in sequence and structure between BluB and the nitroreductase and flavin oxidoreductase enzyme families, BluB is the only enzyme known to fragment a flavin isoalloxazine ring. To explore the catalytic residues involved in this unusual reaction, mutants of BluB impaired in DMB biosynthesis were identified in a genetic screen in the bacterium Sinorhizobium meliloti. Of the 16 unique point mutations identified in the screen, the majority were located in conserved residues in the active site or in the unique "lid" domain proposed to shield the active site from solvent. Steady-state enzyme assays of 12 purified mutant proteins showed a significant reduction in DMB synthesis in all of the mutants, with eight completely defective in DMB production. Ten of these mutants have weaker binding affinities for both oxidized and reduced FMN, though only two have a significant effect on complex stability. These results implicate several conserved residues in BluB's unique ability to fragment FMNH(2) and demonstrate the sensitivity of BluB's active site to structural perturbations. This work lays the foundation for mechanistic studies of this enzyme and further advances our understanding of the structure-function relationship of BluB. Copyright © 2012 The Protein Society.

Transcription blockage by stable H-DNA analogs in vitro

PubMed Central

Pandey, Shristi; Ogloblina, Anna M.; Belotserkovskii, Boris P.; Dolinnaya, Nina G.; Yakubovskaya, Marianna G.; Mirkin, Sergei M.; Hanawalt, Philip C.

2015-01-01

DNA sequences that can form unusual secondary structures are implicated in regulating gene expression and causing genomic instability. H-palindromes are an important class of such DNA sequences that can form an intramolecular triplex structure, H-DNA. Within an H-palindrome, the H-DNA and canonical B-DNA are in a dynamic equilibrium that shifts toward H-DNA with increased negative supercoiling. The interplay between H- and B-DNA and the fact that the process of transcription affects supercoiling makes it difficult to elucidate the effects of H-DNA upon transcription. We constructed a stable structural analog of H-DNA that cannot flip into B-DNA, and studied the effects of this structure on transcription by T7 RNA polymerase in vitro. We found multiple transcription blockage sites adjacent to and within sequences engaged in this triplex structure. Triplex-mediated transcription blockage varied significantly with changes in ambient conditions: it was exacerbated in the presence of Mn2+ or by increased concentrations of K+ and Li+. Analysis of the detailed pattern of the blockage suggests that RNA polymerase is sterically hindered by H-DNA and has difficulties in unwinding triplex DNA. The implications of these findings for the biological roles of triple-stranded DNA structures are discussed. PMID:26101261

Exploring the formation pathways of donor-acceptor catenanes in aqueous dynamic combinatorial libraries.

PubMed

Cougnon, Fabien B L; Au-Yeung, Ho Yu; Pantoş, G Dan; Sanders, Jeremy K M

2011-03-09

The discovery through dynamic combinatorial chemistry (DCC) of a new generation of donor-acceptor [2]catenanes highlights the power of DCC to access unprecedented structures. While conventional thinking has limited the scope of donor-acceptor catenanes to strictly alternating stacks of donor (D) and acceptor (A) aromatic units, DCC is demonstrated in this paper to give access to unusual DAAD, DADD, and ADAA stacks. Each of these catenanes has specific structural requirements, allowing control of their formation. On the basis of these results, and on the observation that the catenanes represent kinetic bottlenecks in the reaction pathway, we propose a mechanism that explains and predicts the structures formed. Furthermore, the spontaneous assembly of catenanes in aqueous dynamic systems gives a fundamental insight into the role played by hydrophobic effect and donor-acceptor interactions when building such complex architectures.

Alternating twist structures formed by electroconvection in the nematic phase of an achiral bent-core molecule.

PubMed

Tanaka, Shingo; Dhara, Surajit; Sadashiva, B K; Shimbo, Yoshio; Takanishi, Yoichi; Araoka, Fumito; Ishikawa, Ken; Takezoe, Hideo

2008-04-01

We report an unusual electroconvection in the nematic phase of a bent-core liquid crystal. In a voltage-frequency diagram, two frequency regions exhibiting prewavy stripe patterns were found, as reported by Wiant We found that these stripes never show extinction dark when cells were rotated under crossed polarizers. Based on the color interchange in between neighboring stripes by the rotation of the cells or an analyzer, twisted molecular orientation is suggested; i.e., the directors are alternately twisted from the top to the bottom surfaces with a pretilt angle in adjacent stripes, which is an analogue of the twisted (splayed) structure observed in surface-stabilized ferroelectric liquid crystal cells. The transmittance spectra calculated using the 4x4 matrix method from the model structure are consistent with the experimental observation.

Perforin Rapidly Induces Plasma Membrane Phospholipid Flip-Flop

PubMed Central

Metkar, Sunil S.; Wang, Baikun; Catalan, Elena; Anderluh, Gregor; Gilbert, Robert J. C.; Pardo, Julian; Froelich, Christopher J.

2011-01-01

The cytotoxic cell granule secretory pathway is essential for host defense. This pathway is fundamentally a form of intracellular protein delivery where granule proteases (granzymes) from cytotoxic lymphocytes are thought to diffuse through barrel stave pores generated in the plasma membrane of the target cell by the pore forming protein perforin (PFN) and mediate apoptotic as well as additional biological effects. While recent electron microscopy and structural analyses indicate that recombinant PFN oligomerizes to form pores containing 20 monomers (20 nm) when applied to liposomal membranes, these pores are not observed by propidium iodide uptake in target cells. Instead, concentrations of human PFN that encourage granzyme-mediated apoptosis are associated with pore structures that unexpectedly favor phosphatidylserine flip-flop measured by Annexin-V and Lactadherin. Efforts that reduce PFN mediated Ca influx in targets did not reduce Annexin-V reactivity. Antigen specific mouse CD8 cells initiate a similar rapid flip-flop in target cells. A lipid that augments plasma membrane curvature as well as cholesterol depletion in target cells enhance flip-flop. Annexin-V staining highly correlated with apoptosis after Granzyme B (GzmB) treatment. We propose the structures that PFN oligomers form in the membrane bilayer may include arcs previously observed by electron microscopy and that these unusual structures represent an incomplete mixture of plasma membrane lipid and PFN oligomers that may act as a flexible gateway for GzmB to translocate across the bilayer to the cytosolic leaflet of target cells. PMID:21931672

Structure of a human monoclonal antibody Fab fragment against gp41 of human immunodeficiency virus type

NASA Technical Reports Server (NTRS)

He, X. M.; Ruker, F.; Casale, E.; Carter, D. C.

1992-01-01

The three-dimensional structure of a human monoclonal antibody (Fab), which binds specifically to a major epitope of the transmembrane protein gp41 of the human immunodeficiency virus type 1, has been determined by crystallographic methods to a resolution of 2.7 A. It has been previously determined that this antibody recognizes the epitope SGKLICTTAVPWNAS, belongs to the subclass IgG1 (kappa), and exhibits antibody-dependent cellular cytotoxicity. The quaternary structure of the Fab is in an extended conformation with an elbow bend angle between the constant and variable domains of 175 degrees. Structurally, four of the hypervariable loops can be classified according to previously recognized canonical structures. The third hypervariable loops of the heavy (H3) and light chain (L3) are structurally distinct. Hypervariable loop H3, residues 102H-109H, is unusually extended from the surface. The complementarity-determining region forms a hydrophobic binding pocket that is created primarily from hypervariable loops L3, H3, and H2.

Structure of a human monoclonal antibody Fab fragment against gp41 of human immunodeficiency virus type 1

NASA Technical Reports Server (NTRS)

He, Xiao M.; Rueker, Florian; Casale, Elena; Carter, Daniel C.

1992-01-01

The three-dimensional structure of a human monoclonal antibody (Fab), which binds specifically to a major epitope of the transmembrane protein gp41 of the human immunodeficiency virus type 1, has been determined by crystallographic methods to a resolution of 2.7 A. It has been previously determined that this antibody recognizes the epitope SGKLICTTAVPWNAS, belongs to the subclass IgG1 (kappa), and exhibits antibody-dependent cellular cytotoxicity. The quaternary structure of the Fab is in an extended conformation with an elbow bend angle between the constant and variable domains of 175 deg. Structurally, four of the hypervariable loops can be classified according to previously recognized canonical structures. The third hypervariable loops of the heavy (H3) and light chain (L3) are structurally distinct. Hypervariable loop H3, residues 102H-109H, is unusually extended from the surface. The complementarity-determining region forms a hydrophobic binding pocket that is created primarily from hypervariable loops L3, H3, and H2.

The role of the unusual threonine string in the conversion of prion protein.

PubMed

Abskharon, Romany; Wang, Fei; Vander Stel, Kayla J; Sinniah, Kumar; Ma, Jiyan

2016-12-16

The conversion of normal prion protein (PrP) into pathogenic PrP conformers is central to prion disease, but the mechanism remains unclear. The α-helix 2 of PrP contains a string of four threonines, which is unusual due to the high propensity of threonine to form β-sheets. This structural feature was proposed as the basis for initiating PrP conversion, but experimental results have been conflicting. We studied the role of the threonine string on PrP conversion by analyzing mouse Prnp a and Prnp b polymorphism that contains a polymorphic residue at the beginning of the threonine string, and PrP mutants in which threonine 191 was replaced by valine, alanine, or proline. The PMCA (protein misfolding cyclic amplification) assay was able to recapitulate the in vivo transmission barrier between PrP a and PrP b . Relative to PMCA, the amyloid fibril growth assay is less restrictive, but it did reflect certain properties of in vivo prion transmission. Our results suggest a plausible theory explaining the apparently contradictory results in the role of the threonine string in PrP conversion and provide novel insights into the complicated relationship among PrP stability, seeded conformational change, and prion structure, which is critical for understanding the molecular basis of prion infectivity.

Natural analogue studies as supplements to biomineralization research

DOE Office of Scientific and Technical Information (OSTI.GOV)

McNeil, M.B.

1995-09-01

Chemical reactions can alter the chemistry and crystal structure of solid objects over archeological or geological times, while preserving external physical shapes. The reactions resulting in these structures offer natural analogues to laboratory experiments in biomineralization and to biologically influenced alteration of nuclear waste packages, and thus, they offer the only available way of validating models that purport waste package behavior over archaeological or geological times. Potential uses of such analogues in the construction and validation of hypothetical mechanisms of microbiological corrosion and biomineralization are reviewed. Evidence from such analogues suggests that biofilms can control materials alteration in ways usuallymore » overlooked. The newly hypothesized mechanisms involve control by biofilms of the cation flow near the solid surface and offer plausible mechanisms for the formation of mixed-cation minerals under conditions that would lead to dealloying in abiotic experiments; they also account for the formation of unusual minerals [such as posnjakite, Cu{sub 4}SO{sub 4}(OH){sub 6{center_dot}}H{sub 2}O] and mineral morphologies unusual in corrosion [malachite, Cu{sub 2}CO{sub 3}(OH){sub 2}, rarely forms botryoidally under corrosion conditions and its occasional presence on archaeological objects that appear to have undergone microbiological corrosion may be related to biofilm phenomena].« less

Structure of lipid kinase p110β/p85β elucidates an unusual SH2-domain-mediated inhibitory mechanism.

PubMed

Zhang, Xuxiao; Vadas, Oscar; Perisic, Olga; Anderson, Karen E; Clark, Jonathan; Hawkins, Phillip T; Stephens, Len R; Williams, Roger L

2011-03-04

Phosphoinositide 3-kinases (PI3Ks) are essential for cell growth, migration, and survival. The structure of a p110β/p85β complex identifies an inhibitory function for the C-terminal SH2 domain (cSH2) of the p85 regulatory subunit. Mutagenesis of a cSH2 contact residue activates downstream signaling in cells. This inhibitory contact ties up the C-terminal region of the p110β catalytic subunit, which is essential for lipid kinase activity. In vitro, p110β basal activity is tightly restrained by contacts with three p85 domains: the cSH2, nSH2, and iSH2. RTK phosphopeptides relieve inhibition by nSH2 and cSH2 using completely different mechanisms. The binding site for the RTK's pYXXM motif is exposed on the cSH2, requiring an extended RTK motif to reach and disrupt the inhibitory contact with p110β. This contrasts with the nSH2 where the pY-binding site itself forms the inhibitory contact. This establishes an unusual mechanism by which p85 SH2 domains contribute to RTK signaling specificities. Copyright © 2011 Elsevier Inc. All rights reserved.

On the spontaneous collective motion of active matter

PubMed Central

Wang, Shenshen; Wolynes, Peter G.

2011-01-01

Spontaneous directed motion, a hallmark of cell biology, is unusual in classical statistical physics. Here we study, using both numerical and analytical methods, organized motion in models of the cytoskeleton in which constituents are driven by energy-consuming motors. Although systems driven by small-step motors are described by an effective temperature and are thus quiescent, at higher order in step size, both homogeneous and inhomogeneous, flowing and oscillating behavior emerges. Motors that respond with a negative susceptibility to imposed forces lead to an apparent negative-temperature system in which beautiful structures form resembling the asters seen in cell division. PMID:21876141

On the spontaneous collective motion of active matter.

PubMed

Wang, Shenshen; Wolynes, Peter G

2011-09-13

Spontaneous directed motion, a hallmark of cell biology, is unusual in classical statistical physics. Here we study, using both numerical and analytical methods, organized motion in models of the cytoskeleton in which constituents are driven by energy-consuming motors. Although systems driven by small-step motors are described by an effective temperature and are thus quiescent, at higher order in step size, both homogeneous and inhomogeneous, flowing and oscillating behavior emerges. Motors that respond with a negative susceptibility to imposed forces lead to an apparent negative-temperature system in which beautiful structures form resembling the asters seen in cell division.

Confined Electroconvective and Flexoelectric Instabilities Deep in the Freedericksz State of Nematic CB7CB.

PubMed

Krishnamurthy, Kanakapura S; Palakurthy, Nani Babu; Yelamaggad, Channabasaveshwar V

2017-06-01

We report wormlike flexoelectric structures evolving deep in the Freedericksz state of a nematic layer of the liquid crystal cyanobiphenyl-(CH2) 7 -cyanobiphenyl. They form in the predominantly splay-bend thin boundary layers and are built up of solitary flexoelectric domains of the Bobylev-Pikin type. Their formation is possibly triggered by the gradient flexoelectric surface instability that remains optically discernible up to unusually high frequencies. The threshold voltage at which the worms form scales as square root of the frequency; in their extended state, worms often appear as labyrinthine structures on a section of loops that separate regions of opposite director deviation. Such asymmetric loops are also derived through pincement-like dissociation of ring-shaped walls. Formation of isolated domains of bulk electroconvection precedes the onset of surface instabilities. In essence, far above the Freedericksz threshold, the twisted nematic layer behaves as a combination of two orthogonally oriented planar half-layers destabilized by localized flexoelectric distortion.

Unusual monosaccharides: components of O-antigenic polysaccharides of microorganisms

NASA Astrophysics Data System (ADS)

Kochetkov, Nikolai K.

1996-09-01

The data on new monosaccharides detected in O-antigenic polysaccharides of Gram-negative bacteria have been surveyed. The results of isolation and structure determination of these unusual monosaccharides have been arranged and described systematically. The NMR spectroscopy techniques are shown to be promising for the O-antigenic polysaccharides structure determination. The information about fine structure of monosaccharides which constitute the base of important class of microbial polysaccharides, is of great significance for applied studies, first of all, the design and synthesis of biologically active substances. The bibliography includes 216 references.

Emergent Rotational Symmetries in Disordered Magnetic Domain Patterns

NASA Astrophysics Data System (ADS)

Su, Run; Seu, Keoki A.; Parks, Daniel; Kan, Jimmy J.; Fullerton, Eric E.; Roy, Sujoy; Kevan, Stephen D.

2011-12-01

Uniaxial systems often form labyrinthine domains that exhibit short-range order but are macroscopically isotropic and would not be expected to exhibit precise symmetries. However, their underlying frustration results in a multitude of metastable configurations of comparable energy, and driving such a system externally might lead to pattern formation. We find that soft x-ray speckle diffraction patterns of the labyrinthine domains in CoPd/IrMn heterostructures reveal a diverse array of hidden rotational symmetries about the magnetization axis, thereby suggesting an unusual form of emergent order in an otherwise disordered system. These symmetries depend on applied magnetic field, magnetization history, and scattering wave vector. Maps of rotational symmetry exhibit intriguing structures that can be controlled by manipulating the applied magnetic field in concert with the exchange bias condition.

Actin filaments as tension sensors.

PubMed

Galkin, Vitold E; Orlova, Albina; Egelman, Edward H

2012-02-07

The field of mechanobiology has witnessed an explosive growth over the past several years as interest has greatly increased in understanding how mechanical forces are transduced by cells and how cells migrate, adhere and generate traction. Actin, a highly abundant and anomalously conserved protein, plays a large role in forming the dynamic cytoskeleton that is so essential for cell form, motility and mechanosensitivity. While the actin filament (F-actin) has been viewed as dynamic in terms of polymerization and depolymerization, new results suggest that F-actin itself may function as a highly dynamic tension sensor. This property may help explain the unusual conservation of actin's sequence, as well as shed further light on actin's essential role in structures from sarcomeres to stress fibers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Emergent rotational symmetries in disordered magnetic domain patterns.

PubMed

Su, Run; Seu, Keoki A; Parks, Daniel; Kan, Jimmy J; Fullerton, Eric E; Roy, Sujoy; Kevan, Stephen D

2011-12-16

Uniaxial systems often form labyrinthine domains that exhibit short-range order but are macroscopically isotropic and would not be expected to exhibit precise symmetries. However, their underlying frustration results in a multitude of metastable configurations of comparable energy, and driving such a system externally might lead to pattern formation. We find that soft x-ray speckle diffraction patterns of the labyrinthine domains in CoPd/IrMn heterostructures reveal a diverse array of hidden rotational symmetries about the magnetization axis, thereby suggesting an unusual form of emergent order in an otherwise disordered system. These symmetries depend on applied magnetic field, magnetization history, and scattering wave vector. Maps of rotational symmetry exhibit intriguing structures that can be controlled by manipulating the applied magnetic field in concert with the exchange bias condition. © 2011 American Physical Society

Crystal Structure of Cockroach Allergen Bla g 2, an Unusual Zinc Binding Aspartic Protease with a Novel Mode of Self-inhibition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gustchina, Alla; Li, Mi; Wunschmann, Sabina

2010-07-19

The crystal structure of Bla g 2 was solved in order to investigate the structural basis for the allergenic properties of this unusual protein. This is the first structure of an aspartic protease in which conserved glycine residues, in two canonical DTG triads, are substituted by different amino acid residues. Another unprecedented feature revealed by the structure is the single phenylalanine residue insertion on the tip of the flap, with the side-chain occupying the S1 binding pocket. This and other important amino acid substitutions in the active site region of Bla g 2 modify the interactions in the vicinity ofmore » the catalytic aspartate residues, increasing the distance between them to {approx}4 {angstrom} and establishing unique direct contacts between the flap and the catalytic residues. We attribute the absence of substantial catalytic activity in Bla g 2 to these unusual features of the active site. Five disulfide bridges and a Zn-binding site confer stability to the protein, which may contribute to sensitization at lower levels of exposure than other allergens.« less

Unusually large oilbodies are highly correlated with lower oil content in Brassica napus.

PubMed

Hu, Zhiyong; Wang, Xinfa; Zhan, Gaomiao; Liu, Guihua; Hua, Wei; Wang, Hanzhong

2009-04-01

Rapeseed cultivars exhibit a wide range of oil content in the mature seeds. Little is known about the relationship between the oilbody structures and the differences in oil contents of Brassica napus cultivars. In the present study, the oilbody morphology and its fate during the embryo development and seedling growth in several cultivars with oil contents ranging from 33.4 to 49.8% were studied. Cultivars with low oil contents (LO), some of the oilbodies were in similar size to those in cultivars with high oil content (HO), while some oilbodies in the LO cultivars were several times bigger (over 5.0 microm). These are much larger than the average size of B. napus seed oilbodies that were previously reported (Mantese et al. Ann Bot 97:999-1010, 2006). The oleosin protein levels and oleosin1 gene transcript abundances in the HO cultivars were clearly higher than in the LO cultivars. The shapes of oilbodies were similar during early stages of embryo development in both HO and LO cultivars, while as the embryos matured, the unusually large oilbodies were generated in the LO cells. After germination, the oilbodies in LO cultivars were consumed more slowly than in HO, and the seed germination rates of LO cultivars were less than those of HO cultivars. The low accumulation of oleosins results in the forming of unusually large oilbodies in LO cultivars.

Anesthesia in a 12 year old boy with somatic overgrowth secondary to pericentric inversion of chromosome 12.

PubMed

Wong, Tina B; Rowell, Jonathan C; Waldhausen, John H T; Parisi, Melissa A; Jonmarker, Christer

2013-03-01

The management of a splenectomy in a boy with an unusual form of somatic overgrowth is presented. Except for a moderately difficult airway, no unusual reactions to anesthesia and surgery were encountered. Possible anesthetic implications of different somatic overgrowth syndromes in children are presented. Copyright © 2013. Published by Elsevier Inc.

Structure of a bacterial toxin-activating acyltransferase.

PubMed

Greene, Nicholas P; Crow, Allister; Hughes, Colin; Koronakis, Vassilis

2015-06-09

Secreted pore-forming toxins of pathogenic Gram-negative bacteria such as Escherichia coli hemolysin (HlyA) insert into host-cell membranes to subvert signal transduction and induce apoptosis and cell lysis. Unusually, these toxins are synthesized in an inactive form that requires posttranslational activation in the bacterial cytosol. We have previously shown that the activation mechanism is an acylation event directed by a specialized acyl-transferase that uses acyl carrier protein (ACP) to covalently link fatty acids, via an amide bond, to specific internal lysine residues of the protoxin. We now reveal the 2.15-Å resolution X-ray structure of the 172-aa ApxC, a toxin-activating acyl-transferase (TAAT) from pathogenic Actinobacillus pleuropneumoniae. This determination shows that bacterial TAATs are a structurally homologous family that, despite indiscernible sequence similarity, form a distinct branch of the Gcn5-like N-acetyl transferase (GNAT) superfamily of enzymes that typically use acyl-CoA to modify diverse bacterial, archaeal, and eukaryotic substrates. A combination of structural analysis, small angle X-ray scattering, mutagenesis, and cross-linking defined the solution state of TAATs, with intermonomer interactions mediated by an N-terminal α-helix. Superposition of ApxC with substrate-bound GNATs, and assay of toxin activation and binding of acyl-ACP and protoxin peptide substrates by mutated ApxC variants, indicates the enzyme active site to be a deep surface groove.

A Mixed-Valent Molybdenum Monophosphate with a Layer Structure: KMo 3P 2O 14

NASA Astrophysics Data System (ADS)

Guesdon, A.; Borel, M. M.; Leclaire, A.; Grandin, A.; Raveau, B.

1994-03-01

A new mixed-valent molybdenum monophosphate with a layer structure KMo 3P 2O 14 has been isolated. It crystallizes in the space group P2 1/ m with a = 8.599(2) Å, b = 6.392(2) Å, c = 10.602(1) Å, and β = 111.65(2)°. The layers [Mo 3P 2O 14] ∞ are parallel to (100) and consist of [MoPO 8] ∞ chains running along limitb→ , in which one MoO 6 octahedron alternates with one PO 4 tetrahedron. In fact, four [MoPO 8] ∞ chains share the corners of their polyhedra and the edges of their octahedra, forming [Mo 4P 4O 24] ∞ columns which are linked through MoO 5 bipyramids along limitc→. The K + ions interleaved between these layers are surrounded by eight oxygens, forming bicapped trigonal prisms KO 8. Besides the unusual trigonal bipyramids MoO 5, this structure is also characterized by a tendency to the localization of the electrons, since one octahedral site is occupied by Mo(V), whereas the other octahedral site and the trigonal bipyramid are occupied by Mo(VI). The similarity of this structure with pure octahedral layer structures suggests the possibility of generating various derivatives, and of ion exchange properties.

Diamonds in ophiolitic mantle rocks and podiform chromitites: An unsolved mystery

NASA Astrophysics Data System (ADS)

Yang, J.; Zhang, Z.; Xu, X.; Ba, D.; Bai, W.; Fabg, Q.; Meng, F.; Chen, S.; Robinson, P. T.; Dobrzhinetskaya, L.

2009-05-01

In recent years ultrahigh pressure minerals, such as diamond and coesite, and other unusual minerals were discovered in chromitites of the Luobusa ophiolite in Tibet, and 4 new minerals have been approved by the CNMMN. These results have raised many questionsWhat are the occurrences of the diamonds, what is the source of their carbon and how were they formed? What is the origin of the chromites hosting the diamonds and at what depth did they form? What is the genetic relationship between the diamonds and the host chromitites? In what geological, geophysical and geochemical environments can the diamonds be formed and how are they preserved? The UHP minerals from Luobusa are controversial because they have not been found in situ and because ophiolites are currently believed to form at shallow levels above oceanic spreading centers in suprasubduction zone environments. More detailed study and experimental work are needed to understand the origin and significance of these unusual minerals and investigations of other ophiolites are needed to determine if such minerals occur elsewhere To approach these problems, we have collected two one-ton samples of harzburgite hosting chromitite orebodies in the Luobusa ophiolite in Tibet. The harzburgite samples were taken close to chromitite orebody 31, from which the diamonds, coesite and other unusual minerals were recovered. We processed these two samples in the same manner as the chromitites and discovered numerous diamonds and more than 50 other mineral species. These preliminary results show that the minerals in the harzburgites are similar to those in the chromitites, suggesting a genetic relationship between them. To determine if such UHP and unusual minerals occur elsewhere, we collected about 1.5 t of chromitite from two orebodies in an ultramafic body in the Polar Urals. Thus far, more than 60 different mineral species have been separated from these ores. The most exciting discovery is the common occurrence of diamond, a typical UHP mineral in the Luobusa chromitites. Other minerals include: (1) native elements: Cr, W, Ni, Co, Si, Al and Ta; (2) carbides: SiC and WC; (3) alloys: Cr-Fe, Si-Al-Fe, Ni-Cu, Ag-Au, Ag-Sn, Fe-Si, Fe-P, and Ag-Zn-Sn; (4) oxides: NiCrFe, PbSn, REE, rutile and Si-bearing rutile, ilmenite, corundum, chromite, MgO, and SnO2; (5) silicates: kyanite, pseudomorphs of octahedral olivine, zircon, garnet, feldspar, and quartz,; (6) sulfides of Fe, Ni, Cu, Mo, Pb, Ab, AsFe, FeNi, CuZn, and CoFeNi; and (7) iron groups: native Fe, FeO, and Fe2O3. These minerals are very similar in composition and structure to those reported from the Luobusa chromitites.

Unusual Structure and Magnetism in MnO Nanoclusters

NASA Astrophysics Data System (ADS)

Ganguly, Shreemoyee; Kabir, Mukul; Sanyal, Biplab; Mookerjee, Abhijit

2011-03-01

We report an unusual structural and magnetic evolution in stoichiometric MnO nanoclusters by an extensive and unbiased search through the potential energy surface within density functional theory. The (MnO)n nanoclusters adopt two-dimensional structures in size ranges in which Mnn nanoclusters are three-dimensional and regardless of the size of the nanocluster, the magnetic coupling is found to be antiferromagnetic, and is strikingly different from Mn-based molecular magnets. Both of these features are explained through the inherent electronic structures of the nanoclusters. We gratefully acknowledge financial support from Swedish Research Links program funded by VR/SIDA and Carl Tryggers Foundation, Sweden.

Poxvirus uracil-DNA glycosylase-An unusual member of the family I uracil-DNA glycosylases: Poxvirus Uracil-DNA Glycosylase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schormann, Norbert; Zhukovskaya, Natalia; Bedwell, Gregory

We report that uracil-DNA glycosylases are ubiquitous enzymes, which play a key role repairing damages in DNA and in maintaining genomic integrity by catalyzing the first step in the base excision repair pathway. Within the superfamily of uracil-DNA glycosylases family I enzymes or UNGs are specific for recognizing and removing uracil from DNA. These enzymes feature conserved structural folds, active site residues and use common motifs for DNA binding, uracil recognition and catalysis. Within this family the enzymes of poxviruses are unique and most remarkable in terms of amino acid sequences, characteristic motifs and more importantly for their novel non-enzymaticmore » function in DNA replication. UNG of vaccinia virus, also known as D4, is the most extensively characterized UNG of the poxvirus family. D4 forms an unusual heterodimeric processivity factor by attaching to a poxvirus-specific protein A20, which also binds to the DNA polymerase E9 and recruits other proteins necessary for replication. D4 is thus integrated in the DNA polymerase complex, and its DNA-binding and DNA scanning abilities couple DNA processivity and DNA base excision repair at the replication fork. In conclusion, the adaptations necessary for taking on the new function are reflected in the amino acid sequence and the three-dimensional structure of D4. We provide an overview of the current state of the knowledge on the structure-function relationship of D4.« less

Unusual (mu-aqua)bis(mu-carboxylate) bridge in homometallic M(II) (M=Mn, Co and Ni) two-dimensional compounds based on the 1,2,3,4-butanetetracarboxylic acid: synthesis, structure, and magnetic properties.

PubMed

Cañadillas-Delgado, Laura; Fabelo, Oscar; Pásan, Jorge; Delgado, Fernando S; Lloret, Francesc; Julve, Miguel; Ruiz-Pérez, Catalina

2007-09-03

The first coordination compounds of 1,2,3,4-butanetetracarboxylate anion (butca4-) of the formula [M2(butca)(H2O)5]n.2nH2O [M=Mn(II) (1), Co(II) (2), and Ni(II) (3)] were prepared and their X-ray crystal structures and magnetic properties investigated. The three complexes have a very similar two-dimensional structure which consists of (4,4) networks, 1 and 2 being isostructural. The tetracarboxylate ligand acts as a 4-fold connector leading to two-dimensional (4,4) networks of metal atoms, this topology being possible because of its planar conformation. The nodes of these networks are formed by dinuclear motifs which exhibit the unusual (mu-aqua)bis(mu-carboxylate) bridging unit which is analogous to that observed in some molecules of biological interest. The variable-temperature magnetic susceptibility measurements of 1-3 show that 1 and 2 are antiferromagnetically coupled systems whereas 3 exhibits a ferromagnetic behavior. The analysis of the magnetic data of 1-3 through a simple dinuclear model allowed the determination of the values of the magnetic coupling (J) -3.6 (1), -1.2 (2), and +1.47 cm(-1) (3) with the Hamiltonian being defined as H=-JSA.SB. The countercomplementarity between the two bridges (aqua and syn-syn carboxylate) accounts for the trend exhibited by the values of the magnetic coupling in this family.

Fragmentary and incidental behaviour of columns, slabs and crystals

PubMed Central

Whiteley, Walter

2014-01-01

Between the study of small finite frameworks and infinite incidentally periodic frameworks, we find the real materials which are large, but finite, fragments that fit into the infinite periodic frameworks. To understand these materials, we seek insights from both (i) their analysis as large frameworks with associated geometric and combinatorial properties (including the geometric repetitions) and (ii) embedding them into appropriate infinite periodic structures with motions that may break the periodic structure. A review of real materials identifies a number of examples with a local appearance of ‘unit cells’ which repeat under isometries but perhaps in unusual forms. These examples also refocus attention on several new classes of infinite ‘periodic’ frameworks: (i) columns—three-dimensional structures generated with one repeating isometry and (ii) slabs—three-dimensional structures with two independent repeating translations. With this larger vision of structures to be studied, we find some patterns and partial results that suggest new conjectures as well as many additional open questions. These invite a search for new examples and additional theorems. PMID:24379423

Investigation of mRNA quadruplex formation in Escherichia coli.

PubMed

Wieland, Markus; Hartig, Jörg S

2009-01-01

The protocol presented here allows for the investigation of the formation of unusual nucleic acid structures in the 5'-untranslated region (UTR) of bacteria by correlating gene expression levels to the in vitro stability of the respective structure. In particular, we describe the introduction of G-quadruplex forming sequences close to the ribosome-binding site (RBS) on the mRNA of a reporter gene and the subsequent read-out of the expression levels. Insertion of a stable secondary structure results in the cloaking of RBS and eventually reduced gene expression levels. The structures and stability of the introduced sequences are further characterized by circular dichroism (CD) spectroscopy and thermal melting experiments. The extent of inhibition is then correlated to the stability of the respective quadruplex structure, allowing judgement of whether factors other than thermodynamic stability affect the formation of a given quadruplex sequence in vivo. Measuring gene expression levels takes 2 d including cloning; CD experiments take 5 hours per experiment.

Is a cross-β-sheet structure of low molecular weight peptides necessary for the formation of fibrils and peptide hydrogels?

PubMed

Ilawe, Niranjan V; Schweitzer-Stenner, Reinhard; DiGuiseppi, David; Wong, Bryan M

2018-04-26

Short peptides have emerged as versatile building blocks for supramolecular structures and hydrogels. In particular, the presence of aromatic amino acid residues and/or aromatic end groups is generally considered to be a prerequisite for initiating aggregation of short peptides into nanotubes or cross β-sheet type fibrils. However, the cationic GAG tripeptide surprisingly violates these rules. Specifically, in water/ethanol mixtures, GAG peptides aggregate into very long crystalline fibrils at temperatures below 35 °C where they eventually form a spanning network structure and, thus, a hydrogel. Two gel phases are formed in this network, and they differ substantially in chirality and thickness of the underlying fibrils, their rheological parameters, and the kinetics of oligomerization, fibrilization, and gel formation. The spectroscopic data strongly suggests that the observed fibrils do not exhibit canonical cross β-sheet structures and are indicative of a yet unknown secondary conformation. To complement our unusual experimental observations in this perspective article, we performed large-scale DFT calculations to probe the geometry and spectroscopic properties of these GAG oligomers. Most importantly, our experimental and computational results yield rather unconventional structures that are not reminiscent of classical cross-β-sheet structures, and we give two extremely likely candidates for oligomer structures that are consistent with experimental amide I' profiles in IR and vibrational circular dichroism (VCD) spectra of the two gel phases.

[Multiple pulmonary hydatidosis with floating balloon appearance and cardiac localization].

PubMed

Afif, H; Aichane, A; Trombati, N; Bahlaoui, A; Bouayad, Z; Boumzebra, M; Maazouzi, W

2000-06-01

Multiple hydatidosis in a thoracic localization is unusual and a cardiac localization very exceptional. We report a case of multiple hydatidosis greatly improved by medical treatment with albendazole which was associated with a cardiac cyst successfully treated by surgical resection. No recurrence has been observed at 4 year follow-p. We point out therapeutic management options in these unusual forms of the disease.

Several novel N-donor tridentate ligands formed in chemical studies of new fac-Re(CO)3 complexes relevant to fac-99mTc(CO)3 radiopharmaceuticals: attack of a terminal amine on coordinated acetonitrile.

PubMed

Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

2010-03-01

To evaluate syntheses of fac-[Re(CO)(3)L](+) complexes in organic solvents, we treated fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6)/BF(4) in acetonitrile with triamine ligands (L). When L had two primary or two tertiary terminal amine groups, the expected fac-[Re(CO)(3)L](+) complexes formed. In contrast, N,N-dimethyldiethylenetriamine (N,N-Me(2)dien) formed an unusual compound, fac-[Re(CO)(3)(DAE)]BF(4) {DAE = (Z)-N'-(2-(2-(dimethylamino)ethylamino)ethyl)acetimidamide = (Me(2)NCH(2)CH(2))NH(CH(2)CH(2)N=C(NH(2))Me)}. DAE is formed by addition of acetonitrile to the N,N-Me(2)dien terminal primary amine, converting this sp(3) nitrogen to an sp(2) nitrogen with a double bond to the original acetonitrile sp carbon. The three Ns bound to Re derive from N,N-Me(2)dien. The pathway to fac-[Re(CO)(3)(DAE)]BF(4) is suggested by a second unusual compound, fac-[Re(CO)(3)(MAE)]PF(6) {MAE = N-methyl-N-(2-(methyl-(2-(methylamino)ethyl)amino)ethyl)acetimidamide = MeN(H)-CH(2)CH(2)-N(Me)-CH(2)CH(2)-N(Me)-C(Me)=NH}, isolated after treating fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6) with N,N',N''-trimethyldiethylenetriamine (N,N',N''-Me(3)dien). MAE chelates via a terminal and a central sp(3) N from N,N',N''-Me(3)dien and via one sp(2) NH in a C(Me)=NH group. This group is derived from acetonitrile by addition of the other N,N',N''-Me(3)dien terminal amine to the nitrile carbon. This addition creates an endocyclic NMe group within a seven-membered chelate ring. The structure and other properties of fac-[Re(CO)(3)(MAE)]PF(6) allow us to propose a reaction scheme for the formation of the unprecedented DAE ligand. The new compounds advance our understanding of the spectral and structural properties of Re analogues of (99m)Tc radiopharmaceuticals.

Scanning electron microscope investigation of the structural growth in thick sputtered coatings

NASA Technical Reports Server (NTRS)

Spalvins, T.

1975-01-01

Sputtered S-Monel, silver, and 304 stainless steel coatings and molybdenum disulfide coatings were deposited on mica and metal substrates with various surface finishes to investigate the structural growth of the coating by scanning electron microscopy. The geometry and the surface morphology of the nodules are characterized. Compositional changes within the coating were analyzed by energy dispersive X-ray analysis. Defects in the surface finish act as preferential nucleation sites and form isolated overlapping and complex nodules and various unusual surface overgrowths on the coating. The nodule boundaries are very vulnerable to chemical etching and these nodules do not disappear after full annealing. Further, they have undesirable effects on mechanical properties; cracks are initiated at the nodules when the coating is stressed by mechanical forces.

Palladium-Catalyzed Asymmetric Alkylation in the Synthesis of Cyclopentanoid and Cycloheptanoid Core Structures Bearing All-Carbon Quaternary Stereocenters

PubMed Central

Hong, Allen Y.; Bennett, Nathan B.; Krout, Michael R.; Jensen, Thomas; Harned, Andrew. M.

2011-01-01

General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems. PMID:22347731

Twist-induced guidance in coreless photonic crystal fiber: A helical channel for light.

PubMed

Beravat, Ramin; Wong, Gordon K L; Frosz, Michael H; Xi, Xiao Ming; Russell, Philip St J

2016-11-01

A century ago, Einstein proposed that gravitational forces were the result of the curvature of space-time and predicted that light rays would deflect when passing a massive celestial object. We report that twisting the periodically structured "space" within a coreless photonic crystal fiber creates a helical channel where guided modes can form despite the absence of any discernible core structure. Using a Hamiltonian optics analysis, we show that the light rays follow closed spiral or oscillatory paths within the helical channel, in close analogy with the geodesics of motion in a two-dimensional gravitational field. The mode diameter shrinks, and its refractive index rises, as the twist rate increases. The birefringence, orbital angular momentum, and dispersion of these unusual modes are explored.

New 3 D Tubular Porous Structure of an Organic-Zincophosphite Framework with Interesting Gas Adsorption and Luminescence Properties.

PubMed

Wang, Chih-Min; Lee, Li-Wei; Chang, Tsung-Yuan; Fan, Bing-Lun; Wang, Chih-Ling; Lin, Hsiu-Mei; Lu, Kuang-Lieh

2016-11-02

A new 3D tubular zinc phosphite, Zn 2 (C 22 H 22 N 8 ) 0.5 (HPO 3 ) 2 ⋅H 2 O (1), incorporating a tetradentate organic ligand was synthesized under hydro(solvo)thermal conditions and structurally characterized by single-crystal X-ray diffraction. Compound 1 is the first example of inorganic zincophosphite chains being interlinked through 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene to form a tubular porous framework with unusual organic-inorganic hybrid channels. The thermal and chemical stabilities, high capacity for CO 2 adsorption compared to that for N 2 adsorption, and interesting optical properties of LED devices fabricated using this compound were also studied. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Peculiar bonding associated with atomic doping and hidden honeycombs in borophene

NASA Astrophysics Data System (ADS)

Lee, Chi-Cheng; Feng, Baojie; D'angelo, Marie; Yukawa, Ryu; Liu, Ro-Ya; Kondo, Takahiro; Kumigashira, Hiroshi; Matsuda, Iwao; Ozaki, Taisuke

2018-02-01

Engineering atomic-scale structures allows great manipulation of physical properties and chemical processes for advanced technology. We show that the B atoms deployed at the centers of honeycombs in boron sheets, borophene, behave as nearly perfect electron donors for filling the graphitic σ bonding states without forming additional in-plane bonds by first-principles calculations. The dilute electron density distribution owing to the weak bonding surrounding the center atoms provides easier atomic-scale engineering and is highly tunable via in-plane strain, promising for practical applications, such as modulating the extraordinarily high thermal conductance that exceeds the reported value in graphene. The hidden honeycomb bonding structure suggests an unusual energy sequence of core electrons that has been verified by our high-resolution core-level photoelectron spectroscopy measurements. With the experimental and theoretical evidence, we demonstrate that borophene exhibits a peculiar bonding structure and is distinctive among two-dimensional materials.

Structure of the human smoothened receptor 7TM bound to an antitumor agent

PubMed Central

Wang, Chong; Wu, Huixian; Katritch, Vsevolod; Han, Gye Won; Huang, Xi-Ping; Liu, Wei; Siu, Fai Yiu; Roth, Bryan L.; Cherezov, Vadim; Stevens, Raymond C.

2013-01-01

The smoothened (SMO) receptor, a key signal transducer in the Hedgehog (Hh) signaling pathway is both responsible for the maintenance of normal embryonic development and implicated in carcinogenesis. The SMO receptor is classified as a class Frizzled (class F) G protein-coupled receptor (GPCR), although the canonical Hh signaling pathway involves the transcription factor Gli and the sequence similarity with class A GPCRs is less than 10%. Here we report the crystal structure at 2.5 Å resolution of the transmembrane domain of the human SMO receptor bound to the small molecule antagonist LY2940680. Although the SMO receptor shares the seven transmembrane helical (7TM) fold, most conserved motifs for class A GPCRs are absent, and the structure reveals an unusually complex arrangement of long extracellular loops stabilized by four disulfide bonds. The ligand binds at the extracellular end of the 7TM bundle and forms extensive contacts with the loops. PMID:23636324

When is an imine not an imine? Unusual reactivity of a series of Cu(II) imine-pyridine complexes and their exploitation for the Henry reaction.

PubMed

Cooper, Christine J; Jones, Matthew D; Brayshaw, Simon K; Sonnex, Benjamin; Russell, Mark L; Mahon, Mary F; Allan, David R

2011-04-14

In this paper we report the synthesis and solid-state structures for a series of pyridine based Cu(II) complexes and preliminary data for the asymmetric Henry reaction. Interestingly, the solid-state structures indicate the incorporation of an alcohol into one of the imine groups of the ligand, forming a rare α-amino ether group. The complexes have been studied via single crystal X-ray diffraction, EPR spectroscopy and mass spectrometry. Intriguingly, it has been observed that the alcohol only adds to one of the imine moieties. Density functional theory (DFT) calculations have also been employed to rationalise the observed structures. The Cu(II) complexes have been tested in the asymmetric Henry reaction (benzaldehyde + nitromethane or nitroethane) with ee's up to 84% being achieved as well as high conversions and modest diastereoselectivities. © The Royal Society of Chemistry 2011

A G-Quadruplex-Containing RNA Activates Fluorescence in a GFP-Like Fluorophore

PubMed Central

Huang, Hao; Suslov, Nikolai B.; Li, Nan-Sheng; Shelke, Sandip A.; Evans, Molly E.; Koldobskaya, Yelena; Rice, Phoebe A.; Piccirilli, Joseph A.

2014-01-01

Spinach is an in vitro selected RNA aptamer that binds a GFP-like ligand and activates its green fluorescence.Spinach is thus an RNA analog of GFP, and has potentially widespread applications for in vivo labeling and imaging. We used antibody-assisted crystallography to determine the structures of Spinach both with and without bound fluorophore at 2.2 and 2.4 Å resolution, respectively. Spinach RNA has an elongated structure containing two helical domains separated by an internal bulge that folds into a G-quadruplex motif of unusual topology. The G-quadruplex motif and adjacent nucleotides comprise a partially pre-formed binding site for the fluorophore.The fluorophore binds in a planar conformation and makes extensive aromatic stacking and hydrogen bond interactions with the RNA. Our findings provide a foundation for structure-based engineering of new fluorophore-binding RNA aptamers. PMID:24952597

Potential applications of ferrocene as a structural feature in antioxidants.

PubMed

Liu, Zai-Qun

2011-04-01

Comparing with the wide usage of ferrocene in novel materials, ferrocene was unusually applied to be a structural feature in designing drugs even though some researchers pointed out that ferrocene and its derivatives possessed potential pharmacological applications. This was due to that low polarity limited bioavailability of ferrocene in vivo. Since ferrocene was inert to the oxidation at atmosphere, it was deduced that synthetic derivatives of ferrocene may be a novel kind of antioxidant, in which other organic groups may enhance the bioavailability of ferrocene, or large conjugated system formed among ferrocenyl and other organic groups may increase the antioxidant effectiveness. Thus, synthetic derivatives of ferrocene were divided into nonconjugated and conjugated ones in this review. For nonconjugated ferrocenyl derivatives, carbon chain or simple group attached one or two cyclopentadienyl rings in ferrocene to form a novel molecule with ferrocenyl group. The aim of synthesis of nonconjugated ferrocenyl compounds was to increase the bioavailability of ferrocene in vivo. On the other hand, the conjugated ferrocenyl derivatives referred to introduce other group to form a conjugated system with the cyclopentadienyl ring in ferrocene. The large conjugated system was beneficial for the single electron to dispense among the whole molecule while forming radicals, and enhanced the antioxidant capacity of the whole molecule. This review summarized the potential usage of ferrocene in antioxidants.

The Biosynthesis of Nitrogen-, Sulfur-, and High-carbon Chain-containing Sugars†

PubMed Central

Lin, Chia-I; McCarty, Reid M.; Liu, Hung-wen

2013-01-01

Carbohydrates serve many structural and functional roles in biology. While the majority of monosaccharides are characterized by the chemical composition: (CH2O)n, modifications including deoxygenation, C-alkylation, amination, O- and N-methylation, which are characteristic of many sugar appendages of secondary metabolites, are not uncommon. Interestingly, some sugar molecules are formed via modifications including amine oxidation, sulfur incorporation, and “high-carbon” chain attachment. Most of these unusual sugars have been identified over the past several decades as components of microbially produced natural products, although a few high-carbon sugars are also found in the lipooligosaccharides of the outer cell walls of Gram-negative bacteria. Despite their broad distribution in nature, these sugars are considered “rare” due to their relative scarcity. The biosynthetic steps that underlie their formation continue to perplex researchers to this day and many questions regarding key transformations remain unanswered. This review will focus on our current understanding of the biosynthesis of unusual sugars bearing oxidized amine substituents, thio-functional groups, and high-carbon chains. PMID:23348524

C 60 -induced Devil's Staircase transformation on a Pb/Si(111) wetting layer

DOE PAGES

Wang, Lin -Lin; Johnson, Duane D.; Tringides, Michael C.

2015-12-03

Density functional theory is used to study structural energetics of Pb vacancy cluster formation on C 60/Pb/Si(111) to explain the unusually fast and error-free transformations between the “Devil's Staircase” (DS) phases on the Pb/Si(111) wetting layer at low temperature (~110K). The formation energies of vacancy clusters are calculated in C 60/Pb/Si(111) as Pb atoms are progressively ejected from the initial dense Pb wetting layer. Vacancy clusters larger than five Pb atoms are found to be stable with seven being the most stable, while vacancy clusters smaller than five are highly unstable, which agrees well with the observed ejection rate ofmore » ~5 Pb atoms per C 60. Furthermore, the high energy cost (~0.8 eV) for the small vacancy clusters to form indicates convincingly that the unusually fast transformation observed experimentally between the DS phases, upon C 60 adsorption at low temperature, cannot be the result of single-atom random walk diffusion but of correlated multi-atom processes.« less

A STRUCTURAL ANALYSIS OF THE MYELIN SHEATH IN THE CENTRAL NERVOUS SYSTEM

PubMed Central

Hirano, Asao; Dembitzer, Herbert M.

1967-01-01

The cerebral white matter of rats subjected to a variety of noxious experimental conditions was examined in the electron microscope. Several unusual configurations of the myelin sheath are identified in addition to the usual configuration. These variations include the presence of (a) formed organelles within the inner and outer loops, (b) isolated islands of cytoplasm in unfused portions of the major dense lines, (c) apparently unconnected cell processes between the sheath and the axon, and (d) concentric, double myelin sheaths. A generalized model of the myelin sheath based on a hypothetical unrolling of the sheath is described. It consists of a shovel-shaped myelin sheet surrounded by a continuous thickened rim of cytoplasm. Most of the unusual myelin configurations are explained as simple variations on this basic theme. With the help of this model, an explanation of the formation of the myelin sheath is offered. This explanation involves the concept that myelin formation can occur at all cytoplasmic areas adjacent to the myelin proper and that adjacent myelin lamellae can move in relation to each other. PMID:6035645

Imaging diagnosis--Complex intrahepatic portosystemic shunt in a dog.

PubMed

D'Anjou, Marc-André; Huneault, Louis

2008-01-01

An unusual form of congenital intrahepatic portosystemic shunt was identified in a 3 1/2-month-old female Labrador Retriever with neurologic signs. Ultrasonography and contrast-enhanced computed tomography were used to characterize the shunt morphology. An unusual, looping right-divisional shunt connected back to the portal vein that formed an ampula in the right-central portion of the liver. An irregularly shaped window-like opening connected the combined right-divisional loop and aneurysmal portal vein, and the caudal vena cava, while this vascular pool gradually fused more cranially. Imaging features of this complex vascular anomaly, which has not been previously reported, are presented.

Magnetic field drift shell splitting - Cause of unusual dayside particle pitch angle distributions during storms and substorms

NASA Technical Reports Server (NTRS)

Sibeck, D. G.; Mcentire, R. W.; Lui, A. T. Y.; Lopez, R. E.; Krimigis, S. M.

1987-01-01

This paper presents a magnetic field drift shell-splitting model for the unusual butterfly and head-and-shoulder energetic (E greater than 25 keV) particle pitch angle distributions (PADs) which appear deep within the dayside magnetosphere during the course of storms and substorms. Drift shell splitting separates the high and low pitch angle particles in nightside injections as they move to the dayside magnetosphere, so that the higher pitch angle particles move radially away from earth. Consequently, butterfly PADs with a surplus of low pitch angle particles form on the inner edge of the injection, but head-and-shoulder PADs with a surplus of high pitch angle particles form on the outer edge. A similar process removes high pitch angle particles from the inner dayside magnetosphere during storms, leaving the remaining lower pitch angle particles to form butterfly PADs on the inner edge of the ring current. A detailed case and statistical study of Charge Composition Explorer/Medium-energy Particle Analyzer observations, as well as a review of previous work, shows most examples of unusual PADs to be consistent with the model.

High-pressure phase transitions of nitinol NiTi to a semiconductor with an unusual topological structure

NASA Astrophysics Data System (ADS)

Liu, Guangtao; Liu, Hanyu; Feng, Xiaolei; Redfern, Simon A. T.

2018-04-01

Systematic ab initio structure simulations have been used to explore the high-pressure behavior of nitinol (NiTi) at zero temperature. Our crystal structure prediction and first-principles calculations reveal that the known B 19 phase is dynamically unstable, and an orthorhombic structure (Pbcm) and a face-centered-cubic B 32 structure (F d 3 ¯m ) become stable above ˜4 and 29 GPa, respectively. The predicted, highest-pressure, B 32 phase is composed of two interpenetrating diamond structures, with a structural topology that is quite distinct from that of the other phases of NiTi. Interestingly, the B 32 phase shows an unusual semiconducting characteristic as a result of its unique band structure and the nature of 3 d orbitals localization, whose expected synthesis pressure is accessible to current experimental techniques.

Aqueous V(V)-peroxo-amino acid chemistry. Synthesis, structural and spectroscopic characterization of unusual ternary dinuclear tetraperoxo vanadium(V)-glycine complexes.

PubMed

Gabriel, C; Kaliva, M; Venetis, J; Baran, P; Rodriguez-Escudero, I; Voyiatzis, G; Zervou, M; Salifoglou, A

2009-01-19

Vanadium participation in cellular events entails in-depth comprehension of its soluble and bioavailable forms bearing physiological ligands in aqueous distributions of binary and ternary systems. Poised to understand the ternary V(V)-H(2)O(2)-amino acid interactions relevant to that metal ion's biological role, we have launched synthetic efforts involving the physiological ligands glycine and H(2)O(2). In a pH-specific fashion, V(2)O(5), glycine, and H(2)O(2) reacted and afforded the unusual complexes (H(3)O)(2)[V(2)(O)(2)(mu(2):eta(2):eta(1)-O(2))(2)(eta(2)-O(2))(2)(C(2)H(5)NO(2))] x 5/4 H(2)O (1) and K(2)[V(2)(O)(2)(mu(2):eta(2):eta(1)-O(2))(2)(eta(2)-O(2))(2)(C(2)H(5)NO(2))] x H(2)O (2). 1 crystallizes in the triclinic space group P1, with a = 7.805(4) A, b = 8.134(5) A, c = 12.010(7) A, alpha = 72.298(9) degrees, beta = 72.991(9) degrees, gamma = 64.111(9) degrees, V = 641.9(6) A(3), and Z = 2. 2 crystallizes in the triclinic space group P1, with a = 7.6766(9) A, b = 7.9534(9) A, c = 11.7494(13) A, alpha = 71.768(2) degrees, beta = 73.233(2) degrees, gamma = 65.660(2) degrees, V = 610.15(12) A(3), and Z = 2. Both complexes 1 and 2 were characterized by UV/visible, LC-MS, FT-IR, Raman, NMR spectroscopy, cyclic voltammetry, and X-ray crystallography. The structures of 1 and 2 reveal the presence of unusual ternary dinuclear vanadium-tetraperoxo-glycine complexes containing [(V(V)=O)(O(2))(2)](-) units interacting through long V-O bonds and an effective glycinate bridge. The latter ligand is present in the dianionic assembly as a bidentate moiety spanning both V(V) centers in a zwitterionic form. The collective physicochemical properties of the two ternary species 1 and 2 project the chemical role of the low molecular mass biosubstrate glycine in binding V(V)-diperoxo units, thereby stabilizing a dinuclear V(V)-tetraperoxo dianion. Structural comparisons of the anions in 1 and 2 with other known dinuclear V(V)-tetraperoxo binary anionic species provide insight into the chemical reactivity of V(V)-diperoxo species in key cellular events such as insulin mimesis and antitumorigenicity, potentially modulated by the presence of glycinate and hydrogen peroxide.

The 3.2 Angstrom Resolution Structure of the Polymorphic Cowpea Chlorotic Mottle Virus Ribonucleoprotein Particle

NASA Astrophysics Data System (ADS)

Speir, Jeffrey Alan

Structural studies of the polymorphic cowpea chlorotic mottle virus have resulted in high resolution structures for two distinct icosahedral ribonucleoprotein particle conformations dependent upon whether acidic or basic pH conditions prevail. CCMV is stable below pH 6.5, however metal-free particles maintain a 10% increase in hydrodynamic volume at pH >=q 7.5. Identification of this swollen' form of CCMV, which can easily be disrupted with 1M NaCl, led to the first reassembly of an icosahedral virus in vitro from purified viral protein and RNA to form infectious particles, and its assembly has been the subject of biochemical and biophysical investigations for over twenty-five years. Under well defined conditions of pH, ionic strength and divalent metal ion concentration, CCMV capsid protein or capsid protein and RNA will reassemble to form icosahedral particles of various sizes, sheets, tubes, rosettes, and a variety of laminar structures which resemble virion structures from non-related virus families. Analysis of native particles at 3.2A resolution and swollen particles at 28A resolution has suggested that the chemical basis for the formation of polymorphic icosahedral and anisometric structures is: (i) hexamers formed of beta-barrel subunits stabilized by an unusual hexameric parallel beta structure made up of their N-termini, (ii) the location of protein-RNA interactions, (iii) divalent metal cation binding sites that regulate quasi-symmetrical subunit associations, (iv) charge repulsion across the same interfaces when lacking divalent metal ions at basic pH, which induces the formation of sixty 20A diameter portals for RNA release, and (v) a novel, C-terminal-based, subunit dimer assembly unit. The use of C- and N-terminal arms in CCMV has not been observed in other icosahedral RNA virus structures determined at near atomic resolution, however, their detailed interactions and roles in stabilizing the quaternary organization of CCMV are related to that found in the atomic structures of the DNA tumor papovaviruses (SV40 and polyoma). The swollen structure is closely similar to the expanded form of tomato bushy stunt virus (TBSV) previously determined at 8A resolution by X-ray crystallography.

Transcription blockage by stable H-DNA analogs in vitro.

PubMed

Pandey, Shristi; Ogloblina, Anna M; Belotserkovskii, Boris P; Dolinnaya, Nina G; Yakubovskaya, Marianna G; Mirkin, Sergei M; Hanawalt, Philip C

2015-08-18

DNA sequences that can form unusual secondary structures are implicated in regulating gene expression and causing genomic instability. H-palindromes are an important class of such DNA sequences that can form an intramolecular triplex structure, H-DNA. Within an H-palindrome, the H-DNA and canonical B-DNA are in a dynamic equilibrium that shifts toward H-DNA with increased negative supercoiling. The interplay between H- and B-DNA and the fact that the process of transcription affects supercoiling makes it difficult to elucidate the effects of H-DNA upon transcription. We constructed a stable structural analog of H-DNA that cannot flip into B-DNA, and studied the effects of this structure on transcription by T7 RNA polymerase in vitro. We found multiple transcription blockage sites adjacent to and within sequences engaged in this triplex structure. Triplex-mediated transcription blockage varied significantly with changes in ambient conditions: it was exacerbated in the presence of Mn(2+) or by increased concentrations of K(+) and Li(+). Analysis of the detailed pattern of the blockage suggests that RNA polymerase is sterically hindered by H-DNA and has difficulties in unwinding triplex DNA. The implications of these findings for the biological roles of triple-stranded DNA structures are discussed. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

Crystal Structures of Copper-depleted and Copper-bound Fungal Pro-tyrosinase

PubMed Central

Fujieda, Nobutaka; Yabuta, Shintaro; Ikeda, Takuya; Oyama, Takuji; Muraki, Norifumi; Kurisu, Genji; Itoh, Shinobu

2013-01-01

Tyrosinase, a dinuclear copper monooxygenase/oxidase, plays a crucial role in the melanin pigment biosynthesis. The structure and functions of tyrosinase have so far been studied extensively, but the post-translational maturation process from the pro-form to the active form has been less explored. In this study, we provide the crystal structures of Aspergillus oryzae full-length pro-tyrosinase in the holo- and the apo-forms at 1.39 and 2.05 Å resolution, respectively, revealing that Phe513 on the C-terminal domain is accommodated in the substrate-binding site as a substrate analog to protect the dicopper active site from substrate access (proteolytic cleavage of the C-terminal domain or deformation of the C-terminal domain by acid treatment transforms the pro-tyrosinase to the active enzyme (Fujieda, N., Murata, M., Yabuta, S., Ikeda, T., Shimokawa, C., Nakamura, Y., Hata, Y., and Itoh, S. (2012) ChemBioChem. 13, 193–201 and Fujieda, N., Murata, M., Yabuta, S., Ikeda, T., Shimokawa, C., Nakamura, Y., Hata, Yl, and Itoh, S. (2013) J. Biol. Inorg. Chem. 18, 19–26). Detailed crystallographic analysis and structure-based mutational studies have shown that the copper incorporation into the active site is governed by three cysteines as follows: Cys92, which is covalently bound to His94 via an unusual thioether linkage in the holo-form, and Cys522 and Cys525 of the CXXC motif located on the C-terminal domain. Molecular mechanisms of the maturation processes of fungal tyrosinase involving the accommodation of the dinuclear copper unit, the post-translational His-Cys thioether cross-linkage formation, and the proteolytic C-terminal cleavage to produce the active tyrosinase have been discussed on the basis of the detailed structural information. PMID:23749993

Geometric Patterns for Neighboring Bases Near the Stacked State in Nucleic Acid Strands.

PubMed

Sedova, Ada; Banavali, Nilesh K

2017-03-14

Structural variation in base stacking has been analyzed frequently in isolated double helical contexts for nucleic acids, but not as often in nonhelical geometries or in complex biomolecular environments. In this study, conformations of two neighboring bases near their stacked state in any environment are comprehensively characterized for single-strand dinucleotide (SSD) nucleic acid crystal structure conformations. An ensemble clustering method is used to identify a reduced set of representative stacking geometries based on pairwise distances between select atoms in consecutive bases, with multiple separable conformational clusters obtained for categories divided by nucleic acid type (DNA/RNA), SSD sequence, stacking face orientation, and the presence or absence of a protein environment. For both DNA and RNA, SSD conformations are observed that are either close to the A-form, or close to the B-form, or intermediate between the two forms, or further away from either form, illustrating the local structural heterogeneity near the stacked state. Among this large variety of distinct conformations, several common stacking patterns are observed between DNA and RNA, and between nucleic acids in isolation or in complex with proteins, suggesting that these might be stable stacking orientations. Noncanonical face/face orientations of the two bases are also observed for neighboring bases in the same strand, but their frequency is much lower, with multiple SSD sequences across categories showing no occurrences of such unusual stacked conformations. The resulting reduced set of stacking geometries is directly useful for stacking-energy comparisons between empirical force fields, prediction of plausible localized variations in single-strand structures near their canonical states, and identification of analogous stacking patterns in newly solved nucleic acid containing structures.

Myasthenia Gravis: Unusual Presentations and Diagnostic Pitfalls.

PubMed

Rodolico, Carmelo; Parisi, Daniela; Portaro, Simona; Biasini, Fiammetta; Sinicropi, Stefano; Ciranni, Annamaria; Toscano, Antonio; Messina, Sonia; Musumeci, Olimpia; Vita, Giuseppe; Girlanda, Paolo

2016-08-30

Myasthenia gravis (MG) is an autoimmune disorder presenting with fluctuating, fatigable muscle weakness. Initial symptoms classically involve ocular and proximal limb muscles. Rarely, MG may onset with unusual features, so it can be misdiagnosed with other neuromuscular diseases. To describe unusual and atypical presentations of MG in a large cohort of patients, considering and discussing diagnostic difficulties and pitfalls. We report on 21 out of 508 MG patients, coming to our department in the last 27 years and presenting with atypical or unusual features. The diagnosis was achieved performing a careful clinical examination, a proper neurophysiological assessment, the neostigmine test, the AChR and MuSK antibodies assay and chest CT-scan. Patients with atypical/unusual MG onset were the 4.4% of all MG patients population. We describe seven different clinical categories: asymmetric distal upper limbs weakness, foot drop, isolated triceps brachii weakness and foot drop, post exertional axial weakness with dropped head, acute facial dyplegia, limb-girdle MG and MG with sudden lower limbs weakness and recurrent falls. Atypical and unusual presentations may increase the risk to misdiagnose or delay MG diagnosis. Isolated limb-girdle presentation is the most frequent atypical form in our series.

The formation of peak rings in large impact craters.

PubMed

Morgan, Joanna V; Gulick, Sean P S; Bralower, Timothy; Chenot, Elise; Christeson, Gail; Claeys, Philippe; Cockell, Charles; Collins, Gareth S; Coolen, Marco J L; Ferrière, Ludovic; Gebhardt, Catalina; Goto, Kazuhisa; Jones, Heather; Kring, David A; Le Ber, Erwan; Lofi, Johanna; Long, Xiao; Lowery, Christopher; Mellett, Claire; Ocampo-Torres, Rubén; Osinski, Gordon R; Perez-Cruz, Ligia; Pickersgill, Annemarie; Poelchau, Michael; Rae, Auriol; Rasmussen, Cornelia; Rebolledo-Vieyra, Mario; Riller, Ulrich; Sato, Honami; Schmitt, Douglas R; Smit, Jan; Tikoo, Sonia; Tomioka, Naotaka; Urrutia-Fucugauchi, Jaime; Whalen, Michael; Wittmann, Axel; Yamaguchi, Kosei E; Zylberman, William

2016-11-18

Large impacts provide a mechanism for resurfacing planets through mixing near-surface rocks with deeper material. Central peaks are formed from the dynamic uplift of rocks during crater formation. As crater size increases, central peaks transition to peak rings. Without samples, debate surrounds the mechanics of peak-ring formation and their depth of origin. Chicxulub is the only known impact structure on Earth with an unequivocal peak ring, but it is buried and only accessible through drilling. Expedition 364 sampled the Chicxulub peak ring, which we found was formed from uplifted, fractured, shocked, felsic basement rocks. The peak-ring rocks are cross-cut by dikes and shear zones and have an unusually low density and seismic velocity. Large impacts therefore generate vertical fluxes and increase porosity in planetary crust. Copyright © 2016, American Association for the Advancement of Science.

An investigation on the preparation of nanocrystalline hydrous zirconia from zirconium tungstate

NASA Astrophysics Data System (ADS)

Antunes, M.; Perottoni, C. A.; Gouvêa, D.; Machado, G.; Zorzi, J. E.

2018-02-01

Hydrous nanocrystalline zirconia was prepared from an unusual precursor—the bimetallic oxide zirconium tungstate (ZrW2O8)—in alkaline medium. Different experimental conditions (NaOH concentration, time and temperature) were used to investigate the effects on crystallographic, morphological, chemical and thermal characteristics of the products. The resulting materials are composed of particles with a crystal structure similar to that of cubic ZrO2 (or a mixture of tetragonal and cubic phases, depending on the synthesis conditions), with particle size around 5 nm and crystallites around 3 nm in diameter. These particles form high surface area agglomerates, exhibiting mesoporosity and capacity for adsorption of water and carbon dioxide. The synthesis mechanism appears to be constituted, first, by a chemical substitution reaction between the WO4 tetrahedra and hydroxyl ions, with subsequent solubilization of the structure. Indeed, excess hydroxyls in the medium form colloidal zirconium ions which polymerize/condense, generating crystalline nuclei in a process facilitated by heterogeneous nucleation and supersaturation. The presence of residual tungsten in all samples appears to be a key element for stabilizing the size and crystalline structure of the materials produced.

Two Macrocycles in One Shot: Synthesis, Spectroscopy, Photophysics, and Tautomerism of 23-Oxahemiporphycene and 21-Oxacorrole-5-carbaldehyde.

PubMed

Ostapko, Jakub; Kelm, Anna; Kijak, Michał; Leśniewska, Barbara; Waluk, Jacek

2018-04-19

The synthesis of 23-oxahemiporphycene, the first monooxa analogue of hemiporphycene, a structural isomer of porphyrin, is reported. Its generation under McMurry reaction conditions is surprisingly accompanied by the appearance of a formyl derivative of oxacorrole, 21-oxacorrole-5-carbaldehyde. A mechanism for the formation of the latter is proposed, relying on pinacol rearrangement of titanium pinacolate. The structures of the most stable tautomeric forms are established for both compounds based on IR and NMR spectra combined with DFT calculations. Spectral and photophysical characteristics are compared with those of structurally similar macrocycles. Replacement of one nitrogen by oxygen in hemiporphycene has only a minor impact. In contrast, for corrole it leads to the enhancement of stability and to strongly reduced rates of nonradiative deactivation of the lowest excited singlet state. This is explained by the planarity of oxacorroles, achieved by removing one of the inner hydrogen atoms from the inner cavity. Unusual crystal packing is observed for the protonated form of 23-oxahemiporphycene, which exhibits a π-π stacked columnar alignment of positively charged macrocycle units. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

S&TR Preview: Smashing Materials to Reveal Unusual Behavior

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hunsberger, Maren; Akin, Minta; Chau, Ricky

2016-01-13

Squeeze a material hard enough, and its structure and properties will change, sometimes dramatically so. With enough heat and pressure, scientists can turn pencil lead (graphite), one of Earth’s softest materials, into diamond, one of its hardest. Apply even more pressure—such as might be found in explosions, detonating nuclear weapons, laser fusion experiments, meteorite impacts, or the hearts of stars and planets—and materials can take stranger forms. Deep in Jupiter’s core, for instance, where pressures likely reach 50 to 100 million times that of Earth’s atmosphere, hydrogen is predicted to be a metallic liquid rather than the familiar transparent gas.

Catastrophic event recorded among Holocene eolianites (Sidi Salem Formation, SE Tunisia)

NASA Astrophysics Data System (ADS)

Frébourg, Gregory; Hasler, Claude-Alain; Davaud, Eric

2010-03-01

A high-energy deposit cuts through the early Holocene eolianites of the Sidi Salem Formation which forms a ridge along the southeastern coast of Tunisia. The sedimentary structures as well as the paleo-altitude and paleo-location of the outcrop state for a subaqueous deposition by an unusually large catastrophic event. Regarding its age and the related uncertainties, it could be either an exceptional storm, or a landslide or impact triggered tsunami. The mega-tsunami of the 8000 BP collapse of the Valle del Bove valley (Etna Volcano) could be this event, for its matching age and calculated run-up height.

Crystal Structure of a Coiled-Coil Domain from Human ROCK I

PubMed Central

Tu, Daqi; Li, Yiqun; Song, Hyun Kyu; Toms, Angela V.; Gould, Christopher J.; Ficarro, Scott B.; Marto, Jarrod A.; Goode, Bruce L.; Eck, Michael J.

2011-01-01

The small GTPase Rho and one of its targets, Rho-associated kinase (ROCK), participate in a variety of actin-based cellular processes including smooth muscle contraction, cell migration, and stress fiber formation. The ROCK protein consists of an N-terminal kinase domain, a central coiled-coil domain containing a Rho binding site, and a C-terminal pleckstrin homology domain. Here we present the crystal structure of a large section of the central coiled-coil domain of human ROCK I (amino acids 535–700). The structure forms a parallel α-helical coiled-coil dimer that is structurally similar to tropomyosin, an actin filament binding protein. There is an unusual discontinuity in the coiled-coil; three charged residues (E613, R617 and D620) are positioned at what is normally the hydrophobic core of coiled-coil packing. We speculate that this conserved irregularity could function as a hinge that allows ROCK to adopt its autoinhibited conformation. PMID:21445309

Structures of Trypanosome Vacuolar Soluble Pyrophosphatases: Anti-Parasitic Drug Targets

PubMed Central

Yang, Yunyun; Ko, Tzu-Ping; Chen, Chun-Chi; Huang, Guozhong; Zheng, Yingying; Liu, Weidong; Wang, Iren; Ho, Meng-Ru; Danny Hsu, Shang-Te; O’Dowd, Bing; Huff, Hannah C.; Huang, Chun-Hsiang; Docampo, Roberto; Oldfield, Eric; Guo, Rey-Ting

2016-01-01

Trypanosomatid parasites are the causative agents of many neglected tropical diseases including the leishmaniases, Chagas disease, and human African trypanosomiasis. They exploit unusual vacuolar soluble pyrophosphatases (VSPs), absent in humans, for cell growth and virulence and as such, are drug targets. Here, we report the crystal structures of VSP1s from Trypanosoma cruzi and T. brucei, together with that of the T. cruzi protein bound to a bisphosphonate inhibitor. Both VSP1s form a hybrid structure containing an (N-terminal) EF-hand domain fused to a (C-terminal) pyrophosphatase domain. The two domains are connected via an extended loop of about 17 residues. Crystallographic analysis and size exclusion chromatography indicate that the VSP1s form tetramers containing head-to-tail dimers. Phosphate and diphosphate ligands bind in the PPase substrate-binding pocket and interact with several conserved residues, and a bisphosphonate inhibitor (BPH-1260) binds to the same site. Based on Cytoscape and other bioinformatics analyses it is apparent that similar folds will be found in most if not all trypanosomatid VSP1s, including those found in insects (Angomonas deanei, Strigomonas culicis), plant pathogens (Phytomonas spp.) and Leishmania spp. Overall, the results are of general interest since they open the way to structure-based drug design for many of the neglected tropical diseases. PMID:26907161

Chamber music: an unusual Helmholtz resonator for song amplification in a Neotropical bush-cricket (Orthoptera, Tettigoniidae).

PubMed

Jonsson, Thorin; Chivers, Benedict D; Robson Brown, Kate; Sarria-S, Fabio A; Walker, Matthew; Montealegre-Z, Fernando

2017-08-15

Animals use sound for communication, with high-amplitude signals being selected for attracting mates or deterring rivals. High amplitudes are attained by employing primary resonators in sound-producing structures to amplify the signal (e.g. avian syrinx). Some species actively exploit acoustic properties of natural structures to enhance signal transmission by using these as secondary resonators (e.g. tree-hole frogs). Male bush-crickets produce sound by tegminal stridulation and often use specialised wing areas as primary resonators. Interestingly, Acanthacara acuta , a Neotropical bush-cricket, exhibits an unusual pronotal inflation, forming a chamber covering the wings. It has been suggested that such pronotal chambers enhance amplitude and tuning of the signal by constituting a (secondary) Helmholtz resonator. If true, the intact system - when stimulated sympathetically with broadband sound - should show clear resonance around the song carrier frequency which should be largely independent of pronotum material, and change when the system is destroyed. Using laser Doppler vibrometry on living and preserved specimens, microcomputed tomography, 3D-printed models and finite element modelling, we show that the pronotal chamber not only functions as a Helmholtz resonator owing to its intact morphology but also resonates at frequencies of the calling song on itself, making song production a three-resonator system. © 2017. Published by The Company of Biologists Ltd.

Possible Signs of Fauna and Flora on Venus

NASA Astrophysics Data System (ADS)

Ksanfomality, Leonid V.; Selivanov, Arnold S.; Gektin, Yuryi M.

2015-08-01

Habitability of planets is a fundamental question of science. Some of exoplanets possess physical conditions close to those of Venus. The planet Venus, despite its dense and hot (735 K) oxygen-free atmosphere of CO2, having a high pressure of 9.2 MPa at the surface, can be a natural laboratory for this kind of studies. The only existing data on the planet’s surface are still the results obtained by the Soviet VENERA landers.The TV experiments of Venera-9 and 10 (October, 1975) and Venera-13 and 14 (March, 1982) delivered 41 panoramas of Venus surface (or their fragments). The experiments were of extreme technical complexity. There have not been any similar missions to Venus in the subsequent 40 and 33 years. In the absence of new landing missions to Venus, the VENERA panoramas have been re-processed by modern means. The results of these missions are studied anew. A dozen of relatively large objects, from a decimeter to half a meter in size, with an unusual morphology have been found which moved very slowly or changed slightly their shape. Certain unusual findings that have a structure similar to the Earth’ fauna and flora were found in different areas of the planet. There are more then 30 papers on the topic published in 2012-2014 (e.g., “Acta Astronautica”, 2014, V. 105, pp. 521-533). Due to the availability of up to eight duplicates of the images obtained and their low level of masking noise, the VENERA archive panoramas permit identifying and exploring some types of hypothetical life forms of Venus. Analysis of treated once again VENERA panoramic images revealed objects that might indicate the presence of about 12 hypothetical forms of Venusian flora and fauna. Among them is ‘amisada’ that stands out with its unusual lizard shape against the stone plates surrounding it.

Endoscopy, histology and electron microscopy analysis of foetal membranes in pregnant South American plains vizcacha reveal unusual excrescences on the yolk sac.

PubMed

Giacchino, Mariela; Inserra, Pablo I F; Lange, Fernando D; Gariboldi, María C; Ferraris, Sergio R; Vitullo, Alfredo D

2018-06-01

The South American hystricognathe Lagostomus maximus is a fossorial rodent whose females show unique reproductive characteristics. They have a 155-day long gestation, show massive polyovulation and a selective process of embryonic resorption in the first half of gestation. In order to explore and perform an in-situ characterization of the reproductive tract, we visualized internal structures through ultrasonography and video-endoscopy in pregnant and non-pregnant females. We describe the finding of protruding structures that lie on the yolk sac and their histological and ultrastructural characterization. The placenta was covered with whitish, small pearl-shaped structures. These structures were also seen on the extra-embryonic space, being the amnion and the umbilical cord free of them. Pearl-shaped structures were composed with loose connective tissue, lacked blood vessels, and showed collagen fibers organized in a spiral form. They were anchored by pedicles to the villous surface of the extraembryonic membrane. We discuss the biological and evolutionary meaning of the pearl-shaped structures that relate L. maximus to the African origin of the South American hystricognathe fauna.

The prediction of crystal structure by merging knowledge methods with first principles quantum mechanics

NASA Astrophysics Data System (ADS)

Ceder, Gerbrand

2007-03-01

The prediction of structure is a key problem in computational materials science that forms the platform on which rational materials design can be performed. Finding structure by traditional optimization methods on quantum mechanical energy models is not possible due to the complexity and high dimensionality of the coordinate space. An unusual, but efficient solution to this problem can be obtained by merging ideas from heuristic and ab initio methods: In the same way that scientist build empirical rules by observation of experimental trends, we have developed machine learning approaches that extract knowledge from a large set of experimental information and a database of over 15,000 first principles computations, and used these to rapidly direct accurate quantum mechanical techniques to the lowest energy crystal structure of a material. Knowledge is captured in a Bayesian probability network that relates the probability to find a particular crystal structure at a given composition to structure and energy information at other compositions. We show that this approach is highly efficient in finding the ground states of binary metallic alloys and can be easily generalized to more complex systems.

Negative-pressure polymorphs made by heterostructural alloying.

PubMed

Siol, Sebastian; Holder, Aaron; Steffes, James; Schelhas, Laura T; Stone, Kevin H; Garten, Lauren; Perkins, John D; Parilla, Philip A; Toney, Michael F; Huey, Bryan D; Tumas, William; Lany, Stephan; Zakutayev, Andriy

2018-04-01

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures-a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2× to 4× lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. This example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties-materials that are otherwise nearly impossible to make.

Phosphate forms an unusual tripodal complex with the Fe–Mn center of sweet potato purple acid phosphatase

PubMed Central

Schenk, Gerhard; Gahan, Lawrence R.; Carrington, Lyle E.; Mitić, Nataša; Valizadeh, Mohsen; Hamilton, Susan E.; de Jersey, John; Guddat, Luke W.

2005-01-01

Purple acid phosphatases (PAPs) are a family of binuclear metalloenzymes that catalyze the hydrolysis of phosphoric acid esters and anhydrides. A PAP in sweet potato has a unique, strongly antiferromagnetically coupled Fe(III)–Mn(II) center and is distinguished from other PAPs by its increased catalytic efficiency for a range of activated and unactivated phosphate esters, its strict requirement for Mn(II), and the presence of a μ-oxo bridge at pH 4.90. This enzyme displays maximum catalytic efficiency (kcat/Km) at pH 4.5, whereas its catalytic rate constant (kcat) is maximal at near-neutral pH, and, in contrast to other PAPs, its catalytic parameters are not dependent on the pKa of the leaving group. The crystal structure of the phosphate-bound Fe(III)–Mn(II) PAP has been determined to 2.5-Å resolution (final Rfree value of 0.256). Structural comparisons of the active site of sweet potato, red kidney bean, and mammalian PAPs show several amino acid substitutions in the sweet potato enzyme that can account for its increased catalytic efficiency. The phosphate molecule binds in an unusual tripodal mode to the two metal ions, with two of the phosphate oxygen atoms binding to Fe(III) and Mn(II), a third oxygen atom bridging the two metal ions, and the fourth oxygen pointing toward the substrate binding pocket. This binding mode is unique among the known structures in this family but is reminiscent of phosphate binding to urease and of sulfate binding to λ protein phosphatase. The structure and kinetics support the hypothesis that the bridging oxygen atom initiates hydrolysis. PMID:15625111

The nature, distribution and genesis of the coesite and stishovite associated with the pseudotachylite of the Vredefort Dome, South Africa

NASA Astrophysics Data System (ADS)

Martini, J. E. J.

1991-04-01

The Vredefort Dome represents the uplift centre of a well known 2.00 Ga old impact structure of unusually large magnitude. Shock features like shatter cones, planar features and high-pressure silica polymorphs are common. The present study deals with the description, mode of occurrence, field distribution and post-shock metamorphic alteration of coesite and stishovite which were poorly documented up to now. These minerals occur as unusually large crystals in the quartzite of the wall rock in contact with very thin pseudotachylite veins. In the pseudotachylite itself, which can be interpreted as a friction and/or a shock recovery melt, fine needles of kyanite are ubiquitous. It is proposed that these thin pseudotachylites (A-type) formed during the transit of the shock wave. They preceded the development of thick pseudotachylite and microbreccia veins (B-type) which formed during the tensional period which immediately followed. From comparison with the model of formation of high-pressure polymorphs in porous sandstone, it is suggested that higher pressure and stress was concentrated along the A-type veins at the arrival of the shock front. At this time the quartz was transformed into a "high-pressure phase" which was probably poorly crystalline. Behind the shock front, that is during the rarefaction, the pressure was progressively released and the polymorphs crystallized from this initial "high-pressure phase". Stishovite crystallized first, followed by coesite. The high-pressure conditions may have lasted an unusually long time due to the magnitude of the Vredefort impact. This long time, probably about one second, may account for the large size of the coesite and stishovite crystals. Most of the high-pressure silica polymorphs are corroded to a variable degree by secondary quartz and preserved only in a restricted area of the impact structure. This alteration is attributed to post-shock metamorphism due to the temperature of the rock before impact plus the heat left after shock recovery. Some of the evidence put forward by authors against the impact model is discussed according to the facts arising from this investigation. It is concluded that an origin by impact remains the simplest and most realistic model to explain the origin of the Vredefort Dome.

Ingestion Reiterada de Cuerpos Extranos. Forma Inusual de Presentacion del Sindrome de Munchausen por Poderes (Reiterated Ingestion of Foreign Bodies. Unusual Form of Presentation of Munchausen Syndrome by Proxy).

ERIC Educational Resources Information Center

Terreros, I. Gomez de; And Others

1996-01-01

An unusual case of Munchausen syndrome by proxy is reported. A mother with a psychiatric record of behavior disorders and family dysfunction perpetrated the ingestion of foreign bodies (for example, earrings, a screw, sewing needles) on a 10-month-old infant with a history of prematurity, repeated visits to emergency rooms, and nonjustified…

Formation and chemical reactivity of carbon fibers prepared by defluorination of graphite fluoride

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

1994-01-01

Defluorination of graphite fluoride (CFX) by heating to temperatures of 250 to 450 C in chemically reactive environments was studied. This is a new and possibly inexpensive process to produce new carbon-based materials. For example, CF 0.68 fibers, made from P-100 carbon fibers, can be defluorinated in BrH2C-CH = CH-CH2Br (1,4-dibromo-2butene) heated to 370 C, and graphitized to produce fibers with an unusually high modulus and a graphite layer structure that is healed and cross-linked. Conversely, a sulfur-doped, visibly soft carbon fiber was produced by defluorinating CF 0.9 fibers, made from P-25, in sulfur (S) vapor at 370 C and then heating to 660 C in nitrogen (N2). Furthermore, defluorination of the CF 0.68 fibers in bromine (Br2) produced fragile, structurally damaged carbon fibers. Heating these fragile fibers to 1100 C in N2 caused further structural damage, whereas heating to 150 C in bromoform (CHBr3) and then to 1100 C in N2 healed the structural defects. The defluorination product of CFX, tentatively called activated graphite, has the composition and molecular structure of graphite, but is chemically more reactive. Activated graphite is a scavenger of manganese (Mn), and can be intercalated with magnesium (Mg). Also, it can easily collect large amounts of an alloy made from copper (Cu) and type 304 stainless steel to form a composite. Finally, there are indications that activated graphite can wet metals or ceramics, thereby forming stronger composites with them than the pristine carbon fibers can form.

Structural Characterization of the Histone Variant macroH2A

PubMed Central

Chakravarthy, Srinivas; Gundimella, Sampath Kumar Y.; Caron, Cecile; Perche, Pierre-Yves; Pehrson, John R.; Khochbin, Saadi; Luger, Karolin

2005-01-01

macroH2A is an H2A variant with a highly unusual structural organization. It has a C-terminal domain connected to the N-terminal histone domain by a linker. Crystallographic and biochemical studies show that changes in the L1 loop in the histone fold region of macroH2A impact the structure and potentially the function of nucleosomes. The 1.6-Å X-ray structure of the nonhistone region reveals an α/β fold which has previously been found in a functionally diverse group of proteins. This region associates with histone deacetylases and affects the acetylation status of nucleosomes containing macroH2A. Thus, the unusual domain structure of macroH2A integrates independent functions that are instrumental in establishing a structurally and functionally unique chromatin domain. PMID:16107708

Peptide adsorption to cyanine dye aggregates revealed by cryo-transmission electron microscopy.

PubMed

von Berlepsch, Hans; Brandenburg, Enrico; Koksch, Beate; Böttcher, Christoph

2010-07-06

The binding interaction between aggregates of the 5-chloro-2-[[5-chloro-3-(3-sulfopropyl)-3H-benzothiazol-2-ylidene]methyl]-3-(3-sulfopropyl)benzothiazolium hydroxide inner salt ammonium salt (CD-1) and alpha-helix, as well as beta-sheet forming de novo designed peptides, was investigated by absorption spectroscopy, circular dichroism spectroscopy, and cryogenic transmission electron microscopy. Both pure dye and pure peptides self-assembled into well-defined supramolecular assemblies in acetate buffer at pH = 4. The dye formed sheetlike and tubular H- and J-aggregates and the peptides alpha-helical coiled-coil assemblies or beta-sheet rich fibrils. After mixing dye and peptide solutions, tubular aggregates with an unusual ultrastructure were found, most likely due to the decoration of dye tubes with monolayers of peptide assemblies based on the strong electrostatic attraction between the oppositely charged species. There was neither indication of a transfer of chirality from the peptides to the dye aggregates nor the opposite effect of a structural transfer from dye aggregates onto the peptides secondary structure.

Interfacial Coupling-Induced Ferromagnetic Insulator Phase in Manganite Film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bangmin; Wu, Lijun; Yin, Wei-Guo

Interfaces with subtle difference in atomic and electronic structures in perovskite ABO3 heterostructures often yield intriguingly different properties, yet their exact roles remain elusive. Here, we report an integrated study of unusual transport, magnetic, and structural properties of Pr0.67Sr0.33MnO3 (PSMO) film on SrTiO3 (STO) substrate. The variations in out-of-plane lattice constant and BO6 octahedral rotation across the PSMO/STO interface strongly depend on the thickness of PSMO films. In the 12-nm film, a new interface-sensitive ferromagnetic polaronic insulator (FI’) phase is formed during the cubic-to-tetragonal phase transition of STO, apparently due to enhanced electron-phonon interaction and atomic disorder in the film.more » The transport properties of the FI’ phase in the 30-nm film are masked because of the reduced interfacial effect and smaller interface-to-volume ratio. This work demonstrates how thickness-dependent interfacial coupling leads to formation of the theoretically predicted novel ferromagnetic-polaronic insulator in systems, as illustrated in a new phase diagram, that are otherwise ferromagnetic metals (FM) in bulk form.« less

Anomalous stress response of ultrahard WB n compounds

DOE PAGES

Li, Quan; Zhou, Dan; Zheng, Weitao; ...

2015-10-29

Boron-rich tungsten borides are premier prototypes of a new class of ultrahard compounds. Here, we show by first-principles calculations that their stress-strain relations display surprisingly diverse and anomalous behavior under a variety of loading conditions. Most remarkable is the dramatically changing bonding configurations and deformation modes with rising boron concentration in WB n (n=2, 3, 4), resulting in significantly different stress responses and unexpected indentation strength variations. This novel phenomenon stems from the peculiar structural arrangements in tungsten borides driven by boron’s ability to form unusually versatile bonding states. Our results elucidate the intriguing deformation mechanisms that define a distinctmore » type of ultrahard material. Here, these new insights underscore the need to explore unconventional structure-property relations in a broad range of transition-metal light-element compounds.« less

Structure of Mycobacterium tuberculosis mtFabD, a malonyl-CoA:acyl carrier protein transacylase (MCAT).

PubMed

Ghadbane, Hemza; Brown, Alistair K; Kremer, Laurent; Besra, Gurdyal S; Fütterer, Klaus

2007-10-01

Mycobacteria display a unique and unusual cell-wall architecture, central to which is the membrane-proximal mycolyl-arabinogalactan-peptidoglycan core (mAGP). The biosynthesis of mycolic acids, which form the outermost layer of the mAGP core, involves malonyl-CoA:acyl carrier protein transacylase (MCAT). This essential enzyme catalyses the transfer of malonyl from coenzyme A to acyl carrier protein AcpM, thus feeding these two-carbon units into the chain-elongation cycle of the type II fatty-acid synthase. The crystal structure of M. tuberculosis mtFabD, the mycobacterial MCAT, has been determined to 3.0 A resolution by multi-wavelength anomalous dispersion. Phasing was facilitated by Ni2+ ions bound to the 20-residue N-terminal affinity tag, which packed between the two independent copies of mtFabD.

Thermal spike effect in sputtering of porous germanium to form surface pattern by high energy heavy ions irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hooda, Sonu; Khan, S. A.; Kanjilal, D.

2016-05-16

Germanium exhibits a remarkable effect when subjected to high energy heavy ions irradiation. A synergic effect of high electronic energy loss (S{sub e} = 16.4 keV nm{sup −1}) and nuclear energy loss (S{sub n} = 0.1 keV nm{sup −1}) of 100 MeV Ag ions irradiation in Ge is presented. The results show that crystalline Ge is insensitive to the ionizing part of energy loss whereas thermal spike generated in the damaged Ge leads to the formation of porous structure. Further, an unusual high sputtering of the porous structure opens up the sub-surface voids to show the surface pattern. We explore the role of electron and phonon confinement to explainmore » this effect.« less

Adenine phosphoribosyltransferase from Sulfolobus solfataricus is an enzyme with unusual kinetic properties and a crystal structure that suggests it evolved from a 6-oxopurine phosphoribosyltransferase.

PubMed

Jensen, Kaj Frank; Hansen, Michael Riis; Jensen, Kristine Steen; Christoffersen, Stig; Poulsen, Jens-Christian Navarro; Mølgaard, Anne; Kadziola, Anders

2015-04-14

The adenine phosphoribosyltransferase (APRTase) encoded by the open reading frame SSO2342 of Sulfolobus solfataricus P2 was subjected to crystallographic, kinetic, and ligand binding analyses. The enzyme forms dimers in solution and in the crystals, and binds one molecule of the reactants 5-phosphoribosyl-α-1-pyrophosphate (PRPP) and adenine or the product adenosine monophosphate (AMP) or the inhibitor adenosine diphosphate (ADP) in each active site. The individual subunit adopts an overall structure that resembles a 6-oxopurine phosphoribosyltransferase (PRTase) more than known APRTases implying that APRT functionality in Crenarchaeotae has its evolutionary origin in this family of PRTases. Only the N-terminal two-thirds of the polypeptide chain folds as a traditional type I PRTase with a five-stranded β-sheet surrounded by helices. The C-terminal third adopts an unusual three-helix bundle structure that together with the nucleobase-binding loop undergoes a conformational change upon binding of adenine and phosphate resulting in a slight contraction of the active site. The inhibitor ADP binds like the product AMP with both the α- and β-phosphates occupying the 5'-phosphoribosyl binding site. The enzyme shows activity over a wide pH range, and the kinetic and ligand binding properties depend on both pH and the presence/absence of phosphate in the buffers. A slow hydrolysis of PRPP to ribose 5-phosphate and pyrophosphate, catalyzed by the enzyme, may be facilitated by elements in the C-terminal three-helix bundle part of the protein.

Deception Island, Antarctica, harbors a diverse assemblage of wood decay fungi.

PubMed

Held, Benjamin W; Blanchette, Robert A

2017-02-01

Very little is known about fungal diversity in Antarctica as compared to other biomes and how these important organisms function in this unusual ecosystem. Perhaps one of the most unusual ecosystems is that of Deception Island; an active volcanic island part of the South Shetland Islands of the Antarctic Peninsula. Here we describe the fungal diversity associated with historic wood from structures on the island, which reveals a diverse fungal assemblage of known wood decay fungi as well as the discovery of undescribed species. The major group of wood decay fungi identified were species of Cadophora and as shown in previous studies in other geographic regions of Antarctica, they caused a soft-rot type of decay in the introduced woods. Additionally, unlike other areas of Antarctica that have been studied, filamentous basidiomycetes (Hypochniciellum spp. and Pholiota spp.) were also identified that have different modes of degradation including brown and white rot. Matches of fungal sequences to known species in temperate regions likely introduced on building materials indicates human influences and volcanic activity have greatly impacted fungal diversity. Lahars (mudslides from volcanic activity) have partially buried many of the structures and the buried environment as well as the moist, warm soils provided conditions conducive for fungal growth that are not found in other regions of Antarctica. The diverse assemblage of decay fungi and different forms of wood decomposition add to the difficulty of conserving wooden structures at these important polar heritage sites. Copyright © 2016 British Mycological Society. Published by Elsevier Ltd. All rights reserved.

Donor assists acceptor binding and catalysis of human α1,6-fucosyltransferase.

PubMed

Kötzler, Miriam P; Blank, Simon; Bantleon, Frank I; Wienke, Martin; Spillner, Edzard; Meyer, Bernd

2013-08-16

α1,6-Core-fucosyltransferase (FUT8) is a vital enzyme in mammalian physiological and pathophysiological processes such as tumorigenesis and progress of, among others, non-small cell lung cancer and colon carcinoma. It was also shown that therapeutic antibodies have a dramatically higher efficacy if the α1,6-fucosyl residue is absent. However, specific and potent inhibitors for FUT8 and related enzymes are lacking. Hence, it is crucial to elucidate the structural basis of acceptor binding and the catalytic mechanism. We present here the first structural model of FUT8 in complex with its acceptor and donor molecules. An unusually large acceptor, i.e., a hexasaccharide from the core of N-glycans, is required as minimal structure. Acceptor substrate binding of FUT8 is being dissected experimentally by STD NMR and SPR and theoretically by molecular dynamics simulations. The acceptor binding site forms an unusually large and shallow binding site. Binding of the acceptor to the enzyme is much faster and stronger if the donor is present. This is due to strong hydrogen bonding between O6 of the proximal N-acetylglucosamine and an oxygen atom of the β-phosphate of GDP-fucose. Therefore, we propose an ordered Bi Bi mechanism for FUT8 where the donor molecule binds first. No specific amino acid is present that could act as base during catalysis. Our results indicate a donor-assisted mechanism, where an oxygen of the β-phosphate deprotonates the acceptor. Knowledge of the mechanism of FUT8 is now being used for rational design of targeted inhibitors to address metastasis and prognosis of carcinomas.

Structural Studies of Geosmin Synthase, a Bifunctional Sesquiterpene Synthase with Alpha-Alpha Domain Architecture that Catalyzes a Unique Cyclization-Fragmentation Reaction Sequence

PubMed Central

Harris, Golda G.; Lombardi, Patrick M.; Pemberton, Travis A.; Matsui, Tsutomu; Weiss, Thomas M.; Cole, Kathryn E.; Köksal, Mustafa; Murphy, Frank V.; Vedula, L. Sangeetha; Chou, Wayne K.W.; Cane, David E.; Christianson, David W.

2015-01-01

Geosmin synthase from Streptomyces coelicolor (ScGS) catalyzes an unusual, metal-dependent terpenoid cyclization and fragmentation reaction sequence. Two distinct active sites are required for catalysis: the N-terminal domain catalyzes the ionization and cyclization of farnesyl diphosphate to form germacradienol and inorganic pyrophosphate (PPi), and the C-terminal domain catalyzes the protonation, cyclization, and fragmentation of germacradienol to form geosmin and acetone through a retro-Prins reaction. A unique αα domain architecture is predicted for ScGS based on amino acid sequence: each domain contains the metal-binding motifs typical of a class I terpenoid cyclase, and each domain requires Mg2+ for catalysis. Here, we report the X-ray crystal structure of the unliganded N-terminal domain of ScGS and the structure of its complex with 3 Mg2+ ions and alendronate. These structures highlight conformational changes required for active site closure and catalysis. Although neither full-length ScGS nor constructs of the C-terminal domain could be crystallized, homology models of the C-terminal domain were constructed based on ~36% sequence identity with the N-terminal domain. Small-angle X-ray scattering experiments yield low resolution molecular envelopes into which the N-terminal domain crystal structure and the C-terminal domain homology model were fit, suggesting possible αα domain architectures as frameworks for bifunctional catalysis. PMID:26598179

Directed evolution approach to a structural genomics project: Rv2002 from Mycobacterium tuberculosis.

PubMed

Yang, Jin Kuk; Park, Min S; Waldo, Geoffrey S; Suh, Se Won

2003-01-21

One of the serious bottlenecks in structural genomics projects is overexpression of the target proteins in soluble form. We have applied the directed evolution technique and prepared soluble mutants of the Mycobacterium tuberculosis Rv2002 gene product, the wild type of which had been expressed as inclusion bodies in Escherichia coli. A triple mutant I6TV47MT69K (Rv2002-M3) was chosen for structural and functional characterizations. Enzymatic assays indicate that the Rv2002-M3 protein has a high catalytic activity as a NADH-dependent 3alpha, 20beta-hydroxysteroid dehydrogenase. We have determined the crystal structures of a binary complex with NAD(+) and a ternary complex with androsterone and NADH. The structure reveals that Asp-38 determines the cofactor specificity. The catalytic site includes the triad Ser-140Tyr-153Lys-157. Additionally, it has an unusual feature, Glu-142. Enzymatic assays of the E142A mutant of Rv2002-M3 indicate that Glu-142 reverses the effect of Lys-157 in influencing the pKa of Tyr-153. This study suggests that the Rv2002 gene product is a unique member of the SDR family and is likely to be involved in steroid metabolism in M. tuberculosis. Our work demonstrates the power of the directed evolution technique as a general way of overcoming the difficulties in overexpressing the target proteins in soluble form.

Fascination and Isolation: A Grounded Theory Exploration of Unusual Sensory Experiences in Adults with Asperger Syndrome

ERIC Educational Resources Information Center

Smith, Richard S.; Sharp, Jonathan

2013-01-01

Unusual sensory experiences are commonly seen in people with Asperger syndrome (AS). They correlate with functional impairments and cause distress. The current study investigates how these experiences have affected nine adults with AS's lives, as well as the coping strategies utilised. Semi-structured interviews were conducted using Instant…

77 FR 64025 - Special Conditions: Airbus Model A318, A319, A320, and A321 Series Airplanes; Interaction of...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-18

... series airplanes with modification 160023 (Sharklet). These airplanes will have novel or unusual design... novel or unusual design features on the model series of airplanes listed above. It is not a rule of... Series Airplanes; Interaction of Systems and Structures AGENCY: Federal Aviation Administration (FAA...

Biological Diversity Comprising Microbial Structures of Antarctic Ice Covered Lakes

NASA Astrophysics Data System (ADS)

Matys, E. D.

2015-12-01

Analysis of microbial membrane lipids is a rapid and non-selective method for evaluating the composition of microbial communities. To fully realise the diagnostic potential of these lipids, we must first understand their structural diversity, biological sources, physiological functions, and pathways of preservation. Particular environmental conditions likely prompt the production of different membrane lipid structures. Antarctica's McMurdo Dry Valleys host numerous ice-covered lakes with sharp chemical gradients that vary in illumination, geochemical structure, and benthic mat morphologies that are structured by nutrient availability and water chemistry. The lipid contents of these benthic mats have not received extensive study nor have the communities yet been thoroughly characterized. Accordingly, a combination of lipid biomarker and nucleic acid sequence data provides the means of assessing species diversity and environmental controls on the composition and diversity of membrane lipid assemblages. We investigated the richness and diversity of benthic microbial communities and accumulated organic matter in Lake Vanda of the McMurdo Dry Valleys. We have identified diverse glycolipids, aminolipids, and phospholipids in addition to many unknown compounds that may be specific to these particular environments. Light levels fluctuate seasonally, favoring low-light-tolerant cyanobacteria and specific lipid assemblages. Adaptations to nutrient limitations are reflected in contrasting intact polar lipid assemblages. For example, under P-limiting conditions, phospholipids are subsidiary to membrane-forming lipids that do not contain P (i.e. ornithine, betaine, and sulfolipids). The bacteriohopanepolyol (BHP) composition is dominated by bacteriohopanetetrol (BHT), a ubiquitous BHP, and 2-methylhopanoids. The relative abundance of 2-methylhopanoids is unprecedented and may reflect the unusual seasonal light regime of this polar environment. By establishing correlations between environmental conditions, microbial community composition and the lipid assemblages of microbial structures in ice-covered lakes of Antarctica's McMurdo Dry Valleys, our data provides important ecological and evolutionary insights into these unusual environments.

[Inflammatory pancreatic disease due to enzyme autodigestion: an exceptional model of glandular crinophagy].

PubMed

Sánchez-Fayos Calabuig, P; Martín Relloso, M Jesús; González Guirado, Agustina; Porres Cubero, Juan Carlos

2007-01-01

The exocrine pancreas is a functionally dangerous structure since it is exposed to digestion by its most aggressive enzymes (proteases, etc) despite self-protective measures such as the synthesis of some of these enzymes in the form of inactive zymogens (trypsinogen, etc.). We review inflammatory pancreatic disease by separately analyzing its classical forms of onset: acute and chronic pancreatitis (AP and CP). There is general consensus that the initial pathogenic event in AP is intraacinar activation of trypsinogen into trypsin, followed by that of the remaining proenzymes, giving rise to an unusual model of autophagic inflammation. In contrast, consensus is lacking on the initial pathogenic event in CP (toxic-metabolic lesion, oxidative stress, ductal hypertension, etc.?), although in some cases a sequence due to recurrent episodes of AP seems evident. The pathogenic features shared by both forms of the disease and which justify some recent attempts to formulate an overall explanation of the pathogenesis of pancreatitis are discussed. Such an explanation would place both forms of pancreatitis within the conceptual framework of an .

The complex evolutionary history of big-eared horseshoe bats (Rhinolophus macrotis complex): insights from genetic, morphological and acoustic data

PubMed Central

Sun, Keping; Kimball, Rebecca T.; Liu, Tong; Wei, Xuewen; Jin, Longru; Jiang, Tinglei; Lin, Aiqing; Feng, Jiang

2016-01-01

Palaeoclimatic oscillations and different landscapes frequently result in complex population-level structure or the evolution of cryptic species. Elucidating the potential mechanisms is vital to understanding speciation events. However, such complex evolutionary patterns have rarely been reported in bats. In China, the Rhinolophus macrotis complex contains a large form and a small form, suggesting the existence of a cryptic bat species. Our field surveys found these two sibling species have a continuous and widespread distribution with partial sympatry. However, their evolutionary history has received little attention. Here, we used extensive sampling, morphological and acoustic data, as well as different genetic markers to investigate their evolutionary history. Genetic analyses revealed discordance between the mitochondrial and nuclear data. Mitochondrial data identified three reciprocally monophyletic lineages: one representing all small forms from Southwest China, and the other two containing all large forms from Central and Southeast China, respectively. The large form showed paraphyly with respect to the small form. However, clustering analyses of microsatellite and Chd1 gene sequences support two divergent clusters separating the large form and the small form. Moreover, morphological and acoustic analyses were consistent with nuclear data. This unusual pattern in the R. macrotis complex might be accounted for by palaeoclimatic oscillations, shared ancestral polymorphism and/or interspecific hybridization. PMID:27748429

Hepatitis Delta Antigen Requires a Flexible Quasi-Double-Stranded RNA Structure To Bind and Condense Hepatitis Delta Virus RNA in a Ribonucleoprotein Complex

PubMed Central

Griffin, Brittany L.; Chasovskikh, Sergey; Dritschilo, Anatoly

2014-01-01

ABSTRACT The circular genome and antigenome RNAs of hepatitis delta virus (HDV) form characteristic unbranched, quasi-double-stranded RNA secondary structures in which short double-stranded helical segments are interspersed with internal loops and bulges. The ribonucleoprotein complexes (RNPs) formed by these RNAs with the virus-encoded protein hepatitis delta antigen (HDAg) perform essential roles in the viral life cycle, including viral replication and virion formation. Little is understood about the formation and structure of these complexes and how they function in these key processes. Here, the specific RNA features required for HDAg binding and the topology of the complexes formed were investigated. Selective 2′OH acylation analyzed by primer extension (SHAPE) applied to free and HDAg-bound HDV RNAs indicated that the characteristic secondary structure of the RNA is preserved when bound to HDAg. Notably, the analysis indicated that predicted unpaired positions in the RNA remained dynamic in the RNP. Analysis of the in vitro binding activity of RNAs in which internal loops and bulges were mutated and of synthetically designed RNAs demonstrated that the distinctive secondary structure, not the primary RNA sequence, is the major determinant of HDAg RNA binding specificity. Atomic force microscopy analysis of RNPs formed in vitro revealed complexes in which the HDV RNA is substantially condensed by bending or wrapping. Our results support a model in which the internal loops and bulges in HDV RNA contribute flexibility to the quasi-double-stranded structure that allows RNA bending and condensing by HDAg. IMPORTANCE RNA-protein complexes (RNPs) formed by the hepatitis delta virus RNAs and protein, HDAg, perform critical roles in virus replication. Neither the structures of these RNPs nor the RNA features required to form them have been characterized. HDV RNA is unusual in that it forms an unbranched quasi-double-stranded structure in which short base-paired segments are interspersed with internal loops and bulges. We analyzed the role of the HDV RNA sequence and secondary structure in the formation of a minimal RNP and visualized the structure of this RNP using atomic force microscopy. Our results indicate that HDAg does not recognize the primary sequence of the RNA; rather, the principle contribution of unpaired bases in HDV RNA to HDAg binding is to allow flexibility in the unbranched quasi-double-stranded RNA structure. Visualization of RNPs by atomic force microscopy indicated that the RNA is significantly bent or condensed in the complex. PMID:24741096

A Cesium Rare-Earth Silicate Cs3 RESi6 O15 (RE=Dy-Lu, Y, In): The Parent of an Unusual Structural Class Featuring a Remarkable 57 Å Unit Cell Axis.

PubMed

Terry, Rylan; Vinton, Daniel; McMillen, Colin D; Kolis, Joseph W

2018-02-19

The structure of Cs 3 RESi 6 O 15 , where RE=Dy-Lu, Y, In, is unusual in that it contains octahedrally coordinated rare-earth ions; their relative orientation dictates the structure, as they rotate about the c-axis supported by the cyclic Si 6 O 15 framework. The repeat unit of the rotation is eight units generating a very long (ca. 57 Å) unit cell axis. This unusual repeat unit is created by the structural flexibility of the hexasilicate ring, which is in turn affected by the size of the rare earth ion as well as the size of alkali ion residing within the silicate layers. Previous work showed for the smaller Sc 3+ ion, the rotation of the octahedra is not sufficient to achieve closure at an integral repeat unit and an incommensurate structure results. The products are prepared as large, high quality single crystals using a high-temperature (650 °C) hydrothermal method with CsOH and F - mineralizers. The presence of fluoride is essential to the formation of the product. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quorum Sensing Influences Burkholderia thailandensis Biofilm Development and Matrix Production.

PubMed

Tseng, Boo Shan; Majerczyk, Charlotte D; Passos da Silva, Daniel; Chandler, Josephine R; Greenberg, E Peter; Parsek, Matthew R

2016-10-01

Members of the genus Burkholderia are known to be adept at biofilm formation, which presumably assists in the survival of these organisms in the environment and the host. Biofilm formation has been linked to quorum sensing (QS) in several bacterial species. In this study, we characterized Burkholderia thailandensis biofilm development under flow conditions and sought to determine whether QS contributes to this process. B. thailandensis biofilm formation exhibited an unusual pattern: the cells formed small aggregates and then proceeded to produce mature biofilms characterized by "dome" structures filled with biofilm matrix material. We showed that this process was dependent on QS. B. thailandensis has three acyl-homoserine lactone (AHL) QS systems (QS-1, QS-2, and QS-3). An AHL-negative strain produced biofilms consisting of cell aggregates but lacking the matrix-filled dome structures. This phenotype was rescued via exogenous addition of the three AHL signals. Of the three B. thailandensis QS systems, we show that QS-1 is required for proper biofilm development, since a btaR1 mutant, which is defective in QS-1 regulation, forms biofilms without these dome structures. Furthermore, our data show that the wild-type biofilm biomass, as well as the material inside the domes, stains with a fucose-binding lectin. The btaR1 mutant biofilms, however, are negative for fucose staining. This suggests that the QS-1 system regulates the production of a fucose-containing exopolysaccharide in wild-type biofilms. Finally, we present data showing that QS ability during biofilm development produces a biofilm that is resistant to dispersion under stress conditions. The saprophyte Burkholderia thailandensis is a close relative of the pathogenic bacterium Burkholderia pseudomallei, the causative agent of melioidosis, which is contracted from its environmental reservoir. Since most bacteria in the environment reside in biofilms, B. thailandensis is an ideal model organism for investigating questions in Burkholderia physiology. In this study, we characterized B. thailandensis biofilm development and sought to determine if quorum sensing (QS) contributes to this process. Our work shows that B. thailandensis produces biofilms with unusual dome structures under flow conditions. Our findings suggest that these dome structures are filled with a QS-regulated, fucose-containing exopolysaccharide that may be involved in the resilience of B. thailandensis biofilms against changes in the nutritional environment. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Negative-pressure polymorphs made by heterostructural alloying

PubMed Central

Perkins, John D.

2018-01-01

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material’s structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures—a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixing two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2× to 4× lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. This example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties—materials that are otherwise nearly impossible to make. PMID:29725620

RE3Mo14O30 and RE2Mo9O19, Two Reduced Rare-Earth Molybdates with Honeycomb-Related Structures ( RE = La-Pr).

PubMed

Forbes, Scott; Kong, Tai; Cava, Robert J

2018-04-02

The previously unreported RE 3 Mo 14 O 30 and RE 2 Mo 9 O 19 phases were synthesized in vacuo from rare-earth oxides, molybdenum oxide, and molybdenum metal using halide fluxes at 875-1000 °C. Both phases adopt structures in the triclinic P1̅ space group albeit with several notable differences. The structures display an ordering of layers along the a direction of the unit cell, forming distinct honeycomb-related lattice arrangements composed of MoO 6 octahedra and vacancies. Mo-Mo bonding and clusters are present; the RE 3 Mo 14 O 30 structure contains Mo dimers and rhomboid tetramers, while the RE 2 Mo 9 O 19 structure contains rhomboid tetramers and an unusual arrangement of planar tetramers, pentamers, and hexamers. The magnetic measurements found the RE 2 Mo 9 O 19 phases to be simple paramagnets, while La 3 Mo 14 O 30 was observed to order antiferromagnetically at 18 K. Electrical resistivity measurements confirmed all of the samples to behave as nondegenerate semiconductors.

Unusual Clinical Presentation of Hemobilia with Recurrent Vasovagal Episodes.

PubMed

Tiwari, Abhinav; Hammad, Tariq; Sharma, Himani; Qamar, Khola; Khan, Mohammad Saud; Khan, Zubair; Nawras, Ali; Sodeman, Thomas

2017-01-01

Hemobilia is caused by the abnormal connection between a blood vessel and the bile duct, which is usually iatrogenic and caused by hepatobiliary procedures. The classic triad of hemobilia includes biliary colic, obstructive jaundice, and gastrointestinal bleeding. We present the case of an 80-year-old man who had laparoscopic cholecystectomy complicated by hemobilia. He had an unusual presentation of hemobilia in the form of transient vasovagal episodes in addition to abdominal pain and hematochezia.

Unusually short chalcogen bonds involving organoselenium: insights into the Se-N bond cleavage mechanism of the antioxidant ebselen and analogues.

PubMed

Thomas, Sajesh P; Satheeshkumar, K; Mugesh, Govindasamy; Guru Row, T N

2015-04-27

Structural studies on the polymorphs of the organoselenium antioxidant ebselen and its derivative show the potential of organic selenium to form unusually short Se⋅⋅⋅O chalcogen bonds that lead to conserved supramolecular recognition units. Se⋅⋅⋅O interactions observed in these polymorphs are the shortest such chalcogen bonds known for organoselenium compounds. The FTIR spectral evolution characteristics of this interaction from solution state to solid crystalline state further validates the robustness of this class of supramolecular recognition units. The strength and electronic nature of the Se⋅⋅⋅O chalcogen bonds were explored using high-resolution X-ray charge density analysis and atons-in-molecules (AIM) theoretical analysis. A charge density study unravels the strong electrostatic nature of Se⋅⋅⋅O chalcogen bonding and soft-metal-like behavior of organoselenium. An analysis of the charge density around Se-N and Se-C covalent bonds in conjunction with the Se⋅⋅⋅O chalcogen bonding modes in ebselen and its analogues provides insights into the mechanism of drug action in this class of organoselenium antioxidants. The potential role of the intermolecular Se⋅⋅⋅O chalcogen bonding in forming the intermediate supramolecular assembly that leads to the bond cleavage mechanism has been proposed in terms of electron density topological parameters in a series of molecular complexes of ebselen with reactive oxygen species (ROS). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cranial morphology and bite force in Chamaeleolis lizards--adaptations to molluscivory?

PubMed

Herrel, Anthony; Holanova, Veronika

2008-01-01

Anolis lizards have become a model system for the study of adaptive radiations as species with similar morphologies occupying similar habitats have arisen independently on all the larger islands in the Caribbean. However, on both, Cuba and Hispaniola unique forms have evolved that seemingly have no counterparts on any of the other Caribbean islands. Anoles of the genus Chamaeleolis comprise such a unique form and have been termed 'twig giants' because of their cryptic life style, slow locomotor mode, and short limbs. However, some of the most unusual features of these lizards are their large heads and molluscivorous diet. Here, we compare head shape, bite force, and muscle structure among sexes and age classes of Chamaeleolis lizards with Anolis crown giants. Our data show that Chamaeleolis lizards have a dramatically different head shape characterized by tall heads with a pronounced temporal ridge and long snouts. Analyses of bite force, surprisingly, show no differences between adult Chamaeleolis and Anolis crown giants. Juveniles of Chamaeleolis, however, have very tall heads for their size and bite harder than Anolis juveniles do. This can be related to the propensity of juveniles of this genus to eat snails, food items for which high bite forces are crucial. This observation is corroborated by the presence of well-developed jaw adductors in juveniles. Thus, our data suggest that the unusual phenotype of adults with large and tall heads may be due to selection on the juvenile life history stages.

Ti 3CrCu 4: A possible 2-D ferromagnetic spin fluctuating system

DOE PAGES

Dhar, S. K.; Provino, A.; Manfrinetti, P.; ...

2016-03-09

Ti 3CrCu 4 is a new ternary compound which crystallizes in the tetragonal Ti 3Pd 5 structure type. The Cr atoms form square nets in the a-b plane (a = 3.124 Å) which are separated by an unusually large distance c = 11.228 Å along the tetragonal axis, thus forming a -2-D Cr-sublattice. The paramagnetic susceptibility is characterized by a low effective moment, μ eff = 1.1 μ B, a low paramagnetic Curie temperature θ P (below 7 K) and a temperature independent χ0 = 6.7 x 10 –4 emu/mol. The magnetization at 1.8 K increases rapidly with field nearlymore » saturating to 0.2 μ B/f.u. The zero field heat capacity C/T shows an upturn below 7 K (~190 mJ/mol K 2 at ~0.1K) which is suppressed in applied magnetic fields and interpreted as suggesting the presence of spin fluctuations. The resistivity at low temperatures shows non-Fermi liquid behavior. Overall, the experimental data thus reveal an unusual magnetic state in Ti 3CrCu 4, which likely has its origin in the layered nature of the Cr sub-lattice and ferromagnetic spin fluctuations. Here, density functional theoretical calculations reveal a sharp Cr density of states peak just above the Fermi level, indicating the propensity of Ti 3CrCu 4 to become magnetic.« less

Evidence for Reduced, Carbon-rich Regions in the Solar Nebula from an Unusual Cometary Dust Particle

NASA Astrophysics Data System (ADS)

De Gregorio, Bradley T.; Stroud, Rhonda M.; Nittler, Larry R.; Kilcoyne, A. L. David

2017-10-01

Geochemical indicators in meteorites imply that most formed under relatively oxidizing conditions. However, some planetary materials, such as the enstatite chondrites, aubrite achondrites, and Mercury, were produced in reduced nebular environments. Because of large-scale radial nebular mixing, comets and other Kuiper Belt objects likely contain some primitive material related to these reduced planetary bodies. Here, we describe an unusual assemblage in a dust particle from comet 81P/Wild 2 captured in silica aerogel by the NASA Stardust spacecraft. The bulk of this ˜20 μm particle is comprised of an aggregate of nanoparticulate Cr-rich magnetite, containing opaque sub-domains composed of poorly graphitized carbon (PGC). The PGC forms conformal shells around tiny 5-15 nm core grains of Fe carbide. The C, N, and O isotopic compositions of these components are identical within errors to terrestrial standards, indicating a formation inside the solar system. Magnetite compositions are consistent with oxidation of reduced metal, similar to that seen in enstatite chondrites. Similarly, the core-shell structure of the carbide + PGC inclusions suggests a formation via FTT reactions on the surface of metal or carbide grains in warm, reduced regions of the solar nebula. Together, the nanoscale assemblage in the cometary particle is most consistent with the alteration of primary solids condensed from a C-rich, reduced nebular gas. The nanoparticulate components in the cometary particle provide the first direct evidence from comets of reduced, carbon-rich regions that were present in the solar nebula.

A new zinc-1,3,5-benzenetricarboxylate framework integrated three distinct subunits (SBUs)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Yi-Ming, E-mail: ymxie@fjirsm.ac.cn

2013-06-01

A new metal-organic framework (MOF) [Zn₅(btc)₃(H₂O)₀.₅(O)₀.₅(DMA)₃]·1.75(DMA) (1; btc=1,3,5-benzenetricarboxylate; DMA=N,N´-dimethyl acetamide) has been solvothermally synthesized. Unusually, three distinct subunits (SBUs), [Zn₂(CO₂)₄(DMA)₂], [(μ₃-H₂O)Zn₃(CO₂)₆(DMA)] and [(µ₄-O)Zn₄(CO₂)₆(DMA)₂] are observed in 1 simultaneously. The integration of three distinct SBUs leads to an interesting Zn-btc framework materials with unusual structural topology. - Graphical abstract: Presented here is a new zinc-1,3,5-benzenetricarboxylate framework integrated three distinct subunits (SBUs). - Highlights: • A new zinc-1,3,5-benzenetricarboxylate framework has been synthesized. • Three distinct subunits (SBUs) are observed in 1 simultaneously. • The integration of three distinct SBUs leads to an unusual structural topology.

Chemotaxis cluster 1 proteins form cytoplasmic arrays in Vibrio cholerae and are stabilized by a double signaling domain receptor DosM.

PubMed

Briegel, Ariane; Ortega, Davi R; Mann, Petra; Kjær, Andreas; Ringgaard, Simon; Jensen, Grant J

2016-09-13

Nearly all motile bacterial cells use a highly sensitive and adaptable sensory system to detect changes in nutrient concentrations in the environment and guide their movements toward attractants and away from repellents. The best-studied bacterial chemoreceptor arrays are membrane-bound. Many motile bacteria contain one or more additional, sometimes purely cytoplasmic, chemoreceptor systems. Vibrio cholerae contains three chemotaxis clusters (I, II, and III). Here, using electron cryotomography, we explore V. cholerae's cytoplasmic chemoreceptor array and establish that it is formed by proteins from cluster I. We further identify a chemoreceptor with an unusual domain architecture, DosM, which is essential for formation of the cytoplasmic arrays. DosM contains two signaling domains and spans the two-layered cytoplasmic arrays. Finally, we present evidence suggesting that this type of receptor is important for the structural stability of the cytoplasmic array.

Molecular growth from a Mo176 to a Mo248 cluster

NASA Astrophysics Data System (ADS)

Müller, A.; Shah, Syed Q. N.; Bögge, H.; Schmidtmann, M.

1999-01-01

In polyoxometalate chemistry a large variety of compounds, clusters and solid-state structures can be formed by the linking together of well-defined metal-oxygen building blocks, . These species exhibit unusual topological and electronic properties, andfind applications ranging from medicine to industrial processes. The recently reported ring-shaped mixed-valence polyoxomolybdates of the type {Mo154} (refs 5, 6) and {Mo176} (refs 7, 8) represent a new class of giant clusters with nanometre-sized cavities and interesting properties for host-guest chemistry. Here we describe the formation of related clusters of the type {Mo248} formed by addition of further units to the inner surface of the {Mo176 } `wheel'. The additional units arrange themselves into two {Mo36} `hub-caps' on the initial wheel-clusters that are not stable in isolation. These findings reveal a new pathway to the development of complex coordination clusters.

Syncytia in plants: cell fusion in endosperm-placental syncytium formation in Utricularia (Lentibulariaceae).

PubMed

Płachno, Bartosz J; Swiątek, Piotr

2011-04-01

The syncytium formed by Utricularia is extremely unusual and perhaps unique among angiosperm syncytia. All typical plant syncytia (articulated laticifers, amoeboid tapetum, the nucellar plasmodium of river weeds) are formed only by fusion of sporophytic cells which possess the same genetic material, unlike Utricularia in which the syncytium possesses nuclei from two different sources: cells of maternal sporophytic nutritive tissue and endosperm haustorium (both maternal and paternal genetic material). How is this kind of syncytium formed and organized and is it similar to other plant syncytial structures? We used light and electron microscopy to reconstruct the step-by-step development of the Utricularia syncytia. The syncytia of Utricularia developed through heterotypic cell fusion involving the digestion of the cell wall, and finally, heterokaryotic multinucleate structures were formed, which possessed different-sized nuclei that were not regularly arranged in the cytoplasm. We showed that these syncytia were characterized by hypertrophy of nuclei, abundant endoplasmic reticulum and organelles, and the occurrence of wall ingrowths. All these characters testify to high activity and may confirm the nutritive and transport functions of the syncytium for the developing embryo. In Utricularia, the formation of the syncytium provides an economical way to redistribute cell components and release nutrients from the digested cell walls, which can now be used for the embryo, and finally to create a large surface for the exchange of nutrients between the placenta and endosperm.

Bis-urea-based supramolecular polymer: the first self-assembled drag reducer for hydrocarbon solvents.

PubMed

Sabadini, Edvaldo; Francisco, Kelly R; Bouteiller, Laurent

2010-02-02

The hydrodynamic drag reduction phenomenon, also termed the Toms effect, is an unusual case involving macromolecules in solution in which the resistance to flow is reduced comparatively to that of the pure solvent. Although the effect is relatively well characterized, it is still unclear from the molecular viewpoint. The presence of some amount of a polymer with high molecular weight can produce large levels of drag reduction in turbulent flow as a result of the interactions of the long structures with the small vortices developed during the flow. For this reason, the effect is very attractive in the pumping process because a significant amount of energy can be saved. In aqueous systems, giant micelles can be spontaneously formed, driven by the hydrophobic effect, and are effective drag reducers. Giant micelles are interesting in promoting drag reduction because the noncovalent and reversible aggregation of the surfactant molecules avoids mechanical degradation, which typically occurs with classical polymers, due to irreversible scission of the backbone. In this letter, we present the first hydrodynamic drag reducer for hydrocarbons based on a self-assembled polymer formed from the reversible aggregation of bis-urea monomers. This system forms two competitive polymeric structures--the tube (T) and the filament (F) forms--which are in equilibrium with each other. Our rheology results in octane and toluene are fully consistent with calorimetry data and show that only the longest form, T, is able to promote the drag reduction effect.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Kaushik, E-mail: kaushikdas2089@gmail.com; Kundu, Sarathi

Long chain fatty acid molecules (e.g., stearic and behenic acids) form a monolayer on water surface in the presence of Ba{sup 2+} ions at low subphase pH (≈ 5.5) and remain as a monolayer before collapse generally occurs at higher surface pressure (π{sub c} > 50 mN/m). Monolayer formation is verified from the surface pressure vs. area per molecule (π-A) isotherms and also from the atomic force microscopy (AFM) analysis of the films deposited by single upstroke of hydrophilic Si (001) substrate through the monolayer covered water surface. At high subphase pH (≈ 9.5), barium stearate molecules form multilayer structuremore » at lower surface pressure which is verified from the π-A isotherms and AFM analysis of the film deposited at 25 mN/m. Such monolayer to multilayer structure formation or monolayer collapse at lower surface pressure is unusual as at this surface pressure generally fatty acid salt molecules form a monolayer on the water surface. Formation of bidentate chelate coordination in the metal containing headgroups is the reason for such monolayer to multilayer transition. However, for longer chain barium behenate molecules only monolayer structure is maintained at that high subphase pH (≈ 9.5) due to the presence of relatively more tail-tail hydrophobic interaction.« less

An unusual form of lipid linkage to the CD45 peptide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeda, Akiko; Maizel, A.L.

1990-11-02

Some protein kinases and phosphatases are myristoylated on their amino terminus, which perhaps contributes to subcellular localization or regulation. Glycoprotein CD45, a hematopoietic tyrosine phosphatase, was examined for fatty acid content. The CD45 protein incorporated ({sup 3}H)myristate, but little ({sup 3}H)palmitate. The label was not metabolized and reincorporated into amino acids or saccharides, as revealed by peptide maps of CD45 labeled with ({sup 3}H)myristate, {sup 14}C-labeled amino acids, ({sup 35}S)methionine, or {sup 125}I, and glycosidase treatments, respectively. The myristate label was resistant to mild alkaline methanolysis and was found in fatty acid and sphingosine, indicating an unusual form of lipidmore » attachment to CD45.« less

Rapid Speech Transmission Index predictions and auralizations of unusual instructional spaces at MIT's new Stata Center

NASA Astrophysics Data System (ADS)

Conant, David A.

2005-04-01

The Stata Center for Computer, Information and Intelligence Sciences, recently opened at the Massachusetts Institute of Technology, includes a variety of oddly-shaped seminar rooms in addition to lecture spaces of somewhat more conventional form. The architects design approach prohibited following conventional, well understood room-acoustical behavior yet MIT and the design team were keenly interested in ensuring that these spaces functioned exceptionally well, acoustically. CATT-Acoustic room modeling was employed to assess RASTI through multiple design iterations for all these spaces. Presented here are computational and descriptive results achieved for these rooms which are highly-regarded by faculty. They all sound peculiarly good, given their unusual form. In addition, binaural auralizations for selected spaces are provided.

Cryptococcus neoformans of Unusual Morphology

PubMed Central

Cruickshank, J. G.; Cavill, R.; Jelbert, M.

1973-01-01

A case of primary cryptococcosis of the lungs was caused by an isolate of Cryptococcus neoformans that assumes a giant form in tissue but which has a normal appearance on artificial culture. Electron microscopy revealed gross enlargement of the capsule and plasma membranes in the tissue form. Images PMID:4121033

Optical transitions in two-dimensional topological insulators with point defects

NASA Astrophysics Data System (ADS)

Sablikov, Vladimir A.; Sukhanov, Aleksei A.

2016-12-01

Nontrivial properties of electronic states in topological insulators are inherent not only to the surface and boundary states, but to bound states localized at structure defects as well. We clarify how the unusual properties of the defect-induced bound states are manifested in optical absorption spectra in two-dimensional topological insulators. The calculations are carried out for defects with short-range potential. We find that the defects give rise to the appearance of specific features in the absorption spectrum, which are an inherent property of topological insulators. They have the form of two or three absorption peaks that are due to intracenter transitions between electron-like and hole-like bound states.

Tolyporphin-An Unusual Green Chlorin-like Dioxobacteriochlorin.

PubMed

Brückner, Christian

2017-10-01

The tolyporphins, a family of green tetrapyrrolic pigments isolated from a cyanobacterium-microbial ecological unit, possess unique carbohydrate-derivatized dioxobacteriochlorin frameworks. A brief overview over the history, synthesis, chemistry and biological properties of the tolyporphins forms the backdrop for highlighting the contribution by Hood et al. (Photochem. Photobiol., 2017, https://doi.org/10.1111/php.12781) who demonstrate the optical properties of tolyporphins to be more similar to those of chlorins than of bacteriochlorins. This property could be correlated with the presence of β-oxo-functionalities. The study continues to clarify the structure, properties and possible roles of these intriguing chromophores with a range of biomedical properties. © 2017 The American Society of Photobiology.

WONKA: objective novel complex analysis for ensembles of protein-ligand structures.

PubMed

Bradley, A R; Wall, I D; von Delft, F; Green, D V S; Deane, C M; Marsden, B D

2015-10-01

WONKA is a tool for the systematic analysis of an ensemble of protein-ligand structures. It makes the identification of conserved and unusual features within such an ensemble straightforward. WONKA uses an intuitive workflow to process structural co-ordinates. Ligand and protein features are summarised and then presented within an interactive web application. WONKA's power in consolidating and summarising large amounts of data is described through the analysis of three bromodomain datasets. Furthermore, and in contrast to many current methods, WONKA relates analysis to individual ligands, from which we find unusual and erroneous binding modes. Finally the use of WONKA as an annotation tool to share observations about structures is demonstrated. WONKA is freely available to download and install locally or can be used online at http://wonka.sgc.ox.ac.uk.

Crystal structure of guanidinium hexafluoridovanadate(III), (CN3H6)3[VF6]: an unusual hybrid compound related to perovskite.

PubMed

Black, Cameron; Lightfoot, Philip

2017-03-01

Vanadium fluorides with novel crystal-chemical features and interesting physical properties can be prepared by solvothermal synthetic routes. The title compound, guanidinium hexafluoridovanadate(III), has a cubic structure (space group Pa-3), exhibiting isolated regular VF 6 octahedral units, which are hydrogen bonded to protonated guanidinium moieties. Although the VF 6 octahedral units are not linked directly together, there are structural similarities between this crystal structure and those of the wider family of perovskite materials, in particular, hybrid perovskites based on extended ligands such as cyanide. In this context, the octahedral tilt system of the present compound is of interest and demonstrates that unusual tilt systems can be mediated via `molecular' linkers which allow only supramolecular rather than covalent interactions.

Structure of the unliganded form of the proprotein convertase furin suggests activation by a substrate-induced mechanism

PubMed Central

Dahms, Sven O.; Arciniega, Marcelino; Steinmetzer, Torsten; Huber, Robert; Than, Manuel E.

2016-01-01

Proprotein convertases (PCs) are highly specific proteases required for the proteolytic modification of many secreted proteins. An unbalanced activity of these enzymes is connected to pathologies like cancer, atherosclerosis, hypercholesterolaemia, and infectious diseases. Novel protein crystallographic structures of the prototypical PC family member furin in different functional states were determined to 1.8–2.0 Å. These, together with biochemical data and modeling by molecular dynamics calculations, suggest essential elements underlying its unusually high substrate specificity. Furin shows a complex activation mechanism and exists in at least four defined states: (i) the “off state,” incompatible with substrate binding as seen in the unliganded enzyme; (ii) the active “on state” seen in inhibitor-bound furin; and the respective (iii) calcium-free and (iv) calcium-bound forms. The transition from the off to the on state is triggered by ligand binding at subsites S1 to S4 and appears to underlie the preferential recognition of the four-residue sequence motif of furin. The molecular dynamics simulations of the four structural states reflect the experimental observations in general and provide approximations of the respective stabilities. Ligation by calcium at the PC-specific binding site II influences the active-site geometry and determines the rotamer state of the oxyanion hole-forming Asn295, and thus adds a second level of the activity modulation of furin. The described crystal forms and the observations of different defined functional states may foster the development of new tools and strategies for pharmacological intervention targeting furin. PMID:27647913

Solution structure of a DNA mimicking motif of an RNA aptamer against transcription factor AML1 Runt domain.

PubMed

Nomura, Yusuke; Tanaka, Yoichiro; Fukunaga, Jun-ichi; Fujiwara, Kazuya; Chiba, Manabu; Iibuchi, Hiroaki; Tanaka, Taku; Nakamura, Yoshikazu; Kawai, Gota; Kozu, Tomoko; Sakamoto, Taiichi

2013-12-01

AML1/RUNX1 is an essential transcription factor involved in the differentiation of hematopoietic cells. AML1 binds to the Runt-binding double-stranded DNA element (RDE) of target genes through its N-terminal Runt domain. In a previous study, we obtained RNA aptamers against the AML1 Runt domain by systematic evolution of ligands by exponential enrichment and revealed that RNA aptamers exhibit higher affinity for the Runt domain than that for RDE and possess the 5'-GCGMGNN-3' and 5'-N'N'CCAC-3' conserved motif (M: A or C; N and N' form Watson-Crick base pairs) that is important for Runt domain binding. In this study, to understand the structural basis of recognition of the Runt domain by the aptamer motif, the solution structure of a 22-mer RNA was determined using nuclear magnetic resonance. The motif contains the AH(+)-C mismatch and base triple and adopts an unusual backbone structure. Structural analysis of the aptamer motif indicated that the aptamer binds to the Runt domain by mimicking the RDE sequence and structure. Our data should enhance the understanding of the structural basis of DNA mimicry by RNA molecules.

Structures of Pseudomonas aeruginosa β-ketoacyl-(acyl-carrier-protein) synthase II (FabF) and a C164Q mutant provide templates for antibacterial drug discovery and identify a buried potassium ion and a ligand-binding site that is an artefact of the crystal form

PubMed Central

Baum, Bernhard; Lecker, Laura S. M.; Zoltner, Martin; Jaenicke, Elmar; Schnell, Robert; Hunter, William N.; Brenk, Ruth

2015-01-01

Bacterial infections remain a serious health concern, in particular causing life-threatening infections of hospitalized and immunocompromised patients. The situation is exacerbated by the rise in antibacterial drug resistance, and new treatments are urgently sought. In this endeavour, accurate structures of molecular targets can support early-stage drug discovery. Here, crystal structures, in three distinct forms, of recombinant Pseudomonas aeruginosa β-ketoacyl-(acyl-carrier-protein) synthase II (FabF) are presented. This enzyme, which is involved in fatty-acid biosynthesis, has been validated by genetic and chemical means as an antibiotic target in Gram-positive bacteria and represents a potential target in Gram-negative bacteria. The structures of apo FabF, of a C164Q mutant in which the binding site is altered to resemble the substrate-bound state and of a complex with 3-(benzoylamino)-2-hydroxybenzoic acid are reported. This compound mimics aspects of a known natural product inhibitor, platensimycin, and surprisingly was observed binding outside the active site, interacting with a symmetry-related molecule. An unusual feature is a completely buried potassium-binding site that was identified in all three structures. Comparisons suggest that this may represent a conserved structural feature of FabF relevant to fold stability. The new structures provide templates for structure-based ligand design and, together with the protocols and reagents, may underpin a target-based drug-discovery project for urgently needed antibacterials. PMID:26249693

Zinc-binding structure of a catalytic amyloid from solid-state NMR.

PubMed

Lee, Myungwoon; Wang, Tuo; Makhlynets, Olga V; Wu, Yibing; Polizzi, Nicholas F; Wu, Haifan; Gosavi, Pallavi M; Stöhr, Jan; Korendovych, Ivan V; DeGrado, William F; Hong, Mei

2017-06-13

Throughout biology, amyloids are key structures in both functional proteins and the end product of pathologic protein misfolding. Amyloids might also represent an early precursor in the evolution of life because of their small molecular size and their ability to self-purify and catalyze chemical reactions. They also provide attractive backbones for advanced materials. When β-strands of an amyloid are arranged parallel and in register, side chains from the same position of each chain align, facilitating metal chelation when the residues are good ligands such as histidine. High-resolution structures of metalloamyloids are needed to understand the molecular bases of metal-amyloid interactions. Here we combine solid-state NMR and structural bioinformatics to determine the structure of a zinc-bound metalloamyloid that catalyzes ester hydrolysis. The peptide forms amphiphilic parallel β-sheets that assemble into stacked bilayers with alternating hydrophobic and polar interfaces. The hydrophobic interface is stabilized by apolar side chains from adjacent sheets, whereas the hydrated polar interface houses the Zn 2+ -binding histidines with binding geometries unusual in proteins. Each Zn 2+ has two bis-coordinated histidine ligands, which bridge adjacent strands to form an infinite metal-ligand chain along the fibril axis. A third histidine completes the protein ligand environment, leaving a free site on the Zn 2+ for water activation. This structure defines a class of materials, which we call metal-peptide frameworks. The structure reveals a delicate interplay through which metal ions stabilize the amyloid structure, which in turn shapes the ligand geometry and catalytic reactivity of Zn 2 .

Johari-Goldstein Relaxation Far Below Tg: Experimental Evidence for the Gardner Transition in Structural Glasses?

NASA Astrophysics Data System (ADS)

Geirhos, K.; Lunkenheimer, P.; Loidl, A.

2018-02-01

Experimental evidence for the Gardner transition, theoretically predicted to arise deep in the glassy state of matter, is scarce. At this transition, the energy landscape sensed by the particles forming the glass is expected to become more complex. In the present Letter, we report the dielectric response of two typical glass formers with well-pronounced Johari-Goldstein β relaxation, following this response down to unprecedented low temperatures, far below the glass transition. As the Johari-Goldstein process is believed to arise from the local structure of the energy landscape, its investigation seems an ideal tool to seek evidence for the Gardner transition. Indeed, we find an unusual broadening of the β relaxation below about 110 K for sorbitol and 100 K for xylitol, in excess of the expected broadening arising from a distribution of energy barriers. These results are well consistent with the presence of the Gardner transition in canonical structural glass formers.

Structure of a eukaryotic cyclic nucleotide-gated channel

PubMed Central

Li, Minghui; Zhou, Xiaoyuan; Wang, Shu; Michailidis, Ioannis; Gong, Ye; Su, Deyuan; Li, Huan; Li, Xueming; Yang, Jian

2018-01-01

Summary Cyclic nucleotide-gated (CNG) channels are essential for vision and olfaction. They belong to the voltage-gated ion channel superfamily but their activities are controlled by intracellular cyclic nucleotides instead of transmembrane voltage. Here we report a 3.5 Å-resolution single-particle electron cryomicroscopy structure of a CNG channel from C. elegans in the cGMP-bound open state. The channel has an unusual voltage-sensor-like domain (VSLD), accounting for its deficient voltage dependence. A C-terminal linker connecting S6 and the cyclic nucleotide-binding domain interacts directly with both the VSLD and pore domain, forming a gating ring that couples conformational changes triggered by cyclic nucleotide binding to the gate. The selectivity filter is lined by the carboxylate side chains of a functionally important glutamate and three rings of backbone carbonyls. This structure provides a new framework for understanding mechanisms of ion permeation, gating and channelopathy of CNG channels and cyclic nucleotide modulation of related channels. PMID:28099415

The Structure of the GM-CSF Receptor Complex Reveals a Distinct Mode of Cytokine Receptor Activation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hansen, Guido; Hercus, Timothy R.; McClure, Barbara J.

Granulocyte-macrophage colony-stimulating factor (GM-CSF) is a pleiotropic cytokine that controls the production and function of blood cells, is deregulated in clinical conditions such as rheumatoid arthritis and leukemia, yet offers therapeutic value for other diseases. Its receptors are heterodimers consisting of a ligand-specific {alpha} subunit and a {beta}c subunit that is shared with the interleukin (IL)-3 and IL-5 receptors. How signaling is initiated remains an enigma. We report here the crystal structure of the human GM-CSF/GM-CSF receptor ternary complex and its assembly into an unexpected dodecamer or higher-order complex. Importantly, mutagenesis of the GM-CSF receptor at the dodecamer interface andmore » functional studies reveal that dodecamer formation is required for receptor activation and signaling. This unusual form of receptor assembly likely applies also to IL-3 and IL-5 receptors, providing a structural basis for understanding their mechanism of activation and for the development of therapeutics.« less

Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

NASA Technical Reports Server (NTRS)

Keller, L. P.; Snead, C.; Rahman, Z.; McKeegan, K. D.

2012-01-01

Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

Structural and Functional Analysis of the Pyocyanin Biosynthetic Protein PhzM from Pseudomonas aeruginosa†‡

PubMed Central

Parsons, James F.; Greenhagen, Bryan T.; Shi, Katherine; Calabrese, Kelly; Robinson, Howard; Ladner, Jane E.

2008-01-01

Pyocyanin is a biologically active phenazine produced by the human pathogen Pseudomonas aeruginosa. It is thought to endow P. aeruginosa with a competitive growth advantage in colonized tissue and is also thought to be a virulence factor in diseases such as cystic fibrosis and AIDS where patients are commonly infected by pathogenic Pseudomonads due to their immunocompromised state. Pyocyanin is also a chemically interesting compound due to its unusual oxidation-reduction activity. Phenazine-1-carboxylic acid, the precursor to the bioactive phenazines, is synthesized from chorismic acid by enzymes encoded in a seven-gene cistron in Pseudomonas aeruginosa and in other Pseudomonads. Phenzine-1-carboxylic acid is believed to be converted to pyocyanin by the sequential actions of the putative S-adenosylmethionine dependent N-methyltransferase PhzM and the putative flavin-dependent hydroxylase PhzS. Here we report the 1.8 Å crystal structure of PhzM solved by single anomalous dispersion. Unlike many methyltransferases, PhzM is a dimer in solution. The 36 kDa PhzM polypeptide folds into three domains. The C-terminal domain exhibits the α/β-hydrolase fold typical of small molecule methyltransferases. Two smaller N-terminal domains form much of the dimer interface. Structural alignments with known methyltransferases show that PhzM is most similar to the plant O-methyltransferases that are characterized by an unusual intertwined dimer interface. The structure of PhzM contains no ligands and the active site is open and solvent exposed when compared to structures of similar enzymes. In vitro experiments using purified PhzM alone demonstrate that it has little or no ability to methylate phenzine-1-carboxylic acid. However, when the putative hydroxylase PhzS is included, pyocyanin is readily produced. This observation suggests that a mechanism has evolved in P. aeruginosa that ensures efficient production of pyocyanin by preventing the formation and release of an unstable and potentially deleterious intermediate. PMID:17253782

Compound eye and ocellar structure for walking and flying modes of locomotion in the Australian ant, Camponotus consobrinus

PubMed Central

Narendra, Ajay; Ramirez-Esquivel, Fiorella; Ribi, Willi A.

2016-01-01

Ants are unusual among insects in that individuals of the same species within a single colony have different modes of locomotion and tasks. We know from walking ants that vision plays a significant role in guiding this behaviour, but we know surprisingly little about the potential contribution of visual sensory structures for a flying mode of locomotion. Here we investigate the structure of the compound eye and ocelli in pedestrian workers, alate females and alate males of an Australian ant, Camponotus consobrinus, and discuss the trade-offs involved in optical sensitivity and spatial resolution. Male ants have more but smaller ommatidia and the smallest interommatidial angles, which is most likely an adaptation to visually track individual flying females. Both walking and flying forms of ants have a similar proportion of specialized receptors sensitive to polarized skylight, but the absolute number of these receptors varies, being greatest in males. Ocelli are present only in the flying forms. Each ocellus consists of a bipartite retina with a horizon-facing dorsal retina, which contains retinula cells with long rhabdoms, and a sky-facing ventral retina with shorter rhabdoms. We discuss the implications of these and their potential for sensing the pattern of polarized skylight. PMID:26975481

Compound eye and ocellar structure for walking and flying modes of locomotion in the Australian ant, Camponotus consobrinus.

PubMed

Narendra, Ajay; Ramirez-Esquivel, Fiorella; Ribi, Willi A

2016-03-15

Ants are unusual among insects in that individuals of the same species within a single colony have different modes of locomotion and tasks. We know from walking ants that vision plays a significant role in guiding this behaviour, but we know surprisingly little about the potential contribution of visual sensory structures for a flying mode of locomotion. Here we investigate the structure of the compound eye and ocelli in pedestrian workers, alate females and alate males of an Australian ant, Camponotus consobrinus, and discuss the trade-offs involved in optical sensitivity and spatial resolution. Male ants have more but smaller ommatidia and the smallest interommatidial angles, which is most likely an adaptation to visually track individual flying females. Both walking and flying forms of ants have a similar proportion of specialized receptors sensitive to polarized skylight, but the absolute number of these receptors varies, being greatest in males. Ocelli are present only in the flying forms. Each ocellus consists of a bipartite retina with a horizon-facing dorsal retina, which contains retinula cells with long rhabdoms, and a sky-facing ventral retina with shorter rhabdoms. We discuss the implications of these and their potential for sensing the pattern of polarized skylight.

Attachment site recognition and regulation of directionality by the serine integrases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rutherford, Karen; Yuan, Peng; Perry, Kay

Serine integrases catalyze the integration of bacteriophage DNA into a host genome by site-specific recombination between ‘attachment sites’ in the phage ( attP ) and the host ( attB ). The reaction is highly directional; the reverse excision reaction between the product attL and attR sites does not occur in the absence of a phage-encoded factor, nor does recombination occur between other pairings of attachment sites. A mechanistic understanding of how these enzymes achieve site-selectivity and directionality has been limited by a lack of structural models. Here, we report the structure of the C-terminal domains of a serine integrase boundmore » to an attP DNA half-site. The structure leads directly to models for understanding how the integrase-bound attP and attB sites differ, why these enzymes preferentially form attP × attB synaptic complexes to initiate recombination, and how attL × attR recombination is prevented. In these models, different domain organizations on attP vs. attB half-sites allow attachment-site specific interactions to form between integrase subunits via an unusual protruding coiled-coil motif. These interactions are used to preferentially synapse integrase-bound attP and attB and inhibit synapsis of integrase-bound attL and attR . The results provide a structural framework for understanding, testing and engineering serine integrase function.« less

Identification of a Unique Fe-S Cluster Binding Site in a Glycyl-Radical Type Microcompartment Shell Protein

PubMed Central

Thompson, Michael C.; Wheatley, Nicole M.; Jorda, Julien; Sawaya, Michael R.; Gidaniyan, Soheil D.; Ahmed, Hoda; Yang, Zhongyu; McCarty, Krystal N.; Whitelegge, Julian P.; Yeates, Todd O.

2014-01-01

Recently, progress has been made toward understanding the functional diversity of bacterial microcompartment (MCP) systems, which serve as protein-based metabolic organelles in diverse microbes. New types of MCPs have been identified, including the glycyl-radical propanediol (Grp) MCP. Within these elaborate protein complexes, BMC-domain shell proteins assemble to form a polyhedral barrier that encapsulates the enzymatic contents of the MCP. Interestingly, the Grp MCP contains a number of shell proteins with unusual sequence features. GrpU is one such shell protein, whose amino acid sequence is particularly divergent from other members of the BMC-domain superfamily of proteins that effectively defines all MCPs. Expression, purification, and subsequent characterization of the protein showed, unexpectedly, that it binds an iron-sulfur cluster. We determined X-ray crystal structures of two GrpU orthologs, providing the first structural insight into the homohexameric BMC-domain shell proteins of the Grp system. The X-ray structures of GrpU, both obtained in the apo form, combined with spectroscopic analyses and computational modeling, show that the metal cluster resides in the central pore of the BMC shell protein at a position of broken 6-fold symmetry. The result is a structurally polymorphic iron-sulfur cluster binding site that appears to be unique among metalloproteins studied to date. PMID:25102080

Structural Insights into the Unusually Strong ATPase Activity of the AAA Domain of the Caenorhabditis elegans Fidgetin-like 1 (FIGL-1) Protein*

PubMed Central

Peng, Wentao; Lin, Zhijie; Li, Weirong; Lu, Jing; Shen, Yuequan; Wang, Chunguang

2013-01-01

The FIGL-1 (fidgetin like-1) protein is a homolog of fidgetin, a protein whose mutation leads to multiple developmental defects. The FIGL-1 protein contains an AAA (ATPase associated with various activities) domain and belongs to the AAA superfamily. However, the biological functions and developmental implications of this protein remain unknown. Here, we show that the AAA domain of the Caenorhabditis elegans FIGL-1 protein (CeFIGL-1-AAA), in clear contrast to homologous AAA domains, has an unusually high ATPase activity and forms a hexamer in solution. By determining the crystal structure of CeFIGL-1-AAA, we found that the loop linking helices α9 and α10 folds into the short helix α9a, which has an acidic surface and interacts with a positively charged surface of the neighboring subunit. Disruption of this charge interaction by mutagenesis diminishes both the ATPase activity and oligomerization capacity of the protein. Interestingly, the acidic residues in helix α9a of CeFIGL-1-AAA are not conserved in other homologous AAA domains that have relatively low ATPase activities. These results demonstrate that the sequence of CeFIGL-1-AAA has adapted to establish an intersubunit charge interaction, which contributes to its strong oligomerization and ATPase activity. These unique properties of CeFIGL-1-AAA distinguish it from other homologous proteins, suggesting that CeFIGL-1 may have a distinct biological function. PMID:23979136

Structural insights into the unusually strong ATPase activity of the AAA domain of the Caenorhabditis elegans fidgetin-like 1 (FIGL-1) protein.

PubMed

Peng, Wentao; Lin, Zhijie; Li, Weirong; Lu, Jing; Shen, Yuequan; Wang, Chunguang

2013-10-11

The FIGL-1 (fidgetin like-1) protein is a homolog of fidgetin, a protein whose mutation leads to multiple developmental defects. The FIGL-1 protein contains an AAA (ATPase associated with various activities) domain and belongs to the AAA superfamily. However, the biological functions and developmental implications of this protein remain unknown. Here, we show that the AAA domain of the Caenorhabditis elegans FIGL-1 protein (CeFIGL-1-AAA), in clear contrast to homologous AAA domains, has an unusually high ATPase activity and forms a hexamer in solution. By determining the crystal structure of CeFIGL-1-AAA, we found that the loop linking helices α9 and α10 folds into the short helix α9a, which has an acidic surface and interacts with a positively charged surface of the neighboring subunit. Disruption of this charge interaction by mutagenesis diminishes both the ATPase activity and oligomerization capacity of the protein. Interestingly, the acidic residues in helix α9a of CeFIGL-1-AAA are not conserved in other homologous AAA domains that have relatively low ATPase activities. These results demonstrate that the sequence of CeFIGL-1-AAA has adapted to establish an intersubunit charge interaction, which contributes to its strong oligomerization and ATPase activity. These unique properties of CeFIGL-1-AAA distinguish it from other homologous proteins, suggesting that CeFIGL-1 may have a distinct biological function.

Micelle structure in a deep eutectic solvent: a small-angle scattering study.

PubMed

Sanchez-Fernandez, A; Edler, K J; Arnold, T; Heenan, R K; Porcar, L; Terrill, N J; Terry, A E; Jackson, A J

2016-05-18

In recent years many studies into green solvents have been undertaken and deep eutectic solvents (DES) have emerged as sustainable and green alternatives to conventional solvents since they may be formed from cheap non-toxic organic precursors. In this study we examine amphiphile behaviour in these novel media to test our understanding of amphiphile self-assembly within environments that have an intermediate polarity between polar and non-polar extremes. We have built on our recently published results to present a more detailed structural characterisation of micelles of sodium dodecylsulfate (SDS) within the eutectic mixture of choline chloride and urea. Here we show that SDS adopts an unusual cylindrical aggregate morphology, unlike that seen in water and other polar solvents. A new morphology transition to shorter aggregates was found with increasing concentration. The self-assembly of SDS was also investigated in the presence of water; which promotes the formation of shorter aggregates.

A spin-liquid with pinch-line singularities on the pyrochlore lattice.

PubMed

Benton, Owen; Jaubert, L D C; Yan, Han; Shannon, Nic

2016-05-26

The mathematics of gauge theories lies behind many of the most profound advances in physics in the past 200 years, from Maxwell's theory of electromagnetism to Einstein's theory of general relativity. More recently it has become clear that gauge theories also emerge in condensed matter, a prime example being the spin-ice materials which host an emergent electromagnetic gauge field. In spin-ice, the underlying gauge structure is revealed by the presence of pinch-point singularities in neutron-scattering measurements. Here we report the discovery of a spin-liquid where the low-temperature physics is naturally described by the fluctuations of a tensor field with a continuous gauge freedom. This gauge structure underpins an unusual form of spin correlations, giving rise to pinch-line singularities: line-like analogues of the pinch points observed in spin-ice. Remarkably, these features may already have been observed in the pyrochlore material Tb2Ti2O7.

A spin-liquid with pinch-line singularities on the pyrochlore lattice

PubMed Central

Benton, Owen; Jaubert, L.D.C.; Yan, Han; Shannon, Nic

2016-01-01

The mathematics of gauge theories lies behind many of the most profound advances in physics in the past 200 years, from Maxwell's theory of electromagnetism to Einstein's theory of general relativity. More recently it has become clear that gauge theories also emerge in condensed matter, a prime example being the spin-ice materials which host an emergent electromagnetic gauge field. In spin-ice, the underlying gauge structure is revealed by the presence of pinch-point singularities in neutron-scattering measurements. Here we report the discovery of a spin-liquid where the low-temperature physics is naturally described by the fluctuations of a tensor field with a continuous gauge freedom. This gauge structure underpins an unusual form of spin correlations, giving rise to pinch-line singularities: line-like analogues of the pinch points observed in spin-ice. Remarkably, these features may already have been observed in the pyrochlore material Tb2Ti2O7. PMID:27225400

An unusual mode of DNA duplex association: Watson-Crick interaction of all-purine deoxyribonucleic acids.

PubMed

Battersby, Thomas R; Albalos, Maria; Friesenhahn, Michel J

2007-05-01

Nucleic acid duplexes associating through purine-purine base pairing have been constructed and characterized in a remarkable demonstration of nucleic acids with mixed sequence and a natural backbone in an alternative duplex structure. The antiparallel deoxyribose all-purine duplexes associate specifically through Watson-Crick pairing, violating the nucleobase size-complementarity pairing convention found in Nature. Sequence-specific recognition displayed by these structures makes the duplexes suitable, in principle, for information storage and replication fundamental to molecular evolution in all living organisms. All-purine duplexes can be formed through association of purines found in natural ribonucleosides. Key to the formation of these duplexes is the N(3)-H tautomer of isoguanine, preferred in the duplex, but not in aqueous solution. The duplexes have relevance to evolution of the modern genetic code and can be used for molecular recognition of natural nucleic acids.

Structures of the glycopeptidolipid antigens of two animal pathogens: Mycobacterium senegalense and Mycobacterium porcinum.

PubMed

López Marín, L M; Lanéelle, M A; Promé, D; Daffé, M

1993-08-01

The structures of the major glycolipid antigens of two animal pathogens Mycobacterium senegalense and Mycobacterium porcinum were elucidated by a combination of fast-atom bombardment mass spectrometry, nuclear magnetic resonance spectroscopy, chemical analyses and radiolabeling experiments. Five glycoconjugates belonging to the class of C-mycoside glycopeptidolipids were characterized in each species. They shared with those recently described in M. peregrinum the same unusual distribution of the disaccharides on the alaninol end of the molecules. Both species showed the presence of the novel sulfated glycopeptidolipid. In addition, some acetylated forms of the glycolipids were also present in the species examined. Identical seroreactivities were observed between the glycolipid antigens extracted from M. senegalense, M. porcinum and M. peregrinum and an antiserum raised against the whole lipid antigens of M. peregrinum. These data reinforce the close taxonomic relationships between the three mycobacterial species and demonstrate the antigenicity of the new variants of mycobacterial glycopeptidolipids.

Exciton characteristics in graphene epoxide.

PubMed

Zhu, Xi; Su, Haibin

2014-02-25

Exciton characteristics in graphene epoxide (GE) are investigated by density functional theory with quasi-particle corrections and many-body interactions. The nature of the exciton is influenced by epoxide content and detailed geometric configurations. Two kinds of excitons are identified in GE: Frenkel-like exciton originated from the sp(2) carbon cluster and charge-transfer exciton formed by localized states involving both oxygen and carbon atoms. The unusual blue shift associated with the Frenkel-like exciton leaking is highlighted. One scaling relationship is proposed to address the power-law dependence of Frenkel-like exciton binding strength on its size. The charge-transfer exciton appears in GE samples with the high oxygen coverage. Particularly, the exciton in GE structures exhibits long lifetime by analyzing both radiative and nonradiative decay processes. This study sheds light on the potential applications of GE-based structures with attractive high quantum yield in light emission and optoelectronic technology.

Apparatus for forming adobe bricks and drilling wells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kinnamon, H. D.

1985-02-12

An improved apparatus for the continuous and relatively labor-free fabrication of adobe bricks and the forcing of well casings into the earth. With regard to forming adobe bricks, a rotating table carries the bricks being processed from one station to the next and a novel means for applying unusually high forming pressures permits immediate forming and ejection of the bricks from the forms while at the same time producing adobe bricks of improved quality and hardness characteristics.

Crystal Structures of Phosphite Dehydrogenase Provide Insights into Nicotinamide Cofactor Regeneration

PubMed Central

Zou, Yaozhong; Zhang, Houjin; Brunzelle, Joseph S.; Johannes, Tyler W.; Woodyer, Ryan; Hung, John E.; Nair, Nikhil; van der Donk, Wilfred A.; Zhao, Huimin; Nair, Satish K.

2015-01-01

The enzyme phosphite dehydrogenase (PTDH) catalyzes the NAD+-dependent conversion of phosphite to phosphate and represents the first biological catalyst that has been characterized to carry out the enzymatic oxidation of phosphorus. Despite over a decade’s worth of investigation into both the mechanism of its unusual reaction, as well as its utility in cofactor regeneration, there has been a lack of any structural data on PTDH. Here we present the co-crystal structure of an engineered thermostable variant of PTDH bound to NAD+ (1.7 Å resolution), as well as four other co-crystal structures of thermostable PTDH and its variants with different ligands (all between 1.85 – 2.3 Å resolution). These structures provide a molecular framework for understanding prior mutational analysis, and point to additional residues, located in the active site, that may contribute to the enzymatic activity of this highly unusual catalyst. PMID:22564171

The unusual and dynamic character of PX-DNA

DOE PAGES

Niu, Dong; Jiang, Hualin; Sha, Ruojie; ...

2015-07-15

PX-DNA is a four-stranded DNA structure that has been implicated in the recognition of homology, either continuously, or in an every-other-half-turn fashion. Some of the structural features of the molecule have been noted previously, but the structure requires further characterization. Here, we report atomic force microscopic characterization of PX molecules that contain periodically placed biotin groups, enabling the molecule to be labeled by streptavidin molecules at these sites. In comparison with conventional double stranded DNA and with antiparallel DNA double crossover molecules, it is clear that PX-DNA is a more dynamic structure. Moreover, the spacing between the nucleotide pairs alongmore » the helix axis is shorter, suggesting a mixed B/A structure. Circular dichroism spectroscopy indicates unusual features in the PX molecule that are absent in both the molecules to which it is compared.« less

Crystal Structures of Phosphite Dehydrogenase Provide Insights into Nicotinamide Cofactor Regeneration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zou, Yaozhong; Zhang, Houjin; Brunzelle, Joseph S.

The enzyme phosphite dehydrogenase (PTDH) catalyzes the NAD{sup +}-dependent conversion of phosphite to phosphate and represents the first biological catalyst that has been shown to conduct the enzymatic oxidation of phosphorus. Despite investigation for more than a decade into both the mechanism of its unusual reaction and its utility in cofactor regeneration, there has been a lack of any structural data for PTDH. Here we present the cocrystal structure of an engineered thermostable variant of PTDH bound to NAD{sup +} (1.7 {angstrom} resolution), as well as four other cocrystal structures of thermostable PTDH and its variants with different ligands (allmore » between 1.85 and 2.3 {angstrom} resolution). These structures provide a molecular framework for understanding prior mutational analysis and point to additional residues, located in the active site, that may contribute to the enzymatic activity of this highly unusual catalyst.« less

14 CFR 29.307 - Proof of structure.

Code of Federal Regulations, 2010 CFR

2010-01-01

... loading condition accounting for the environment to which the structure will be exposed in operation... measurement tests; (5) Landing gear drop tests; and (6) Any additional tests required for new or unusual...

Tarsal tunnel syndrome

MedlinePlus

Tibial nerve dysfunction; Neuropathy - posterior tibial nerve; Peripheral neuropathy - tibial nerve; Tibial nerve entrapment ... Tarsal tunnel syndrome is an unusual form of peripheral neuropathy . It occurs when there is damage to the ...

Mechanism for the occurrence of paramagnetic planes within magnetically ordered cerium systems

NASA Astrophysics Data System (ADS)

Kioussis, Nicholas; Cooper, Bernard R.; Banerjea, Amitava

1988-11-01

Hybridization of moderately delocalized f electrons with band electrons gives rise to a highly anisotropic two-ion interaction. Previously it has been shown that such an interaction explains the experimentally observed unusual magnetic behavior of CeBi, yielding a phase transition from a higher-temperature type-I (↑↓) to a lower-temperature type-IA (↑↑↓↓) antiferromagnetic structure. If the hybridization-mediated interaction is the key to understanding the magnetic behavior of such moderately delocalized f-electron systems, we should expect to be able to understand on this basis the even more unusual magnetic behavior of CeSb. In CeSb, there is a sequence of magnetic structures in which the higher-temperature structures involve a periodic stacking of paramagnetic \\{001\\} planes alternating with magnetically ordered \\{001\\} planes of [001]-moment alignment. In this paper we show that such a coexistence of paramagnetic and magnetically ordered Ce3+ sites can be understood on the basis of the hybridization-mediated interionic interaction when there are cubic crystal-field (CF) interactions of comparable strength. The tendency to form paramagnetic planes is found to increase with increasing CF strength (Γ7 ground state); and the stability of the up-down paramagnetic plane arrangement at high temperatures is shown to arise from the reconciliation of the magnetic ordering with the CF interactions. We also find that for a certain range of parameters a different novel situation occurs, with a fully nonmagnetic (singlet) ground state for the Ce3+ ion. This singlet state is not Kondo-like, and occurs in such a way that the system would be expected to fluctuate between two differently polarized states, one of which is the singlet state.

Hemocyanin of the molluscan Concholepas concholepas exhibits an unusual heterodecameric array of subunits.

PubMed

De Ioannes, Pablo; Moltedo, Bruno; Oliva, Harold; Pacheco, Rodrigo; Faunes, Fernando; De Ioannes, Alfredo E; Becker, María Inés

2004-06-18

We describe here the structure of the hemocyanin from the Chilean gastropod Concholepas concholepas (CCH), emphasizing some attributes that make it interesting among molluscan hemocyanins. CCH exhibits a predominant didecameric structure as revealed by electron microscopy and a size of 8 MDa by gel filtration, and, in contrast with other mollusc hemocyanins, its stabilization does not require additional Ca(2+) and/or Mg(2+) in the medium. Polyacrylamide gel electrophoresis studies, analyses by a MonoQ FPLC column, and Western blots with specific monoclonal antibodies showed that CCH is made by two subunits noncovalently linked, named CCH-A and CCH-B, with molecular masses of 405 and 350 kDa, respectively. Interestingly, one of the subunits undergoes changes within the macromolecule; we demonstrated that CCH-A has an autocleavage site that under reducing conditions is cleaved to yield two polypeptides, CCH-A1 (300 kDa) and CCH-A2 (108 kDa), whereas CCH-B remains unchanged. The CCH-A nick occurs at 4 degrees C, increases at 37 degrees C, and is not inhibited by the addition of protease inhibitors and/or divalent cations. Since the CCH structure is a heterodimer, we investigated whether subunits would be either intermingled, forming heterodecamers, or assembled as two homogeneous decamers. Light scattering and electron microscope studies of the in vitro reassociation of purified CCH subunits demonstrated that the sole addition of Mg(2+) is needed for its reassembly into the native decameric molecule; no homodecamer reorganization was found with either CCH-A or CCH-B subunits alone. Our evidence showed that C. concholepas hemocyanin is an unusual example of heterodecameric organization.

The structure of human SFPQ reveals a coiled-coil mediated polymer essential for functional aggregation in gene regulation

PubMed Central

Lee, Mihwa; Sadowska, Agata; Bekere, Indra; Ho, Diwei; Gully, Benjamin S.; Lu, Yanling; Iyer, K. Swaminathan; Trewhella, Jill; Fox, Archa H.; Bond, Charles S.

2015-01-01

SFPQ, (a.k.a. PSF), is a human tumor suppressor protein that regulates many important functions in the cell nucleus including coordination of long non-coding RNA molecules into nuclear bodies. Here we describe the first crystal structures of Splicing Factor Proline and Glutamine Rich (SFPQ), revealing structural similarity to the related PSPC1/NONO heterodimer and a strikingly extended structure (over 265 Å long) formed by an unusual anti-parallel coiled-coil that results in an infinite linear polymer of SFPQ dimers within the crystals. Small-angle X-ray scattering and transmission electron microscopy experiments show that polymerization is reversible in solution and can be templated by DNA. We demonstrate that the ability to polymerize is essential for the cellular functions of SFPQ: disruptive mutation of the coiled-coil interaction motif results in SFPQ mislocalization, reduced formation of nuclear bodies, abrogated molecular interactions and deficient transcriptional regulation. The coiled-coil interaction motif thus provides a molecular explanation for the functional aggregation of SFPQ that directs its role in regulating many aspects of cellular nucleic acid metabolism. PMID:25765647

Crystal structures of the CPAP/STIL complex reveal its role in centriole assembly and human microcephaly

PubMed Central

Cottee, Matthew A; Muschalik, Nadine; Wong, Yao Liang; Johnson, Christopher M; Johnson, Steven; Andreeva, Antonina; Oegema, Karen; Lea, Susan M; Raff, Jordan W; van Breugel, Mark

2013-01-01

Centrioles organise centrosomes and template cilia and flagella. Several centriole and centrosome proteins have been linked to microcephaly (MCPH), a neuro-developmental disease associated with small brain size. CPAP (MCPH6) and STIL (MCPH7) are required for centriole assembly, but it is unclear how mutations in them lead to microcephaly. We show that the TCP domain of CPAP constitutes a novel proline recognition domain that forms a 1:1 complex with a short, highly conserved target motif in STIL. Crystal structures of this complex reveal an unusual, all-β structure adopted by the TCP domain and explain how a microcephaly mutation in CPAP compromises complex formation. Through point mutations, we demonstrate that complex formation is essential for centriole duplication in vivo. Our studies provide the first structural insight into how the malfunction of centriole proteins results in human disease and also reveal that the CPAP–STIL interaction constitutes a conserved key step in centriole biogenesis. DOI: http://dx.doi.org/10.7554/eLife.01071.001 PMID:24052813

Negative-pressure polymorphs made by heterostructural alloying

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siol, Sebastian; Holder, Aaron; Steffes, James

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures - a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixingmore » two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2x to 4x lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. Lastly, this example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties - materials that are otherwise nearly impossible to make.« less

Inherent flexibility of CLIC6 revealed by crystallographic and solution studies.

PubMed

Ferofontov, Alisa; Strulovich, Roi; Marom, Milit; Giladi, Moshe; Haitin, Yoni

2018-05-02

Chloride intracellular channels (CLICs) are a family of unique proteins, that were suggested to adopt both soluble and membrane-associated forms. Moreover, following this unusual metamorphic change, CLICs were shown to incorporate into membranes and mediate ion conduction in vitro, suggesting multimerization upon membrane insertion. Here, we present a 1.8 Å resolution crystal structure of the CLIC domain of mouse CLIC6 (mCLIC6). The structure reveals a monomeric arrangement and shows a high degree of structural conservation with other CLICs. Small-angle X-ray scattering (SAXS) analysis of mCLIC6 demonstrated that the overall solution structure is similar to the crystallographic conformation. Strikingly, further analysis of the SAXS data using ensemble optimization method unveiled additional elongated conformations, elucidating high structural plasticity as an inherent property of the protein. Moreover, structure-guided perturbation of the inter-domain interface by mutagenesis resulted in a population shift towards elongated conformations of mCLIC6. Additionally, we demonstrate that oxidative conditions induce an increase in mCLIC6 hydrophobicity along with mild oligomerization, which was enhanced by the presence of membrane mimetics. Together, these results provide mechanistic insights into the metamorphic nature of mCLIC6.

Negative-pressure polymorphs made by heterostructural alloying

DOE PAGES

Siol, Sebastian; Holder, Aaron; Steffes, James; ...

2018-04-20

The ability of a material to adopt multiple structures, known as polymorphism, is a fascinating natural phenomenon. Various polymorphs with unusual properties are routinely synthesized by compression under positive pressure. However, changing a material's structure by applying tension under negative pressure is much more difficult. We show how negative-pressure polymorphs can be synthesized by mixing materials with different crystal structures - a general approach that should be applicable to many materials. Theoretical calculations suggest that it costs less energy to mix low-density structures than high-density structures, due to less competition for space between the atoms. Proof-of-concept experiments confirm that mixingmore » two different high-density forms of MnSe and MnTe stabilizes a Mn(Se,Te) alloy with a low-density wurtzite structure. This Mn(Se,Te) negative-pressure polymorph has 2x to 4x lower electron effective mass compared to MnSe and MnTe parent compounds and has a piezoelectric response that none of the parent compounds have. Lastly, this example shows how heterostructural alloying can lead to negative-pressure polymorphs with useful properties - materials that are otherwise nearly impossible to make.« less

Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption.

PubMed

Wu, Hui; Chua, Yong Shen; Krungleviciute, Vaiva; Tyagi, Madhusudan; Chen, Ping; Yildirim, Taner; Zhou, Wei

2013-07-17

UiO-66 is a highly important prototypical zirconium metal-organic framework (MOF) compound because of its excellent stabilities not typically found in common porous MOFs. In its perfect crystal structure, each Zr metal center is fully coordinated by 12 organic linkers to form a highly connected framework. Using high-resolution neutron power diffraction technique, we found the first direct structural evidence showing that real UiO-66 material contains significant amount of missing-linker defects, an unusual phenomenon for MOFs. The concentration of the missing-linker defects is surprisingly high, ∼10% in our sample, effectively reducing the framework connection from 12 to ∼11. We show that by varying the concentration of the acetic acid modulator and the synthesis time, the linker vacancies can be tuned systematically, leading to dramatically enhanced porosity. We obtained samples with pore volumes ranging from 0.44 to 1.0 cm(3)/g and Brunauer-Emmett-Teller surface areas ranging from 1000 to 1600 m(2)/g, the largest values of which are ∼150% and ∼60% higher than the theoretical values of defect-free UiO-66 crystal, respectively. The linker vacancies also have profound effects on the gas adsorption behaviors of UiO-66, in particular CO2. Finally, comparing the gas adsorption of hydroxylated and dehydroxylated UiO-66, we found that the former performs systematically better than the latter (particularly for CO2) suggesting the beneficial effect of the -OH groups. This finding is of great importance because hydroxylated UiO-66 is the practically more relevant, non-air-sensitive form of this MOF. The preferred gas adsorption on the metal center was confirmed by neutron diffraction measurements, and the gas binding strength enhancement by the -OH group was further supported by our first-principles calculations.

Skin, ear and testis--unusual sites of tuberculosis.

PubMed

Ene, Cătălina Elena; Toma, Claudia; Belaconi, Ionela; Dumitrache-Rujinski, Stefan; Jipa, Daniela; Tudor, Adrian; Leonte, Diana; Bogdan, Miron Alexandru

2016-01-01

Pulmonary localization is the most common site of tuberculosis (TB)and the most contagious form. Extrapulmonary tuberculosis with the rarest and most unexpected localizations represents a significant proportion of all cases of tuberculosis and remains an important public health problem. We report three unusual TB locations: skin, ear and testis occurred in three immunocompetent patients. In the case of skin and testicular lesions, diagnosis was based on pathological confirmation of granulomas with caseous necrosis. In the third case the diagnosis was made possible by identification of positive Acid-Fast Bacilli smear and positive culture from othic drainage fluid. The outcome at all three patients was good with antituberculous treatment. These unusual localization of tuberculosis also highlight the possibility of extrapulmonary tuberculosis as a differential diagnosis in many common diseases.

14 CFR 27.307 - Proof of structure.

Code of Federal Regulations, 2010 CFR

2010-01-01

... loading condition accounting for the environment to which the structure will be exposed in operation... measurement tests; (5) Landing gear drop tests; and (6) Any additional test required for new or unusual design...

Sun Allergy

MedlinePlus

... occurs on skin that has been exposed to sunlight. The most common form of sun allergy is ... have unusual, bothersome skin reactions after exposure to sunlight. For severe or persistent symptoms, you may need ...

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

NASA Astrophysics Data System (ADS)

Kelp, G.; Tätte, T.; Pikker, S.; Mändar, H.; Rozhin, A. G.; Rauwel, P.; Vanetsev, A. S.; Gerst, A.; Merisalu, M.; Mäeorg, U.; Natali, M.; Persson, I.; Kessler, V. G.

2016-03-01

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300 °C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400 °C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped. Electronic supplementary information (ESI) available: IR spectrum of additives found in the residual butanol layer formed during precursor preparation. See DOI: 10.1039/c5nr07942j

Live celloidosome structures based on the assembly of individual cells by colloid interactions.

PubMed

Fakhrullin, Rawil F; Brandy, Marie-Laure; Cayre, Olivier J; Velev, Orlin D; Paunov, Vesselin N

2010-10-14

A new class of colloid structures, celloidosomes, has been developed which represent hollow microcapsules whose membranes consist of a single monolayer of living cells. Two routes for producing these structures were designed based on templating of: (i) air bubbles and (ii) anisotropic microcrystals of calcium carbonate with living cells, which allowed us to fabricate celloidosomes of spherical, rhombohedral and needle-like morphologies. Air microbubbles were templated by yeast cells coated with poly(allylamine hydrochloride) (PAH), then coated with carboxymethylcellulose and rehydrated resulting in the formation of spherical multicellular structures. Similarly, calcium carbonate microcrystals of anisotropic shapes were coated with several consecutive layers of oppositely charged polyelectrolytes to obtain a positive surface charge which was used to immobilise yeast cells coated with anionic polyelectrolyte of their surfaces. After dissolving of sacrificial cores, hollow multicellular structures were obtained. The viability of the cells in the produced structures was confirmed by using fluorescein diacetate. In order to optimize the separation of celloidosomes from free cells magnetic nanoparticles were immobilised onto the surface of templates prior to the cells deposition, which greatly facilitated the separation using a permanent magnet. Two alternative approaches were developed to form celloidosome structures using magnetically functionalised core-shell microparticles which resulted in the formation of celloidosomes with needle-like and cubic-like geometries which follows the original morphology of the calcium carbonate microcrystals. Our methods for fabrication of celloidosomes may found applications in the development of novel symbiotic bio-structures, artificial multicellular organisms and in tissue engineering. The unusual structure of celloidosomes resembles the primitive forms of multicellular species, like Volvox, and other algae and could be regarded as one possible mechanism of the evolutionary development of multicellularity.

Chinese Graduate Students' Perspectives on Home Schooling

ERIC Educational Resources Information Center

Romanowski, Michael H.

2007-01-01

Although an established alternative form of American education, the concept of home schooling is just beginning to surface in China. Few Chinese have knowledge of home schooling yet alone consider this form of education. However, graduate students studying in the field of education are aware of this unusual alternative to traditional schooling,…

Processing of fish lg heavy chain transcripts diverse splicing patterns and unusual nonsense mediated decay

USDA-ARS?s Scientific Manuscript database

Alternate pathways of RNA processing play an important role in the expression of the secreted (S) and membrane (Mb) forms of immunoglobulin (Ig) heavy (H) chain isotypes in all vertebrates. Interestingly, while the differential splicing mechanism and the splice sites that generate the two forms of I...

AN UNUSUAL PATTERN OF GENE FLOW BETWEEN THE TWO SOCIAL FORMS OF THE FIRE ANT SOLENOPSIS INVICTA.

PubMed

Ross, Kenneth G; Shoemaker, D DeWayne

1993-10-01

Uncertainty over the role of shifts in social behavior in the process of speciation in social insects has stimulated interest in determining the extent of gene flow between conspecific populations differing in colony social organization. Allele and genotype frequencies at 12 neutral polymorphic protein markers, as well as the numbers of alleles at the sex-determining locus (loci), are shown here to be consistent with significant ongoing gene flow between two geographically adjacent populations of Solenopsis invicta that differ in colony queen number. Data from a thirteenth protein marker that is under strong differential selection in the two social forms confirm that such gene flow occurs. Data from this selected locus, combined with knowledge of the reproductive biology of the two social forms, further suggest that interform gene flow is largely unidirectional and mediated through males only. This unusual pattern of gene flow results from the influence of the unique social enviroments of the two forms on the behavior of workers and on the reproductive physiology of sexuals. © 1993 The Society for the Study of Evolution.

Enantioseparation of angiotensin II receptor type 1 blockers: evaluation of 6-substituted carbamoyl benzimidazoles on immobilized polysaccharide-based chiral stationary phases. Unusual temperature behavior.

PubMed

Su, Ran; Hou, Zhun; Sang, Lihong; Zhou, Zhi-Ming; Fang, Hao; Yang, Xinying

2017-09-15

Enantioseparation of thirteen 6-substituted carbamoyl benzimidazoles by high-performance liquid chromatography (HPLC) was investigated using two immobilized polysaccharide-based chiral stationary phases (CSPs), Chiralpak IC and Chiralpak IA, in normal-phase mode. Most of the examined compounds were completely resolved. The effects of a polar alcohol modifier, analyte structure, and column temperature on the chiral recognition were investigated. Furthermore, the structure-retention relationship was evaluated, and thermodynamic parameters were calculated from plots of ln k' or ln α versus 1/T. The thermodynamic parameters indicated that the separations were enthalpy-driven. Moreover, nonlinear van't Hoff plots were obtained on Chiralpak IA. However, two unusual phenomena were observed: (1) an unusual increase in retention with increasing temperature with linear van't Hoff plots on Chiralpak IC and (2) an extremely high T iso value (i.e., several thousand degrees centigrade). Copyright © 2017 Elsevier B.V. All rights reserved.

Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stadie, Nicholas P.; Murialdo, Maxwell; Ahn, Channing C.

2015-11-25

Methane adsorption at high pressures and across a wide range of temperatures was investigated on the surface of three porous carbon adsorbents with complementary structural properties. The measured adsorption equilibria were analyzed using a method that can accurately account for nonideal fluid properties and distinguish between absolute and excess quantities of adsorption, and that also allows the direct calculation of the thermodynamic potentials relevant to adsorption. On zeolite-templated carbon (ZTC), a material that exhibits extremely high surface area with optimal pore size and homogeneous structure, methane adsorption occurs with unusual thermodynamic properties that are greatly beneficial for deliverable gas storage:more » an enthalpy of adsorption that increases with site occupancy, and an unusually low entropy of the adsorbed phase. The origin of these properties is elucidated by comparison of the experimental results with a statistical mechanical model. The results indicate that temperature-dependent clustering (i.e., reduced configurations) of the adsorbed phase due to enhanced lateral interactions can account for the peculiarities of methane adsorbed on ZTC.« less

Endodontic management of an unusual maxillary first molar with a single buccal root.

PubMed

Nayak, Gurudutt; Dahiya, Surya; Singh, Inderpreet; Mohammad, Faiz Hasan

2014-05-01

The aim of this clinical article is to describe the unusual anatomy that was detected in a maxillary first molar during routine endodontic treatment. Variation in Root and Root canal morphology especially in multirooted teeth presents a constant challenge for a clinician in their detection and management. The literature is replete with cases that have extra canal or Root but cases with fused Root and fewer numbers of canals are sparse. This case report describes the endodontic management of one such unusual case of maxillary first molar presenting with a single fused buccal and a palatal Root. The confirmatory diagnosis of this morphologic aberration was done with the help of spiral computerized tomography, which revealed that the contralateral tooth also had a similar morphology. Dental practitioners should always be aware of the fact that abnormalities need not be in form of extra Roots or Root canals; anomalies can also be in form of fewer number of Roots or Root canals. A thorough knowledge of the complexities and variations of the Root canal system would help in avoiding some of the common iatrogenic access opening errors like perforations and excessive tooth removal caused during the search for the missing or extracanal.

Structure, biosynthesis and function of unusual lipids A from nodule-inducing and N2-fixing bacteria.

PubMed

Choma, Adam; Komaniecka, Iwona; Zebracki, Kamil

2017-02-01

This review focuses on the chemistry and structures of (Brady)rhizobium lipids A, indispensable parts of lipopolysaccharides. These lipids contain unusual (ω-1) hydroxylated very long chain fatty acids, which are synthesized by a very limited group of bacteria, besides rhizobia. The significance and requirement of the very long chain fatty acids for outer membrane stability as well as the genetics of the synthesis pathway are discussed. The biological role of these fatty acids for bacterial life in extremely different environments (soil and intracellular space within nodules) is also considered. Copyright © 2016 Elsevier B.V. All rights reserved.

Descriptions and biological notes on three unusual mantellid tadpoles (Amphibia: Anura: Mantellidae) from southeastern Madagascar

USGS Publications Warehouse

Altig, R.; McDiarmid, R.W.

2006-01-01

The morphologies of three unusual tadpoles from slow-flowing, sandy-bottomed, rain forest streams in southeastern Madagascar are described. The large oral apparatus of the tadpole of Boophis picturatus Glaw, Vences, Andreone, and Vallan, 2001 lacks all keratinized structures and has an elaborately-folded lower labium with five, radially oriented, flattopped ridges. The tadpole of Mantidactylus guttulatus (Boulenger, 1881) lacks all keratinized mouthparts and has three immense papillae where the upper jaw normally occurs. The tadpole of Mantidactylus lugubris (Dumeril, 1853) has an ornate oral apparatus involving greatly hypertrophied derivatives of jaw serrations and unique structures on the lower labium that resemble labial teeth.

Microfibril angle in wood of Scots pine trees (Pinus sylvestris) after irradiation from the Chernobyl nuclear reactor accident.

PubMed

Tulik, Mirela; Rusin, Aleksandra

2005-03-01

The secondary cell wall structure of tracheids of Scots pine (Pinus sylvestris L.), especially the angle of microfibrils in the S(2) layer, was examined in wood deposited prior to and after the Chernobyl accident in 1986. Microscopic analysis was carried out on wood samples collected in October 1997 from breast height of three pine trees 16, 30 and 42 years old. The polluted site was located in a distance of 5 km south from the Chernobyl nuclear power plant where radioactive contamination in 1997 was 3.7 x 10(5) kBq m(-2). Anatomical analysis showed that the structure of the secondary cell wall in tracheids formed after the Chernobyl accident was changed. Changes occurred both in S(2) and S(3) layers. The angle of microfibrils in S(2) layer in wood deposited after the Chernobyl accident was different in comparison to this measured in wood formed prior to the disaster. The intensity of the changes, i.e. alteration of the microfibrils angle in S(2) layer and unusual pattern of the S(3) layer, depended on the age of the tree and was most intensive in a young tree.

Structure and Dynamics of Current Sheets in 3D Magnetic Fields with the X-line

NASA Astrophysics Data System (ADS)

Frank, Anna G.; Bogdanov, S. Yu.; Bugrov, S. G.; Markov, V. S.; Dreiden, G. V.; Ostrovskaya, G. V.

2004-11-01

Experimental results are presented on the structure of current sheets formed in 3D magnetic fields with singular lines of the X-type. Two basic diagnostics were used with the device CS - 3D: two-exposure holographic interferometry and magnetic measurements. Formation of extended current sheets and plasma compression were observed in the presence of the longitudinal magnetic field component aligned with the X-line. Plasma density decreased and the sheet thickness increased with an increase of the longitudinal component. We succeeded to reveal formation of the sheets taking unusual shape, namely tilted and asymmetric sheets, in plasmas with the heavy ions. These current sheets were obviously different from the planar sheets formed in 2D magnetic fields, i.e. without longitudinal component. Analysis of typical plasma parameters made it evident that plasma dynamics and current sheet evolution should be treated on the base of the two-fluid approach. Specifically it is necessary to take into account the Hall currents in the plane perpendicular to the X-line, and the dynamic effects resulting from interaction of the Hall currents and the 3D magnetic field. Supported by RFBR, grant 03-02-17282, and ISTC, project 2098.

Self-assembly of the general membrane-remodeling protein PVAP into sevenfold virus-associated pyramids.

PubMed

Daum, Bertram; Quax, Tessa E F; Sachse, Martin; Mills, Deryck J; Reimann, Julia; Yildiz, Özkan; Häder, Sabine; Saveanu, Cosmin; Forterre, Patrick; Albers, Sonja-Verena; Kühlbrandt, Werner; Prangishvili, David

2014-03-11

Viruses have developed a wide range of strategies to escape from the host cells in which they replicate. For egress some archaeal viruses use a pyramidal structure with sevenfold rotational symmetry. Virus-associated pyramids (VAPs) assemble in the host cell membrane from the virus-encoded protein PVAP and open at the end of the infection cycle. We characterize this unusual supramolecular assembly using a combination of genetic, biochemical, and electron microscopic techniques. By whole-cell electron cryotomography, we monitored morphological changes in virus-infected host cells. Subtomogram averaging reveals the VAP structure. By heterologous expression of PVAP in cells from all three domains of life, we demonstrate that the protein integrates indiscriminately into virtually any biological membrane, where it forms sevenfold pyramids. We identify the protein domains essential for VAP formation in PVAP truncation mutants by their ability to remodel the cell membrane. Self-assembly of PVAP into pyramids requires at least two different, in-plane and out-of-plane, protein interactions. Our findings allow us to propose a model describing how PVAP arranges to form sevenfold pyramids and suggest how this small, robust protein may be used as a general membrane-remodeling system.

Complete genome sequence of Methanospirillum hungatei type strain JF1

DOE PAGES

Gunsalus, Robert; Cook, Lauren E.; Crable, Bryan R.; ...

2016-01-06

Methanospirillum hungatei strain JF1 (DSM 864) is a methane-producing archaeon and is the type species of the genus Methanospirillum, which belongs to the family Methanospirillaceae within the order Methanomicrobiales. Its genome was selected for sequencing due to its ability to utilize hydrogen and carbon dioxide and/or formate as a sole source of energy. Ecologically, M. hungatei functions as the hydrogen- and/or formate-using partner with many species of syntrophic bacteria. Its morphology is distinct from other methanogens with the ability to form long chains of cells (up to 100 m in length), which are enclosed within a sheath-like structure, and terminalmore » cells with polar flagella. The genome of M. hungatei strain JF1 is the first completely sequenced genome of the family Methanospirillaceae, and it has a circular genome of 3,544,738 bp containing 3,239 protein coding and 68 RNA genes. Furthermore, the large genome of M. hungatei JF1 suggests the presence of unrecognized biochemical/physiological properties that likely extend to the other Methanospirillaceae and include the ability to form the unusual sheath-like structure and to successfully interact with syntrophic bacteria.« less

Control of trace element toxicity in Chesapeake Bay by dominant phytoplankton. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanders, J.G.; Riedel, G.F.; Connell, D.B.

1992-02-01

Copper (Cu) and arsenic (As), but not chromium (Cr), underwent large changes in chemical form during the development and senescence of natural phytoplankton blooms. In general, the percentage of organically-associated Cu was lowest during periods of rapid cell growth and highest during periods of cell decline or periods of dominance by red tide-forming dinoflagellates, a pattern tied to periods of release of organic compounds during either bloom senescence or during unusual algal blooms. Chromium, in contrast, was unreactive. The end result of biological mediation of both As and Cu was to increase the proportion of the element present in amore » less toxic form, at least to phytoplankton, thus affecting the potential toxicity of either element to a natural ecosystem. The results of the project provide a framework for the construction of general predictive models of likely trace element behavior in productive ecosystems and provide a conceptual theory of how such toxic contaminants may affect ecosystem structure and food webs within Chesapeake Bay. Predictive models of ecosystem impact will require further experimentation with multi-trophic level food chains.« less

Phase behaviour of disordered proteins underlying low density and high permeability of liquid organelles

NASA Astrophysics Data System (ADS)

Wei, Ming-Tzo; Elbaum-Garfinkle, Shana; Holehouse, Alex S.; Chen, Carlos Chih-Hsiung; Feric, Marina; Arnold, Craig B.; Priestley, Rodney D.; Pappu, Rohit V.; Brangwynne, Clifford P.

2017-11-01

Many intracellular membraneless organelles form via phase separation of intrinsically disordered proteins (IDPs) or regions (IDRs). These include the Caenorhabditis elegans protein LAF-1, which forms P granule-like droplets in vitro. However, the role of protein disorder in phase separation and the macromolecular organization within droplets remain elusive. Here, we utilize a novel technique, ultrafast-scanning fluorescence correlation spectroscopy, to measure the molecular interactions and full coexistence curves (binodals), which quantify the protein concentration within LAF-1 droplets. The binodals of LAF-1 and its IDR display a number of unusual features, including 'high concentration' binodal arms that correspond to remarkably dilute droplets. We find that LAF-1 and other in vitro and intracellular droplets are characterized by an effective mesh size of ∼3-8 nm, which determines the size scale at which droplet properties impact molecular diffusion and permeability. These findings reveal how specific IDPs can phase separate to form permeable, low-density (semi-dilute) liquids, whose structural features are likely to strongly impact biological function.

Evidence for Reduced, Carbon-rich Regions in the Solar Nebula from an Unusual Cometary Dust Particle

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Gregorio, Bradley T.; Stroud, Rhonda M.; Nittler, Larry R.

Geochemical indicators in meteorites imply that most formed under relatively oxidizing conditions. However, some planetary materials, such as the enstatite chondrites, aubrite achondrites, and Mercury, were produced in reduced nebular environments. Because of large-scale radial nebular mixing, comets and other Kuiper Belt objects likely contain some primitive material related to these reduced planetary bodies. Here, we describe an unusual assemblage in a dust particle from comet 81P/Wild 2 captured in silica aerogel by the NASA Stardust spacecraft. The bulk of this ∼20 μ m particle is comprised of an aggregate of nanoparticulate Cr-rich magnetite, containing opaque sub-domains composed of poorlymore » graphitized carbon (PGC). The PGC forms conformal shells around tiny 5–15 nm core grains of Fe carbide. The C, N, and O isotopic compositions of these components are identical within errors to terrestrial standards, indicating a formation inside the solar system. Magnetite compositions are consistent with oxidation of reduced metal, similar to that seen in enstatite chondrites. Similarly, the core–shell structure of the carbide + PGC inclusions suggests a formation via FTT reactions on the surface of metal or carbide grains in warm, reduced regions of the solar nebula. Together, the nanoscale assemblage in the cometary particle is most consistent with the alteration of primary solids condensed from a C-rich, reduced nebular gas. The nanoparticulate components in the cometary particle provide the first direct evidence from comets of reduced, carbon-rich regions that were present in the solar nebula.« less

Crystallization and preliminary X-ray data of the FadA adhesin from Fusobacterium nucleatum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nithianantham, Stanley; Xu, Minghua; Wu, Nan

2006-12-01

The FadA adhesin from F. nucleatum, which is involved in bacterial attachment and invasion of human oral epithelial cells, has been crystallized in space group P6{sub 1} or P6{sub 5}, and X-ray data have been collected to 1.9 Å resolution. Fusobacterium nucleatum is a Gram-negative anaerobe prevalent in the oral cavity that is associated with periodontal disease, preterm birth and infections in other parts of the human body. The bacteria attach to and invade epithelial and endothelial cells in the gum tissue and elsewhere via a 13.7 kDa adhesin protein FadA (Fusobacterium adhesin A). FadA exists in two forms: themore » intact form (pre-FadA), consisting of 129 amino acids, and the mature form (mFadA), which lacks an 18-residue signal sequence. Both forms have been expressed in Escherichia coli and purified. mFadA has been crystallized. The crystals belong to the hexagonal space group P6{sub 1} or P6{sub 5}, with unit-cell parameters a = b = 59.3, c = 125.7 Å and one molecule per asymmetric unit. The crystals exhibit an unusually high solvent content of 74%. Synchrotron X-ray data have been collected to 1.9 Å. The crystals are suitable for X-ray structure determination. The crystal structure of FadA may provide a basis for the development of therapeutic agents to combat periodontal disease and other infections associated with F. nucleatum.« less

An unusual fragmentation of oxetane-embedded tetracyclic ketal systems.

PubMed

Rao, G Hari Mangeswara; Khan, Faiz Ahmed

2013-11-01

An unusual route for the synthesis of functionalized cyclobutane derivatives starting from functionalized norbornane derivatives is reported. Base-induced fragmentation of an oxetanol-type moiety embedded in a tetracyclic norbornyl ketal leads to a cyclobutane-fused derivative as the major or exclusive product. The fragmentation reaction for bridgehead-bromine-substituted derivatives was much faster than for the corresponding chlorine-substituted substrates. The functionalized cyclobutane product was formed exclusively in high yield in the former case, while the latter furnished a minor uncyclized side product in varying yields.

The unusual canangafruticosides A-E: five monoterpene glucosides, two monoterpenes and a monoterpene glucoside diester of the aryldihydronaphthalene lignan dicarboxylic acid from leaves of Cananga odorata var. fruticosa.

PubMed

Nagashima, Jiro; Matsunami, Katsuyoshi; Otsuka, Hideaki; Lhieochaiphant, Duangporn; Lhieochaiphant, Sorasak

2010-09-01

From the leaves of Cananga odorata var. fruticosa, five unusual monoterpene glucosides, named canangafruticosides A-E (1-5), along with two unusual non-glucosidic monoterpenes (6, 7) were isolated. An aryldihydronaphthalene-type lignan dicarboxylate (8) was also isolated, with two moles of canangafruticoside A (1) on its ester moiety. This lignan also showed strong blue fluorescence emission under basic conditions. The structures of these compounds were elucidated by means of spectroscopic methods, with their absolute configurations determined by application of the modified Mosher's method to a compound chemically derived from canangafruticoside E. (c) 2010 Elsevier Ltd. All rights reserved.

Penning ionization electron spectroscopy of CO 2 clusters in collision with metastable rare gas atoms

NASA Astrophysics Data System (ADS)

Maruyama, Ryo; Tanaka, Hideyasu; Yamakita, Yoshihiro; Misaizu, Fuminori; Ohno, Koichi

2000-09-01

Penning ionization electron spectra (PIES) of CO 2 clusters have been observed for the first time. An unusually fast electron band with excess kinetic energies of 1.4-2.9 eV with respect to the monomer band for the ionic X state was observed for CO 2 clusters in collision with He*(2 3S) atoms. While for PIES with Ne*(3 3P), no such unusual band was observed. The unusual band is ascribed to autoionization into stable structures of ionic clusters to which direct ionization processes are almost impossible due to very small Franck-Condon overlaps associated with a very large geometry difference between the ionic and neutral clusters.

Production of a Pyrrole Antibiotic by a Marine Bacterium1

PubMed Central

Burkholder, Paul R.; Pfister, Robert M.; Leitz, Frederick H.

1966-01-01

Evidence is presented for the isolation and identification of bacteria able to synthesize an unusual antibiotic containing five bromine atoms per molecule. The identification and taxonomic position of these bacteria was made by use of a computer in conjunction with traditional methods. These microorganisms and closely related strains have been isolated on various occasions from tropical water in the vicinity of Puerto Rico. One bacterium, a pseudomonad, has been given the name Pseudomonas bromoutilis because of its distinctive capability. The antibiotic has been extracted, purified, and obtained in crystal form, and its structure has been determined. Although clinical tests of its properties were not encouraging, it may be of significant value and interest from an ecological standpoint. Images Fig. 1 PMID:4380876

Magnetic domains and defects in ferromagnetic liquid crystal colloids realized with optical patterning

NASA Astrophysics Data System (ADS)

Hess, Andrew; Liu, Qingkun; Smalyukh, Ivan

A promising approach in designing composite materials with unusual physical behavior combines solid nanostructures and orientationally ordered soft matter at the mesoscale. Such composites not only inherit properties of their constituents but also can exhibit emergent behavior, such as ferromagnetic ordering of colloidal metal nanoparticles forming mesoscopic magnetization domains when dispersed in a nematic liquid crystal. Here we demonstrate the optical patterning of domain structures and topological defects in such ferromagnetic liquid crystal colloids which allows for altering their response to magnetic fields. Our findings reveal the nature of the defects in this soft matter system which is different as compared to non-polar nematic and ferromagnetic systems alike. This research was supported by the NSF Grant DMR-1420736.

S&TR Preview: Smashing Materials to Reveal Unusual Behavior

ScienceCinema

Hunsberger, Maren; Akin, Minta; Chau, Ricky

2018-06-12

Squeeze a material hard enough, and its structure and properties will change, sometimes dramatically so. With enough heat and pressure, scientists can turn pencil lead (graphite), one of Earth’s softest materials, into diamond, one of its hardest. Apply even more pressure—such as might be found in explosions, detonating nuclear weapons, laser fusion experiments, meteorite impacts, or the hearts of stars and planets—and materials can take stranger forms. Deep in Jupiter’s core, for instance, where pressures likely reach 50 to 100 million times that of Earth’s atmosphere, hydrogen is predicted to be a metallic liquid rather than the familiar transparent gas.

A Specially Constructed Metallograph for Use at Elevated Temperatures

NASA Technical Reports Server (NTRS)

Jenkins, Joe E; Buchele, Donald R; Long, Roger A

1951-01-01

A Metallographic microscope was developed with provision for heating a specimen to 1800 F in protective atmospheres, that is, vacuum or gas. A special objective was constructed of reflecting elements with an unusually long working distance (7/16 in.) and a high numerical aperture (0.5). Changes in specimen microstructure were observed and recorded on 35-millimeter motion-picture film. The resulting pictures were projected as motion pictures and individual frames were cut and enlargements made for close observation. Structural changes upon heating a 0.35-percent annealed carbon steel and a 5-percent tin phosphor bronze specimen were observed and recorded. Newly formed microstructure were revealed by selective vacuum etching and specimen relief resulting from recrystallization and varying grain orientation.

Structural characterizations and magnetic properties of three new reduced molybdenum phosphates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang Xiao; Xu Jiqing; Yu Jiehui

2007-06-15

Three new molybdophosphates, [Co(dien){sub 2}].(H{sub 3}dien){sub 6}.{l_brace}[CoMo{sub 12}O{sub 24}(OH){sub 6}(HPO{sub 4}){sub 2}(PO{sub 4}){sub 6}][Co(Hdien)]{sub 2}[CoMo{sub 12}O{sub 24} (OH){sub 6}(PO{sub 4}){sub 8}]{r_brace}.(dien).4H{sub 3}O.5H{sub 2}O (1) (H{sub 3}dien){sub 4}[MMo{sub 12}O{sub 24}(OH){sub 6}(HPO{sub 4}){sub 4}(PO{sub 4}){sub 4}].10H{sub 2}O [M=Co for (2), Ni for (3); dien=diethylenetriamine], have been synthesized by employing hydrothermal method and characterized by single crystal X-ray diffraction. Compound 1 is built up of Co[P{sub 4}Mo{sub 6}]{sub 2} units as the structural motif covalently linked by [Co(Hdien)] complex subunits to yield an unusual 1-D chain. Compounds 2 and 3 are isomorphic and both display covalent discrete M[P{sub 4}Mo{sub 6}]{sub 2} cluster structuresmore » which are linked by the hydrogen bonds to form 3-D supramolecular networks. Both 1 and 2 display antiferromagnetic interaction and these three compounds all exhibit intensive photoluminescence. - Graphical abstract: Three new reduced molybdophoshpates based on P{sub 4}MO{sub 6} building blocks have been hydrothermally synthesized. 1 is the first covalent 1-D chain consisting of two kinds of forms of M[P{sub 4}MO{sub 6}]{sub 2} units, standing forms A and lying forms B, while 2 and 3 possess 3-D supramolecular network structures. These three compounds all display photoluminescence.« less

Detection of unusual strains of RV in patients with acute diarrhoea in Mexico.

PubMed

del R González-Losa, Maria; Rodríguez-Angulo, Elsa; Manzano-Cabrera, Luis; Mejía-Cámara, Javier; Puerto-Solís, Marylin

2005-04-01

Group A rotaviruses are a major cause of acute gastroenteritis in infants. Human strains with a short RNA pattern generally exhibit subgroup I, G2, P1B[4] specificity, those with a long RNA pattern show subgroup II, G1, G3 or G4, P1A[8] specificity. The presence of strains with unusual specificities has been reported worldwide over the last decade. To determine antigenic diversity among rotaviruses isolated from patients with diarrhoea. A laboratory-based survey study was carried out with faecal samples from patients with acute gastroenteritis form January to April 2000. To classify the samples PAGE and ELISA with specific antibodies to serotype G and P and RT-PCR were carried out. Twenty one specimens from patients with dehydrating diarrhoea had unusual specifies. Nine specimens had unusual combination of long pattern and subgroup I. Twelve specimens with short pattern belong to G1 serotype. As far as the serotypes and genotypes concern 11 samples were P1A, P[4] and one specimen was P1A, P[9]. These results demonstrated the unexpected presence of unusual strains of rotavirus in Mexico. Detection of strains with both human and animal characteristics may indicate interspecies transmission of RV between humans and animals.

Mechanism for starch granule ghost formation deduced from structural and enzyme digestion properties.

PubMed

Zhang, Bin; Dhital, Sushil; Flanagan, Bernadine M; Gidley, Michael J

2014-01-22

After heating in excess water under little or no shear, starch granules do not dissolve completely but persist as highly swollen fragile forms, commonly termed granule "ghosts". The macromolecular architecture of these ghosts has not been defined, despite their importance in determining characteristic properties of starches. In this study, amylase digestion of isolated granule ghosts from maize and potato starches is used as a probe to study the mechanism of ghost formation, through microstructural, mesoscopic, and molecular scale analyses of structure before and after digestion. Digestion profiles showed that neither integral nor surface proteins/lipids were crucial for control of either ghost digestion or integrity. On the basis of the molecular composition and conformation of enzyme-resistant fractions, it was concluded that the condensed polymeric surface structure of ghost particles is mainly composed of nonordered but entangled amylopectin (and some amylose) molecules, with limited reinforcement through partially ordered enzyme-resistant structures based on amylose (for maize starch; V-type order) or amylopectin (for potato starch; B-type order). The high level of branching and large molecular size of amylopectin is proposed to be the origin for the unusual stability of a solid structure based primarily on temporary entanglements.

A New Unusual Ice-induced Sedimentary Structure: the Silt Mushroom

PubMed Central

Jianhua, Zhong; Liangtian, Ni; Ningliang, Sun; Chuang, Liu; Bing, Hao; Mengchun, Cao; xin, Chen; Ke, Luo; Shengxin, Liu; Leitong, Huang; Guanqun, Yang; Shaojie, Wang; Feifei, Su; Xuejing, He; Yanqiu, Xue

2016-01-01

Upon channel bars or point bars within the lows of the Yellow River, a new sedimentary structure, named ‘silt mushroom’, has been observed. The process of their formation is interpreted to be via the ice process. The name, the silt mushroom comes from their figurative form. This is because they look somewhat similar to mushroom’s in size and shape; being in the range of 1 to 10 cm in diameter, with the medium 3–5 cm, and on average 10 cm in height, occuring generally in groups, and occasionally in isolation in relatively soft silt. They develop in the transition from winter to spring, and are convincingly related to ice processes. Ice-induced silt mushrooms are best examined in association with the many other newly discovered ice-induced sedimentary structures (over 20 kinds). Clearly, up to now, ice processes have been significantly underestimated. With the substantial discovery of the ice-induced silt mushroom, it opens up new questions. This is because its structure mirrors the same sedimentary structures found in rocks, questioning their genesis, and sedimentary environment analysis. This achievement is significant not only in sedimentology, but also in palaeogeography, palaeoclimate, geological engineering, hydraulics and fluviology. PMID:27833155

Structures of E. coli peptide deformylase bound to formate: insight into the preference for Fe2+ over Zn2+ as the active site metal.

PubMed

Jain, Rinku; Hao, Bing; Liu, Ren-Peng; Chan, Michael K

2005-04-06

E. coli peptide deformylase (PDF) catalyzes the deformylation of nascent polypeptides generated during protein synthesis. While PDF was originally thought to be a zinc enzyme, subsequent studies revealed that the active site metal is iron. In an attempt to understand this unusual metal preference, high-resolution structures of Fe-, Co-, and Zn-PDF were determined in complex with its deformylation product, formate. In all three structures, the formate ion binds the metal and forms hydrogen-bonding interactions with the backbone nitrogen of Leu91, the amide side chain of Gln50, and the carboxylate side chain of Glu133. One key difference, however, is how the formate binds the metal. In Fe-PDF and Co-PDF, formate binds in a bidentate fashion, while in Zn-PDF, it binds in a monodentate fashion. Importantly, these structural results provide the first clues into the origins of PDF's metal-dependent activity differences. On the basis of these structures, we propose that the basis for the higher activity of Fe-PDF stems from the better ability of iron to bind and activate the tetrahedral transition state required for cleavage of the N-terminal formyl group.

Secondary metabolites of cyanobacteria Nostoc sp.

NASA Astrophysics Data System (ADS)

Kobayashi, Akio; Kajiyama, Shin-Ichiro

1998-03-01

Cyanobacteria attracted much attention recently because of their secondary metabolites with potent biological activities and unusual structures. This paper reviews some recent studies on the isolation, structural, elucidation and biological activities of the bioactive compounds from cyanobacteria Nostoc species.

Unusual extension of the first branchial cleft anomaly.

PubMed

Ada, Mehmet; Korkut, Nazim; Güvenç, M Güven; Acioğlu, Engin; Yilmaz, Süleyman; Cevikbaş, Uğur

2006-03-01

First branchial cleft is the only branchial structure that persists as the external ear canal, while all other clefts are resorbed. Incomplete obliteration and the degree of closure cause the varied types of first branchial cleft anomalies. They were classified based on the anatomical and histological features. We present an unusual type of first branchial cleft anomaly involving the external auditory canal, the middle ear and the nasopharynx through the eustachian tube.

An unusual caffeic acid derived bicyclic [2.2.2] octane lignan and other constituents from Cordia rufescens.

PubMed

do Vale, Ademir E; David, Jorge M; dos Santos, Edlene O; David, Juceni P; e Silva, Lidercia C R C; Bahia, Marcus V; Brandão, Hugo N

2012-04-01

This work reports isolation of an unusual lignan with a bicyclic [2.2.2] octene skeleton, named rufescenolide (1), from stems of Cordia rufescens, along with β-sitosterol, stigmasterol, syringaldehyde, 3-β-O-D-glucopyranosyl-sitosterol, methyl caffeate, 4-methoxy-protocatechuic acid and methyl rosmarinate. Structural characterizations employed IR spectroscopic, ESIHRMS and mono and dimensional NMR spectroscopy. Copyright © 2011 Elsevier Ltd. All rights reserved.

Exploring Tectonic Activity on Vesta and Ceres

NASA Astrophysics Data System (ADS)

Buczkowski, D.; Scully, J. E. C.; Raymond, C. A.; Russell, C. T.

2017-12-01

Images of Vesta and Ceres taken by the Dawn spacecraft revealed large-scale linear structural features on both asteroids. We evaluate their morphology to determine 1) what processes caused them to form and 2) what implications this has for the history of Vesta and Ceres as planetary bodies. The Divalia Fossae are wide troughs bounded by steep scarps that encircle Vesta roughly aligned with the equator. Fault plane analysis suggests that their formation was triggered by the impact event that formed the Rheasilvia basin. The Saturnalia Fossae extend from Divalia to the northern polar region; fault plane analysis ties their formation to the Veneneia basin impact event. Also, it has been suggested that the elongate hill Brumalia Tholus could have been formed as a magmatic intrusion utilizing the subsurface Albalonga fracture as a conduit to the surface, intruding into and deforming the rock above it. Kilometer-scale linear structures cross much of the eastern hemisphere of Ceres. Many structures appear to be radial to the large craters Urvara and Yalode, and likely formed due to impact processes. However, the Samhain Catenae do not have any obvious relationship to a crater and the lack of raised rims makes it unlikely that these are secondary impacts; they are also crosscut by linear features radial to Urvara and Yalode, indicating they are not fractures formed during those impact events. Instead, the morphology of these structures more closely resembles that of pit crater chains (buried normal faults), and show en echelon orientation and S-shaped linkages. Polygonal craters, which form where there is pervasive subsurface fracturing, are widespread on Ceres, and those polygonal craters proximal to the Samhain Catenae have straight crater rims aligned with the structures. Several craters on Ceres have fractured floors, similar to lunar floor-fractured craters (FFCs), which are theorized to form from floor uplift due to magmatic intrusion. Large (>50 km) Ceres FFCs can have both radial and concentric fractures at the crater center, and/or concentric fractures near the crater wall. Smaller craters have a v-shaped moat separating the wall scarp from the crater interior, but different interior morphologies. A depth vs. diameter analysis shows that the Ceres FFCs are unusually shallow, consistent with the magmatic intrusion models.

The cohering telomeres of Oxytricha.

PubMed Central

Oka, Y; Thomas, C A

1987-01-01

We have studied the process by which purified Oxytricha macronuclear DNA associates with itself to form large aggregates. The various macronuclear DNA molecules all have the same terminal or telomeric DNA sequences that are shown below. 5' C4A4C4A4C4--mean length----G4T4G4T4G4T4G4T4G4 G4T4G4T4G4T4G4T4G4-----2.4 kb------C4A4C4A4C4. When incubated at high concentrations, these telomeric sequences cohere with one another to form an unusual structure--one that is quite different from any DNA structure so far described. The evidence for this is the following: 1) These sequences cohere albeit slowly, in the presence of relatively high concentrations of Na+, and no other cation tested. This contrasts with the rapid coherence of complementary single-chain terminals of normal DNA (sticky ends) which occurs in the presence of any cation tested. 2) If the cohered form is transferred into buffers containing a special cation, K+, it becomes much more resistant to dissociation by heating. We estimate that K+ increases the thermal stability by 25 degrees or more. The only precedent known (to us) for a cation-specific stabilization is that seen in the quadruplex structure formed by poly I. The thermal stability of double helical macronuclear DNA depends on the cation concentration, but not the cation type. Limited treatment with specific nucleases show that the 3' and 5'-ended strands are essential for the formation of the cohering structure. Once in the cohered form, the telomeric sequences are protected from the action of nucleases. Coherence is inhibited by specific, but not by non-specific, synthetic oligomers, and by short telomeric fragments with or without their terminal single chains. We conclude that the coherence occurs by the formation of a novel condensed structure that involves the terminal nucleotides in three or four chains. Images PMID:3120149

Presence of mycobacterial L-forms in human blood: Challenge of BCG vaccination

PubMed Central

Markova, Nadya; Slavchev, Georgi; Michailova, Lilia

2015-01-01

Possible persistence of bacteria in human blood as cell wall deficient forms (L-forms) represents a top research priority for microbiologists. Application of live BCG vaccine and L-form transformation of vaccine strain may display a new intriguing aspect concerning the opportunity for occurrence of unpredictable colonization inside the human body by unusual microbial life forms. L-form cultures were isolated from 141 blood samples of people previously vaccinated with BCG, none with a history of exposure to tuberculosis. Innovative methodology to access the unusual L-form elements derived from human blood was developed. The methodology outlines the path of transformation of non- cultivable L-form element to cultivable bacteria and their adaptation for growth in vitro. All isolates showed typical L-forms growth features (“fried eggs” colonies and biofilm). Electron microscopy revealed morphology evidencing peculiar characteristics of bacterial L-form population (cell wall deficient polymorphic elements of variable shape and size). Regular detection of acid fast bacteria in smears of isolated blood L-form cultures, led us to start their identification by using specific Mycobactrium spp. genetic tests. Forty five of 97 genetically tested blood cultures provided specific positive signals for mycobacteria, confirmed by at least one of the 3 specific assays (16S rRNA PCR; IS6110 Real Time PCR and spoligotyping). In conclusion, the obtained genetic evidence suggests that these L-forms are of mycobacterial origin. As the investigated people had been vaccinated with BCG, we can assume that the identified mycobacterial L-forms may be produced by persisting live BCG vaccine. PMID:25874947

Isolated Potato Virus A coat protein possesses unusual properties and forms different short virus-like particles.

PubMed

Ksenofontov, Alexander L; Dobrov, Eugeny N; Fedorova, Natalia V; Serebryakova, Marina V; Prusov, Andrei N; Baratova, Ludmila A; Paalme, Viiu; Järvekülg, Lilian; Shtykova, Eleonora V

2018-05-01

In our previous study, we have observed that the isolated coat proteins (CP) of the Potyvirus Potato Virus A (PVA) virions exhibit an intrinsic tendency to self-associate into various multimeric forms containing some fractions of cross-β-structure. In this report, we studied the effect of solution conditions on the structure and dissociation of isolated PVA CP using a number of complementary physicochemical methods. Analysis of the structure of PVA CP in solution was performed by limited proteolysis with MALDI-TOF mass spectrometry analysis, transmission electron microscopy, intrinsic fluorescence spectroscopy, and synchrotron small angle X-ray scattering (SAXS). Overall structural characteristics of PVA CP obtained by combination of these methods and ab initio shape reconstruction by SAXS show that PVA CP forms large multi-subunit particles. We demonstrate that a mixture of compact virus-like particles (VLP) longer than 30 nm is assembled on dialysis of isolated CP into neutral pH buffer (at low ionic strength). Under conditions of high ionic strength (0.5 M NaCl) and high pH (pH 10.5), PVA dissociates into low compactness oval-shaped particles of approximately 30 subunits (20-30 nm). The results of limited trypsinolysis of these particles (enzyme/substrate ratio 1:100, 30 min) showed the existence of non-cleavable core-fragment, consisting of 137 amino acid residues. Trypsin treatment removed only a short N-terminal fragment in the intact virions. These particles are readily reassembled into regular VLPs by changing pH back to neutral. It is possible that these particles may represent some kind of intermediate in PVA assembly in vitro and in vivo.

An Unusual Mound

NASA Image and Video Library

2014-03-26

With its cracked, blistery appearance, this mound near the center of a very large, over 5-kilometer diameter mid-latitude crater poses an interesting question: how did this form? This image is from NASA Mars Reconnaissance Orbiter.

Unusual 4-hydroxybenzaldehyde synthase activity from tissue cultures of the vanilla orchid Vanilla planifolia.

PubMed

Podstolski, Andrzej; Havkin-Frenkel, Daphna; Malinowski, Jacek; Blount, Jack W; Kourteva, Galina; Dixon, Richard A

2002-11-01

Tissue cultures of the vanilla orchid, Vanilla planifolia, produce the flavor compound vanillin (4-hydroxy-3-methoxybenzaldehyde) and vanillin precursors such as 4-hydroxybenzaldehyde. A constitutively expressed enzyme activity catalyzing chain shortening of a hydroxycinnamic acid, believed to be the first reaction specific for formation of vanilla flavor compounds, was identified in these cultures. The enzyme converts 4-coumaric acid non-oxidatively to 4-hydroxybenzaldehyde in the presence of a thiol reagent but with no co-factor requirement. Several forms of this 4-hydroxybenzaldehyde synthase (4HBS) were resolved and partially purified by a combination of hydrophobic interaction, ion exchange and gel filtration chromatography. These forms appear to be interconvertible. The unusual properties of the 4HBS, and its appearance in different protein fractions, raise questions as to its physiological role in vanillin biosynthesis in vivo.

Centenarian scientists: an unusual cluster newly formed in the 20th century.

PubMed

Sri Kantha, S

2001-12-01

From biographical data sources on ranking scientists, I was able to identify 35 centenarians. Among these, only one (Michel Chevereul from France) lived before the 20th century. Since the remaining 34 individuals became centenarians only from 1965, I propose that centenarian scientists are an unusual cluster, first formed in the 20th century. Among these, all except one (Alice Hamilton) were men. Six centenarian scientists, including Hamilton, had received professional medical training. The nationality ranks of the 34 centenarian scientists identified in the 20th century show 26 Americans, 6 British, one German and one French. Four of the 26 Americans were immigrants from Europe. At least three centenarians, namely Michael Heidelberger, Nathaniel Kleitman and Victor Hamburger, belong to the 'Nobel class' category, being pioneers in the disciplines of immunochemistry, sleep physiology and neuroembryology respectively.

The structure of and origin of nodular chromite from the Troodos ophiolite, Cyprus, revealed using high-resolution X-ray computed tomography and electron backscatter diffraction

NASA Astrophysics Data System (ADS)

Prichard, H. M.; Barnes, S. J.; Godel, B.; Reddy, S. M.; Vukmanovic, Z.; Halfpenny, A.; Neary, C. R.; Fisher, P. C.

2015-03-01

Nodular chromite is a characteristic feature of ophiolitic podiform chromitite and there has been much debate about how it forms. Nodular chromite from the Troodos ophiolite in Cyprus is unusual in that it contains skeletal crystals enclosed within the centres of the nodules and interstitial to them. 3D imaging and electron backscatter diffraction have shown that the skeletal crystals within the nodules are single crystals that are surrounded by a rim of polycrystalline chromite. 3D analysis reveals that the skeletal crystals are partially or completely formed cage or hopper structures elongated along the < 111 > axis. The rim is composed of a patchwork of chromite grains that are truncated on the outer edge of the rim. The skeletal crystals formed first from a magma supersaturated in chromite and silicate minerals crystallised from melt trapped between the chromite skeletal crystal blades as they grew. The formation of skeletal crystals was followed by a crystallisation event which formed a silicate-poor rim of chromite grains around the skeletal crystals. These crystals show a weak preferred orientation related to the orientation of the core skeletal crystal implying that they formed by nucleation and growth on this core, and did not form by random mechanical aggregation. Patches of equilibrium adcumulate textures within the rim attest to in situ development of such textures. The nodules were subsequently exposed to chromite undersaturated magma resulting in dissolution, recorded by truncated grain boundaries in the rim and a smooth outer surface to the nodule. None of these stages of formation require a turbulent magma. Lastly the nodules impinged on each other causing local deformation at points of contact.

Trappeindia himalayensis gen. et sp. nov., a sequestrate fungus with potential affinity to Strobilomyces (Basidiomycotina, Boletales)

Treesearch

M.A. Castellano; S.L. Miller; L. Singh; T.N. Lakhanpal

2012-01-01

An unusual sequestrate fungus forming ectomycorrhizae with Cedrus deodora (Roxb.) Laud. forms sporocarps in the northwestern Himalayas of India during spring. It has a dark brown to black peridium with a solid, white to brown, loculate gleba containing spherical, reticulate spores. It resembles no described genus and is described here as ...

Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Yong-Hui; Huang, Jingsong; Sheng, Xiaolan

In neighboring layers of bilayer (and few-layer) graphenes, both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi-pi bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by upmore » to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi-pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. Moreover, the existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.« less

Nitrogen-Doping Enables Covalent-Like pi-pi Bonding between Graphenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Yong-Hui; Huang, Jingsong; Sumpter, Bobby G

The neighboring layers in bi-layer (and few-layer) graphenes of both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene molecules . Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi pi bonding in bi-layer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can bemore » enhanced by up to 50% compared to the pristine graphene bi-layers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. The existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.« less

Exopolysaccharides from extremophiles: from fundamentals to biotechnology.

PubMed

Nicolaus, Barbara; Kambourova, Margarita; Oner, Ebru Toksoy

2010-09-01

Exopolysaccharides (EPSs) make up a substantial component of the extracellular polymers surrounding most microbial cells in extreme environments like Antarctic ecosystems, saline lakes, geothermal springs or deep sea hydrothermal vents. The extremophiles have developed various adaptations, enabling them to compensate for the deleterious effects of extreme conditions, e.g. high temperatures, salt, low pH or temperature, high radiation. Among these adaptation strategies, EPS biosynthesis is one of the most common protective mechanisms. The unusual metabolic pathways revealed in some extremophiles raised interest in extremophilic microorganisms as potential producers of EPSs with novel and unusual characteristics and functional activities under extreme conditions. Even though the accumulated knowledge on the structural and theological properties of EPSs from extremophiles is still very limited, it reveals a variety in properties, which may not be found in more traditional polymers. Both extremophilic microorganisms and their EPSs suggest several biotechnological advantages, like short fermentation processes for thermophiles and easily formed and stable emulsions of EPSs from psychrophiles. Unlike mesophilic producers of EPSs, many of them being pathogenic, extremophilic microorganisms provide non-pathogenic products, appropriate for applications in the food, pharmaceutical and cosmetics industries as emulsifiers, stabilizers, gel agents, coagulants, thickeners and suspending agents. The commercial value of EPSs synthesized by microorganisms from extreme habitats has been established recently.

QM/MM studies of the mechanism of unusual bifunctional fructose-1,6-bisphosphate aldolase/phosphatase.

PubMed

Hou, Qianqian; Sheng, Xiang; Liu, Yongjun

2014-06-21

Archaeal fructose-1,6-bisphosphate aldolase/phosphatase (FBPA/P) is a newly identified unusual bifunctional enzyme (Nature, 2010, 464, 1077), which contains one single catalytic domain but catalyzes two chemically distinct reactions of gluconeogenesis. It is different from the ordinary enzymes whose active sites are responsible for a specific reaction. To explore the catalytic characteristic of FBPA/P, the aldol condensation mechanism of bifunctional FBPA/P has been investigated using quantum mechanics/molecular mechanics (QM/MM) method. The whole reaction process can be divided into two half-reactions involving seven elementary steps. A Schiff base intermediate is theoretically confirmed, agreeing well with the recently resolved crystal structures (Nature, 2011, 478, 538). The free energy barrier of the rate-limiting step is calculated to be 22.2 kcal mol(-1), which is a concerted process of a nucleophilic attack by the enolic carbon to the ketonic carbon and a proton transfer from Tyr229 to the ketonic oxygen. Lys232 plays an important role in forming a Schiff base intermediate with the substrate (DHAP). Tyr229 functions as a proton shuttle during the catalysis. This is the first theoretical study on the aldol condensation mechanism of FBPA/P, which may provide useful information for understanding bifunctional enzymes.

Nitrogen Doping Enables Covalent-Like π–π Bonding between Graphenes

DOE PAGES

Tian, Yong-Hui; Huang, Jingsong; Sheng, Xiaolan; ...

2015-07-07

In neighboring layers of bilayer (and few-layer) graphenes, both AA and AB stacking motifs are known to be separated at a distance corresponding to van der Waals (vdW) interactions. In this Letter, we present for the first time a new aspect of graphene chemistry in terms of a special chemical bonding between the giant graphene "molecules". Through rigorous theoretical calculations, we demonstrate that the N-doped graphenes (NGPs) with various doping levels can form an unusual two-dimensional (2D) pi-pi bonding in bilayer NGPs bringing the neighboring NGPs to significantly reduced interlayer separations. The interlayer binding energies can be enhanced by upmore » to 50% compared to the pristine graphene bilayers that are characterized by only vdW interactions. Such an unusual chemical bonding arises from the pi-pi overlap across the vdW gap while the individual layers maintain their in-plane pi-conjugation and are accordingly planar. Moreover, the existence of the resulting interlayer covalent-like bonding is corroborated by electronic structure calculations and crystal orbital overlap population (COOP) analyses. In NGP-based graphite with the optimal doping level, the NGP layers are uniformly stacked and the 3D bulk exhibits metallic characteristics both in the in-plane and along the stacking directions.« less

Biosourced polymetallic catalysis: A surprising and efficient means to promote the Knoevenagel condensation

NASA Astrophysics Data System (ADS)

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-03-01

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix ‘Tordis’ (Salix schwerinii x S. viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore an innovative methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the direct use of polymetallic salts derived from plants as “Lewis acid” catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, XRD, FT-IR in order to elucidate the chemical composition, structure and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to conventional catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

PubMed Central

Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

1982-01-01

Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

Acardiac twin with externalized intestine adherent to placenta: unusual manifestation of omphalocele.

PubMed

Emery, Shawn Clark; Vaux, Keith K; Pretorius, Dolores; Masliah, Eliezer; Benirschke, Kurt

2004-01-01

TRAP (twin reversed arterial perfusion) syndrome produces an acardiac twin (acardiac monster, acardius, acardiacus, chorioangiopagus parasiticus, etc.). Acardiacs result from monozygotic multiple births in which three anatomic anomalies occur: (1) a fetus' cardiac development is disturbed; (2) artery-artery anastomosis carries blood from a normal ("pump") twin to the acardiac; (3) vein-vein anastomosis carries blood from the acardiac back to the normal twin. Whether reversal of blood flow in the acardiac results from or causes cardiac dysmorphogenesis has not been resolved. Acardiac twins demonstrate a complex constellation of malformations usually thought to result from reversed blood flow; omphalocele is particularly common. We report monochorionic monoamnionic male twins in which an acardiac twin demonstrated externalized intestines adherent to the placenta. The twins were delivered from a 30-year-old primigravida mother by cesarean section without maternal complications at 33 w. The mother has no significant past medical history. The macerated acardius had a 4-cm long attenuated umbilical cord with indeterminate number of vessels. Structures rostral to the thorax were absent save for one poorly developed hand and arm. The abdomen contained loose mesenchyme and no organs. The entire intestine (21 cm) along with two testes was located in a sac on the surface of the placenta. No histopathologic anomalies of formed structures were identified aside from spatial relationships and incomplete development. The normal twin required no intensive care and is doing well. To our knowledge, this is the first report of externalized intestine, which may represent an unusual consequence of omphalocele.

From the Cover: Genome analysis of the smallest free-living eukaryote Ostreococcus tauri unveils many unique features

NASA Astrophysics Data System (ADS)

Derelle, Evelyne; Ferraz, Conchita; Rombauts, Stephane; Rouzé, Pierre; Worden, Alexandra Z.; Robbens, Steven; Partensky, Frédéric; Degroeve, Sven; Echeynié, Sophie; Cooke, Richard; Saeys, Yvan; Wuyts, Jan; Jabbari, Kamel; Bowler, Chris; Panaud, Olivier; Piégu, Benoît; Ball, Steven G.; Ral, Jean-Philippe; Bouget, François-Yves; Piganeau, Gwenael; de Baets, Bernard; Picard, André; Delseny, Michel; Demaille, Jacques; van de Peer, Yves; Moreau, Hervé

2006-08-01

The green lineage is reportedly 1,500 million years old, evolving shortly after the endosymbiosis event that gave rise to early photosynthetic eukaryotes. In this study, we unveil the complete genome sequence of an ancient member of this lineage, the unicellular green alga Ostreococcus tauri (Prasinophyceae). This cosmopolitan marine primary producer is the world's smallest free-living eukaryote known to date. Features likely reflecting optimization of environmentally relevant pathways, including resource acquisition, unusual photosynthesis apparatus, and genes potentially involved in C4 photosynthesis, were observed, as was downsizing of many gene families. Overall, the 12.56-Mb nuclear genome has an extremely high gene density, in part because of extensive reduction of intergenic regions and other forms of compaction such as gene fusion. However, the genome is structurally complex. It exhibits previously unobserved levels of heterogeneity for a eukaryote. Two chromosomes differ structurally from the other eighteen. Both have a significantly biased G+C content, and, remarkably, they contain the majority of transposable elements. Many chromosome 2 genes also have unique codon usage and splicing, but phylogenetic analysis and composition do not support alien gene origin. In contrast, most chromosome 19 genes show no similarity to green lineage genes and a large number of them are specialized in cell surface processes. Taken together, the complete genome sequence, unusual features, and downsized gene families, make O. tauri an ideal model system for research on eukaryotic genome evolution, including chromosome specialization and green lineage ancestry. genome heterogeneity | genome sequence | green alga | Prasinophyceae | gene prediction

Normal form from biological motion despite impaired ventral stream function.

PubMed

Gilaie-Dotan, S; Bentin, S; Harel, M; Rees, G; Saygin, A P

2011-04-01

We explored the extent to which biological motion perception depends on ventral stream integration by studying LG, an unusual case of developmental visual agnosia. LG has significant ventral stream processing deficits but no discernable structural cortical abnormality. LG's intermediate visual areas and object-sensitive regions exhibit abnormal activation during visual object perception, in contrast to area V5/MT+ which responds normally to visual motion (Gilaie-Dotan, Perry, Bonneh, Malach, & Bentin, 2009). Here, in three studies we used point light displays, which require visual integration, in adaptive threshold experiments to examine LG's ability to detect form from biological and non-biological motion cues. LG's ability to detect and discriminate form from biological motion was similar to healthy controls. In contrast, he was significantly deficient in processing form from non-biological motion. Thus, LG can rely on biological motion cues to perceive human forms, but is considerably impaired in extracting form from non-biological motion. Finally, we found that while LG viewed biological motion, activity in a network of brain regions associated with processing biological motion was functionally correlated with his V5/MT+ activity, indicating that normal inputs from V5/MT+ might suffice to activate his action perception system. These results indicate that processing of biologically moving form can dissociate from other form processing in the ventral pathway. Furthermore, the present results indicate that integrative ventral stream processing is necessary for uncompromised processing of non-biological form from motion. Copyright © 2011 Elsevier Ltd. All rights reserved.

Structure, reactivity and electronic properties of Mn doped Ni13 clusters

NASA Astrophysics Data System (ADS)

Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

2013-06-01

In this work we have studied the structural and magnetic properties of Ni13 cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H2 molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni12Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni12MnH2. Our analysis of the stability and HOMO-LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H2 absorption in the doped NiMnm alloy clusters. This has been reported earlier for smaller Nin clusters [1].

Quantum Requirement for Photosynthesis in Chlorophyll-Deficient Plants with Unusual Lamellar Structures

PubMed Central

Schmid, Georg H.; Gaffron, Hans

1967-01-01

Neither an over-all deficiency of chlorophyll, nor an increased enzymatic capacity for maximal rates, nor an unusual lamellar structure was found to change the number of quanta required for the evolution of one molecule of oxygen in healthy aurea mutants of tobacco. The average minimal quantum number remains 10 (efficiency 0.1) as in many algae and typical higher plants. Most of the time the optimal efficiency depends on the availability of some far-red radiation, particularly in the blue region of the spectrum where blue light alone is rather inefficient. These results fit an explanation offered earlier in connection with the hydrogen or acetate photometabolism of algae in far-red light. PMID:19873573

Atomistic simulation of cubic and tetragonal phases of U-Mo alloy: Structure and thermodynamic properties

NASA Astrophysics Data System (ADS)

Starikov, S. V.; Kolotova, L. N.; Kuksin, A. Yu.; Smirnova, D. E.; Tseplyaev, V. I.

2018-02-01

We studied structure and thermodynamic properties of cubic and tetragonal phases of pure uranium and U-Mo alloys using atomistic simulations: molecular dynamics and density functional theory. The main attention was paid to the metastable γ0 -phase that is formed in U-Mo alloys at low temperature. Structure of γ0 -phase is similar to body-centered tetragonal (bct) lattice with displacement of a central atom in the basic cell along [ 001 ] direction. Such displacements have opposite orientations for part of the neighbouring basic cells. In this case, such ordering of the displacements can be designated as antiferro-displacement. Formation of such complex structure may be interpreted through forming of short U-U bonds. At heating, the tetragonal structure transforms into cubic γs -phase, still showing ordering of central atom displacements. With rise in temperature, γs -phase transforms to γ-phase with a quasi body-centered cubic (q-bcc) lattice. The local positions of uranium atoms in γ-phase correspond to γs -phase, however, orientations of the central atom displacements become disordered. Transition from γ0 to γ can be considered as antiferro-to paraelastic transition of order-disorder type. This approach to the structure description of uranium alloy allows to explain a number of unusual features found in the experiments: anisotropy of lattice at low temperature; remarkably high self-diffusion mobility in γ-phase; decreasing of electrical resistivity at heating for some alloys. In addition, important part of this work is the development of new interatomic potential for U-Mo system made with taking into account details of studied structures.

The Structure of the Plakin Domain of Plectin Reveals an Extended Rod-like Shape*

PubMed Central

Carballido, Ana M.

2016-01-01

Plakins are large multi-domain proteins that interconnect cytoskeletal structures. Plectin is a prototypical plakin that tethers intermediate filaments to membrane-associated complexes. Most plakins contain a plakin domain formed by up to nine spectrin repeats (SR1–SR9) and an SH3 domain. The plakin domains of plectin and other plakins harbor binding sites for junctional proteins. We have combined x-ray crystallography with small angle x-ray scattering (SAXS) to elucidate the structure of the plakin domain of plectin, extending our previous analysis of the SR1 to SR5 region. Two crystal structures of the SR5-SR6 region allowed us to characterize its uniquely wide inter-repeat conformational variability. We also report the crystal structures of the SR7-SR8 region, refined to 1.8 Å, and the SR7–SR9 at lower resolution. The SR7–SR9 region, which is conserved in all other plakin domains, forms a rigid segment stabilized by uniquely extensive inter-repeat contacts mediated by unusually long helices in SR8 and SR9. Using SAXS we show that in solution the SR3–SR6 and SR7–SR9 regions are rod-like segments and that SR3–SR9 of plectin has an extended shape with a small central kink. Other plakins, such as bullous pemphigoid antigen 1 and microtubule and actin cross-linking factor 1, are likely to have similar extended plakin domains. In contrast, desmoplakin has a two-segment structure with a central flexible hinge. The continuous versus segmented structures of the plakin domains of plectin and desmoplakin give insight into how different plakins might respond to tension and transmit mechanical signals. PMID:27413182

Extremophiles: developments of their special functions and potential resources.

PubMed

Fujiwara, Shinsuke

2002-01-01

Extremophilles are valuable resources in biotechnology. Enzymes from extremophiles are expected to fill the gap between biological and chemical processes due to their unusual properties. Especially enzymes from hyperthermophiles that can grow at above 90 degrees C were devoted owing to its extraordinary thermostability and denaturant tolerance. Screening trials of hyperthermophilic microorganisms were performed by a number of microbiologists and various unique strains were isolated from natural environments. One of the most successful uses of thermostable enzymes was DNA polymerase in the polymerase chain reaction (PCR). Thermostable enzymes are used in the chemical, food, pharmaceutical, paper and textile industries. Recombinant forms of thermostable enzymes that have been expressed in Escherichia coli are commonly utilized in industrial applications however their enzymatic characteristics and tertiary structure are different from the native ones produced in the original strains. In vitro heat treatment induces a structural conversion of the recombinant protein to its natural form. High temperature itself plays an important role in determining the specific characteristics and tertiary structure of the enzyme. Recent studies have revealed that hyperthermophiles can grow under numerous conditions not only in geothermal or deep-sea thermal environments. Technological advances have allowed DNA to be isolated from natural environments. Now genes could be isolated from microorganisms that have not been cultured. In this review, innovative approaches to hunt genes from natural environments without pure culturing of microorganisms are also discussed.

A naturally occurring, noncanonical GTP aptamer made of simple tandem repeats

PubMed Central

Curtis, Edward A; Liu, David R

2014-01-01

Recently, we used in vitro selection to identify a new class of naturally occurring GTP aptamer called the G motif. Here we report the discovery and characterization of a second class of naturally occurring GTP aptamer, the “CA motif.” The primary sequence of this aptamer is unusual in that it consists entirely of tandem repeats of CA-rich motifs as short as three nucleotides. Several active variants of the CA motif aptamer lack the ability to form consecutive Watson-Crick base pairs in any register, while others consist of repeats containing only cytidine and adenosine residues, indicating that noncanonical interactions play important roles in its structure. The circular dichroism spectrum of the CA motif aptamer is distinct from that of A-form RNA and other major classes of nucleic acid structures. Bioinformatic searches indicate that the CA motif is absent from most archaeal and bacterial genomes, but occurs in at least 70 percent of approximately 400 eukaryotic genomes examined. These searches also uncovered several phylogenetically conserved examples of the CA motif in rodent (mouse and rat) genomes. Together, these results reveal the existence of a second class of naturally occurring GTP aptamer whose sequence requirements, like that of the G motif, are not consistent with those of a canonical secondary structure. They also indicate a new and unexpected potential biochemical activity of certain naturally occurring tandem repeats. PMID:24824832

Synthesis and Structure of an Extended Cluster Lead(II) Carboxylate, [Pb{(CO)(9)Co(3)(&mgr;(3)-CCO(2))}(2)](n)(). Role of Core Metals in Cluster-Derived Hydrogenation Catalysts.

PubMed

Lei, Xinjian; Shang, Maoyu; Patil, Atul; Wolf, Eduardo E.; Fehlner, Thomas P.

1996-05-22

The reaction of lead acetate with (CO)(9)Co(3)(&mgr;(3)-CCOOH) leads to the formation of [Pb{(CO)(9)Co(3)(&mgr;(3)-CCO(2))}(2)](n)(), I, in high yield. The structure of I exhibits unusual six-coordinate Pb(II) centers with two asymmetrical chelating cluster carboxylates (C(22)Co(6)PbO(22); triclinic P&onemacr;; a = 8.119(1), b = 14.346(2), c = 14.660(2) Å; alpha = 102.18(1), beta = 99.01(1), gamma = 97.30(1) degrees; Z = 2). One oxygen of each cluster carboxylate ligand bridges between adjacent lead atoms such that a chainlike extended structure is found in the solid state without the presence of solvent or water. I is converted stepwise on pyrolysis into two metastable forms of solid materials (designated LT and HT), each of which has been characterized spectroscopically. The hydrogenation of 2-butenal as a test reaction shows that the LT catalyst exhibits selectivities similar to previous LT materials derived from other cobalt cluster metal carboxylates and that the HT material is totally inactive. The observed release of the lead core metal under HT activation conditions totally inactivates the catalyst and demonstrates exposure of the core metal in the HT form of these novel catalysts.

Savant memory for digits in a case of synaesthesia and Asperger syndrome is related to hyperactivity in the lateral prefrontal cortex.

PubMed

Bor, Daniel; Billington, Jac; Baron-Cohen, Simon

2007-10-01

SINGLE CASE: DT is a savant with exceptional abilities in numerical memory and mathematical calculations. DT also has an elaborate form of synaesthesia for visually presented digits. Further more, DT also has Asperger syndrome (AS). We carried out two preliminary investigations to establish whether these conditions may contribute to his savant abilities. In an fMRI digit span study, DT showed hyperactivity in lateral prefrontal cortex when encoding digits, compared with controls. In addition, while controls showed raised lateral prefrontal activation in response to structured (compared to unstructured) sequences of digits, DT's neural activity did not differ between these two conditions. In addition, controls showed a significant performance advantage for structured, compared with unstructured sequences whereas no such pattern was found for DT. We suggest that this performance pattern reflects that DT focuses less on external mathematical structure, since for him all digit sequences have internal structure linked to his synaesthesia. Finally, DT did not activate extra-striate regions normally associated with synaesthesia, suggesting that he has an unusual and more abstract and conceptual form of synaesthesia. This appears to generate structured, highly-chunked content that enhances encoding of digits and aids both recall and calculation. People with AS preferentially attend to local features of stimuli. To test this in DT, we administered the Navon task. Relative to controls, DT was faster at finding a target at the local level, and was less distracted by interference from the global level. The propensity to focus on local detail, in concert with a form of synaesthesia that provides structure to all digits, may account for DT's exceptional numerical memory and calculation ability. This neural and cognitive pattern needs to be tested in a series of similar cases, and with more constrained control groups, to confirm the significance of this association.

Reversible dimer formation and stability of the anti-tumour single-chain Fv antibody MFE-23 by neutron scattering, analytical ultracentrifugation, and NMR and FT-IR spectroscopy.

PubMed

Lee, Yie Chia; Boehm, Mark K; Chester, Kerry A; Begent, Richard H J; Perkins, Stephen J

2002-06-28

MFE-23 is a single chain Fv (scFv) antibody molecule used to target colorectal cancer through its high affinity for the tumour marker carcinoembryonic antigen (CEA). ScFv molecules are formed from peptide-linked antibody V(H) and V(L) domains, and many of these form dimers. Our recent crystal structure for MFE-23 showed that this formed an unusual symmetric back-to-back association of two monomers that is consistent with a domain-swapped diabody structure. Neutron scattering and modelling fits showed that MFE-23 existed as compact V(H)-V(L)-linked monomers at therapeutically relevant concentrations below 1 mg/ml. Size-exclusion gel chromatography showed that the monomeric and dimeric forms of MFE-23 could be separated, and that the proportions of these two forms depended on the starting MFE-23 concentration. Sedimentation equilibrium experiments by analytical ultracentrifugation at nine concentrations of MFE-23 indicated a reversible monomer-dimer self-association equilibrium with an association constant of 1.9x10(3)-2.2x10(3) M(-1). Sedimentation velocity experiments using the time derivative g(s(*)) method showed that MFE-23-His has a concentration-dependent weight average sedimentation coefficient that increased from 1.8 S for the monomer to about 3-6 S for the dimer. Both values agreed with those calculated from the MFE-23 crystal structure. In relation to the thermal stability of MFE-23, denaturation experiments by (1)H NMR and FT-IR spectroscopy showed that the molecule is stable up to 47 degrees C, after which denaturation was irreversible. MFE-23 dimerisation is discussed in terms of a new model for diabody structures, in which the V(H) and V(L) domains in the monomer are able to dissociate and reassociate to form a dimer, or diabody, but in which symmetric back-to-back contacts between the two monomers are formed. This dimerisation in solution is attributed to the complementary nature of the C-terminal surface of the MFE-23 monomer. Crystal structures for seven other scFv molecules have shown that, while the contact residues for symmetric back-to-back dimer formation in MFE-23 are not fully conserved, in principle, back-to-back contacts can be formed in these too. This offers possibilities for the creation of other forms of scFv molecules. (c) 2002 Elsevier Science Ltd.

Psiguadials A and B, two novel meroterpenoids with unusual skeletons from the leaves of Psidium guajava.

PubMed

Shao, Meng; Wang, Ying; Liu, Zhong; Zhang, Dong-Mei; Cao, Hui-Hui; Jiang, Ren-Wang; Fan, Chun-Lin; Zhang, Xiao-Qi; Chen, He-Ru; Yao, Xin-Sheng; Ye, Wen-Cai

2010-11-05

Psiguadials A (1) and B (2), two novel sesquiterpenoid-diphenylmethane meroterpenoids with unusual skeletons, along with a pair of known epimers, psidial A (3) and guajadial (4), were isolated from the leaves of Psidium guajava. Their structures with absolute configurations were elucidated by means of NMR, X-ray diffraction, and quantum chemical CD calculation. Compounds 1, 2, and 4 exhibited potent inhibitory effects on the growth of human hepatoma cells.

Highly deformable bones: unusual deformation mechanisms of seahorse armor.

PubMed

Porter, Michael M; Novitskaya, Ekaterina; Castro-Ceseña, Ana Bertha; Meyers, Marc A; McKittrick, Joanna

2013-06-01

Multifunctional materials and devices found in nature serve as inspiration for advanced synthetic materials, structures and robotics. Here, we elucidate the architecture and unusual deformation mechanisms of seahorse tails that provide prehension as well as protection against predators. The seahorse tail is composed of subdermal bony plates arranged in articulating ring-like segments that overlap for controlled ventral bending and twisting. The bony plates are highly deformable materials designed to slide past one another and buckle when compressed. This complex plate and segment motion, along with the unique hardness distribution and structural hierarchy of each plate, provide seahorses with joint flexibility while shielding them against impact and crushing. Mimicking seahorse armor may lead to novel bio-inspired technologies, such as flexible armor, fracture-resistant structures or prehensile robotics. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Inverted micellar intermediates and the transitions between lamellar, cubic, and inverted hexagonal lipid phases. II. Implications for membrane-membrane interactions and membrane fusion.

PubMed Central

Siegel, D P

1986-01-01

Results of a kinetic model of thermotropic L alpha----HII phase transitions are used to predict the types and order-of-magnitude rates of interactions between unilamellar vesicles that can occur by intermediates in the L alpha----HII phase transition. These interactions are: outer monolayer lipid exchange between vesicles; vesicle leakage subsequent to aggregation; and (only in systems with ratios of L alpha and HII phase structural dimensions in a certain range or with unusually large bilayer lateral compressibilities) vesicle fusion with retention of contents. It was previously proposed that inverted micellar structures mediate membrane fusion. These inverted micellar structures are thought to form in all systems with such transitions. However, I show that membrane fusion probably occurs via structures that form from these inverted micellar intermediates, and that fusion should occur in only a sub-set of lipid systems that can adopt the HII phase. For single-component phosphatidylethanolamine (PE) systems with thermotropic L alpha----HII transitions, lipid exchange should be observed starting at temperatures several degrees below TH and at all higher temperatures, where TH is the L alpha----HII transition temperature. At temperatures above TH, the HII phase forms between apposed vesicles, and eventually ruptures them (leakage). In most single-component PE systems, fusion via L alpha----HII transition intermediates should not occur. This is the behavior observed by Bentz, Ellens, Lai, Szoka, et al. in PE vesicle systems. Fusion is likely to occur under circumstances in which multilamellar samples of lipid form the so-called "inverted cubic" or "isotropic" phase. This is as observed in the mono-methyl DOPE system (Ellens, H., J. Bentz, and F. C. Szoka. 1986. Fusion of phosphatidylethanolamine containing liposomes and the mechanism of the L alpha-HII phase transition. Biochemistry. In press.) In lipid systems with L alpha----HII transitions driven by cation binding (e.g., Ca2+-cardiolipin), fusion should be more frequent than in thermotropic systems. PMID:3719075

Elaiophores in Gomesa bifolia (Sims) M.W. Chase & N.H. Williams (Oncidiinae: Cymbidieae: Orchidaceae): structure and oil secretion

PubMed Central

Aliscioni, Sandra S.; Torretta, Juan P.; Bello, Mariano E.; Galati, Beatriz G.

2009-01-01

Background and Aims Oils are an unusual floral reward in Orchidaceae, being produced by specialized glands called elaiophores. Such glands have been described in subtribe Oncidiinae for a few species. The aims of the present study were to identify the presence of elaiophores in Gomesa bifolia, to study their structure and to understand how the oil is secreted. Additionally, elaiophores of G. bifolia were compared with those of related taxa within the Oncidiinae. Methods Elaiophores were identified using Sudan III. Their structure was examined by using light, scanning electron and transmission electron microscopy. Key Results Secretion of oils was from the tips of callus protrusions. The secretory cells each had a large, centrally located nucleus, highly dense cytoplasm, abundant plastids containing lipid globules associated with starch grains, numerous mitochondria, an extensive system of rough and smooth endoplasmatic reticulum, and electron-dense dictyosomes. The outer tangential walls were thick, with a loose cellulose matrix and a few, sparsely distributed inconspicuous cavities. Electron-dense structures were observed in the cell wall and formed a lipid layer that covered the cuticle of the epidermal cells. The cuticle as viewed under the scanning electron microscope was irregularly rugose. Conclusions The elaiophores of G. bifolia are of the epithelial type. The general structure of the secretory cells resembles that described for other species of Oncidiinae, but some unique features were encountered for this species. The oil appears to pass through the outer tangential wall and the cuticle, covering the latter without forming cuticular blisters. PMID:19692391

A rare polyglycine type II-like helix motif in naturally occurring proteins.

PubMed

Warkentin, Eberhard; Weidenweber, Sina; Schühle, Karola; Demmer, Ulrike; Heider, Johann; Ermler, Ulrich

2017-11-01

Common structural elements in proteins such as α-helices or β-sheets are characterized by uniformly repeating, energetically favorable main chain conformations which additionally exhibit a completely saturated hydrogen-bonding network of the main chain NH and CO groups. Although polyproline or polyglycine type II helices (PP II or PG II ) are frequently found in proteins, they are not considered as equivalent secondary structure elements because they do not form a similar self-contained hydrogen-bonding network of the main chain atoms. In this context our finding of an unusual motif of glycine-rich PG II -like helices in the structure of the acetophenone carboxylase core complex is of relevance. These PG II -like helices form hexagonal bundles which appear to fulfill the criterion of a (largely) saturated hydrogen-bonding network of the main-chain groups and therefore may be regarded in this sense as a new secondary structure element. It consists of a central PG II -like helix surrounded by six nearly parallel PG II -like helices in a hexagonal array, plus an additional PG II -like helix extending the array outwards. Very related structural elements have previously been found in synthetic polyglycine fibers. In both cases, all main chain NH and CO groups of the central PG II -helix are saturated by either intra- or intermolecular hydrogen-bonds, resulting in a self-contained hydrogen-bonding network. Similar, but incomplete PG II -helix patterns were also previously identified in a GTP-binding protein and an antifreeze protein. © 2017 Wiley Periodicals, Inc.

Internal Structure of 15 nm 3-Helix Micelle Revealed by Small-Angle Neutron Scattering and Coarse-Grained MD Simulation.

PubMed

Ang, JooChuan; Ma, Dan; Lund, Reidar; Keten, Sinan; Xu, Ting

2016-10-10

3-Helix micelles (3HM) formed by self-assembly of peptide-polymer conjugate amphiphiles have shown promise as a nanocarrier platform due to their long-circulation, deep tumor penetration, selective accumulation in tumor, and ability to cross the blood-brain barrier (BBB) for glioblastoma therapy. There is a need to understand the structural contribution to the high in vivo stability and performance of 3HM. Using selective deuteration, the contrast variation technique in small-angle neutron scattering, and coarse-grained molecular dynamics simulation, we determined the spatial distribution of each component within 3HM. Our results show a slightly deformed polyethylene glycol (PEG) conformation within the micelle that is radially offset from its conjugation site toward the exterior of the micelle and a highly solvated shell. Surprisingly, ∼85 v/v % of 3HM is water, unusually higher than any micellar nanocarrier based on our knowledge. The result will provide important structural insights for future studies to uncover the molecular origin of 3HM's in vivo performance, and development of the nanocarriers.

Structure of Mycobacterium tuberculosis mtFabD, a malonyl-CoA:acyl carrier protein transacylase (MCAT)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghadbane, Hemza; Brown, Alistair K.; Kremer, Laurent

2007-10-01

Binding of Ni{sup 2+} ions to the uncleaved affinity tag facilitated de novo phasing of the crystal structure of M. tuberculosis mtFabD to 3.0 Å resolution. Mycobacteria display a unique and unusual cell-wall architecture, central to which is the membrane-proximal mycolyl-arabinogalactan-peptidoglycan core (mAGP). The biosynthesis of mycolic acids, which form the outermost layer of the mAGP core, involves malonyl-CoA:acyl carrier protein transacylase (MCAT). This essential enzyme catalyses the transfer of malonyl from coenzyme A to acyl carrier protein AcpM, thus feeding these two-carbon units into the chain-elongation cycle of the type II fatty-acid synthase. The crystal structure of M. tuberculosismore » mtFabD, the mycobacterial MCAT, has been determined to 3.0 Å resolution by multi-wavelength anomalous dispersion. Phasing was facilitated by Ni{sup 2+} ions bound to the 20-residue N-terminal affinity tag, which packed between the two independent copies of mtFabD.« less

Synthon preference in the cocrystal of 3,4,5-trifluorophenylboronic acid with urea.

PubMed

Kopczyńska, Karolina; Marek, Paulina H; Banaś, Bartłomiej; Madura, Izabela D

2017-11-01

The comprehensive description of the crystal structure of a novel 1:1 cocrystal of 3,4,5-trifluorophenylboronic acid with urea, C 6 H 4 BF 3 O 2 ·CH 4 N 2 O, is presented. Both components are good candidates for crystal engineering as they can create a variety of supramolecular synthons. The preference for the formation of different hetrosynthons is verified based on theoretical calculations. The syn-anti conformation of boronic acid has been found to be the most favourable in the formation of intermolecular interactions with urea. Moreover, the distortions present in the boron coordination sphere have been described quantitatively based on experimental data according to bond-valence vector model calculations. The results revealed that the deformation of the sphere is typical for a syn-anti conformation of boronic acids. The supramolecular structure of the cocrystal is composed of large synthons in the form of layers made up of O-H...O and N-H...O hydrogen bonds. The layers are joined via N-H...F hydrogen bonds which are unusual for urea cocrystal structures.

3D visualization of sheath folds in Ancient Roman marble wall coverings from Ephesos, Turkey

NASA Astrophysics Data System (ADS)

Wex, Sebastian; Passchier, Cees W.; de Kemp, Eric A.; İlhan, Sinan

2014-10-01

Archaeological excavations and restoration of a palatial Roman housing complex in Ephesos, Turkey yielded 40 wall-decorating plates of folded mylonitic marble (Cipollino verde), derived from the internal Hellenides near Karystos, Greece. Cipollino verde was commonly used for decoration purposes in Roman buildings. The plates were serial-sectioned from a single quarried block of 1,25 m3 and provided a research opportunity for detailed reconstruction of the 3D geometry of meterscale folds in mylonitized marble. A GOCAD model is used to visualize the internal fold structures of the marble, comprising curtain folds and multilayered sheath folds. The sheath folds are unusual in that they have their intermediate axis normal to the parent layering. This agrees with regional tectonic studies, which suggest that Cipollino verde structures formed by local constrictional non-coaxial flow. Sheath fold cross-section geometry, exposed on the surface of a plate or outcrop, is found to be independent of the intersection angle of the fold structure with the studied plane. Consequently, a single surface cannot be used as an indicator of the three-dimensional geometry of transected sheath folds.

Unusual behavior in magnesium-copper cluster matter produced by helium droplet mediated deposition.

PubMed

Emery, S B; Xin, Y; Ridge, C J; Buszek, R J; Boatz, J A; Boyle, J M; Little, B K; Lindsay, C M

2015-02-28

We demonstrate the ability to produce core-shell nanoclusters of materials that typically undergo intermetallic reactions using helium droplet mediated deposition. Composite structures of magnesium and copper were produced by sequential condensation of metal vapors inside the 0.4 K helium droplet baths and then gently deposited onto a substrate for analysis. Upon deposition, the individual clusters, with diameters ∼5 nm, form a cluster material which was subsequently characterized using scanning and transmission electron microscopies. Results of this analysis reveal the following about the deposited cluster material: it is in the un-alloyed chemical state, it maintains a stable core-shell 5 nm structure at sub-monolayer quantities, and it aggregates into unreacted structures of ∼75 nm during further deposition. Surprisingly, high angle annular dark field scanning transmission electron microscopy images revealed that the copper appears to displace the magnesium at the core of the composite cluster despite magnesium being the initially condensed species within the droplet. This phenomenon was studied further using preliminary density functional theory which revealed that copper atoms, when added sequentially to magnesium clusters, penetrate into the magnesium cores.

Neutron diffraction study and anomalous negative thermal expansion in non-superconducting PrFe1-xRuxAsO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yiu, Yuen; Garlea, Vasile O; McGuire, Michael A

2012-01-01

Neutron powder diraction has been used to investigate the structural and magnetic behavior of the isoelectronically doped Fe pnictide material PrFe1-xRuxAsO. Substitution of Ru for Fe sup- presses the structural and magnetic phase transitions that occur in the undoped compound PrFeAsO. Contrary to the behavior usually observed in 1111 pnictide materials, the suppression of both the structural and magnetic transitions does not result in the emergence of superconductivity or any other new ground state. Interestingly, PrFeAsO itself shows an unusual negative thermal expansion (NTE) along the c-axis, from 60K down to at least 4K; this does not occur in superconductingmore » samples such as those formed by doping with fluorine on the oxygen site. We nd that NTE is present for all concentrations of PrFe1-xRuxAsO with x ranging from 0.05 to 0.75. These results suggest that the absence of superconductivity in these materials could be related to the presence of NTE.« less

Crystallographic Study of a Novel Sub-Nanomolar Inhibitor Provides Insight on the Binding Interactions of Alkenyldiarylmethanes with Human Immunodeficiency Virus-1 (HIV-1) Reverse Transcriptase†

PubMed Central

Cullen, Matthew D.; Ho, William C.; Bauman, Joseph D.; Das, Kalyan; Arnold, Eddy; Hartman, Tracy L.; Watson, Karen M.; Buckheit, Robert W.; Pannecouque, Christophe; De Clercq, Erik; Cushman, Mark

2009-01-01

Two crystal structures have been solved for separate complexes of alkenyldiarylmethane (ADAM) non-nucleoside reverse transcriptase inhibitors (NNRTI) 3 and 4 with HIV-1 reverse transcriptase (RT). The structures reveal inhibitor binding is exclusively hydrophobic in nature and the shape of the inhibitor-bound NNRTI binding pocket is unique among other reported inhibitor-RT crystal structures. Primarily, ADAMs 3 and 4 protrude from a large gap in the backside of the binding pocket, placing portions of the inhibitors unusually close to the polymerase active site and allowing 3 to form a weak hydrogen bond with Lys223. The lack of additional stabilizing interactions, beyond the observed hydrophobic surface contacts, between 4 and RT is quite perplexing given the extreme potency of the compound (IC50 ≤ nM). ADAM 4 was designed to be hydrolytically stable in blood plasma, and an investigation of its hydrolysis in rat plasma demonstrated it has a significantly prolonged half-life in comparison to ADAM lead compounds 1 and 2. PMID:19775161

Unusual Sleep Experiences, Dissociation, and Schizotypy: Evidence for a Common Domain

PubMed Central

Koffel, Erin; Watson, David

2009-01-01

This paper reviews studies that have examined associations between unusual sleep experiences (including nightmares, vivid dreaming, narcolepsy symptoms, and complex nighttime behaviors) and dissociation and schizotypy. Using correlational studies and structural analyses, evidence is provided that unusual sleep experiences, dissociation, and schizotypy belong to a common domain. It is demonstrated that unusual sleep experiences show specificity to dissociation and schizotypy compared to other daytime symptoms (e.g., anxiety, depression, substance use) and other sleep disturbances (e.g., insomnia, lassitude/fatigue). The paper also outlines the methodological limitations of the existing evidence and makes suggestions for future research. Finally, three models for the overlap of daytime and nighttime symptoms are reviewed, including biological abnormalities, trauma, and personality traits. Although further research is needed, it is suggested that daytime and nighttime symptoms result from problems with sleep-wake state boundaries, which may be precipitated by stress or trauma. In addition, association between daytime and nighttime symptoms can be attributed to the higher order personality trait of Oddity. PMID:19581031

Autoerotic asphyxial deaths: analysis of nineteen fatalities in Alberta, 1978 to 1989.

PubMed

Tough, S C; Butt, J C; Sanders, G L

1994-04-01

This paper presents an unusual form of sexual (masturbatory) activity and brings this unusual cause of death to wider medical attention and understanding. All 19 cases of autoerotic asphyxial death that occurred between 1978 and 1989 in the province of Alberta, Canada were reviewed. The fatal victim of autoerotic asphyxia is typically a single male aged 15 to 29 years. Autoerotic sexual activity is typically performed in isolation; often there is evidence of repetitive practice. The accidental death usually results when the "safety" mechanism designed to alleviate neck compression fails. Often the first sign of the activity (usually a surprise to family and friends) is death itself. Physicians who are alert to the practice may suggest counselling when patients present with sexual concerns, unusual marks around the neck or evidence of abrasions to limbs suggesting bondage or other masochistic practices.

Myopericytoma proliferating in an unusual anastomosing multinodular fashion.

PubMed

Inoue, Takuya; Misago, Noriyuki; Asami, Akihiko; Tokunaga, Osamu; Narisawa, Yutaka

2016-05-01

We herein describe a case of myopericytoma that proliferated in an unusual fashion. Myopericytoma is described as a group of rare, benign, dermal or subcutaneous tumors that are characterized histologically by a striking, concentric, perivascular proliferation of spindle cells and showing apparent differentiation towards perivascular myoid cells. Myopericytoma forms a morphological continuum with myofibroma/myofibromatosis, glomus tumor and angioleiomyoma. The patient was a 64-year-old woman who demonstrated a recurrent ulcer on an atrophic plaque on her left shin. A histopathological examination of the plaque demonstrated that tumor cells proliferated in an anastomosing multinodular fashion along the vessels in the dermis and subcutaneous tissue. In those nodules, there were numerous, small, concentric proliferations of myoid-appearing spindle cells around small vascular lumina. The present case is an unusual example of myopericytoma, manifesting in a characteristic anastomosing, multinodular, infiltrating fashion. © 2015 Japanese Dermatological Association.

Structure of the membrane domain of respiratory complex I.

PubMed

Efremov, Rouslan G; Sazanov, Leonid A

2011-08-07

Complex I is the first and largest enzyme of the respiratory chain, coupling electron transfer between NADH and ubiquinone to the translocation of four protons across the membrane. It has a central role in cellular energy production and has been implicated in many human neurodegenerative diseases. The L-shaped enzyme consists of hydrophilic and membrane domains. Previously, we determined the structure of the hydrophilic domain. Here we report the crystal structure of the Esherichia coli complex I membrane domain at 3.0 Å resolution. It includes six subunits, NuoL, NuoM, NuoN, NuoA, NuoJ and NuoK, with 55 transmembrane helices. The fold of the homologous antiporter-like subunits L, M and N is novel, with two inverted structural repeats of five transmembrane helices arranged, unusually, face-to-back. Each repeat includes a discontinuous transmembrane helix and forms half of a channel across the membrane. A network of conserved polar residues connects the two half-channels, completing the proton translocation pathway. Unexpectedly, lysines rather than carboxylate residues act as the main elements of the proton pump in these subunits. The fourth probable proton-translocation channel is at the interface of subunits N, K, J and A. The structure indicates that proton translocation in complex I, uniquely, involves coordinated conformational changes in six symmetrical structural elements.

Use of Multiple Fluorescent Labels in Biological Sensing

DTIC Science & Technology

2006-05-01

resulting in labels that are brighter and have longer Stokes shifts than the current standard; (B) to make excimer- and exciplex -forming probes for...2) to make excimer- and exciplex -forming probes for repetitive DNA sequences such as telomeres and centromeres, and to demonstrate them both...between fluorophores, and characterized unusual interactions, including water-soluble excimers and exciplexes . We investigated multiple ways to

The Shape of Things: The Origin of Young Children's Knowledge of the Names and Properties of Geometric Forms

ERIC Educational Resources Information Center

Verdine, Brian N.; Lucca, Kelsey R.; Golinkoff, Roberta M.; Hirsh-Pasek, Kathryn; Newcombe, Nora S.

2016-01-01

How do toddlers learn the names of geometric forms? Previous work suggests that preschoolers have fragmentary knowledge and that defining properties are not understood until well into elementary school. The current study investigated when children first begin to understand shape names and how they apply those labels to unusual instances. We tested…

206. Big Witch Road grade separation structure. This concrete box ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

206. Big Witch Road grade separation structure. This concrete box culvert, built in 1950, is unusual in that the culvert's concrete bottom extends beyond the structure to the ends of its perpendicular wing walls. Facing northeast. - Blue Ridge Parkway, Between Shenandoah National Park & Great Smoky Mountains, Asheville, Buncombe County, NC

Floral rewards in the tribe Sisyrinchieae (Iridaceae): oil as an alternative to pollen and nectar?

PubMed

Silvério, Adriano; Nadot, Sophie; Souza-Chies, Tatiana T; Chauveau, Olivier

2012-12-01

Iridaceae is one of the few families in which floral oils are produced and collected by pollinators as a resource. Perigonal nectaries and trichomal elaiophores are highly unusual within the tribe Sisyrinchieae. Both structures occur mainly on the staminal column, while they are usually distributed on the tepals in the other tribes of the subfamily Iridoideae. Sisyrinchieae is the largest tribe of Iridaceae present on the American continent, and the diversity observed may be related to the exceptional development of trichomal elaiophores within the genus Sisyrinchium, but knowledge concerning the other types of nuptial glandular structures within the tribe is still limited, preventing us from estimating their implication for species diversity. Structural observations and histochemical tests were performed to identify and characterize glandular structures and pollen rewards within the flowers of the genera Orthrosanthus, Sisyrinchium and Solenomelus. Perigonal nectaries were detected only in Solenomelus segethi, and trichomal elaiophores were characterized only within Sisyrinchium. All species showed large amounts of additional resources available for pollinators in the form of pollenkitt and polysaccharides present in the cytoplasm of the pollen grains. The results are discussed in a phylogenetic context, with regard to pollinators and floral rewards reported for the tribe Sisyrinchieae.

The vertical disk structure of the edge-on spiral galaxy NGC 3079

NASA Technical Reports Server (NTRS)

Veilleux, S.; Bland-Hawthorn, Jonathan; Cecil, G.; Tully, R. B.

1993-01-01

NGC 3079 is an edge-on SB(s)c galaxy at a redshift of 1225 km/s relative to the Local Group. Earlier researchers found a spectacular 'figure-eight' radio structure aligned along the minor axis of the galaxy, centered on the nucleus, and extending 3 kpc above and below the plane. The geometry of this structure and the evidence of unusually high nuclear gas velocities suggest that a wind-type outflow from the nucleus is taking place. The disk of NGC 3079 is also remarkable: it is extremely rich in H 2 regions and is the only unambiguous example of a galaxy outside M31 and our own Galaxy to exhibit 'Heiles-like' shells. Other researchers have also identified a nebulosity with a ragged X-shaped morphology formed by a system of lumpy filaments with individual lengths of 3 - 5 kpc. They suggest that this material is ambient halo gas entrained into the boundary layers of the nuclear outflow. The complex structure of the line emission in NGC 3079 makes this object an ideal target for an imaging spectroscopic study. The present paper reports the preliminary results of such a study.

Extraordinary wavelength reduction in terahertz graphene-cladded photonic crystal slabs

PubMed Central

Williamson, Ian A. D.; Mousavi, S. Hossein; Wang, Zheng

2016-01-01

Photonic crystal slabs have been widely used in nanophotonics for light confinement, dispersion engineering, nonlinearity enhancement, and other unusual effects arising from their structural periodicity. Sub-micron device sizes and mode volumes are routine for silicon-based photonic crystal slabs, however spectrally they are limited to operate in the near infrared. Here, we show that two single-layer graphene sheets allow silicon photonic crystal slabs with submicron periodicity to operate in the terahertz regime, with an extreme 100× wavelength reduction from graphene’s large kinetic inductance. The atomically thin graphene further leads to excellent out-of-plane confinement, and consequently photonic-crystal-slab band structures that closely resemble those of ideal two-dimensional photonic crystals, with broad band gaps even when the slab thickness approaches zero. The overall photonic band structure not only scales with the graphene Fermi level, but more importantly scales to lower frequencies with reduced slab thickness. Just like ideal 2D photonic crystals, graphene-cladded photonic crystal slabs confine light along line defects, forming waveguides with the propagation lengths on the order of tens of lattice constants. The proposed structure opens up the possibility to dramatically reduce the size of terahertz photonic systems by orders of magnitude. PMID:27143314

Discoipyrroles A-D: Isolation, Structure Determination and Synthesis of Potent Migration Inhibitors from Bacillus hunanensis

PubMed Central

Hu, Youcai; Potts, Malia B.; Colosimo, Dominic; Herrera-Herrera, Mireya L.; Legako, Aaron G.; Yousufuddin, Muhammed; White, Michael A.; MacMillan, John B.

2013-01-01

Discoidin domain receptor 2 (DDR2) is a receptor tyrosine kinase involved in a variety of cellular response pathways, including regulation of cell growth, proliferation and motility. Using a newly developed platform to identify the signaling pathway/molecular target of natural products, we identified a family of alkaloid natural products, discoipyrroles A–D (1–4), from Bacillus hunanensis that inhibit the DDR2 signaling pathway. The structure of 1–4, determined by detailed 2D NMR methods and confirmed by X-ray crystallographic analysis has an unusual 3H-benzo[ d]pyrrolo][1,3]oxazine-3,5-dione core. Discoipyrroles A–D potently inhibit DDR2 dependent migration of BR5 fibroblasts and show selective cytotoxicity to DDR2 mutant cell lung cancer cell lines (IC50 120–400 nM). Examination of the biosynthesis has led to the conclusion that the discoipyrroles are formed through a non-enzymatic process, leading to a one-pot total synthesis of 1. PMID:23984625

Semi-metallic Be5C2 monolayer global minimum with quasi-planar pentacoordinate carbons and negative Poisson's ratio.

PubMed

Wang, Yu; Li, Feng; Li, Yafei; Chen, Zhongfang

2016-05-03

Designing new materials with novel topological properties and reduced dimensionality is always desirable for material innovation. Here we report the design of a two-dimensional material, namely Be5C2 monolayer on the basis of density functional theory computations. In Be5C2 monolayer, each carbon atom binds with five beryllium atoms in almost the same plane, forming a quasi-planar pentacoordinate carbon moiety. Be5C2 monolayer appears to have good stability as revealed by its moderate cohesive energy, positive phonon modes and high melting point. It is the lowest-energy structure with the Be5C2 stoichiometry in two-dimensional space and therefore holds some promise to be realized experimentally. Be5C2 monolayer is a gapless semiconductor with a Dirac-like point in the band structure and also has an unusual negative Poisson's ratio. If synthesized, Be5C2 monolayer may find applications in electronics and mechanics.

Closed-cage tungsten oxide clusters in the gas phase.

PubMed

Singh, D M David Jeba; Pradeep, T; Thirumoorthy, Krishnan; Balasubramanian, Krishnan

2010-05-06

During the course of a study on the clustering of W-Se and W-S mixtures in the gas phase using laser desorption ionization (LDI) mass spectrometry, we observed several anionic W-O clusters. Three distinct species, W(6)O(19)(-), W(13)O(29)(-), and W(14)O(32)(-), stand out as intense peaks in the regular mass spectral pattern of tungsten oxide clusters suggesting unusual stabilities for them. Moreover, these clusters do not fragment in the postsource decay analysis. While trying to understand the precursor material, which produced these clusters, we found the presence of nanoscale forms of tungsten oxide. The structure and thermodynamic parameters of tungsten clusters have been explored using relativistic quantum chemical methods. Our computed results of atomization energy are consistent with the observed LDI mass spectra. The computational results suggest that the clusters observed have closed-cage structure. These distinct W(13) and W(14) clusters were observed for the first time in the gas phase.

Molecular dynamics simulations and CD spectroscopy reveal hydration-induced unfolding of the intrinsically disordered LEA proteins COR15A and COR15B from Arabidopsis thaliana.

PubMed

Navarro-Retamal, Carlos; Bremer, Anne; Alzate-Morales, Jans; Caballero, Julio; Hincha, Dirk K; González, Wendy; Thalhammer, Anja

2016-10-07

The LEA (late embryogenesis abundant) proteins COR15A and COR15B from Arabidopsis thaliana are intrinsically disordered under fully hydrated conditions, but obtain α-helical structure during dehydration, which is reversible upon rehydration. To understand this unusual structural transition, both proteins were investigated by circular dichroism (CD) and molecular dynamics (MD) approaches. MD simulations showed unfolding of the proteins in water, in agreement with CD data obtained with both HIS-tagged and untagged recombinant proteins. Mainly intramolecular hydrogen bonds (H-bonds) formed by the protein backbone were replaced by H-bonds with water molecules. As COR15 proteins function in vivo as protectants in leaves partially dehydrated by freezing, unfolding was further assessed under crowded conditions. Glycerol reduced (40%) or prevented (100%) unfolding during MD simulations, in agreement with CD spectroscopy results. H-bonding analysis indicated that preferential exclusion of glycerol from the protein backbone increased stability of the folded state.

New LaMAsH(x) (M = Co, Ni, or Cu) arsenides with covalent M-H chains.

PubMed

Mizoguchi, Hiroshi; Park, SangWon; Hiraka, Haruhiro; Ikeda, Kazutaka; Otomo, Toshiya; Hosono, Hideo

2014-12-17

A new series of tetragonal LaPtSi-type mixed-anion arsenides, LaMAsH(x) (M = Co, Ni, or Cu), has been synthesized using high-temperature and high-pressure techniques. The crystal structure of these intermetallic compounds determined via powder neutron diffraction is composed of a 3D framework of three connected planes with the La ions filling the cavities in the structure. Each late transition-metal ion M, all of which have relatively large electronegativities, behaves like a main group element and forms a planar coordination configuration with three As ions. The trigonal-bipyramidal coordination adopted by the H in the cavity, HM2La3, is compressed along the C3 axis, and unusual M-H chains run along the x and y directions, reinforcing the covalent framework. These chains, which are unique in solids, are stabilized by covalent interactions between the M 4s and H 1s orbitals.

Recent progress on borophene: Growth and structures

NASA Astrophysics Data System (ADS)

Kong, Longjuan; Wu, Kehui; Chen, Lan

2018-06-01

Boron is the neighbor of carbon on the periodic table and exhibits unusual physical characteristics derived from electron-deficient, highly delocalized covalent bonds. As the nearest neighbor of carbon, boron is in many ways similar to carbon, such as having a short covalent radius and the flexibility to adopt sp 2 hybridization. Hence, boron could be capable of forming monolayer structural analogues of graphene. Although many theoretical papers have reported finding two-dimensional allotropes of boron, there had been no experimental evidence for such atom-thin boron nanostructures until 2016. Recently, the successful synthesis of single-layer boron (referred to as borophene) on the Ag(111) substrate opens the era of boron nanostructures. In this brief review, we will discuss the progress that has been made on borophene in terms of synthetic techniques, characterizations and the atomic models. However, borophene is just in infancy; more efforts are expected to be made in future on the controlled synthesis of quality samples and tailoring its physical properties.

Cascades of alternating pitchfork and flip bifurcations in H-bridge inverters

NASA Astrophysics Data System (ADS)

Avrutin, Viktor; Zhusubaliyev, Zhanybai T.; Mosekilde, Erik

2017-04-01

Power electronic DC/AC converters (inverters) play an important role in modern power engineering. These systems are also of considerable theoretical interest because their dynamics is influenced by the presence of two vastly different forcing frequencies. As a consequence, inverter systems may be modeled in terms of piecewise smooth maps with an extremely high number of switching manifolds. We have recently shown that models of this type can demonstrate a complicated bifurcation structure associated with the occurrence of border collisions. Considering the example of a PWM H-bridge single-phase inverter, the present paper discusses a number of unusual phenomena that can occur in piecewise smooth maps with a very large number of switching manifolds. We show in particular how smooth (pitchfork and flip) bifurcations may form a macroscopic pattern that stretches across the overall bifurcation structure. We explain the observed bifurcation phenomena, show under which conditions they occur, and describe them quantitatively by means of an analytic approximation.

DNA-directed mutations. Leading and lagging strand specificity

NASA Technical Reports Server (NTRS)

Sinden, R. R.; Hashem, V. I.; Rosche, W. A.

1999-01-01

The fidelity of replication has evolved to reproduce B-form DNA accurately, while allowing a low frequency of mutation. The fidelity of replication can be compromised, however, by defined order sequence DNA (dosDNA) that can adopt unusual or non B-DNA conformations. These alternative DNA conformations, including hairpins, cruciforms, triplex DNAs, and slipped-strand structures, may affect enzyme-template interactions that potentially lead to mutations. To analyze the effect of dosDNA elements on spontaneous mutagenesis, various mutational inserts containing inverted repeats or direct repeats were cloned in a plasmid containing a unidirectional origin of replication and a selectable marker for the mutation. This system allows for analysis of mutational events that are specific for the leading or lagging strands during DNA replication in Escherichia coli. Deletions between direct repeats, involving misalignment stabilized by DNA secondary structure, occurred preferentially on the lagging strand. Intermolecular strand switch events, correcting quasipalindromes to perfect inverted repeats, occurred preferentially during replication of the leading strand.

Unusual seismogenic soft-sediment deformation structures in Cambrian epicratonic carbonate deposits, western Colorado, U.S.A

NASA Astrophysics Data System (ADS)

Myrow, P.; Chen, J.

2013-12-01

A wide variety of unusual penecontemporaneous deformation structures exist in grainstone and flat-pebble conglomerate beds of the Upper Cambrian strata, western Colorado, including slide scarps, thrusted beds, irregular blocks and internally deformed beds. Slide scarps are characterized by concave-up, sharp surfaces that truncate one or more underlying beds. Thrusted beds record movement of a part of a bed onto itself along a moderate to steeply inclined (generally 25°-40°) ramp. The hanging wall lenses in cases show fault-bend geometries, with either intact or mildly deformed bedding. Irregular bedded to internally deformed blocks isolated on generally flat upper bedding surfaces are similar in composition to the underlying beds. These features represent parts of beds that were detached, moved up onto, and some distances across, the laterally adjacent undisturbed bed surfaces. The blocks moved either at the sediment-water interface or intrastratally at shallow depths within overlying muddy deposits. Finally, internally deformed beds have large blocks, fitted fabrics of highly irregular fragments, and contorted lamination, which represent heterogeneous deformation, such as brecciation and liquefaction. The various deformation structures were most probably triggered by earthquakes, considering the nature of deformation (regional distribution of liquefaction structures, and the brittle segmentation and subsequent transportation of semi-consolidated beds) and the reactivation of Mesoproterozoic, crustal-scale shear zones in the central Rockies during the Late Cambrian. Features produced by initial brittle deformation are unusual relative to most reported seismites, and may represent poorly recognized to unrecognized seismogenic structures in the rock record.

Haenamindole, an unusual diketopiperazine derivative from a marine-derived Penicillium sp. KCB12F005.

PubMed

Kim, Jong Won; Ko, Sung-Kyun; Son, Sangkeun; Shin, Kee-Sun; Ryoo, In-Ja; Hong, Young-Soo; Oh, Hyuncheol; Hwang, Bang Yeon; Hirota, Hiroshi; Takahashi, Shunji; Kim, Bo Yeon; Osada, Hiroyuki; Jang, Jae-Hyuk; Ahn, Jong Seog

2015-11-15

During the chemical investigation of marine-derived fungus, an unusual diketopiperazine (DKP) alkaloid, haenamindole (1), was isolated from a culture of the marine-derived fungus Penicillium sp. KCB12F005. The structure of 1, which possesses benzyl-hydroxypiperazindione and phenyl-pyrimidoindole rings system in the molecule, was elucidated by analysis of NMR and MS data. The stereochemistry of 1 was determined by ROESY and advanced Marfey's method. Copyright © 2015 Elsevier Ltd. All rights reserved.

Growth strategies to control tapering in Ge nanowires

NASA Astrophysics Data System (ADS)

Periwal, P.; Baron, T.; Gentile, P.; Salem, B.; Bassani, F.

2014-04-01

We report the effect of PH3 on the morphology of Au catalyzed Ge nanowires (NWs). Ge NWs were grown on Si (111) substrate at 400 °C in the presence of PH3, using vapor-liquid-solid method by chemical vapor deposition. We show that high PH3/GeH4 ratio causes passivation at NW surface. At high PH3 concentration phosphorous atoms attach itself on NW surface and form a self-protection coating that prevents conformal growth and leads to taper free nanostructures. However, in case of low PH3 flux the combination of axial and radial growth mechanism occurs resulting in conical structure. We have also investigated axial PH3-intrinsic junctions in Ge NWs. The unusual NW shape is attributed to a combination of catalyzed, uncatalyzed and diffusion induced growth.

Kuznetsov-Ma Soliton Dynamics Based on the Mechanical Effect of Light

NASA Astrophysics Data System (ADS)

Xiong, Hao; Gan, Jinghui; Wu, Ying

2017-10-01

A Kuznetsov-Ma soliton that exhibits an unusual pulsating dynamics has attracted particular attention in hydrodynamics and plasma physics in the context of understanding nonlinear coherent phenomena. Here, we demonstrate theoretically the formation of a novel form of Kuznetsov-Ma soliton in a microfabricated optomechanical array, where both photonic and phononic evolutionary dynamics exhibit periodic structure and coherent localized behavior enabled by radiation-pressure coupling of optical fields and mechanical oscillations, which is a manifestation of the unique property of optomechanical systems. Numerical calculations of the optomechanical dynamics show an excellent agreement with this theory. In addition to providing insight into optomechanical nonlinearity, optomechanical Kuznetsov-Ma soliton dynamics fundamentally broadens the regime of cavity optomechanics and may find applications in on-chip manipulation of light propagation.

Venus - Cycle 1, 2, and 3 Images of Imdr Region

NASA Technical Reports Server (NTRS)

1992-01-01

This set of three Magellan images shows a small volcano, lava plains distorted into 'wrinkle ridges', and some unusual wispy-appearing surface deposits. The images were acquired during the first, second and third mapping cycles of the mission, in March 1991, November 1991 and July 1992, respectively. The area shown is about 400 kilometers by 100 kilometers (248 by 62 miles) and is centered near 47.5 degrees south latitude, 226 degrees east longitude, in the Imdr region of Venus. The middle image, from the second cycle, was acquired with the spacecraft facing toward the west (left), while the other images were acquired with an identical east-looking geometry. The differing appearance of the second image has intrigued Magellan scientists, because of the possibility that the bright patches observed in cycle 2 may have been caused by rearrangement of loose soil material between March and November, 1991. However, by duplicating the cycle 1 viewing geometry in cycle 3, the surface change theory has been tentatively ruled out. Instead, the radar brightness variations are attributed to reflections from an undulating surface, such as sand ripples or small dunes, that have an asymmetry in the east-west direction. The deposits are apparently associated with a 78 kilometers (48 miles) diameter impact crater, Stowe, which lies about 500 kilometers (310 miles) to the northeast. The fine-grained material created during the impact event may have settled out to form the unusual surface deposits observed here. Scientists are now trying to determine if the proposed ripple structures formed at the time of the impact, or are the result of ongoing wind action at the surface. Data quality during portions of cycle 3 was adversely affected by a faulty transmitter aboard the spacecraft, leading to the missing strips in the bottom image.

Antibacterial action of a heat-stable form of L-amino acid oxidase isolated from king cobra (Ophiophagus hannah) venom.

PubMed

Lee, Mui Li; Tan, Nget Hong; Fung, Shin Yee; Sekaran, Shamala Devi

2011-03-01

The major l-amino acid oxidase (LAAO, EC 1.4.3.2) of king cobra (Ophiophagus hannah) venom is known to be an unusual form of snake venom LAAO as it possesses unique structural features and unusual thermal stability. The antibacterial effects of king cobra venom LAAO were tested against several strains of clinical isolates including Staphylococcus aureus, Staphylococcus epidermidis, Pseudomonas aeruginosa, Klebsiella pneumoniae, and Escherichia coli using broth microdilution assay. For comparison, the antibacterial effects of several antibiotics (cefotaxime, kanamycin, tetracycline, vancomycin and penicillin) were also examined using the same conditions. King cobra venom LAAO was very effective in inhibiting the two Gram-positive bacteria (S. aureus and S. epidermidis) tested, with minimum inhibitory concentration (MIC) of 0.78μg/mL (0.006μM) and 1.56μg/mL (0.012μM) against S. aureus and S. epidermidis, respectively. The MICs are comparable to the MICs of the antibiotics tested, on a weight basis. However, the LAAO was only moderately effective against three Gram-negative bacteria tested (P. aeruginosa, K. pneumoniae and E. coli), with MIC ranges from 25 to 50μg/mL (0.2-0.4μM). Catalase at the concentration of 1mg/mL abolished the antibacterial effect of LAAO, indicating that the antibacterial effect of the enzyme involves generation of hydrogen peroxide. Binding studies indicated that king cobra venom LAAO binds strongly to the Gram-positive S. aureus and S. epidermidis, but less strongly to the Gram-negative E. coli and P. aeruginosa, indicating that specific binding to bacteria is important for the potent antibacterial activity of the enzyme. Copyright © 2010 Elsevier Inc. All rights reserved.

The short interspersed repetitive element of Trypanosoma cruzi, SIRE, is part of VIPER, an unusual retroelement related to long terminal repeat retrotransposons

PubMed Central

Vázquez, Martín; Ben-Dov, Claudia; Lorenzi, Hernan; Moore, Troy; Schijman, Alejandro; Levin, Mariano J.

2000-01-01

The short interspersed repetitive element (SIRE) of Trypanosoma cruzi was first detected when comparing the sequences of loci that encode the TcP2β genes. It is present in about 1,500–3,000 copies per genome, depending on the strain, and it is distributed in all chromosomes. An initial analysis of SIRE sequences from 21 genomic fragments allowed us to derive a consensus nucleotide sequence and structure for the element, consisting of three regions (I, II, and III) each harboring distinctive features. Analysis of 158 transcribed SIREs demonstrates that the consensus is highly conserved. The sequences of 51 cDNAs show that SIRE is included in the 3′ end of several mRNAs, always transcribed from the sense strand, contributing the polyadenylation site in 63% of the cases. This study led to the characterization of VIPER (vestigial interposed retroelement), a 2,326-bp-long unusual retroelement. VIPER's 5′ end is formed by the first 182 bp of SIRE, whereas its 3′ end is formed by the last 220 bp of the element. Both SIRE moieties are connected by a 1,924-bp-long fragment that carries a unique ORF encoding a complete reverse transcriptase-RNase H gene whose 15 C-terminal amino acids derive from codons specified by SIRE's region II. The amino acid sequence of VIPER's reverse transcriptase-RNase H shares significant homology to that of long terminal repeat retrotransposons. The fact that SIRE and VIPER sequences are found only in the T. cruzi genome may be of relevance for studies concerning the evolution and the genome flexibility of this protozoan parasite. PMID:10688909

Hexakis(3,6-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)cyclohexane: Closed-shell [6]Radialene or Open-shell Hexa-radicaloid?

PubMed

Wu, Jishan; Feng, Jiaqi; Gopalakrishna, Tullimilli Y; Phan, Hoa

2018-04-19

We report a star-shaped hexaquinocyclohexane molecule 4c, which turns out to be a closed-shell extended [6]radialene with a twisted-boat conformation according to X-ray crystallographic analysis. It was formed by an unusually slow decay of its in situ generated open-shell valence isomer, the hexa-radicaloid 4o, with a half-life time of about 156 min at room temperature. Reaction progress kinetic analysis revealed a large energy barrier of about 95.5 ± 4.3 kJ/mol at room temperature from the hexa-radical form 4o to the contorted [6]radialene form 4c, because the transformation need overcome large steric repulsion between the neighbouring phenoxyl units. Compound 4c can be chemically reduced to radical anion and dianion, and the dianion is actually a diradical dianion, with a calculated diradical character of 71.9%. This study demonstrated the unique chemical bonding nature of contorted quinoidal π-conjugated molecules and a very unusual valence isomerization process. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transcriptional Regulation, Metal Binding Properties and Structure of Pden1597, an Unusual Zinc Transport Protein from Paracoccus denitrificans*

PubMed Central

Handali, Melody; Neupane, Durga P.; Roychowdhury, Hridindu; Yukl, Erik T.

2015-01-01

ATP-binding cassette (ABC) transporters of the cluster 9 family are ubiquitous among bacteria and essential for acquiring Zn2+ and Mn2+ from the environment or, in the case of pathogens, from the host. These rely on a substrate-binding protein (SBP) to coordinate the relevant metal with high affinity and specificity and subsequently release it to a membrane permease for translocation into the cytoplasm. Although a number of cluster 9 SBP structures have been determined, the structural attributes conferring Zn2+ or Mn2+ specificity remain ambiguous. Here we describe the gene expression profile, in vitro metal binding properties, and crystal structure of a new cluster 9 SBP from Paracoccus denitrificans we have called AztC. Although all of our results strongly indicate Zn2+ over Mn2+ specificity, the Zn2+ ion is coordinated by a conserved Asp residue only observed to date as a metal ligand in Mn2+-specific SBPs. The unusual sequence properties of this protein are shared among close homologues, including members from the human pathogens Klebsiella pneumonia and Enterobacter aerogenes, and would seem to suggest a subclass of Zn2+-specific transporters among the cluster 9 family. In any case, the unusual coordination environment of AztC expands the already considerable range of those available to Zn2+-specific SBPs and highlights the presence of a His-rich loop as the most reliable indicator of Zn2+ specificity. PMID:25787075

Transcriptional regulation, metal binding properties and structure of Pden1597, an unusual zinc transport protein from Paracoccus denitrificans

DOE PAGES

Handali, Melody; Neupane, Durga P.; Roychowdhury, Hridindu; ...

2015-03-18

Here, ATP-binding cassette (ABC) transporters of the cluster 9 family are ubiquitous among bacteria and essential for acquiring Zn 2+ and Mn 2+ from the environment or, in the case of pathogens, from the host. These rely on a substrate-binding protein (SBP) to coordinate the relevant metal with high affinity and specificity and subsequently release it to a membrane permease for translocation into the cytoplasm. Although a number of cluster 9 SBP structures have been determined, the structural attributes conferring Zn 2+ or Mn 2+ specificity remain ambiguous. Here we describe the gene expression profile, in vitro metal binding properties,more » and crystal structure of a new cluster 9 SBP from Paracoccus denitrificans we have called AztC. Although all of our results strongly indicate Zn 2+ over Mn 2+ specificity, the Zn 2+ ion is coordinated by a conserved Asp residue only observed to date as a metal ligand in Mn 2+-specific SBPs. The unusual sequence properties of this protein are shared among close homologues, including members from the human pathogens Klebsiella pneumonia and Enterobacter aerogenes, and would seem to suggest a subclass of Zn 2+-specific transporters among the cluster 9 family. In any case, the unusual coordination environment of AztC expands the already considerable range of those available to Zn 2+-specific SBPs and highlights the presence of a His-rich loop as the most reliable indicator of Zn 2+ specificity.« less

HUBBLE PHOTOGRAPHS WARPED GALAXY AS CAMERA PASSES MILESTONE

NASA Technical Reports Server (NTRS)

2002-01-01

NASA's Hubble Space Telescope has captured an image of an unusual edge-on galaxy, revealing remarkable details of its warped dusty disk and showing how colliding galaxies spawn the formation of new generations of stars. The dust and spiral arms of normal spiral galaxies, like our own Milky Way, appear flat when viewed edge-on. This month's Hubble Heritage image of ESO 510-G13 shows a galaxy that, by contrast, has an unusual twisted disk structure, first seen in ground-based photographs obtained at the European Southern Observatory (ESO) in Chile. ESO 510-G13 lies in the southern constellation Hydra, roughly 150 million light-years from Earth. Details of the structure of ESO 510-G13 are visible because the interstellar dust clouds that trace its disk are silhouetted from behind by light from the galaxy's bright, smooth central bulge. The strong warping of the disk indicates that ESO 510-G13 has recently undergone a collision with a nearby galaxy and is in the process of swallowing it. Gravitational forces distort the structures of the galaxies as their stars, gas, and dust merge together in a process that takes millions of years. Eventually the disturbances will die out, and ESO 510-G13 will become a normal-appearing single galaxy. In the outer regions of ESO 510-G13, especially on the right-hand side of the image, we see that the twisted disk contains not only dark dust, but also bright clouds of blue stars. This shows that hot, young stars are being formed in the disk. Astronomers believe that the formation of new stars may be triggered by collisions between galaxies, as their interstellar clouds smash together and are compressed. The Heritage Team used Hubble's Wide Field Planetary Camera 2 (WFPC2) to observe ESO 510-G13 in April 2001. Pictures obtained through blue, green, and red filters were combined to make this color-composite image, which emphasizes the contrast between the dusty spiral arms, the bright bulge, and the blue star-forming regions. During the observations of ESO 510-G13, WFPC2 passed the milestone of taking its 100,000th image since its installation in the telescope by shuttle astronauts in 1993. Image Credit: NASA and the Hubble Heritage Team (STScI/AURA) Acknowledgment: C. Conselice (U. Wisconsin/STScI)

Unusual fast-growing ovarian cystic teratoma during pregnancy presenting with intracystic fat "floating balls" appearance.

PubMed

Donnadieu, Anne Claire; Deffieux, Xavier; Le Ray, Camille; Mordefroid, Marie; Frydman, René; Fernandez, Hervé

2006-12-01

A large ovarian cyst was diagnosed at 22 weeks' of gestation in a 32-year-old woman. The ultrasonographic appearance of the ovarian cyst was unusual with multiple mobile, spherical echogenic structures floating in the cystic mass, called intracystic "fat balls." Right adnexectomy was performed by laparotomy at 28 weeks' of gestation, because of rapid growth and overall size exceeding 20 cm. Pathological examination confirmed ovarian cystic teratoma. Usually, dermoid cysts are slow-growing, even in premenopausal women. The exact mechanism related to the fast growth during pregnancy is unknown. It could be related to an unusual pattern of estrogen (E)/P receptors expression in the cystic teratoma. This case shows that a fast-growing, mature ovarian cystic teratoma may occur during pregnancy.

Unusual intraosseous fossilized soft tissues from the Middle Triassic Nothosaurus bone

NASA Astrophysics Data System (ADS)

Surmik, Dawid; Rothschild, Bruce M.; Pawlicki, Roman

2017-04-01

Fossilized soft tissues, occasionally found together with skeletal remains, provide insights to the physiology and functional morphology of extinct organisms. Herein, we present unusual fossilized structures from the cortical region of bone identified in isolated skeletal remains of Middle Triassic nothosaurs from Upper Silesia, Poland. The ribbed or annuli-shaped structures have been found in a sample of partially demineralized coracoid and are interpreted as either giant red blood cells or as blood vessel walls. The most probable function is reinforcing the blood vessels from changes of nitrogen pressure in air-breathing diving reptiles. These structures seem to have been built of extensible muscle layers which prevent the vessel damage during rapid ascent. Such suspected function presented here is parsimonious with results of previous studies, which indicate rarity of the pathological modification of bones associated with decompression syndrome in Middle Triassic nothosaurs.

Multipole Superconductivity in Nonsymmorphic Sr_{2}IrO_{4}.

PubMed

Sumita, Shuntaro; Nomoto, Takuya; Yanase, Youichi

2017-07-14

Discoveries of marked similarities to high-T_{c} cuprate superconductors point to the realization of superconductivity in the doped J_{eff}=1/2 Mott insulator Sr_{2}IrO_{4}. Contrary to the mother compound of cuprate superconductors, several stacking patterns of in-plane canted antiferromagnetic moments have been reported, which are distinguished by the ferromagnetic components as -++-, ++++, and -+-+. In this paper, we clarify unconventional features of the superconductivity coexisting with -++- and -+-+ structures. Combining the group theoretical analysis and numerical calculations for an effective J_{eff}=1/2 model, we show unusual superconducting gap structures in the -++- state protected by nonsymmorphic magnetic space group symmetry. Furthermore, our calculation shows that the Fulde-Ferrell-Larkin-Ovchinnikov superconductivity is inevitably stabilized in the -+-+ state since the odd-parity magnetic -+-+ order makes the band structure asymmetric by cooperating with spin-orbit coupling. These unusual superconducting properties are signatures of magnetic multipole order in nonsymmorphic crystal.

Multipole Superconductivity in Nonsymmorphic Sr2IrO4

NASA Astrophysics Data System (ADS)

Sumita, Shuntaro; Nomoto, Takuya; Yanase, Youichi

2017-07-01

Discoveries of marked similarities to high-Tc cuprate superconductors point to the realization of superconductivity in the doped Jeff=1 /2 Mott insulator Sr2IrO4. Contrary to the mother compound of cuprate superconductors, several stacking patterns of in-plane canted antiferromagnetic moments have been reported, which are distinguished by the ferromagnetic components as -++-, ++++, and -+-+ . In this paper, we clarify unconventional features of the superconductivity coexisting with -++- and -+-+ structures. Combining the group theoretical analysis and numerical calculations for an effective Jeff=1 /2 model, we show unusual superconducting gap structures in the -++- state protected by nonsymmorphic magnetic space group symmetry. Furthermore, our calculation shows that the Fulde-Ferrell-Larkin-Ovchinnikov superconductivity is inevitably stabilized in the -+-+ state since the odd-parity magnetic -+-+ order makes the band structure asymmetric by cooperating with spin-orbit coupling. These unusual superconducting properties are signatures of magnetic multipole order in nonsymmorphic crystal.

Atrophia maculosa varioliformis cutis.

PubMed

Kuflik, Julianne H; Schwartz, Robert A; Becker, Kenneth A; Lambert, W Clark

2005-10-01

Atrophia maculosa varioliformis cutis is a rare disease characterized by spontaneously formed facial scars in young adults. Its etiology is unknown; there may be an underlying defect of dermal elastin. We discuss a patient with this unusual disorder and review its literature.

Three-Dimensional Multiscale, Multistable, and Geometrically Diverse Microstructures with Tunable Vibrational Dynamics Assembled by Compressive Buckling.

PubMed

Ning, Xin; Wang, Heling; Yu, Xinge; Soares, Julio A N T; Yan, Zheng; Nan, Kewang; Velarde, Gabriel; Xue, Yeguang; Sun, Rujie; Dong, Qiyi; Luan, Haiwen; Lee, Chan Mi; Chempakasseril, Aditya; Han, Mengdi; Wang, Yiqi; Li, Luming; Huang, Yonggang; Zhang, Yihui; Rogers, John

2017-04-11

Microelectromechanical systems remain an area of significant interest in fundamental and applied research due to their wide ranging applications. Most device designs, however, are largely two-dimensional and constrained to only a few simple geometries. Achieving tunable resonant frequencies or broad operational bandwidths requires complex components and/or fabrication processes. The work presented here reports unusual classes of three-dimensional (3D) micromechanical systems in the form of vibratory platforms assembled by controlled compressive buckling. Such 3D structures can be fabricated across a broad range of length scales and from various materials, including soft polymers, monocrystalline silicon, and their composites, resulting in a wide scope of achievable resonant frequencies and mechanical behaviors. Platforms designed with multistable mechanical responses and vibrationally de-coupled constituent elements offer improved bandwidth and frequency tunability. Furthermore, the resonant frequencies can be controlled through deformations of an underlying elastomeric substrate. Systematic experimental and computational studies include structures with diverse geometries, ranging from tables, cages, rings, ring-crosses, ring-disks, two-floor ribbons, flowers, umbrellas, triple-cantilever platforms, and asymmetric circular helices, to multilayer constructions. These ideas form the foundations for engineering designs that complement those supported by conventional, microelectromechanical systems, with capabilities that could be useful in systems for biosensing, energy harvesting and others.

Relationship between sugar chain structure and biological activity of recombinant human erythropoietin produced in Chinese hamster ovary cells.

PubMed Central

Takeuchi, M; Inoue, N; Strickland, T W; Kubota, M; Wada, M; Shimizu, R; Hoshi, S; Kozutsumi, H; Takasaki, S; Kobata, A

1989-01-01

Two forms of erythropoietin, EPO-bi and EPO-tetra, with different biological activities were isolated from the culture medium of a recombinant Chinese hamster ovary cell line, B8-300, into which the human erythropoietin gene had been introduced. EPO-bi, an unusual form, showed only one-seventh the in vivo activity and 3 times higher in vitro activity of the previously described recombinant human EPO (standard EPO). In contrast, EPO-tetra showed both in vivo and in vitro activities comparable to those of the standard EPO. EPO-bi, EPO-tetra, and the standard EPO had the same amino acid composition and immunoreactivity. However, structural analyses of their N-linked sugar chains revealed that EPO-bi contains the biantennary complex type as the major sugar chain, while EPO-tetra and the standard EPO contain the tetraantennary complex type as the major sugar chain. From examination of various preparations of recombinant human EPO, we found a positive correlation between the in vivo activity of EPO and the ratio of tetraantennary to biantennary oligosaccharides. These results suggest that higher branching of the N-linked sugar chains is essential for effective expression of in vivo biological activity of EPO. PMID:2813359

Identification of structural determinants controlling human and mouse stromelysin-3 proteolytic activities.

PubMed

Noël, A; Santavicca, M; Stoll, I; L'Hoir, C; Staub, A; Murphy, G; Rio, M C; Basset, P

1995-09-29

Matrix metalloproteinases (matrixins) constitute a group of extracellular proteinases belonging to the metzincin superfamily. They are involved in both physiological and pathological tissue remodeling processes, including those associated with cancer progression. Stromelysin-3, which is expressed in most invasive human carcinomas, is a matrix metalloproteinase with unusual functional properties. In particular, its mature form does not cleave any of the major extracellular matrix components. To define critical structural determinants involved in controlling stromelysin-3 proteolytic activity, we have used site-directed mutagenesis. We show that the deletion of at least 175 C-terminal amino-acids is sufficient to endow mouse stromelysin-3 with activities against casein, laminin, and type IV collagen. In the case of the human enzyme, however, a further and single Ala-235-->Pro substitution is necessary to observe similar activities. Ala-235, which characterizes human stromelysin-3 among matrixins, is located immediately after the C terminus of the "Met-turn," which forms a hydrophobic basis for the catalytic zinc atom in the metzincin family. We conclude that human stromelysin-3 has gained specific functional properties during evolution by amino acid substitution in the catalytic zinc environment, and that it represents an attractive target for specific inhibitors that may be used to prevent cancer progression.

Interfacial Coupling-Induced Ferromagnetic Insulator Phase in Manganite Film

DOE PAGES

Zhang, Bangmin; Wu, Lijun; Yin, Wei-Guo; ...

2016-06-08

Interfaces with subtle differences in atomic and electronic structures in perovskite ABO 3 heterostructures often yield intriguingly different properties, yet their exact roles remain elusive. Here, we report an integrated study of unusual transport, magnetic, and structural properties of Pr 0.67Sr 0.33MnO 3 film on SrTiO 3 substrate. The variations in the out-of-plane lattice constant and BO 6 octahedral rotation across the Pr 0.67Sr 0.33MnO 3/SrTiO 3 interface strongly depend on the thickness of the Pr 0.67Sr 0.33MnO 3 film. In the 12-nm film, a new interface-sensitive ferromagnetic polaronic insulator (FI') phase is formed during the cubic-to-tetragonal phase transition ofmore » SrTiO 3, apparently due to the enhanced electron–phonon interaction and atomic disorder in the film. The transport properties of the FI' phase in the 30-nm film are masked because of the reduced interfacial coupling and smaller interface-to-volume ratio. In conclusion, this work demonstrates how thickness-dependent interfacial coupling leads to the formation of a theoretically predicted ferromagnetic–polaronic insulator, as illustrated in a new phase diagram, that is otherwise ferromagnetic metal (FM) in bulk form.« less

The Universe's Most Extreme Star-forming Galaxies

NASA Astrophysics Data System (ADS)

Casey, Caitlin

2017-06-01

Dusty star-forming galaxies host the most intense stellar nurseries in the Universe. Their unusual characteristics (SFRs=200-2000Msun/yr, Mstar>1010 Msun) pose a unique challenge for cosmological simulations and galaxy formation theory, particularly at early times. Although rare today, they were factors of 1000 times more prevalent at z~2-5, contributing significantly to the buildup of the Universe's stellar mass and the formation of high-mass galaxies. At even earlier times (within 1Gyr post Big Bang) they could have played a pivotal role in enriching the IGM. However, an ongoing debate lingers as to their evolutionary origins at high-redshift, whether or not they are triggered by major mergers of gas-rich disk galaxies, or if they are solitary galaxies continually fed pristine gas from the intergalactic medium. Furthermore, their presence in early protoclusters, only revealed quite recently, pose intriguing questions regarding the collapse of large scale structure. I will discuss some of the latest observational programs dedicated to understanding dust-obscuration in and gas content of the early Universe, their context in the cosmic web, and future long-term observing campaigns that may reveal their relationship to `normal’ galaxies, thus teaching us valuable lessons on the physical mechanisms of galaxy growth and the collapse of large scale structure in an evolving Universe.

Interfacial Coupling-Induced Ferromagnetic Insulator Phase in Manganite Film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bangmin; Wu, Lijun; Yin, Wei-Guo

Interfaces with subtle differences in atomic and electronic structures in perovskite ABO 3 heterostructures often yield intriguingly different properties, yet their exact roles remain elusive. Here, we report an integrated study of unusual transport, magnetic, and structural properties of Pr 0.67Sr 0.33MnO 3 film on SrTiO 3 substrate. The variations in the out-of-plane lattice constant and BO 6 octahedral rotation across the Pr 0.67Sr 0.33MnO 3/SrTiO 3 interface strongly depend on the thickness of the Pr 0.67Sr 0.33MnO 3 film. In the 12-nm film, a new interface-sensitive ferromagnetic polaronic insulator (FI') phase is formed during the cubic-to-tetragonal phase transition ofmore » SrTiO 3, apparently due to the enhanced electron–phonon interaction and atomic disorder in the film. The transport properties of the FI' phase in the 30-nm film are masked because of the reduced interfacial coupling and smaller interface-to-volume ratio. In conclusion, this work demonstrates how thickness-dependent interfacial coupling leads to the formation of a theoretically predicted ferromagnetic–polaronic insulator, as illustrated in a new phase diagram, that is otherwise ferromagnetic metal (FM) in bulk form.« less

The group migration of Dictyostelium cells is regulated by extracellular chemoattractant degradation.

PubMed

Garcia, Gene L; Rericha, Erin C; Heger, Christopher D; Goldsmith, Paul K; Parent, Carole A

2009-07-01

Starvation of Dictyostelium induces a developmental program in which cells form an aggregate that eventually differentiates into a multicellular structure. The aggregate formation is mediated by directional migration of individual cells that quickly transition to group migration in which cells align in a head-to-tail manner to form streams. Cyclic AMP acts as a chemoattractant and its production, secretion, and degradation are highly regulated. A key protein is the extracellular phosphodiesterase PdsA. In this study we examine the role and localization of PdsA during chemotaxis and streaming. We find that pdsA(-) cells respond chemotactically to a narrower range of chemoattractant concentrations compared with wild-type (WT) cells. Moreover, unlike WT cells, pdsA(-) cells do not form streams at low cell densities and form unusual thick and transient streams at high cell densities. We find that the intracellular pool of PdsA is localized to the endoplasmic reticulum, which may provide a compartment for storage and secretion of PdsA. Because we find that cAMP synthesis is normal in cells lacking PdsA, we conclude that signal degradation regulates the external cAMP gradient field generation and that the group migration behavior of these cells is compromised even though their signaling machinery is intact.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kreel, Nathan E.; Tabita, F. Robert; Berg, Ivan

Archaeal ribulose 1, 5-bisphospate carboxylase/oxygenase (RubisCO) is differentiated from other RubisCO enzymes and is classified as a form III enzyme, as opposed to the form I and form II RubisCOs typical of chemoautotrophic bacteria and prokaryotic and eukaryotic phototrophs. The form III enzyme from archaea is particularly interesting as several of these proteins exhibit unusual and reversible sensitivity to molecular oxygen, including the enzyme from Archaeoglobus fulgidus. Previous studies with A. fulgidus RbcL2 had shown the importance of Met-295 in oxygen sensitivity and pointed towards the potential significance of another residue (Ser-363) found in a hydrophobic pocket that is conservedmore » in all RubisCO proteins. In the current study, further structure/function studies have been performed focusing on Ser-363 of A. fulgidus RbcL2; various changes in this and other residues of the hydrophobic pocket point to and definitively establish the importance of Ser-363 with respect to interactions with oxygen. In addition, previous findings had indicated discrepant CO 2/O 2 specificity determinations of the Thermococcus kodakaraensis RubisCO, a close homolog of A. fulgidus RbcL2. As a result, it is shown here that the T. kodakaraensis enzyme exhibits a similar substrate specificity as the A. fulgidus enzyme and is also oxygen sensitive, with equivalent residues involved in oxygen interactions.« less

Molecular modularity and asymmetry of the molluscan mantle revealed by a gene expression atlas.

PubMed

Herlitze, Ines; Marie, Benjamin; Marin, Frédéric; Jackson, Daniel J

2018-06-01

Conchiferan molluscs construct a biocalcified shell that likely supported much of their evolutionary success. However, beyond broad proteomic and transcriptomic surveys of molluscan shells and the shell-forming mantle tissue, little is known of the spatial and ontogenetic regulation of shell fabrication. In addition, most efforts have been focused on species that deposit nacre, which is at odds with the majority of conchiferan species that fabricate shells using a crossed-lamellar microstructure, sensu lato. By combining proteomic and transcriptomic sequencing with in situ hybridization we have identified a suite of gene products associated with the production of the crossed-lamellar shell in Lymnaea stagnalis. With this spatial expression data we are able to generate novel hypotheses of how the adult mantle tissue coordinates the deposition of the calcified shell. These hypotheses include functional roles for unusual and otherwise difficult-to-study proteins such as those containing repetitive low-complexity domains. The spatial expression readouts of shell-forming genes also reveal cryptic patterns of asymmetry and modularity in the shell-forming cells of larvae and adult mantle tissue. This molecular modularity of the shell-forming mantle tissue hints at intimate associations between structure, function, and evolvability and may provide an elegant explanation for the evolutionary success of the second largest phylum among the Metazoa.

The Group Migration of Dictyostelium Cells Is Regulated by Extracellular Chemoattractant Degradation

PubMed Central

Garcia, Gene L.; Rericha, Erin C.; Heger, Christopher D.; Goldsmith, Paul K.

2009-01-01

Starvation of Dictyostelium induces a developmental program in which cells form an aggregate that eventually differentiates into a multicellular structure. The aggregate formation is mediated by directional migration of individual cells that quickly transition to group migration in which cells align in a head-to-tail manner to form streams. Cyclic AMP acts as a chemoattractant and its production, secretion, and degradation are highly regulated. A key protein is the extracellular phosphodiesterase PdsA. In this study we examine the role and localization of PdsA during chemotaxis and streaming. We find that pdsA− cells respond chemotactically to a narrower range of chemoattractant concentrations compared with wild-type (WT) cells. Moreover, unlike WT cells, pdsA− cells do not form streams at low cell densities and form unusual thick and transient streams at high cell densities. We find that the intracellular pool of PdsA is localized to the endoplasmic reticulum, which may provide a compartment for storage and secretion of PdsA. Because we find that cAMP synthesis is normal in cells lacking PdsA, we conclude that signal degradation regulates the external cAMP gradient field generation and that the group migration behavior of these cells is compromised even though their signaling machinery is intact. PMID:19477920

Color synesthesia. Insight into perception, emotion, and consciousness

PubMed Central

Safran, Avinoam B.; Sanda, Nicolae

2015-01-01

Purpose of review Synesthesia is an extraordinary perceptual phenomenon, in which individuals experience unusual percepts elicited by the activation of an unrelated sensory modality or by a cognitive process. Emotional reactions are commonly associated. The condition prompted philosophical debates on the nature of perception and impacted the course of art history. It recently generated a considerable interest among neuroscientists, but its clinical significance apparently remains underevaluated. This review focuses on the recent studies regarding variants of color synesthesia, the commonest form of the condition. Recent findings Synesthesia is commonly classified as developmental and acquired. Developmental forms predispose to changes in primary sensory processing and cognitive functions, usually with better performances in certain aspects and worse in others, and to heightened creativity. Acquired forms of synesthesia commonly arise from drug ingestion or neurological disorders, including thalamic lesions and sensory deprivation (e.g., blindness). Cerebral exploration using structural and functional imaging has demonstrated distinct patterns in cortical activation and brain connectivity for controls and synesthetes. Artworks of affected painters are most illustrative of the nature of synesthetic experiences. Summary Results of the recent investigations on synesthesia offered a remarkable insight into the mechanisms of perception, emotion and consciousness, and deserve attention both from neuroscientists and from clinicians. PMID:25545055

Color synesthesia. Insight into perception, emotion, and consciousness.

PubMed

Safran, Avinoam B; Sanda, Nicolae

2015-02-01

Synesthesia is an extraordinary perceptual phenomenon, in which individuals experience unusual percepts elicited by the activation of an unrelated sensory modality or by a cognitive process. Emotional reactions are commonly associated. The condition prompted philosophical debates on the nature of perception and impacted the course of art history. It recently generated a considerable interest among neuroscientists, but its clinical significance apparently remains underevaluated. This review focuses on the recent studies regarding variants of color synesthesia, the commonest form of the condition. Synesthesia is commonly classified as developmental and acquired. Developmental forms predispose to changes in primary sensory processing and cognitive functions, usually with better performances in certain aspects and worse in others, and to heightened creativity. Acquired forms of synesthesia commonly arise from drug ingestion or neurological disorders, including thalamic lesions and sensory deprivation (e.g., blindness). Cerebral exploration using structural and functional imaging has demonstrated distinct patterns in cortical activation and brain connectivity for controls and synesthetes. Artworks of affected painters are most illustrative of the nature of synesthetic experiences. Results of the recent investigations on synesthesia offered a remarkable insight into the mechanisms of perception, emotion and consciousness, and deserve attention both from neuroscientists and from clinicians.

Utilization of Microwave Spectroscopy to Identify and Probe Reaction Dynamics of Hsno, a Crucial Biological Signaling Molecule

NASA Astrophysics Data System (ADS)

Nava, Matthew; Martin-Drumel, Marie-Aline; Stanton, John F.; Cummins, Christopher; McCarthy, Michael C.

2016-06-01

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries. Its existence and stability in vivo, however, remain controversial. By means of Fourier-transform microwave spectroscopy, we establish that HSNO is spontaneously formed in high concentration when NO and H2S gases are simply mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed with high efficiency by the reaction H2S and N2O3 to produce HSNO and HNO2, where N2O3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H2S may form HNO and HSSH. The length of the S--N bond has been derived to high precision from isotopic studies, and is found to be unusually long, 1.84 Å -- the longest S--N bond reported to date for an SNO compound. The present structural and reactivity investigations of this elusive molecule provide a firm fundation to better understand its physiological chemistry and propensity to undergo S--N bond homolysis in vivo.

Large impacts in the Baltic shield with special attention to the Uppland structure

NASA Technical Reports Server (NTRS)

Henkel, H.; Lilljequist, R.

1992-01-01

Within the Baltic Shield several very large structures have been identified and are suspected to be of meteorite impact origin. Some of these deeply eroded circular features are presented with special attention to the Uppland structure, where several indications point toward an impact origin in the mid-Proterozoic. The structures exceed 100 km in diameter and the topographic expression is inferior or absent. An arcuate arrangement of lithologies occurs around the margin of the structures and the central regions show conform magnetic and positive gravity anomalies. The Uppland structure is approximately 320 km in diameter as expressed by morphological, geological, and geophysical concentric patterns. The central part is topographically remarkably flat and is characterized by an unusual irregular fracture pattern. A subcircular central tonalite with density of 2.81 Mg(sup -3) gives a positive gravity anomaly of 35 mgal and the gravimetric profile is very similar to that of Manicouagan and Vredefort. The tonalite constitutes a huge antiform, 80 km in diameter, probably representing a 12-km structural uplift of infracrustal rocks. The flancs of the tonalite are characterized by recrystallized pseudotachylitic breccia dykes and breccia zones. Around the central parts amphibolite-grade metamorphic rocks appear as large fragments within a fine-grained granite interpreted as a thermally annealed melt rock. Several occurrences of breccia dykes and breccia-bearing melts have been identified about 100 km from the gravimetric center of the structure. Impact-related ore deposits are located around the margin of the structure and are interpreted as preexisting downfaulted iron formations, and deposits formed from remobilization of these preimpact occurrences. The so-called ball ores are interpreted to have formed by fluid injection similar to the formation of breccia dykes. The extensive hydrothermal alteration along the outer margin of the structure have created extreme soda and K-enriched rocks ('leptites') from preexisting gneiss granites and supracrustal sedimentary gneisses.

77 FR 70941 - Special Conditions: Embraer S.A., Model EMB-550 Airplane; Interaction of Systems and Structures

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-28

... primary structure is metal with composite empennage and control surfaces. The Model EMB-550 airplane is...., Model EMB-550 Airplane; Interaction of Systems and Structures AGENCY: Federal Aviation Administration... conditions for the Embraer S.A. Model EMB-550 airplane. This airplane will have a novel or unusual design...

Crystal Structure of the Full-Length Feline Immunodeficiency Virus Capsid Protein Shows an N-Terminal β-Hairpin in the Absence of N-Terminal Proline

PubMed Central

Folio, Christelle; Sierra, Natalia; Dujardin, Marie; Alvarez, Guzman

2017-01-01

Feline immunodeficiency virus (FIV) is a member of the Retroviridae family. It is the causative agent of an acquired immunodeficiency syndrome (AIDS) in cats and wild felines. Its capsid protein (CA) drives the assembly of the viral particle, which is a critical step in the viral replication cycle. Here, the first atomic structure of full-length FIV CA to 1.67 Å resolution is determined. The crystallized protein exhibits an original tetrameric assembly, composed of dimers which are stabilized by an intermolecular disulfide bridge induced by the crystallogenesis conditions. The FIV CA displays a standard α-helical CA topology with two domains, separated by a linker shorter than other retroviral CAs. The β-hairpin motif at its amino terminal end, which interacts with nucleotides in HIV-1, is unusually long in FIV CA. Interestingly, this functional β-motif is formed in this construct in the absence of the conserved N-terminal proline. The FIV CA exhibits a cis Arg–Pro bond in the CypA-binding loop, which is absent in known structures of lentiviral CAs. This structure represents the first tri-dimensional structure of a functional, full-length FIV CA. PMID:29120364

A rare case of isolated macronodular hepatic tuberculosis (Tuberculous) in an immunocompetent patient.

PubMed

Kayar, Yusuf; Ekinci, Iskender; Turkdogan, Figen Tunali; Atay, Musa; Soytas, Rabia Bag; Kayar, Nuket Bayram

2015-11-01

Tuberculosis is one of the most common and well described infectious diseases, with a world wide distribution and a vast spectrum of clinical manifestations. There are three forms of hepatic tuberculosis. Diffuse hepatic involvement with pulmonary or miliary tuberculosis, diffuse hepatic infiltration without recognizable pulmonary involvement is the second form and the third very rare form presents as a focal/local tuberculoma or abscess. In this case report we describe an unusual appearance of macronodular tuberculomas of the liver.

A life detection problem in a High Arctic microbial community

NASA Astrophysics Data System (ADS)

Rogers, J. D.; Perreault, N. N.; Niederberger, T. D.; Lichten, C.; Whyte, L. G.; Nadeau, J. L.

2010-03-01

Fluorescent labeling of bacterial cell walls, DNA, and metabolic processes demonstrates high (potentially single molecule) sensitivity, is non-invasive, and in some cases can differentiate strains and species. Robust microscopes such as the custom instruments presented here can provide good image quality in the field and are potentially suitable for flight. However, ambiguous or false-positive results with bacterial stains can occur and can create difficulties in interpretation even on Earth. We present a "real" life detection problem in a sample of biofilms taken from the Canadian High Arctic. The samples consisted of numerous small sulfur-oxidizing bacteria and larger structures resembling fungi or diatoms. The identity of these latter structures remained ambiguous until electron microscopy and X-ray spectroscopy were performed, indicating that they were unusual sulfur minerals probably precipitated by the bacterial communities. While such mineral structures may possibly serve as biosignatures after the cells have disappeared, it is important that they not be mistaken for cells themselves. It is also possible that unusual mineral structures will be performed under extraterrestrial conditions, so great care is needed to differentiate cell structures from minerals.

An Unusual Hydrophobic Core Confers Extreme Flexibility to HEAT Repeat Proteins

PubMed Central

Kappel, Christian; Zachariae, Ulrich; Dölker, Nicole; Grubmüller, Helmut

2010-01-01

Alpha-solenoid proteins are suggested to constitute highly flexible macromolecules, whose structural variability and large surface area is instrumental in many important protein-protein binding processes. By equilibrium and nonequilibrium molecular dynamics simulations, we show that importin-β, an archetypical α-solenoid, displays unprecedentedly large and fully reversible elasticity. Our stretching molecular dynamics simulations reveal full elasticity over up to twofold end-to-end extensions compared to its bound state. Despite the absence of any long-range intramolecular contacts, the protein can return to its equilibrium structure to within 3 Å backbone RMSD after the release of mechanical stress. We find that this extreme degree of flexibility is based on an unusually flexible hydrophobic core that differs substantially from that of structurally similar but more rigid globular proteins. In that respect, the core of importin-β resembles molten globules. The elastic behavior is dominated by nonpolar interactions between HEAT repeats, combined with conformational entropic effects. Our results suggest that α-solenoid structures such as importin-β may bridge the molecular gap between completely structured and intrinsically disordered proteins. PMID:20816072

Hinge-like structure induced unusual properties of black phosphorus and new strategies to improve the thermoelectric performance

PubMed Central

Qin, Guangzhao; Yan, Qing-Bo; Qin, Zhenzhen; Yue, Sheng-Ying; Cui, Hui-Juan; Zheng, Qing-Rong; Su, Gang

2014-01-01

We systematically investigated the geometric, electronic and thermoelectric (TE) properties of bulk black phosphorus (BP) under strain. The hinge-like structure of BP brings unusual mechanical responses such as anisotropic Young's modulus and negative Poisson's ratio. A sensitive electronic structure of BP makes it transform among metal, direct and indirect semiconductors under strain. The maximal figure of merit ZT of BP is found to be 0.72 at 800 K that could be enhanced to 0.87 by exerting an appropriate strain, revealing BP could be a potential medium-high temperature TE material. Such strain-induced enhancements of TE performance are often observed to occur at the boundary of the direct-indirect band gap transition, which can be attributed to the increase of degeneracy of energy valleys at the transition point. By comparing the structure of BP with SnSe, a family of potential TE materials with hinge-like structure are suggested. This study not only exposes various novel properties of BP under strain, but also proposes effective strategies to seek for better TE materials. PMID:25374306

Unusual hydrogen bonding patterns in AF (aminofluorene) and AAF (acetylaminofluorene) modified DNA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Broyde, S.; Hingerty, B.E.; Shapiro, R.

1989-01-01

New structures are presented for AF and AAF modified DNAs that place the carcinogen in the minor groove of a B-DNA helix. These structures employ non-Watson-Crick base pairing schemes with syn guanine at the modification site. 32 refs., 9 figs.

Pre-Ediacaran to Ediacaran Radiation in the Vindhyan Supergroup, India

NASA Astrophysics Data System (ADS)

Srivastava, P.

2009-04-01

The Vindhyan Supergroup is globally acknowledged amongst the best repositories of the Proterozoic life evidences. Fossils of the Vindhyan Supergroup exhibit extensive diversity and variable biologic affinities represented by: bacteria, cyanobacteria, algae, fungi, acritarchs, metaphytes and metazoans (including members of the Ediacaran Fauna). The size of fossils ranges from less than a micron to almost a meter. As the Ediacaran fauna has already been recorded from the uppermost Vindhyans that is from the Bhander Group, strata lying beneath and above the Ediacaran fossil bearing horizons, exhibit presence of a vast range of fossils (both micro and mega fossils) inclining towards variable biologic affinities stated earlier. Besides identified fossils, a number of peculiar morphologies (due to deviation of morphologies from conventional structures), present in various stratigraphic horizons of the entire Vindhyan Supergroup, have also been observed. It is very difficult to identify and decide biologic affinities of these peculiar morphologies or bizarre fossil forms. In thin sections of Lower Vindhyan cherts (of Semri Group), microfossils resembling, a Volvox colony like structure and a vase- shaped body without an opening, Lichen- like or fungal forms in which a sac encompassing a coiled filament may possibly indicate a symbiotic relationship are unique. Megascopic branching and associated Grypania like structure is another form preserved as an impression on a micritic limestone slab. A very unusual and interesting fossil is a transparent disc of about one mm in diameter, composed of numerous chromosome-like structures or the appendages of an unidentified mesoscopic insect- like organism. In Upper Vindhyans, microscopic unidentified forms (in thin sections of chert) include acritarchs and acanthomorphs of variable morphologies and a dividing cell like structure interpreted as rhodophycean form or a cleaving embryo of an animal affinity. Among the carbonaceous fossils, peculiar morphologies are branched filaments that have attached sporangia-like vesicles, Chuaria-like body comprising cluster of very small sized spheroids resemble with scale like structure; a chrysophycean alga or a multicellular tissue of a metaphyte. Another carbonaceous fossil represents a possible metazoan exhibiting an elongate body and a mid-gut like structure or a voucheriacean alga. Although the biologic affinities of these forms can be a matter of debate, their biogenic nature is almost undoubted. The presence of such forms in the Vindhyans, well exhibits pre-Ediacaran - Ediacaran radiation, advancement in morphology and a gradual evolution of life during the Palaeoproterozoic- Neoproterozoic period that is the time of Vindhyan deposition. In addition, presence of large- sized acritarchs, especially the presence of an age marker acanthomorph; Trachystrichosphaera sp. in Bhander Group (Uppermost Vindhyans) also suggests Vendian as an upper age limit of the Vindhyan Supergroup (which is also supported by the presence of Ediacaran fauna from the uppermost Vindhyans.

Diagnosis of systemic lupus erythematosus in an unusual presentation: what a primary care physician should know.

PubMed

Pramanik, Bimalendu

2014-01-01

Systemic Lupus Erythematosus (SLE) is a multisystem autoimmune disease affecting millions of people worldwide. It can affect any organ systems of the body. However, all systems may not be involved initially rather than they may be affected gradually, sometimes over years. Diagnosis depends on characteristic clinical features and laboratory test results. Some features such as skin rash, joint symptoms and oral ulcers are common in SLE. But initial presentation of many patients is unusual because either they do not have these common features of the disease or the presentation mimics other illnesses. As a result, delayed diagnosis and misdiagnosis are common. Therefore, high index of initial suspicion of SLE is critical. In clinical practice, SLE should be suspected in any patient presenting with an unexplained disease process involving two or more organ systems. To make a diagnosis in an unusual presentation, thorough clinical evaluation with details history of both present and past illnesses as well as laboratory tests for SLE should be performed. Usually primary-care physicians first evaluate SLE patients; but there is no single article, where all the information on when to suspect SLE in an unusual presentation, is available in an integrated form. In this article, a list of conditions, when SLE should be suspected in an unusual presentation, has been given and some relatively common areas with diagnostic challenges of SLE have been briefly described. To prepare this manuscript, most articles have been identified through 'Pubmed' search using keywords-atypical/ unusual presentation of SLE, case reports on SLE, gastrointestinal manifestations of SLE, neuropsychiatric SLE, diagnostic challenges with SLE, etc. Selected most articles are from currently medline-indexed journals.

Cow Dung Ingestion and Inhalation Dependence: A Case Report

ERIC Educational Resources Information Center

Khairkar, Praveen; Tiple, Prashant; Bang, Govind

2009-01-01

Although abuse of several unusual inhalants had been documented, addiction to cow dung fumes or their ashes has not been reported in medical literature as yet. We are reporting a case of cow dung dependence in ingestion and inhalational form.

Classical and unusual imaging appearances of melorheostosis.

PubMed

Suresh, S; Muthukumar, T; Saifuddin, A

2010-08-01

This comprehensive review will discuss the classical and unusual radiological features of melorheostosis, which is an uncommon, non-hereditary, benign, sclerosing mesodermal disease with an incidence of 0.9 cases per million. The presentation of melorheostosis in the appendicular skeleton (more commonly involved) and in the axial skeleton (very few documented case reports) will be discussed. The aim of the review is to illustrate the associations and rare, but recognized, complications of the disorder. The role of cross-sectional imaging in the form of magnetic resonance imaging (MRI) and computed tomography (CT) in revealing the spectrum of disease manifestation and differentiation from other disease entities and malignancy will be explored.

Suicidal hanging within an automobile.

PubMed

Blanco Pampin, J M; López-Abajo Rodriguez, B A

2001-12-01

Accidental asphyxia related to cars has been described in different reports, but suicidal hanging in an automobile is very unusual. Two cases of suicidal hanging inside an automobile are described, illustrating an unusual form of hanging. In one case, the deceased used his belt as a ligature, and the point of attachment was the window of the car. The second victim used the safety belt of the passenger seat. In both cases, the automobile engine was turned off, all the windows were closed, and the door locks were blocked. The medicolegal cause of hanging was based on the scene of the investigation, police and witness reports, social history, autopsy findings, and toxicologic examinations.

Occurrence of an Unusual Hopanoid-containing Lipid A Among Lipopolysaccharides from Bradyrhizobium Species*

PubMed Central

Komaniecka, Iwona; Choma, Adam; Mazur, Andrzej; Duda, Katarzyna A.; Lindner, Buko; Schwudke, Dominik; Holst, Otto

2014-01-01

The chemical structures of the unusual hopanoid-containing lipid A samples of the lipopolysaccharides (LPS) from three strains of Bradyrhizobium (slow-growing rhizobia) have been established. They differed considerably from other Gram-negative bacteria in regards to the backbone structure, the number of ester-linked long chain hydroxylated fatty acids, as well as the presence of a tertiary residue that consisted of at least one molecule of carboxyl-bacteriohopanediol or its 2-methyl derivative. The structural details of this type of lipid A were established using one- and two-dimensional NMR spectroscopy, chemical composition analyses, and mass spectrometry techniques (electrospray ionization Fourier-transform ion cyclotron resonance mass spectrometry and MALDI-TOF-MS). In these lipid A samples the glucosamine disaccharide characteristic for enterobacterial lipid A was replaced by a 2,3-diamino-2,3-dideoxy-d-glucopyranosyl-(GlcpN3N) disaccharide, deprived of phosphate residues, and substituted by an α-d-Manp-(1→6)-α-d-Manp disaccharide substituting C-4′ of the non-reducing (distal) GlcpN3N, and one residue of galacturonic acid (d-GalpA) α-(1→1)-linked to the reducing (proximal) amino sugar residue. Amide-linked 12:0(3-OH) and 14:0(3-OH) were identified. Some hydroxy groups of these fatty acids were further esterified by long (ω-1)-hydroxylated fatty acids comprising 26–34 carbon atoms. As confirmed by mass spectrometry techniques, these long chain fatty acids could form two or three acyloxyacyl residues. The triterpenoid derivatives were identified as 34-carboxyl-bacteriohopane-32,33-diol and 34-carboxyl-2β-methyl-bacteriohopane-32,33-diol and were covalently linked to the (ω-1)-hydroxy group of very long chain fatty acid in bradyrhizobial lipid A. Bradyrhizobium japonicum possessed lipid A species with two hopanoid residues. PMID:25371196

A mobile loop near the active site acts as a switch between the dual activities of a viral protease/deubiquitinase

PubMed Central

Ayach, Maya; Fieulaine, Sonia

2017-01-01

The positive-strand RNA virus Turnip yellow mosaic virus (TYMV) encodes an ovarian tumor (OTU)-like protease/deubiquitinase (PRO/DUB) protein domain involved both in proteolytic processing of the viral polyprotein through its PRO activity, and in removal of ubiquitin chains from ubiquitylated substrates through its DUB activity. Here, the crystal structures of TYMV PRO/DUB mutants and molecular dynamics simulations reveal that an idiosyncratic mobile loop participates in reversibly constricting its unusual catalytic site by adopting "open", "intermediate" or "closed" conformations. The two cis-prolines of the loop form a rigid flap that in the most closed conformation zips up against the other side of the catalytic cleft. The intermediate and closed conformations also correlate with a reordering of the TYMV PRO/DUB catalytic dyad, that then assumes a classical, yet still unusually mobile, OTU DUB alignment. Further structure-based mutants designed to interfere with the loop's mobility were assessed for enzymatic activity in vitro and in vivo, and were shown to display reduced DUB activity while retaining PRO activity. This indicates that control of the switching between the dual PRO/DUB activities resides prominently within this loop next to the active site. Introduction of mutations into the viral genome revealed that the DUB activity contributes to the extent of viral RNA accumulation both in single cells and in whole plants. In addition, the conformation of the mobile flap was also found to influence symptoms severity in planta. Such mutants now provide powerful tools with which to study the specific roles of reversible ubiquitylation in viral infection. PMID:29117247

Entropic Anomaly Observed in Lipid Polymorphisms Induced by Surfactant Peptide SP-B(1-25).

PubMed

Tran, Nhi; Kurian, Justin; Bhatt, Avni; McKenna, Robert; Long, Joanna R

2017-10-05

The N-terminal 25 amino-acid residues of pulmonary surfactant protein B (SP-B 1-25 ) induces unusual lipid polymorphisms in a model lipid system, 4:1 DPPC/POPG, mirroring the lipid composition of native pulmonary surfactant. It is widely suggested that SP-B 1-25 -induced lipid polymorphisms within the alveolar aqueous subphase provide a structural platform for rapid lipid adsorption to the air-water interface. Here, we characterize in detail the phase behavior of DPPC and POPG in hydrated lipid assemblies containing therapeutic levels of SP-B 1-25 using 2 H and 31 P solid state NMR spectroscopy. The appearance of a previously observed isotropic lipid phase is found to be highly dependent on the thermal cycling of the samples. Slow heating of frozen samples leads to phase separation of DPPC into a lamellar phase whereas POPG lipids interact with the peptide to form an isotropic phase at physiologic temperature. Rapid heating of frozen samples to room temperature leads to strongly isotropic phase behavior for both DPPC and POPG lipids, with DPPC in exchange between isotropic and interdigitated phases. 31 P T 2 relaxation times confirm the isotropic phase to be consistent with a lipid cubic phase. The observed phases exhibit thermal stability up to physiologic temperature (37 °C) and are consistent with the formation of a ripple phase containing a large number of peptide-induced membrane structural defects enabling rapid transit of lipids between lipid lamellae. The coexistance of a lipid cubic phase with interdigitated lipids suggests a specific role for the highly conserved N-terminus of SP-B in stabilizing this unusual lipid polymorphism.

Genome, transcriptome, and secretome analysis of wood decay fungus Postia placenta supports unique mechanisms of lignocellulose conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez, Diego; Challacombe, Jean; Morgenstern, Ingo

2009-02-04

Brown-rot fungi such as Postia placenta are common inhabitants of forest ecosystems and are also largely responsible for the destructive decay of wooden structures. Rapid depolymerization of cellulose is a distinguishing feature of brown-rot, but the biochemical mechanisms and underlying genetics are poorly understood. Systematic examination of the P. placenta genome, transcriptome, and secretome revealed unique extracellular enzyme systems, including an unusual repertoire of extracellular glycoside hydrolases. Genes encoding exocellobiohydrolases and cellulose-binding domains, typical of cellulolytic microbes, are absent in this efficient cellulose-degrading fungus. When P. placenta was grown in media containing cellulose as sole carbon source, transcripts corresponding tomore » many hemicellulases and to a single putative β-1-4 endoglucanase were expressed at high levels relative to glucose grown cultures. These transcript profiles were confirmed by direct identification of peptides by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Also upregulated under cellulolytic culture conditions were putative iron reductases, quinone reductase, and structurally divergent oxidases potentially involved in extracellular generation of Fe(II) and H2O2. These observations are consistent with a biodegradative role for Fenton chemistry in which Fe(II) and H2O2 react to form hydroxyl radicals, highly reactive oxidants capable of depolymerizing cellulose. The P. placenta genome resources provide unparalleled opportunities for investigating such unusual mechanisms of cellulose conversion. More broadly, the genome offers insight into the diversification of lignocellulose degrading mechanisms in fungi. In particular, comparisons between P. placenta and the closely related white-rot fungus, Phanerochaete chrysosporium support an evolutionary shift from white-rot to brown-rot during which efficient depolymerization of lignin was lost.« less

Genome, transcriptome, and secretome analysis of wood decay fungus postia placenta supports unique mechanisms of lignocellulose conversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez, Diego; Challacombe, Jean F; Misra, Monica

2008-01-01

Brown-rot fungi such as Postia placenta are common inhabitants of forest ecosystems and are also largely responsible for the destructive decay of wooden structures. Rapid depolymerization of cellulose is a distinguishing feature of brown-rot, but the biochemical mechanisms and underlying genetics are poorly understood. Systematic examination of the P. placenta genome, transcriptome and secretome revealed unique extracellular enzyme systems, including an unusual repertoire of extracellular glycoside hydrolases. Genes encoding exocellobiohydrolases and cellulose-binding domains, typical of cellulolytic microbes, are absent in this efficient cellulose-degrading fungus. When P. placenta was grown in medium containing cellulose as sole carbon source, transcripts corresponding tomore » many hemicellulases and to a single putative {beta}-1-4 endoglucanase were expressed at high levels relative to glucose grown cultures. These transcript profiles were confirmed by direct identification of peptides by liquid chromatography-tandem mass spectrometry (LC{center_dot}MSIMS). Also upregulated during growth on cellulose medium were putative iron reductases, quinone reductase, and structurally divergent oxidases potentially involved in extracellular generation of Fe(II) and H202. These observations are consistent with a biodegradative role for Fenton chemistry in which Fe(II) and H202 react to form hydroxyl radicals, highly reactive oxidants capable of depolymerizing cellulose. The P. placenta genome resources provide unparalleled opportunities for investigating such unusual mechanisms of cellulose conversion. More broadly, the genome offers insight into the diversification of lignocellulose degrading mechanisms in fungi. Comparisons to the closely related white-rot fungus Phanerochaete chrysosporium support an evolutionary shift from white-rot to brown-rot during which the capacity for efficient depolymerization of lignin was lost.« less

Genome, transcriptome, and secretome analysis of wood decay fungus Postia placenta supports unique mechanisms of lignocellulose conversion

PubMed Central

Martinez, Diego; Challacombe, Jean; Morgenstern, Ingo; Hibbett, David; Schmoll, Monika; Kubicek, Christian P.; Ferreira, Patricia; Ruiz-Duenas, Francisco J.; Martinez, Angel T.; Kersten, Phil; Hammel, Kenneth E.; Vanden Wymelenberg, Amber; Gaskell, Jill; Lindquist, Erika; Sabat, Grzegorz; Splinter BonDurant, Sandra; Larrondo, Luis F.; Canessa, Paulo; Vicuna, Rafael; Yadav, Jagjit; Doddapaneni, Harshavardhan; Subramanian, Venkataramanan; Pisabarro, Antonio G.; Lavín, José L.; Oguiza, José A.; Master, Emma; Henrissat, Bernard; Coutinho, Pedro M.; Harris, Paul; Magnuson, Jon Karl; Baker, Scott E.; Bruno, Kenneth; Kenealy, William; Hoegger, Patrik J.; Kües, Ursula; Ramaiya, Preethi; Lucas, Susan; Salamov, Asaf; Shapiro, Harris; Tu, Hank; Chee, Christine L.; Misra, Monica; Xie, Gary; Teter, Sarah; Yaver, Debbie; James, Tim; Mokrejs, Martin; Pospisek, Martin; Grigoriev, Igor V.; Brettin, Thomas; Rokhsar, Dan; Berka, Randy; Cullen, Dan

2009-01-01

Brown-rot fungi such as Postia placenta are common inhabitants of forest ecosystems and are also largely responsible for the destructive decay of wooden structures. Rapid depolymerization of cellulose is a distinguishing feature of brown-rot, but the biochemical mechanisms and underlying genetics are poorly understood. Systematic examination of the P. placenta genome, transcriptome, and secretome revealed unique extracellular enzyme systems, including an unusual repertoire of extracellular glycoside hydrolases. Genes encoding exocellobiohydrolases and cellulose-binding domains, typical of cellulolytic microbes, are absent in this efficient cellulose-degrading fungus. When P. placenta was grown in medium containing cellulose as sole carbon source, transcripts corresponding to many hemicellulases and to a single putative β-1–4 endoglucanase were expressed at high levels relative to glucose-grown cultures. These transcript profiles were confirmed by direct identification of peptides by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Also up-regulated during growth on cellulose medium were putative iron reductases, quinone reductase, and structurally divergent oxidases potentially involved in extracellular generation of Fe(II) and H2O2. These observations are consistent with a biodegradative role for Fenton chemistry in which Fe(II) and H2O2 react to form hydroxyl radicals, highly reactive oxidants capable of depolymerizing cellulose. The P. placenta genome resources provide unparalleled opportunities for investigating such unusual mechanisms of cellulose conversion. More broadly, the genome offers insight into the diversification of lignocellulose degrading mechanisms in fungi. Comparisons with the closely related white-rot fungus Phanerochaete chrysosporium support an evolutionary shift from white-rot to brown-rot during which the capacity for efficient depolymerization of lignin was lost. PMID:19193860

Structures of Pseudomonas aeruginosa β-ketoacyl-(acyl-carrier-protein) synthase II (FabF) and a C164Q mutant provide templates for antibacterial drug discovery and identify a buried potassium ion and a ligand-binding site that is an artefact of the crystal form

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baum, Bernhard; Lecker, Laura S. M.; Zoltner, Martin

Three crystal structures of recombinant P. aeruginosa FabF are reported: the apoenzyme, an active-site mutant and a complex with a fragment of a natural product inhibitor. The characterization provides reagents and new information to support antibacterial drug discovery. Bacterial infections remain a serious health concern, in particular causing life-threatening infections of hospitalized and immunocompromised patients. The situation is exacerbated by the rise in antibacterial drug resistance, and new treatments are urgently sought. In this endeavour, accurate structures of molecular targets can support early-stage drug discovery. Here, crystal structures, in three distinct forms, of recombinant Pseudomonas aeruginosa β-ketoacyl-(acyl-carrier-protein) synthase II (FabF)more » are presented. This enzyme, which is involved in fatty-acid biosynthesis, has been validated by genetic and chemical means as an antibiotic target in Gram-positive bacteria and represents a potential target in Gram-negative bacteria. The structures of apo FabF, of a C164Q mutant in which the binding site is altered to resemble the substrate-bound state and of a complex with 3-(benzoylamino)-2-hydroxybenzoic acid are reported. This compound mimics aspects of a known natural product inhibitor, platensimycin, and surprisingly was observed binding outside the active site, interacting with a symmetry-related molecule. An unusual feature is a completely buried potassium-binding site that was identified in all three structures. Comparisons suggest that this may represent a conserved structural feature of FabF relevant to fold stability. The new structures provide templates for structure-based ligand design and, together with the protocols and reagents, may underpin a target-based drug-discovery project for urgently needed antibacterials.« less

Phase transformations in 40-60-GPa shocked gneisses from the Haughton Crater (Canada): An Analytical Transmission Electron Microscopy (ATEM) study

NASA Technical Reports Server (NTRS)

Martinez, I.; Guyot, F.; Schaerer, U.

1992-01-01

In order to better understand phase transformations, chemical migration, and isotopic disequilibrium in highly shocked rocks, we have performed a microprobe and an ATEM study on gneisses shocked up to 60 GPa from the Haughton Crater. This study reveals the following chemical and structural characteristics: (1) SiO2 dominant areas are formed by a mixture of pure SiO2 polycrystalline quartz identified by electron diffraction pattern and chemical analysis and a silica-rich amorphous phase containing minor amounts of aluminium, potassium, and iron; (2) Areas with biotitelike composition are formed by less than 200-nm grains of iron-rich spinels embedded in a silica-rich amorphous phase that is very similar to the one described above; (3) Layers with feldsparlike composition are constituted by 100-200-nm-sized alumina-rich grains (the indexation of the crystalline structure is under progress) and the silica-rich amorphous phase; (4) Zones characterized by the unusual Al/Si ratio close to 1 are formed by spinel grains (200-nm-sized) embedded in the same silica-rich amorphous phase; and (5) The fracturated sillimanites contain domains with a lamellar structure, defined by the intercalation of 100-nm-wide lamellae of mullite crystals and of a silica-rich amorphous phase. These mullite crystals preserved the crystallographical orientation of the preshock sillimanite. All compositional domains, identified at the microprobe scale, can thus be explained by a mixture in different proportion between the following phases: (1) a silica-rich amorphous phase, with minor Al and K; (2) quartz crystals; (3) spinel crystals and alumina-rich crystals; (4) sillimanite; and (5) mullite. Such mixtures of amorphous phases and crystals in different proportions explain disturbed isotope systems in these rocks and chemical heterogeneities observed on the microprobe.

The surface of Mars: An unusual laboratory that preserves a record of catastrophic and unusual events

USGS Publications Warehouse

Chapman, M.G.

2009-01-01

Catastrophic and unusual events on Earth such as bolide impacts, megafloods, supereruptions, flood volcanism, and subice volcanism may have devastating effects when they occur. Although these processes have unique characteristics and form distinctive features and deposits, we have diffi culties identifying them and measuring the magnitude of their effects. Our diffi culties with interpreting these processes and identifying their consequences are understandable considering their infrequency on Earth, combined with the low preservation potential of their deposits in the terrestrial rock record. Although we know these events do happen, they are infrequent enough that the deposits are poorly preserved on the geologically active face of the Earth, where erosion, volcanism, and tectonism constantly change the surface. Unlike the Earth, on Mars catastrophic and unusual features are well preserved because of the slow modifi cation of the surface. Signifi cant precipitation has not occurred on Mars for billions of years and there appears to be no discrete crustal plates to have undergone subduction and destruction. Therefore the ancient surface of Mars preserves geologic features and deposits that result from these extraordinary events. Also, unlike the other planets, Mars is the most similar to our own, having an atmosphere, surface ice, volcanism, and evidence of onceflowing water. So although our understanding of precursors, processes, and possible biological effects of catastrophic and unusual processes is limited on Earth, some of these mysteries may be better understood through investigating the surface of Mars. ?? 2009 The Geological Society of America.

A crotonyl-CoA reductase-carboxylase independent pathway for assembly of unusual alkylmalonyl-CoA polyketide synthase extender units

NASA Astrophysics Data System (ADS)

Ray, Lauren; Valentic, Timothy R.; Miyazawa, Takeshi; Withall, David M.; Song, Lijiang; Milligan, Jacob C.; Osada, Hiroyuki; Takahashi, Shunji; Tsai, Shiou-Chuan; Challis, Gregory L.

2016-12-01

Type I modular polyketide synthases assemble diverse bioactive natural products. Such multienzymes typically use malonyl and methylmalonyl-CoA building blocks for polyketide chain assembly. However, in several cases more exotic alkylmalonyl-CoA extender units are also known to be incorporated. In all examples studied to date, such unusual extender units are biosynthesized via reductive carboxylation of α, β-unsaturated thioesters catalysed by crotonyl-CoA reductase/carboxylase (CCRC) homologues. Here we show using a chemically-synthesized deuterium-labelled mechanistic probe, and heterologous gene expression experiments that the unusual alkylmalonyl-CoA extender units incorporated into the stambomycin family of polyketide antibiotics are assembled by direct carboxylation of medium chain acyl-CoA thioesters. X-ray crystal structures of the unusual β-subunit of the acyl-CoA carboxylase (YCC) responsible for this reaction, alone and in complex with hexanoyl-CoA, reveal the molecular basis for substrate recognition, inspiring the development of methodology for polyketide bio-orthogonal tagging via incorporation of 6-azidohexanoic acid and 8-nonynoic acid into novel stambomycin analogues.

Organoelement chemistry: promising growth areas and challenges

NASA Astrophysics Data System (ADS)

Abakumov, G. A.; Piskunov, A. V.; Cherkasov, V. K.; Fedushkin, I. L.; Ananikov, V. P.; Eremin, D. B.; Gordeev, E. G.; Beletskaya, I. P.; Averin, A. D.; Bochkarev, M. N.; Trifonov, A. A.; Dzhemilev, U. M.; D'yakonov, V. A.; Egorov, M. P.; Vereshchagin, A. N.; Syroeshkin, M. A.; Jouikov, V. V.; Muzafarov, A. M.; Anisimov, A. A.; Arzumanyan, A. V.; Kononevich, Yu N.; Temnikov, M. N.; Sinyashin, O. G.; Budnikova, Yu H.; Burilov, A. R.; Karasik, A. A.; Mironov, V. F.; Storozhenko, P. A.; Shcherbakova, G. I.; Trofimov, B. A.; Amosova, S. V.; Gusarova, N. K.; Potapov, V. A.; Shur, V. B.; Burlakov, V. V.; Bogdanov, V. S.; Andreev, M. V.

2018-05-01

The chemistry of organoelement compounds is now one of the most rapidly developing fields of research, regarding both fundamental science and solution of applied problems. This review covers a variety of classes of organoelement compounds, ranging from molecules with highly labile carbon–element bonds to compounds with stable bonds that form the basis of novel structural materials and demonstrates their role in scientific research and industrial production. The use of Grignard reagents in modern organic synthesis and application of catalytic cyclomagnesiation and cycloalumination reactions for the preparation of difficult-to-access metallacycles are considered. The electron transfer processes in redox-active derivatives of Group 14 elements and the role of radical ions in these processes are discussed. Considerable attention is paid to organometallic compounds, first of all, as catalysts; the dynamic nature of catalysis with these compounds is noted. Unusual strained metallacycles of high thermal stability, zirconacyclocumulenes, which also exhibit catalytic activity, are described. Complexes with redox-active ligands that substantially affect the reactivity of the metal centre and directly participate in reactions with various substrates as well as organometallic compounds of lanthanides are considered. Modern environmentally benign methods for the synthesis of organosilicon compounds and production of unique materials based on them are discussed. Particular Sections are devoted to organophosphorus compounds, including those exhibiting therapeutic properties and possessing unusual optical characteristics, and organic chalcogen compounds, which find use as ligands and biologically active molecules. The bibliography includes 1045 references.

An Atypical α/β-Hydrolase Fold Revealed in the Crystal Structure of Pimeloyl-Acyl Carrier Protein Methyl Esterase BioG from Haemophilus influenzae.

PubMed

Shi, Jie; Cao, Xinyun; Chen, Yaozong; Cronan, John E; Guo, Zhihong

2016-12-06

Pimeloyl-acyl carrier protein (ACP) methyl esterase is an α/β-hydrolase that catalyzes the last biosynthetic step of pimeloyl-ACP, a key intermediate in biotin biosynthesis. Intriguingly, multiple nonhomologous isofunctional forms of this enzyme that lack significant sequence identity are present in diverse bacteria. One such esterase, Escherichia coli BioH, has been shown to be a typical α/β-hydrolase fold enzyme. To gain further insights into the role of this step in biotin biosynthesis, we have determined the crystal structure of another widely distributed pimeloyl-ACP methyl esterase, Haemophilus influenzae BioG, at 1.26 Å. The BioG structure is similar to the BioH structure and is composed of an α-helical lid domain and a core domain that contains a central seven-stranded β-pleated sheet. However, four of the six α-helices that flank both sides of the BioH core β-sheet are replaced with long loops in BioG, thus forming an unusual α/β-hydrolase fold. This structural variation results in a significantly decreased thermal stability of the enzyme. Nevertheless, the lid domain and the residues at the lid-core interface are well conserved between BioH and BioG, in which an analogous hydrophobic pocket for pimelate binding as well as similar ionic interactions with the ACP moiety are retained. Biochemical characterization of site-directed mutants of the residues hypothesized to interact with the ACP moiety supports a similar substrate interaction mode for the two enzymes. Consequently, these enzymes package the identical catalytic function under a considerably different protein surface.

Crystal structure of the DNA polymerase III β subunit (β-clamp) from the extremophile Deinococcus radiodurans.

PubMed

Niiranen, Laila; Lian, Kjersti; Johnson, Kenneth A; Moe, Elin

2015-02-27

Deinococcus radiodurans is an extremely radiation and desiccation resistant bacterium which can tolerate radiation doses up to 5,000 Grays without losing viability. We are studying the role of DNA repair and replication proteins for this unusual phenotype by a structural biology approach. The DNA polymerase III β subunit (β-clamp) acts as a sliding clamp on DNA, promoting the binding and processivity of many DNA-acting proteins, and here we report the crystal structure of D. radiodurans β-clamp (Drβ-clamp) at 2.0 Å resolution. The sequence verification process revealed that at the time of the study the gene encoding Drβ-clamp was wrongly annotated in the genome database, encoding a protein of 393 instead of 362 amino acids. The short protein was successfully expressed, purified and used for crystallisation purposes in complex with Cy5-labeled DNA. The structure, which was obtained from blue crystals, shows a typical ring-shaped bacterial β-clamp formed of two monomers, each with three domains of identical topology, but with no visible DNA in electron density. A visualisation of the electrostatic surface potential reveals a highly negatively charged outer surface while the inner surface and the dimer forming interface have a more even charge distribution. The structure of Drβ-clamp was determined to 2.0 Å resolution and shows an evenly distributed electrostatic surface charge on the DNA interacting side. We hypothesise that this charge distribution may facilitate efficient movement on encircled DNA and help ensure efficient DNA metabolism in D. radiodurans upon exposure to high doses of ionizing irradiation or desiccation.

The coherence of synthetic telomeres.

PubMed Central

Acevedo, O L; Dickinson, L A; Macke, T J; Thomas, C A

1991-01-01

The chromosomal telomeres of Oxytricha were synthesized and their ability to cohere examined on non-denaturing acrylamide gels containing the stabilizing cation K+. At least 5 different mobility species were observed, in addition to that of the monomeric telomere. By cohering synthetic telomeres containing different lengths of subtelomeric DNA, we showed that each of the different mobility species was a dimer of two telomeres. Since the different mobility species did not differ in numbers or sequences of nucleotides, they must correspond to different molecular shapes probably caused by different degrees of bending of the dimer. Paradoxically, telomeres with longer subtelomeric stems cohered more efficiently. In the presence of K+, solutions had to be heated to over 90 degrees before the telomeres separated. Various synthetic constructs, restriction endonuclease and dimethyl sulfate protection experiments showed that the only nucleotides involved in the cohered structures were the 16 base 'tails' of sequence 3'G4T4G4T4. Extension of this motif was actually inimical to coherence. Oligomers containing 2 G4T4 motifs protected their GN7 positions by forming dimers, those with 5 G4T4 could do so by internal folding, but the 3' terminal group of G4 was left unprotected. This suggests that only four groups of G4 are necessary for the cohered structure. Single-chain specific nuclease, S1, as well as osmium tetroxide, which oxidizes the thymine residues of single chains, reacted less efficiently with the cohered structures. Synthetic telomeres containing inosine replacing guanosine were not observed to cohere, indicating that the C2-NH2 is strongly stabilizing. The cohered structures appear to be unusually compact and sturdy units in which four G4 blocks form quadruplexes stabilized by K+. A new model for the cohered structure is presented. Images PMID:1648206

Structural organisation and lipid composition of the epicuticular accessory layer of infective larvae of Trichinella spiralis.

PubMed

Gounaris, K; Smith, V P; Selkirk, M E

1996-05-22

The epicuticle of infective larvae of Trichinella spiralis represents the interface between this intracellular nematode parasite and the cytosol of mammalian skeletal muscle. The macromolecular structures that make up the epicuticle were studied by freeze-fracture electron microscopy and compositional analysis. Three fracture planes were observed: one with a typical plasma membrane-type bilayer organisation which was overlaid by two extended layers of lipid in an inverted cylindrical configuration. This overall structure remained unchanged in response to variations in temperature between 20 degrees C and 45 degrees C. The lipid cylinders were on average 6.8 nm in diameter, with randomly-associated particles that were not dissociated by high-salt treatment, indicative of hydrophobically associated proteins. The majority of the lipids were non-polar, consisting of cholesterol, cholesterol esters, mono- and tri-glycerides, and free fatty acids. Three major classes of phospholipids were identified: phosphatidylethanolamine, phosphatidylglycerol and phosphatidylcholine. Total lipid extracts did not adopt an inverted cylindrical or micellar configuration on isolation, but formed flat sheets of lamellae as did the purified polar and non-polar fractions of the lipids. Isolated lipids did not undergo thermally-induced polymorphism between 20 degrees C and 60 degrees C and there was no pH dependency of the structures adopted. The fatty acid saturation levels of the phospholipids were compatible with the observation that they did not form polymorphic structures on isolation. We suggest that this unusual configuration is probably stabilised by the associated (glyco)proteins and may be required for selective permeation of nutrients from the host cell cytosol and/or for maintaining the high curvature of the parasite within the cell.

Synthesis and characterization of two novel chiral-type formate frameworks templated by protonated diethylamine and ammonium cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mączka, Mirosław, E-mail: m.maczka@int.pan.wroc.pl; Gągor, Anna; Hanuza, Jerzy

2017-01-15

Two novel formate frameworks templated by ammonium and diethylammonium (DEtA{sup +}) cations have been synthesized. Chemical analysis as well as optical, Raman and IR studies showed partial substitution of nickel ions by Cr(III) or Fe(III). X-ray diffraction revealed that these compounds crystallize in the chiral-type structure of P6{sub 3}22 symmetry. The oxygen atoms from formate ligands form octahedral coordination around the metal centers and the octahedra are bridged by the formate groups in the anti-anti mode configuration forming the hexagonal structure with large channels expanding along the c direction. The channels are filled with disordered DEtA{sup +} and NH{sub 4}{supmore » +} ions and they show unusual compression with the c/a ratio of only 0.862 and 0.852 for the iron- and chromium-containing compound, respectively. Magnetic studies revealed that the both compounds order magnetically at low temperatures but the ordering temperature is significantly higher for the iron compound (37 K) compared to the chromium analogue (26 K). - Graphical abstract: Temperature dependence of magnetization M of DEtAFeNi showing magnetic order at 37 K. - Highlights: • Two novel chiral formates of P6{sub 3}22 symmetry were synthesized. • The structures contain strongly compressed hexagonal channels filled with disordered cations. • The obtained compounds exhibit magnetic order at low temperatures. • Raman, IR and absorption spectra prove incorporation of Cr(III) and Fe(III) in the frameworks.« less

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

DOE PAGES

Lin, Yu; Welchman, Evan; Thonhauser, Timo; ...

2017-03-15

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 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 weavingmore » 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.« less

Infrared spectra of cyanoacetaldehyde (NCCH2CHO): a potential prebiotic compound of astrochemical interest.

PubMed

Benidar, Abdessamad; Georges, Robert; Guillemin, Jean-Claude; Mó, Otilia; Yáñez, Manuel

2013-08-26

Cyanoacetaldehyde (NC-CH2CH=O) and its isomer, cyanovinylalcohol (NC-CH=CH-OH), as possible components of the interstellar medium, comets, or planetary atmospheres, exist in equilibrium in the gas phase, although the latter compound is very much in the minority (2%). The recording and analysis of the gas-phase infrared spectrum of the former compound within the 4000-500 cm(-1) spectroscopic range and the potential presence of the latter isomer, which could be vital for their detection in these media, are reported. CCSD(T) and G4 high-level ab initio methods, as well as density functional theory calculations, predict the existence of two stable rotamers of cyanoacetaldehyde. The global minimum has a structure with an unusual O-C-C-C dihedral angle (150°) that falls between the antiperiplanar (180°) and anticlinal forms (120°). The second rotamer, which is about 4.0 kJ mol(-1) less stable in terms of free energy, has a planar structure that corresponds to the synperiplanar form (O-C-C-C dihedral angle: 0°). The absorption vibrational bands of the two aldehyde rotamers that are present in the mixture lead to a spectrum with a very complex structure in the region of deformation movements, in which several low-intensity bands overlap. A complete and unambiguous assignment of the experimental spectrum has been achieved by using the calculated harmonic and anharmonic vibrational frequencies. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yu; Welchman, Evan; Thonhauser, Timo

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 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 weavingmore » 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.« less

How to become a tree without wood--biomechanical analysis of the stem of Carica papaya L.

PubMed

Kempe, A; Lautenschläger, T; Lange, A; Neinhuis, C

2014-01-01

Carica papaya L. does not contain wood, according to the botanical definition of wood as lignified secondary xylem. Despite its parenchymatous secondary xylem, these plants are able to grow up to 10-m high. This is surprising, as wooden structural elements are the ubiquitous strategy for supporting height growth in plants. Proposed possible alternative principles to explain the compensation for lack of wood in C. papaya are turgor pressure of the parenchyma, lignified phloem fibres in the bark, or a combination of the two. Interestingly, lignified tissue comprises only 5-8% of the entire stem mass. Furthermore, the phloem fibres do not form a compact tube enclosing the xylem, but instead form a mesh tubular structure. To investigate the mechanism of papaya's unusually high mechanical strength, a set of mechanical measurements were undertaken on whole stems and tissue sections of secondary phloem and xylem. The structural Young's modulus of mature stems reached 2.5 GPa. Since this is low compared to woody plants, the flexural rigidity of papaya stem construction may mainly be based on a higher second moment of inertia. Additionally, stem turgor pressure was determined indirectly by immersing specimens in sucrose solutions of different osmolalities, followed by mechanical tests; turgor pressure was between 0.82 and 1.25 MPa, indicating that turgor is essential for flexural rigidity of the entire stem. © 2013 German Botanical Society and The Royal Botanical Society of the Netherlands.

Very unusual "needle- and pencil-like" uric acid crystals in the urine unmasked by infrared spectroscopy investigation.

PubMed

Baroni, S; Garigali, G; Primiano, A; Gervasoni, J; Fogazzi, G B

2018-04-01

In this paper we describe a case with very unusual "needle- and pencil-like" crystals, partly similar to those reported by other investigators, who considered them as due to uric acid. Quite importantly, infrared spectroscopy investigation which, to our knowledge, we have been the first to perform on this type of crystals, confirmed their nature as uric acid structures. This case demonstrates that the planet of urinary crystals still has several unknown facets and still deserves exploration. Copyright © 2018 Elsevier B.V. All rights reserved.

Guapsidial A and Guadials B and C: Three New Meroterpenoids with Unusual Skeletons from the Leaves of Psidium guajava.

PubMed

Jian, Yu-Qing; Huang, Xiao-Jun; Zhang, Dong-Mei; Jiang, Ren-Wang; Chen, Min-Feng; Zhao, Bing-Xin; Wang, Ying; Ye, Wen-Cai

2015-06-15

A novel sesquiterpene-based Psidium meroterpenoid, possessing an unusual coupling pattern, and two new monoterpene-based meroterpenoids with unprecedented skeletons were isolated from the leaves of Psidium guajava. Their structures and absolute configurations were elucidated by spectroscopic, X-ray diffraction, and computational methods. The plausible biosynthetic pathway of these meroterpenoids as well as their cytotoxicities toward HepG2 and HepG2/ADM cells were also discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Moon - 'Ghost' craters formed during Mare filling.

NASA Technical Reports Server (NTRS)

Cruikshank, D. P.; Hartmann, W. K.; Wood, C. A.

1973-01-01

This paper discusses formation of 'pathological' cases of crater morphology due to interaction of craters with molten lavas. Terrestrial observations of such a process are discussed. In lunar maria, a number of small impact craters (D less than 10 km) may have been covered by thin layers of fluid lavas, or formed in molten lava. Some specific lunar examples are discussed, including unusual shallow rings resembling experimental craters deformed by isostatic filling.

An unusually strong Einstein ring in the radio source PKS1830 - 211

NASA Technical Reports Server (NTRS)

Jauncey, D. L.; Reynolds, J. E.; Tzioumis, A. K.; Murphy, D. W.; Preston, R. A.; Jones, D. L.; Meier, D. L.; Hoard, D. W.; Lobdell, E. T.; Skjerve, L.

1991-01-01

High-resolution radio images of PKS1830 - 211 are obtained to study the possibility that the double structure is a gravitationally lensed object. The VLBI observations, taken from interferometric radiotelescope networks, reveal an elliptical ring that connects two bright spots of similar composition. Because the lens and the lensed object are closely aligned, and because of the structure of the two spots, the source is concluded to be a radio Einstein ring. The source is found to be close to the galactic plane, and the lens and the lensed object are extragalactic. The source is also found to be unusually bright, suggesting that it is aligned with a bright background source or amplified by some mechanism related to a source that is not so bright.

A new insight into the three-dimensional architecture of the Golgi complex: Characterization of unusual structures in epididymal principal cells

PubMed Central

Martínez-Martínez, Narcisa; Martínez-Alonso, Emma; Tomás, Mónica; Neumüller, Josef; Pavelka, Margit

2017-01-01

Principal epididymal cells have one of the largest and more developed Golgi complex of mammalian cells. In the present study, we have used this cell as model for the study of the three-dimensional architecture of the Golgi complex of highly secretory and endocytic cells. Electron tomography demonstrated the presence in this cell type of some unknown or very unusual Golgi structures such as branched cisternae, pocket-like cisternal invaginations or tubular connections. In addition, we have used this methodology and immunoelectron microscopy to analyze the close relationship between this organelle and both the endoplasmic reticulum and microtubules, and to describe in detail how these elements interact with compact and non-compact regions of the ribbon. PMID:28957389

Synthesis of sodium polyhydrides at high pressures

NASA Astrophysics Data System (ADS)

Struzhkin, Viktor V.; Kim, Duck Young; Stavrou, Elissaios; Muramatsu, Takaki; Mao, Ho-Kwang; Pickard, Chris J.; Needs, Richard J.; Prakapenka, Vitali B.; Goncharov, Alexander F.

2016-07-01

The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials.

Testing the item-order account of design effects using the production effect.

PubMed

Jonker, Tanya R; Levene, Merrick; Macleod, Colin M

2014-03-01

A number of memory phenomena evident in recall in within-subject, mixed-lists designs are reduced or eliminated in between-subject, pure-list designs. The item-order account (McDaniel & Bugg, 2008) proposes that differential retention of order information might underlie this pattern. According to this account, order information may be encoded when a common form of processing is used alone in a list (e.g., reading), but not when an unusual form of processing is used (e.g., generation) or when a common form and an unusual form are mixed within a list. The production effect--better memory for words said aloud than for words read silently--shows this same design-contingent pattern. In 2 experiments, we investigated whether differential order retention might underlie the production effect. Consistent with the item-order account, we found that retention of order information was better in pure silent lists than in either pure aloud lists or mixed lists, as measured using an order reconstruction test. Moreover, in Experiment 2, order was better preserved in free recall of pure silent lists than of either pure aloud or mixed lists. Thus, production joins the set of tasks identified by McDaniel and Bugg (2008), and our findings suggest a role for order processing in explaining the production effect.

A dominantly inherited form of arthrogryposis multiplex congenita with unusual dermatoglyphics.

PubMed

Sack, G H

1978-12-01

A father and daughter with arthrogryposis multiplex congenita and similar dermatoglyphic patterns are described. No evidence was found of chromosomal abnormality, neuropathy or myopathy, and there were no other affected family members. The findings are compatible with autosomal dominant inheritance.

Four-coordinate, 14-electron Ru(II) complexes: unusual trigonal pyramidal geometry enforced by bis(phosphino)silyl ligation.

PubMed

MacInnis, Morgan C; McDonald, Robert; Ferguson, Michael J; Tobisch, Sven; Turculet, Laura

2011-08-31

Unprecedented diamagnetic, four-coordinate, formally 14-electron (Cy-PSiP)RuX (Cy-PSiP = [κ(3)-(2-R(2)PC(6)H(4))(2)SiMe](-); X = amido, alkoxo) complexes that do not require agostic stabilization and that adopt a highly unusual trigonal pyramidal coordination geometry are reported. The tertiary silane [(2-Cy(2)PC(6)H(4))(2)SiMe]H ((Cy-PSiP)H) reacted with 0.5 [(p-cymene)RuCl(2)](2) in the presence of Et(3)N and PCy(3) to afford [(Cy-PSiP)RuCl](2) (1) in 74% yield. Treatment of 1 with KO(t)Bu led to the formation of (Cy-PSiP)RuO(t)Bu (2, 97% yield), which was crystallographically characterized and shown to adopt a trigonal pyramidal coordination geometry in the solid state. Treatment of 1 with NaN(SiMe(3))(2) led to the formation of (Cy-PSiP)RuN(SiMe(3))(2) (3, 70% yield), which was also found to adopt a trigonal pyramidal coordination geometry in the solid state. The related anilido complexes (Cy-PSiP)RuNH(2,6-R(2)C(6)H(3)) (4, R = H; 5, R = Me) were also prepared in >90% yields by treating 1 with LiNH(2,6-R(2)C(6)H(3)) (R = H, Me) reagents. The solid state structure of 5 indicates a monomeric trigonal pyramidal complex that features a C-H agostic interaction. Complexes 2 and 3 were found to react readily with 1 equiv of H(2)O to form the dimeric hydroxo-bridged complex [(Cy-PSiP)RuOH](2) (6, 94% yield), which was crystallographically characterized. Complexes 2 and 3 also reacted with 1 equiv of PhOH to form the new 18-electron η(5)-oxocyclohexadienyl complex (Cy-PSiP)Ru(η(5)-C(6)H(5)O) (7, 84% yield). Both amido and alkoxo (Cy-PSiP)RuX complexes reacted with H(3)B·NHRR' reagents to form bis(σ-B-H) complexes of the type (Cy-PSiP)RuH(η(2):η(2)-H(2)BNRR') (8, R = R' = H; 9, R = R' = Me; 10, R = H, R' = (t)Bu), which illustrates that such four-coordinate (Cy-PSiP)RuX (X = amido, alkoxo) complexes are able to undergo multiple E-H (E = main group element) bond activation steps. Computational methods were used to investigate structurally related PCP, PPP, PNP, and PSiP four-coordinate Ru complexes and confirmed the key role of the strongly σ-donating silyl group of the PSiP ligand set in enforcing the unusual trigonal pyramidal coordination geometry featured in complexes 2-5, thus substantiating a new strategy for the synthesis of low-coordinate Ru species. The mechanism of the activation of ammonia-borane by such low-coordinate (R-PSiP)RuX (X = amido, alkoxo) species was also studied computationally and was determined to proceed most likely in a stepwise fashion via intramolecular deprotonation of ammonia and subsequent borane B-H bond oxidative addition steps.

Unusual fentanyl patch administration.

PubMed

Thomas, Sandra; Winecker, Ruth; Pestaner, Joseph P

2008-06-01

Fentanyl is an extremely potent narcotic analgesic that is becoming more popular as a drug of abuse. Because of the unique way in which the drug is packaged and delivered, the potential for unusual methods of abuse exists. We report the first case of true fentanyl patch ingestion in the medical literature. Initially, though unusual, cases of fentanyl ingestion were thought to have been reported, but further investigation of the literature revealed that in other case reports the patches had been held in the mouth and chewed. Because no reports of swallowing the patch had been published, suicide was initially a strong consideration in this case; however, further investigation showed that the decedent and his brother enjoyed swallowing the patches for quick "highs." Cases such as these serve to remind medical examiners and law enforcement officials of the value of performing thorough death investigations by performing complete autopsies with toxicological testing and correlating with investigation information to form an opinion with regard to the cause and manner of death.

Geophysical survey of the proposed Tsenkher impact structure, Gobi Altai, Mongolia

NASA Astrophysics Data System (ADS)

Ormö, Jens; Gomez-Ortiz, David; Komatsu, Goro; Bayaraa, Togookhuu; Tserendug, Shoovdor

2010-03-01

We have performed forward magnetic and gravity modeling of data obtained during the 2007 expedition to the 3.7km in diameter, circular, Tsenkher structure, Mongolia, in order to evaluate the cause of its formation. Extensive occurrences of brecciated rocks, mainly in the form of an ejecta blanket outside the elevated rim of the structure, support an explosive origin (e.g., cosmic impact, explosive volcanism). The host rocks in the area are mainly weakly magnetic, silica-rich sandstones, and siltstones. A near absence of surface exposures of volcanic rocks makes any major volcanic structures (e.g., caldera) unlikely. Likewise, the magnetic models exclude any large, subsurface, intrusive body. This is supported by an 8mGal gravity low over the structure indicating a subsurface low density body. Instead, the best fit is achieved for a bowl-shaped structure with a slight central rise as expected for an impact crater of this size in mainly sedimentary target. The structure can be either root-less (i.e., impact crater) or rooted with a narrow feeder dyke with relatively higher magnetic susceptibility and density (i.e., volcanic maar crater). The geophysical signature, the solitary appearance, the predominantly sedimentary setting, and the comparably large size of the Tsenkher structure favor the impact crater alternative. However, until mineralogical/geochemical evidence for an impact is presented, the maar alternative remains plausible although exceptional as it would make the Tsenkher structure one of the largest in the world in an unusual setting for maar craters.

1,3-Oxazole-based selective picomolar inhibitors of cytosolic human carbonic anhydrase II alleviate ocular hypertension in rabbits: Potency is supported by X-ray crystallography of two leads.

PubMed

Ferraroni, Marta; Lucarini, Laura; Masini, Emanuela; Korsakov, Mikhail; Scozzafava, Andrea; Supuran, Claudiu T; Krasavin, Mikhail

2017-09-01

Two lead 1,3-oxazole-based carbonic anhydrase inhibitors (CAIs) earlier identified as selective, picomolar inhibitors of hCA II (a cytosolic target for treatment of glaucoma) have been investigated further. Firstly, they were found to be conveniently synthesized on multigram scale, which enables further development. These compounds were found to be comparable in efficacy to dorzolamide eye drops when applied in the eye drop form as well. Finally, the reasons for unusually high potency of these compounds became understood from their high-resolution X-ray crystallography structures. These data significantly expand our understanding of heterocycle-based primary sulfonamides, many of which have recently emerged from our labs - particularly, from the corneal permeability standpoint. Copyright © 2017 Elsevier Ltd. All rights reserved.

All-printed thin-film transistors from networks of liquid-exfoliated nanosheets

NASA Astrophysics Data System (ADS)

Kelly, Adam G.; Hallam, Toby; Backes, Claudia; Harvey, Andrew; Esmaeily, Amir Sajad; Godwin, Ian; Coelho, João; Nicolosi, Valeria; Lauth, Jannika; Kulkarni, Aditya; Kinge, Sachin; Siebbeles, Laurens D. A.; Duesberg, Georg S.; Coleman, Jonathan N.

2017-04-01

All-printed transistors consisting of interconnected networks of various types of two-dimensional nanosheets are an important goal in nanoscience. Using electrolytic gating, we demonstrate all-printed, vertically stacked transistors with graphene source, drain, and gate electrodes, a transition metal dichalcogenide channel, and a boron nitride (BN) separator, all formed from nanosheet networks. The BN network contains an ionic liquid within its porous interior that allows electrolytic gating in a solid-like structure. Nanosheet network channels display on:off ratios of up to 600, transconductances exceeding 5 millisiemens, and mobilities of >0.1 square centimeters per volt per second. Unusually, the on-currents scaled with network thickness and volumetric capacitance. In contrast to other devices with comparable mobility, large capacitances, while hindering switching speeds, allow these devices to carry higher currents at relatively low drive voltages.

Dirac State in Giant Magnetoresistive Materials

NASA Astrophysics Data System (ADS)

Wu, Y.; Jo, N. H.; Ochi, M.; Huang, L.; Mou, D.; Kong, T.; Mun, E.; Wang, L.; Lee, Y.; Bud'Ko, S. L.; Canfield, P. C.; Trivedi, N.; Arito, R.; Kaminski, A.

We use ultrahigh resolution, tunable, vacuum ultraviolet laser-based angle-resolved photoemission spectroscopy (ARPES) to study the electronic properties of materials that recently were discovered to display titanic magnetoresistance. We find that that several of these materials have Dirac-like features in their band structure. In some materials those features are ``ordinary'' Dirac cones, while in others the linear Dirac dispersion of two crossing bands forms a linear object in 3D momentum space. Our observation poses an important question about the role of Dirac dispersion in the unusually high, non-saturating magnetoresistance of these materials. Research was supported by the US DOE, Office of Basic Energy Sciences under Contract No. DE-AC02-07CH11358; Gordon and Betty Moore Foundation EPiQS Initiative (Grant No. GBMF4411); CEM, a NSF MRSEC, under Grant No. DMR-1420451.

Chiral Sugars Drive Enantioenrichment in Prebiotic Amino Acid Synthesis.

PubMed

Wagner, Alexander J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán; Blackmond, Donna G

2017-04-26

Chiral pentose sugars mediate the enantioselective synthesis of amino acid precursors, with the magnitude of the chiral induction dictated by a subtle cooperativity between sugar hydroxyl groups. Ribose and lyxose give opposite chiral preferences, and theoretical calculations reveal the pseudoenantiomeric nature of transition state structures from the two sugars. Prebiotically plausible mixtures of natural d-sugars lead to enantioenrichment of natural l-amino acid precursors. Temporal monitoring and kinetic modeling of the reaction reveal an unusual dynamic kinetic resolution that shifts toward an enantioselective pathway over time, providing an amplification mechanism for the transfer of chiral information. This work adds to growing evidence for synergy in the etiology of the single chirality of the two most important classes of biological molecules, the sugars that make up DNA and RNA and the amino acids that form proteins.

Genetic heterogeneity in wild isolates of cellular slime mold social groups.

PubMed

Sathe, Santosh; Kaushik, Sonia; Lalremruata, Albert; Aggarwal, Ramesh K; Cavender, James C; Nanjundiah, Vidyanand

2010-07-01

This study addresses the issues of spatial distribution, dispersal, and genetic heterogeneity in social groups of the cellular slime molds (CSMs). The CSMs are soil amoebae with an unusual life cycle that consists of alternating solitary and social phases. Because the social phase involves division of labor with what appears to be an extreme form of "altruism", the CSMs raise interesting evolutionary questions regarding the origin and maintenance of sociality. Knowledge of the genetic structure of social groups in the wild is necessary for answering these questions. We confirm that CSMs are widespread in undisturbed forest soil from South India. They are dispersed over long distances via the dung of a variety of large mammals. Consistent with this mode of dispersal, most social groups in the two species examined for detailed study, Dictyostelium giganteum and Dictyostelium purpureum, are multi-clonal.

Chiral Sugars Drive Enantioenrichment in Prebiotic Amino Acid Synthesis

PubMed Central

2017-01-01

Chiral pentose sugars mediate the enantioselective synthesis of amino acid precursors, with the magnitude of the chiral induction dictated by a subtle cooperativity between sugar hydroxyl groups. Ribose and lyxose give opposite chiral preferences, and theoretical calculations reveal the pseudoenantiomeric nature of transition state structures from the two sugars. Prebiotically plausible mixtures of natural d-sugars lead to enantioenrichment of natural l-amino acid precursors. Temporal monitoring and kinetic modeling of the reaction reveal an unusual dynamic kinetic resolution that shifts toward an enantioselective pathway over time, providing an amplification mechanism for the transfer of chiral information. This work adds to growing evidence for synergy in the etiology of the single chirality of the two most important classes of biological molecules, the sugars that make up DNA and RNA and the amino acids that form proteins. PMID:28470050

Structural basis for diversity in the SAM clan of riboswitches.

PubMed

Trausch, Jeremiah J; Xu, Zhenjiang; Edwards, Andrea L; Reyes, Francis E; Ross, Phillip E; Knight, Rob; Batey, Robert T

2014-05-06

In bacteria, sulfur metabolism is regulated in part by seven known families of riboswitches that bind S-adenosyl-l-methionine (SAM). Direct binding of SAM to these mRNA regulatory elements governs a downstream secondary structural switch that communicates with the transcriptional and/or translational expression machinery. The most widely distributed SAM-binding riboswitches belong to the SAM clan, comprising three families that share a common SAM-binding core but differ radically in their peripheral architecture. Although the structure of the SAM-I member of this clan has been extensively studied, how the alternative peripheral architecture of the other families supports the common SAM-binding core remains unknown. We have therefore solved the X-ray structure of a member of the SAM-I/IV family containing the alternative "PK-2" subdomain shared with the SAM-IV family. This structure reveals that this subdomain forms extensive interactions with the helix housing the SAM-binding pocket, including a highly unusual mode of helix packing in which two helices pack in a perpendicular fashion. Biochemical and genetic analysis of this RNA reveals that SAM binding induces many of these interactions, including stabilization of a pseudoknot that is part of the regulatory switch. Despite strong structural similarity between the cores of SAM-I and SAM-I/IV members, a phylogenetic analysis of sequences does not indicate that they derive from a common ancestor.

Structure and Calcium Binding Properties of a Neuronal Calcium-Myristoyl Switch Protein, Visinin-Like Protein 3.

PubMed

Li, Congmin; Lim, Sunghyuk; Braunewell, Karl H; Ames, James B

2016-01-01

Visinin-like protein 3 (VILIP-3) belongs to a family of Ca2+-myristoyl switch proteins that regulate signal transduction in the brain and retina. Here we analyze Ca2+ binding, characterize Ca2+-induced conformational changes, and determine the NMR structure of myristoylated VILIP-3. Three Ca2+ bind cooperatively to VILIP-3 at EF2, EF3 and EF4 (KD = 0.52 μM and Hill slope of 1.8). NMR assignments, mutagenesis and structural analysis indicate that the covalently attached myristoyl group is solvent exposed in Ca2+-bound VILIP-3, whereas Ca2+-free VILIP-3 contains a sequestered myristoyl group that interacts with protein residues (E26, Y64, V68), which are distinct from myristate contacts seen in other Ca2+-myristoyl switch proteins. The myristoyl group in VILIP-3 forms an unusual L-shaped structure that places the C14 methyl group inside a shallow protein groove, in contrast to the much deeper myristoyl binding pockets observed for recoverin, NCS-1 and GCAP1. Thus, the myristoylated VILIP-3 protein structure determined in this study is quite different from those of other known myristoyl switch proteins (recoverin, NCS-1, and GCAP1). We propose that myristoylation serves to fine tune the three-dimensional structures of neuronal calcium sensor proteins as a means of generating functional diversity.

Structure of human Aichi virus and implications for receptor binding.

PubMed

Zhu, Ling; Wang, Xiangxi; Ren, Jingshan; Kotecha, Abhay; Walter, Thomas S; Yuan, Shuai; Yamashita, Teruo; Tuthill, Tobias J; Fry, Elizabeth E; Rao, Zihe; Stuart, David I

2016-09-05

Aichi virus (AiV), an unusual and poorly characterized picornavirus, classified in the genus Kobuvirus, can cause severe gastroenteritis and deaths in children below the age of five years, especially in developing countries 1,2 . The seroprevalence of AiV is approximately 60% in children under the age of ten years and reaches 90% later in life 3,4 . There is no available vaccine or effective antiviral treatment. Here, we describe the structure of AiV at 3.7 Å. This first high-resolution structure for a kobuvirus is intermediate between those of the enteroviruses and cardioviruses, with a shallow, narrow depression bounded by the prominent VP0 CD loops (linking the C and D strands of the β-barrel), replacing the depression known as the canyon, frequently the site of receptor attachment in enteroviruses. VP0 is not cleaved to form VP2 and VP4, so the 'VP2' β-barrel structure is complemented with a unique extended structure on the inside of the capsid. On the outer surface, a polyproline helix structure, not seen previously in picornaviruses is present at the C terminus of VP1, a position where integrin binding motifs are found in some other picornaviruses. A peptide corresponding to this polyproline motif somewhat attenuates virus infectivity, presumably blocking host-cell attachment. This may guide cellular receptor identification.

Crystal structure and function of an unusual dimeric Hsp20.1 provide insight into the thermal protection mechanism of small heat shock proteins.

PubMed

Liu, Liang; Chen, Jiyun; Yang, Bo; Wang, Yonghua

2015-03-06

Small heat shock proteins (sHSPs) are ubiquitous chaperones that play a vital role in protein homeostasis. sHSPs are characterized by oligomeric architectures and dynamic exchange of subunits. The flexible oligomeric assembling associating with function remains poorly understood. Based on the structural data, it is certainly agreed that two dimerization models depend on the presence or absence of a β6 strand to differentiate nonmetazoan sHSPs from metazoan sHSPs. Here, we report the Sulfolobus solfataricus Hsp20.1 ACD dimer structure, which shows a distinct dimeric interface. We observed that, in the absence of β6, Hsp20.1 dimer does not depend on β7 strand for forming dimer interface as metazoan sHSPs, nor dissociates to monomers. This is in contrast to other published sHSPs. Our structure reveals a variable, highly polar dimer interface that has advantages for rapid subunits exchange and substrate binding. Remarkably, we find that the C-terminal truncation variant has chaperone activity comparable to that of wild-type despite lack of the oligomer structure. Our further study indicates that the N-terminal region is essential for the oligomer and dimer binding to the target protein. Together, the structure and function of Hsp20.1 give more insight into the thermal protection mechanism of sHSPs. Copyright © 2015 Elsevier Inc. All rights reserved.

Novel base-pairing interactions at the tRNA wobble position crucial for accurate reading of the genetic code

PubMed Central

Rozov, Alexey; Demeshkina, Natalia; Khusainov, Iskander; Westhof, Eric; Yusupov, Marat; Yusupova, Gulnara

2016-01-01

Posttranscriptional modifications at the wobble position of transfer RNAs play a substantial role in deciphering the degenerate genetic code on the ribosome. The number and variety of modifications suggest different mechanisms of action during messenger RNA decoding, of which only a few were described so far. Here, on the basis of several 70S ribosome complex X-ray structures, we demonstrate how Escherichia coli tRNALysUUU with hypermodified 5-methylaminomethyl-2-thiouridine (mnm5s2U) at the wobble position discriminates between cognate codons AAA and AAG, and near-cognate stop codon UAA or isoleucine codon AUA, with which it forms pyrimidine–pyrimidine mismatches. We show that mnm5s2U forms an unusual pair with guanosine at the wobble position that expands general knowledge on the degeneracy of the genetic code and specifies a powerful role of tRNA modifications in translation. Our models consolidate the translational fidelity mechanism proposed previously where the steric complementarity and shape acceptance dominate the decoding mechanism. PMID:26791911

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation

PubMed Central

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-01-01

Zn hyperaccumulator (Arabidobsis halleri) and Zn accumulator Salix “Tordis” (Salix schwerinii × Salix viminalis) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis. PMID:29637065

Biosourced Polymetallic Catalysis: A Surprising and Efficient Means to Promote the Knoevenagel Condensation.

PubMed

Deyris, Pierre-Alexandre; Bert, Valérie; Diliberto, Sébastien; Boulanger, Clotilde; Petit, Eddy; Legrand, Yves-Marie; Grison, Claude

2018-01-01

Zn hyperaccumulator ( Arabidobsis halleri ) and Zn accumulator Salix "Tordis" ( Salix schwerinii × Salix viminalis ) have shown their interest in the phytoextraction of polluted brownfields. Herein, we explore a novel methodology based on the chemical valorization of Zn-rich biomass produced by these metallophyte plants. The approach is based on the use of polymetallic salts derived from plants as bio-based catalysts in organic chemistry. The formed ecocatalysts were characterized via ICP-MS, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) in order to precise the chemical composition, structure, and behavior of the formed materials. The Doebner-Knoevenagel reaction was chosen as model reaction to study their synthetic potential. Significant differences to usual catalysts such as zinc (II) chloride are observed. They can principally be related to a mixture of unusual mineral species. DFT calculations were carried out on these salts in the context of the Gutmann theory. They allow the rationalization of experimental results. Finally, these new bio-based polymetallic catalysts illustrated the interest of this concept for green and sustainable catalysis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Sadanand; Pablo, Juan J. de

Recently, novel organic glassy materials that exhibit remarkable stability have been prepared by vapor deposition. The thermophysical properties of these new ''stable'' glasses are equivalent to those that common glasses would exhibit after aging over periods lasting thousands of years. The origin of such enhanced stability has been elusive; in the absence of detailed models, past studies have discussed the formation of new polyamorphs or that of nanocrystals to explain the observed behavior. In this work, an atomistic molecular model of trehalose, a disaccharide of glucose, is used to examine the properties of vapor-deposited stable glasses. Consistent with experiment, themore » model predicts the formation of stable glasses having a higher density, a lower enthalpy, and higher onset temperatures than those of the corresponding ''ordinary'' glass formed by quenching the bulk liquid. Simulations reveal that newly formed layers of the growing vapor-deposited film exhibit greater mobility than the remainder of the material, thereby enabling a reorganization of the film as it is grown. They also reveal that ''stable'' glasses exhibit a distinct layered structure in the direction normal to the substrate that is responsible for their unusual properties.« less

Ouachita Mountains, Oklahoma as seen from STS-58

NASA Image and Video Library

1993-10-30

STS058-91-058 (18 Oct-1 Nov 1993) --- In this unusually clear view, the Ouachita Mountains of southeastern Oklahoma are framed on the north by Lake Eufaula on the South Canadian River, and on the south by the Red River. Sandstone, shale and chert (similar to flint) deposited in a sea several thousand feet deep were squeezed up to form the mountains about 250 million years ago. During the ensuing time, erosion of the western end of the Ouachita Mountains has emphasized linear ridges of resistant rock in the plunging anticlines and synclines, causing relief of 800 meters (2,600 feet) or more. Clouds formed by upslope winds border both the north and south sides of one of the most dramatic plunging synclines (in a syncline the rock layers dip toward the center of the structure). Toward the west, densely forested mountains give way to gently rolling, less rocky terrain and a drier climate which is better suited to farming. The mountains centered on Broken Bow, in the lower right corner of the scene, display abundant timber clearcuts that are being regenerated.

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Seonghyeon; Kwak, Jongheon; Choi, Chungryong

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b-polystyrene- b-poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79,more » and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).« less

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

DOE PAGES

Ahn, Seonghyeon; Kwak, Jongheon; Choi, Chungryong; ...

2017-11-08

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b-polystyrene- b-poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79,more » and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).« less

The formation and evolution of earth-mass dark matter microhalos and their impact on indirect probes of dark matter

NASA Astrophysics Data System (ADS)

Ishiyama, Tomoaki

2013-07-01

Earth-mass dark matter microhalos with a size of ~100 AU are the first structures formed in the universe, if the dark matter of the universe is made of neutralinos. We report the results of ultra-high-resolution cosmological N-body simulations of the formation and evolution of these microhalos. We found that microhalos have the central density cusps of the form ρ ∝ r-1.5, much steeper than the cusps of larger dark halos. The central regions of these microhalos survive the encounters with stars except in the very inner region of the galaxy down to the radius of a few hundreds parsecs from the galactic center. The annihilation signals from the nearest microhalos are observed as gamma-ray point sources (radius less than 1'), with unusually large proper motions of ~0.2 deg per year. Their surface brightnesses are ~10% of that of the galactic center. Their signal-to-noise ratios might be better if they are far from the galactic plane.

The Origin of Magnetite Crystals in ALH84001 Carbonate Disks

NASA Technical Reports Server (NTRS)

Thomas-Keprta, K. L.; Clemett, S. J.; Wentworth, S. J.; McKay, D. S.; Gibson, E. K., Jr.

2012-01-01

Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks believed to have formed approx 3.9 Ga ago at beginning of the Noachian epoch. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose origins have become the source of considerable debate. One group of hypotheses argues that these magnetites are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of magnetite and carbonate may be unrelated; that is, from the perspective of the carbonate the magnetite is allochthonous. We have sought to resolve between these hypotheses through the detailed characterized of the compositional and structural relationships between the carbonate disks, their associated magnetites and the orthopyroxene matrix in which they are embedded. Comparison of these results with experimental thermal decomposition studies of sideritic carbonates conducted under a range of heating scenarios suggests that the magnetite nanocrystals in the ALH84001 carbonate disks are not the products of thermal decomposition.

The cnidarian nematocyst: a miniature extracellular matrix within a secretory vesicle.

PubMed

Ozbek, Suat

2011-10-01

Nematocysts are the taxon-defining features of all cnidarians including jellyfish, sea anemones, and corals. They are highly sophisticated organelles used for the capture of prey and defense. The nematocyst capsule is produced within a giant post-Golgi vesicle, which is continuously fed by proteins from the secretory pathway. Mature nematocysts consist of a hollow capsule body in which a long tubule is coiled up that, upon discharge, is expelled in a harpoon-like fashion. This is accompanied by the release of a toxin cocktail stored in the capsule matrix. Nematocyst discharge, which is one of the fastest processes in biology, is driven by an extreme osmotic pressure of about 150 bar. The molecular analysis of the nematocyst has from the beginning indicated a collagenous nature of the capsule structure. In particular, a large family of unusual minicollagens has been demonstrated to form the highly resistant scaffold of the capsule. Recent findings on the molecular composition of Hydra nematocysts have confirmed the notion of a specialized extracellular matrix, which is assembled during an intracellular secretion process to form the most complex predatory apparatus at the cellular level.

Trypanosoma brucei Metacaspase 4 Is a Pseudopeptidase and a Virulence Factor*

PubMed Central

Proto, William R.; Castanys-Munoz, Esther; Black, Alana; Tetley, Laurence; Moss, Catherine X.; Juliano, Luiz; Coombs, Graham H.; Mottram, Jeremy C.

2011-01-01

Metacaspases are caspase family cysteine peptidases found in plants, fungi, and protozoa but not mammals. Trypanosoma brucei is unusual in having five metacaspases (MCA1–MCA5), of which MCA1 and MCA4 have active site substitutions, making them possible non-enzymatic homologues. Here we demonstrate that recombinant MCA4 lacks detectable peptidase activity despite maintaining a functional peptidase structure. MCA4 is expressed primarily in the bloodstream form of the parasite and associates with the flagellar membrane via dual myristoylation/palmitoylation. Loss of function phenotyping revealed critical roles for MCA4; rapid depletion by RNAi caused lethal disruption to the parasite's cell cycle, yet the generation of MCA4 null mutant parasites (Δmca4) was possible. Δmca4 had normal growth in axenic culture but markedly reduced virulence in mice. Further analysis revealed that MCA4 is released from the parasite and is specifically processed by MCA3, the only metacaspase that is both palmitoylated and enzymatically active. Accordingly, we have identified that the multiple metacaspases in T. brucei form a membrane-associated proteolytic cascade to generate a pseudopeptidase virulence factor. PMID:21949125

New Insights into the Origin of Magnetite Crystals in ALH84001 Carbonate Disks

NASA Technical Reports Server (NTRS)

Thomas-Keptra, Katie L.; Clemett, S. J.; Wentworth S. J.; Mckay, D. S.; Gibson, E. K., Jr.

2010-01-01

Martian meteorite ALH84001 preserves evidence of interaction with aqueous fluids while on Mars in the form of microscopic carbonate disks believed to have formed approx.3.9 Ga ago at beginning of the Noachian epoch. Intimately associated within and throughout these carbonate disks are nanocrystal magnetites (Fe3O4) with unusual chemical and physical properties, whose ori gins have become the source of considerable debate. One group of hypotheses argues that these magnetites are the product of partial thermal decomposition of the host carbonate. Alternatively, the origins of magnetite and carbonate may be unrelated: that is, from the perspective of the carbonate the magnetite is allochthonous. We have sought to resolve between these hypotheses through the detailed characterized of the compositional and structural relationships between the carbonate disks, their associated magnetites and the orthopyroxene matrix in which they are embedded [1]. Comparison of these results with experimental thermal decomposition studies of sideritic carbonates conducted under a range of heating scenarios suggests that the magnetite nanocrystals in the ALH84001 carbonate disks are not the products of thermal decomposition.

Extremophilic and extremotolerant actinomycetes in different soil types

NASA Astrophysics Data System (ADS)

Zenova, G. M.; Manucharova, N. A.; Zvyagintsev, D. G.

2011-04-01

Problems on the resistance of soil actinomycetes to various environmental factors (pH, salinity, temperature, and moisture) are discussed. Actinomycetes as a special group of prokaryotes were revealed to have a greater range of tolerance to these factors than was thought earlier. The regularities of the distribution of extremophilic and extremotolerant actinomycetes developing in unusual for mycelial bacteria conditions, their structural-functional characteristics, and their taxonomic composition were determined. The predominance of acidophilic representatives of the Micromonospora genus in acid soils (typical peat, soddy-podzolic, and taiga podzol) and the haloalkaliphilic Streptomyces pluricilirescens and S. prunicolor species in desert saline soils are shown. The specific features of the actinomycete complexes on thermal fields of the weakly developed stratified volcanic soils are described. In these complexes, the thermophilic forms were represented only by species of the Micromonospora genus; and the mesophilic forms, by Microbispora species. In the periodically heated desert soils, among the thermophilic actinomycetes, representatives of rare Actinomadura, Saccharopolyspora and Streptosporangium genera along with Streptomyces species were indicated. The mechanisms of the resistance of the actinomycetes to the extreme environmental conditions are discussed.

Novel base-pairing interactions at the tRNA wobble position crucial for accurate reading of the genetic code.

PubMed

Rozov, Alexey; Demeshkina, Natalia; Khusainov, Iskander; Westhof, Eric; Yusupov, Marat; Yusupova, Gulnara

2016-01-21

Posttranscriptional modifications at the wobble position of transfer RNAs play a substantial role in deciphering the degenerate genetic code on the ribosome. The number and variety of modifications suggest different mechanisms of action during messenger RNA decoding, of which only a few were described so far. Here, on the basis of several 70S ribosome complex X-ray structures, we demonstrate how Escherichia coli tRNA(Lys)(UUU) with hypermodified 5-methylaminomethyl-2-thiouridine (mnm(5)s(2)U) at the wobble position discriminates between cognate codons AAA and AAG, and near-cognate stop codon UAA or isoleucine codon AUA, with which it forms pyrimidine-pyrimidine mismatches. We show that mnm(5)s(2)U forms an unusual pair with guanosine at the wobble position that expands general knowledge on the degeneracy of the genetic code and specifies a powerful role of tRNA modifications in translation. Our models consolidate the translational fidelity mechanism proposed previously where the steric complementarity and shape acceptance dominate the decoding mechanism.

Novel base-pairing interactions at the tRNA wobble position crucial for accurate reading of the genetic code

NASA Astrophysics Data System (ADS)

Rozov, Alexey; Demeshkina, Natalia; Khusainov, Iskander; Westhof, Eric; Yusupov, Marat; Yusupova, Gulnara

2016-01-01

Posttranscriptional modifications at the wobble position of transfer RNAs play a substantial role in deciphering the degenerate genetic code on the ribosome. The number and variety of modifications suggest different mechanisms of action during messenger RNA decoding, of which only a few were described so far. Here, on the basis of several 70S ribosome complex X-ray structures, we demonstrate how Escherichia coli tRNALysUUU with hypermodified 5-methylaminomethyl-2-thiouridine (mnm5s2U) at the wobble position discriminates between cognate codons AAA and AAG, and near-cognate stop codon UAA or isoleucine codon AUA, with which it forms pyrimidine-pyrimidine mismatches. We show that mnm5s2U forms an unusual pair with guanosine at the wobble position that expands general knowledge on the degeneracy of the genetic code and specifies a powerful role of tRNA modifications in translation. Our models consolidate the translational fidelity mechanism proposed previously where the steric complementarity and shape acceptance dominate the decoding mechanism.

NGC 1291

NASA Image and Video Library

2007-11-14

This image from NASA Galaxy Evolution Explorer shows the galaxy NGC 1291, located about 33 million light-years away in the constellation Eridanus. NGC 1291 is notable for its unusual inner bar and outer ring structure.

Functional characterization and crystal structure of thermostable amylase from Thermotoga petrophila, reveals high thermostability and an unusual form of dimerization.

PubMed

Hameed, Uzma; Price, Ian; Ikram-Ul-Haq; Ke, Ailong; Wilson, David B; Mirza, Osman

2017-10-01

Thermostable α-amylases have many industrial applications and are therefore continuously explored from novel sources. We present the characterization of a novel putative α-amylase gene product (Tp-AmyS) cloned from Thermotoga petrophila. The purified recombinant enzyme is highly thermostable and able to hydrolyze starch into dextrin between 90 and 100°C, with optimum activity at 98°C and pH8.5. The activity increased in the presence of Rb 1+ , K 1+ and Ca 2+ ions, whereas other ions inhibited activity. The crystal structure of Tp-AmyS at 1.7Å resolution showed common features of the GH-13 family, however was apparently found to be a dimer. Several residues from one monomer interacted with a docked acarbose, an inhibitor of Tp-AmyS, in the other monomer, suggesting catalytic cooperativity within the dimer. The most striking feature of the dimer was that it resembled the dimerization of salivary amylase from a previous crystal structure, and thus could be a functional feature of some amylases. Copyright © 2017 Elsevier B.V. All rights reserved.

Educating Exceptional Children: Current Issue for Educators

ERIC Educational Resources Information Center

Specht, Jacqueline

2004-01-01

The Oxford dictionary defines exceptionality as "forming an exception; very unusual; outstandingly good." A thesaurus provides the following synonyms: outstanding, excellent, brilliant, antonym of ordinary. In education and psychology textbooks and journals, however, it is often defined in ways that focus on limitations, with synonyms…

[Trapped temporal horn, an unusual form of obstructive hydrocephalus: 5 case-reports].

PubMed

Abderrahmen, K; Gdoura, Y; Kallel, J; Jemel, H

2016-04-01

"Entrapped temporal horn" is an unusual form of obstructive hydrocephalus which is due to an obstacle at the trigone of the lateral ventricle that seals off the temporal horn that may act as a space occupying process. In this study, our aim was to assess the clinical presentation, imaging, pathophysiology and the management of this entity. The medical records of patients with entrapped temporal horn diagnosed between January 2003 and December 2012 were reviewed retrospectively. Five patients were identified. In four cases, the condition developed after cranial surgery; an infant having two revisions of a ventriculoperitoneal shunt; an adult operated for a glioblastoma, an infant operated on for cerebral hydatidosis and an infant operated for an occipital encephalocele. In the last patient, the entrapped temporal horn revealed sarcoidosis. Trapped temporal horn syndrome can act as a space occupying process and requires surgical management. Internal shunting provides good results. However, the long term outcome depends on the etiology. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

Vortex arrays and ciliary tangles underlie the feeding-swimming tradeoff in starfish larvae

NASA Astrophysics Data System (ADS)

Gilpin, William; Prakash, Vivek N.; Prakash, Manu

2016-11-01

Many marine invertebrates have larval stages covered in linear arrays of beating cilia, which propel the animal while simultaneously entraining planktonic prey. These bands are strongly conserved across taxa spanning four major superphyla, and they are responsible for the unusual morphologies of many invertebrates. However, few studies have investigated their underlying hydrodynamics. Here, we study the ciliary bands of starfish larvae, and discover a beautiful pattern of slowly-evolving vortices that surrounds the swimming animals. Closer inspection of the bands reveals unusual ciliary "tangles" analogous to topological defects that break-up and re-form as the animal adjusts its swimming stroke. Quantitative experiments and modeling demonstrate that these vortices create a physical tradeoff between feeding and swimming in heterogenous environments, which manifests as distinct flow patterns or "eigenstrokes" representing each behavior-potentially implicating neuronal control of cilia. This quantitative interplay between larval form and hydrodynamic function generalizes to other invertebrates, and illustrates the potential effects of active boundary conditions in other biological and synthetic systems.

Computational and Experimental Characterization of Five Crystal Forms of Thymine: Packing Polymorphism, Polytypism/Disorder and Stoichiometric 0.8-Hydrate.

PubMed

Braun, Doris E; Gelbrich, Thomas; Wurst, Klaus; Griesser, Ulrich J

2016-06-01

New polymorphs of thymine emerged in an experimental search for solid forms, which was guided by the computationally generated crystal energy landscape. Three of the four anhydrates (AH) are homeoenergetic ( A° - C ) and their packing modes differ only in the location of oxygen and hydrogen atoms. AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Anhydrates AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Analysis of the crystal energy landscape for alternative AH C hydrogen bonded ribbon motifs identified a number of different packing modes, whose 3D structures were calculated to deviate by less than 0.24 kJ mol -1 in lattice energy. These structures provide models for stacking faults. The three anhydrates A ° - C show strong similarity in their powder X-ray diffraction, thermoanalytical and spectroscopic (IR and Raman) characteristics. The already known anhydrate AH A ° was identified as the thermodynamically most stable form at ambient conditions; AH B and AH C are metastable but show high kinetic stability. The hydrate of thymine is stable only at water activities ( a w ) > 0.95 at temperatures ≤ 25 °C. It was found to be a stoichiometric hydrate despite being a channel hydrate with an unusual water:thymine ratio of 0.8:1. Depending on the dehydration conditions, either AH C or AH D is obtained. The hydrate is the only known precursor to AH D . This study highlights the value and complementarity of simultaneous explorations of computationally and experimentally generated solid form landscapes of a small molecule anhydrate ↔ hydrate system.

Computational and Experimental Characterization of Five Crystal Forms of Thymine: Packing Polymorphism, Polytypism/Disorder and Stoichiometric 0.8-Hydrate

PubMed Central

Braun, Doris E.; Gelbrich, Thomas; Wurst, Klaus; Griesser, Ulrich J.

2017-01-01

New polymorphs of thymine emerged in an experimental search for solid forms, which was guided by the computationally generated crystal energy landscape. Three of the four anhydrates (AH) are homeoenergetic (A° – C) and their packing modes differ only in the location of oxygen and hydrogen atoms. AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Anhydrates AHs A° and B are ordered phases, whereas AH C shows disorder (X-ray diffuse scattering). Analysis of the crystal energy landscape for alternative AH C hydrogen bonded ribbon motifs identified a number of different packing modes, whose 3D structures were calculated to deviate by less than 0.24 kJ mol–1 in lattice energy. These structures provide models for stacking faults. The three anhydrates A° – C show strong similarity in their powder X-ray diffraction, thermoanalytical and spectroscopic (IR and Raman) characteristics. The already known anhydrate AH A° was identified as the thermodynamically most stable form at ambient conditions; AH B and AH C are metastable but show high kinetic stability. The hydrate of thymine is stable only at water activities (aw) > 0.95 at temperatures ≤ 25 °C. It was found to be a stoichiometric hydrate despite being a channel hydrate with an unusual water:thymine ratio of 0.8:1. Depending on the dehydration conditions, either AH C or AH D is obtained. The hydrate is the only known precursor to AH D. This study highlights the value and complementarity of simultaneous explorations of computationally and experimentally generated solid form landscapes of a small molecule anhydrate ↔ hydrate system. PMID:28663717

Formation of brucite and cronstedtite-bearing mineral assemblages on Ceres

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.

2014-01-01

Dwarf planet Ceres is the largest body in the main asteroid belt with a rocky surface and uncertain internal structure. Spectra of Ceres in near- and mid-infrared wavelengths are consistent with the occurrence of brucite, Mg-bearing carbonates, and an Fe-rich phyllosilicate cronstedtite. Spectra of 10 Hygiea and 324 Bamberga imply similar compositions. Here, we considered stabilities of these minerals to constrain their origin. Cronstedtite is most stable at the temperature of ˜0 °C at moderately oxidizing aqueous conditions and at high water/rock ratios. Although cronstedtite could form on planetesimals, the apparent lack of serpentine may indicate its formation by Ceres' temporary surface solutions. Brucite forms at a low activity of dissolved SiO2, at a low fugacity of CO2, and at highly alkaline pH. Brucite and cronstedtite do not form together and may not form deep in the Ceres' interior. The absence of Mg serpentine from Ceres' surface materials and the unlikely occurrence of very olivine-rich rocks do not indicate a formation of brucite through serpentinization of such rocks. Brucite could form by transient near-surface fluids which do not equilibrate with silicates. Temporary fluids could deposit Mg carbonates before, after, or together with brucite at near-surface conditions that favor CO2 degassing. Regardless of Ceres' internal structure, internal thermal and aqueous processes may not affect cold near-surface layers. Percolation of interior fluids is not consistent with the lack of detection of low-solubility salts. However, impacts of ice-rich targets during the Late Heavy Bombardment could account for transient aqueous environments and unusual surface mineralogies of Ceres, Hygiea, and Bamberga. Brucite and Mg carbonates could have formed through hydration and carbonation of MgO evaporated from silicates. Apparently abundant carbonates may indicate an ample impact oxidation of organic matter, and the occurrence of brucite with cronstedtite may reflect turbulent and disequilibrium environments. Clay-like homogeneous surface materials on Ceres could be gravitationally sorted deposits of impact clouds.

NREL Researchers Create New Materials With Unusual Properties | News | NREL

Science.gov Websites

show how such new low-density materials can be made - with unique properties remarkably different from compounds with atomic structures that didn't match, the researchers theorized that mixing two different high manganese telluride (MnTe) that have different crystal structures - the approach known as heterostructural

Composite structural materials

NASA Technical Reports Server (NTRS)

Ansell, G. S.; Loewy, R. G.; Wiberley, S. E.

1982-01-01

Research in the basic composition, characteristics, and processng science of composite materials and their constituents is balanced against the mechanics, conceptual design, fabrication, and testing of generic structural elements typical of aerospace vehicles so as to encourage the discovery of unusual solutions to problems. Detailed descriptions of the progress achieved in the various component parts of his program are presented.

The Effect of Microgravity on the Growth of Silica Nanostructures

NASA Technical Reports Server (NTRS)

Smith, D. D.; Sibille, L.; Cronise, R.; Oldenburg, S. J.; Wolfe, D.; Halas, N. J.

2001-01-01

The process of the formation of structures from coagulating ensembles is fundamentally important since the collective behavior of the constituents often results in dramatically improved or unusual mechanical, thermal, chemical, and optical properties. In this study we examine the effect of microgravity on the formation of silica structures, specifically particles and gels.

Structure and Active Stie Residues of Pg1D, an N-Acetyltransferase from the Bacillosamine Synthetic Pathway Required for N-Glycan Synthesis in Campylobacter jejuni

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rangarajan,E.; Ruane, K.; Sulea, T.

2008-01-01

Campylobacter jejuni is highly unusual among bacteria in forming N-linked glycoproteins. The heptasaccharide produced by its pgl system is attached to protein Asn through its terminal 2, 4-diacetamido-2, 4,6-trideoxy-d-Glc (QuiNAc4NAc or N, N'-diacetylbacillosamine) moiety. The crucial, last part of this sugar's synthesis is the acetylation of UDP-2-acetamido-4-amino-2, 4,6-trideoxy-d-Glc by the enzyme PglD, with acetyl-CoA as a cosubstrate. We have determined the crystal structures of PglD in CoA-bound and unbound forms, refined to 1.8 and 1.75 Angstroms resolution, respectively. PglD is a trimer of subunits each comprised of two domains, an N-terminal {alpha}/{beta}-domain and a C-terminal left-handed {beta}-helix. Few structural differencesmore » accompany CoA binding, except in the C-terminal region following the {beta}-helix (residues 189-195), which adopts an extended structure in the unbound form and folds to extend the {beta}-helix upon binding CoA. Computational molecular docking suggests a different mode of nucleotide-sugar binding with respect to the acetyl-CoA donor, with the molecules arranged in an 'L-shape', compared with the 'in-line' orientation in related enzymes. Modeling indicates that the oxyanion intermediate would be stabilized by the NH group of Gly143', with His125' the most likely residue to function as a general base, removing H+ from the amino group prior to nucleophilic attack at the carbonyl carbon of acetyl-CoA. Site-specific mutations of active site residues confirmed the importance of His125', Glu124', and Asn118. We conclude that Asn118 exerts its function by stabilizing the intricate hydrogen bonding network within the active site and that Glu124' may function to increase the pKa of the putative general base, His125'.« less

Topological mechanics: from metamaterials to active matter

NASA Astrophysics Data System (ADS)

Vitelli, Vincenzo

2015-03-01

Mechanical metamaterials are artificial structures with unusual properties, such as negative Poisson ratio, bistability or tunable acoustic response, which originate in the geometry of their unit cell. At the heart of such unusual behavior is often a mechanism: a motion that does not significantly stretch or compress the links between constituent elements. When activated by motors or external fields, these soft motions become the building blocks of robots and smart materials. In this talk, we discuss topological mechanisms that possess two key properties: (i) their existence cannot be traced to a local imbalance between degrees of freedom and constraints (ii) they are robust against a wide range of structural deformations or changes in material parameters. The continuum elasticity of these mechanical structures is captured by non-linear field theories with a topological boundary term similar to topological insulators and quantum Hall systems. We present several applications of these concepts to the design and experimental realization of 2D and 3D topological structures based on linkages, origami, buckling meta-materials and lastly active media that break time-reversal symmetry.

Determining the structure of tetragonal Y 2WO 6 and the site occupation of Eu 3+ dopant

NASA Astrophysics Data System (ADS)

Huang, Jinping; Xu, Jun; Li, Hexing; Luo, Hongshan; Yu, Xibin; Li, Yikang

2011-04-01

The compound Y 2WO 6 is prepared by solid state reaction at 750 °C using sodium chloride as mineralizer. Its structure is solved by ab-initio methods from X-ray powder diffraction data. This low temperature phase of yttrium tungstate crystallizes in tetragonal space group P4/ nmm (No. 129), Z=2, a=5.2596(2) Å, c=8.4158(4) Å. The tungsten atoms in the structure adopt an unusual [WO 6] distorted cubes coordination, connecting [YO 6] distorted cubes with oxygen vacancies at the O 2 layers while other yttrium ions Y 2 form [YO 8] cube coordination. Y 3+ ions occupy two crystallographic sites of 2 c ( C4v symmetry) and 2 a ( D2d symmetry) in the Y 2WO 6 host lattice. With Eu 3+ ions doped, the high resolution emission spectrum of Y 2WO 6:Eu 3+ suggests that Eu 3+ partly substituted for Y 3+ in these two sites. The result of the Rietveld structure refinement shows that the Eu 3+ dopants preferentially enter the 2 a site. The uniform cube coordination environment of Eu 3+ ions with the identical eight Eu-O bond lengths is proposed to be responsible for the intense excitation of long wavelength ultraviolet at 466-535 nm.

Double-spiral magnetic structure of the Fe/Cr multilayer revealed by nuclear resonance reflectivity

NASA Astrophysics Data System (ADS)

Andreeva, M. A.; Baulin, R. A.; Chumakov, A. I.; Rüffer, R.; Smirnov, G. V.; Babanov, Y. A.; Devyaterikov, D. I.; Milyaev, M. A.; Ponomarev, D. A.; Romashev, L. N.; Ustinov, V. V.

2018-01-01

We have studied the magnetization depth profiles in a [57Fe (dFe) /Cr (dCr) ]30 multilayer with ultrathin Fe layers and nominal thickness of the chromium spacers dCr≈2.0 nm using nuclear resonance scattering of synchrotron radiation. The presence of a broad pure-magnetic half-order (1/2) Bragg reflection has been detected at zero external field. The joint fit of the reflectivity curves and Mössbauer spectra of reflectivity measured near the critical angle and at the "magnetic" peak reveals that the magnetic structure of the multilayer is formed by two spirals, one in the odd and another one in the even iron layers, with the opposite signs of rotation. The double-spiral structure starts from the surface with the almost-antiferromagnetic alignment of the adjacent Fe layers. The rotation of the two spirals leads to nearly ferromagnetic alignment of the two magnetic subsystems at some depth, where the sudden turn of the magnetic vectors by ˜180∘ (spin flop) appears, and both spirals start to rotate in opposite directions. The observation of this unusual double-spiral magnetic structure suggests that the unique properties of giant magnetoresistance devices can be further tailored using ultrathin magnetic layers.

Multiple Aromaticity and Antiaromaticity in Silicon Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhai, Hua JIN.; Kuznetsov, A E.; Boldyrev, Alexander I.

A series of silicon clusters containing four atoms but with different charge states (Si{sub 4}{sup 2+}, Si{sub 4}, Si{sub 4}{sup 2-}, and NaSi{sub 4}{sup -}) were studied by photoelectron spectroscopy and ab initio calculations. Structure evolution and chemical bonding in this series were interpreted in terms of aromaticity and antiaromaticity, which allowed the prediction of how structures of the four-atom silicon clusters change upon addition or removal of two electrons. It is shown that Si{sub 4}{sup 2+} is square-planar, analogous to the recently discovered aromatic Al{sub 4}{sup 2-} cluster. Upon addition of two electrons, neutral Si{sub 4} becomes {sigma}-antiaromatic andmore » exhibits a rhombus distortion. Adding two more electrons to Si{sub 4} leads to two energetically close structures of Si{sub 4}{sup 2-}: either a double antiaromatic parallelogram structure or an aromatic system with a butterfly distortion. Because of the electronic instability of doubly charged Si{sub 4}{sup 2-}, a stabilizing cation (Na{sup +}) was used to produce Si{sub 4}{sup 2-} in the gas phase in the form of Na{sup +}[Si{sub 4}{sup 2-}], which was characterized experimentally by photoelectron spectroscopy. Multiple antiaromaticity in the parallelogram Na{sup +}[Si{sub 4}{sup 2-}] species is highly unusual.« less

Novel dimeric interface and electrostatic recognition in bacterial Cu,Zn superoxide dismutase

PubMed Central

Bourne, Yves; Redford, Susan M.; Steinman, Howard M.; Lepock, James R.; Tainer, John A.; Getzoff, Elizabeth D.

1996-01-01

Eukaryotic Cu,Zn superoxide dismutases (CuZnSODs) are antioxidant enzymes remarkable for their unusually stable β-barrel fold and dimer assembly, diffusion-limited catalysis, and electrostatic guidance of their free radical substrate. Point mutations of CuZnSOD cause the fatal human neurodegenerative disease amyotrophic lateral sclerosis. We determined and analyzed the first crystallographic structure (to our knowledge) for CuZnSOD from a prokaryote, Photobacterium leiognathi, a luminescent symbiont of Leiognathid fish. This structure, exemplifying prokaryotic CuZnSODs, shares the active-site ligand geometry and the topology of the Greek key β-barrel common to the eukaryotic CuZnSODs. However, the β-barrel elements recruited to form the dimer interface, the strategy used to forge the channel for electrostatic recognition of superoxide radical, and the connectivity of the intrasubunit disulfide bond in P. leiognathi CuZnSOD are discrete and strikingly dissimilar from those highly conserved in eukaryotic CuZnSODs. This new CuZnSOD structure broadens our understanding of structural features necessary and sufficient for CuZnSOD activity, highlights a hitherto unrecognized adaptability of the Greek key β-barrel building block in evolution, and reveals that prokaryotic and eukaryotic enzymes diverged from one primordial CuZnSOD and then converged to distinct dimeric enzymes with electrostatic substrate guidance. PMID:8917495

Solution structure of a highly stable DNA duplex conjugated to a minor groove binder.

PubMed Central

Kumar, S; Reed, M W; Gamper, H B; Gorn, V V; Lukhtanov, E A; Foti, M; West, J; Meyer, R B; Schweitzer, B I

1998-01-01

The tripeptide 1,2-dihydro-(3 H )-pyrrolo[3,2- e ]indole-7-carboxylate (CDPI3) binds to the minor groove of DNA with high affinity. When this minor groove binder is conjugated to the 5'-end of short oligonucleotides the conjugates form unusually stable hybrids with complementary DNA and thus may have useful diagnostic and/or therapeutic applications. In order to gain an understanding of the structural interactions between the CDPI3minor groove binding moiety and the DNA, we have determined and compared the solution structure of a duplex consisting of oligodeoxyribonucleotide 5'-TGATTATCTG-3' conjugated at the 5'-end to CDPI3 and its complementary strand to an unmodified control duplex of the same sequence using nuclear magnetic resonance techniques. Thermal denaturation studies indicated that the hybrid of this conjugate with its complementary strand had a melting temperature that was 30 degrees C higher compared with the unmodified control duplex. Following restrained molecular dynamics and relaxation matrix refinement, the solution structure of the CDPI3-conjugated DNA duplex demonstrated that the overall shape of the duplex was that of a straight B-type helix and that the CDPI3moiety was bound snugly in the minor groove, where it was stabilized by extensive van der Waal's interactions. PMID:9443977

Solution structure of a highly stable DNA duplex conjugated to a minor groove binder.

PubMed

Kumar, S; Reed, M W; Gamper, H B; Gorn, V V; Lukhtanov, E A; Foti, M; West, J; Meyer, R B; Schweitzer, B I

1998-02-01

The tripeptide 1,2-dihydro-(3 H )-pyrrolo[3,2- e ]indole-7-carboxylate (CDPI3) binds to the minor groove of DNA with high affinity. When this minor groove binder is conjugated to the 5'-end of short oligonucleotides the conjugates form unusually stable hybrids with complementary DNA and thus may have useful diagnostic and/or therapeutic applications. In order to gain an understanding of the structural interactions between the CDPI3minor groove binding moiety and the DNA, we have determined and compared the solution structure of a duplex consisting of oligodeoxyribonucleotide 5'-TGATTATCTG-3' conjugated at the 5'-end to CDPI3 and its complementary strand to an unmodified control duplex of the same sequence using nuclear magnetic resonance techniques. Thermal denaturation studies indicated that the hybrid of this conjugate with its complementary strand had a melting temperature that was 30 degrees C higher compared with the unmodified control duplex. Following restrained molecular dynamics and relaxation matrix refinement, the solution structure of the CDPI3-conjugated DNA duplex demonstrated that the overall shape of the duplex was that of a straight B-type helix and that the CDPI3moiety was bound snugly in the minor groove, where it was stabilized by extensive van der Waal's interactions.

Structural Changes in PEO-PPO-PEO Gels Induced by Methylparaben and Dexamethasone Observed Using Time-Resolved SAXS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meznarich, Norman A.K.; Juggernauth, K Anne; Batzli, Kiersten M

2011-11-17

Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymers (commercially available as Pluronic surfactants) micellize and structurally arrange into cubic quasicrystalline lattices as their temperature is raised. This structural evolution is seen macroscopically as a gelation, and the presence of these ordered phases can be controlled through both polymer concentration and temperature. The presence of added solutes within the dispersions can also affect the onset and kinetics of structure formation. Here we investigate the structures formed in Pluronic F127 solutions ranging from 20 to 30% with two pharmaceutical additives [methylparaben (MP) and dexamethasone (DX)] using small-angle X-ray scattering (SAXS). We observe bothmore » the progressive evolution and breakdown of these structures as the temperature is increased from 0 to 80 °C. Additionally, we conducted time-resolved SAXS measurements to elucidate the kinetics of the structural evolution. On the basis of the evolution of scattering peaks as the samples were being heated, we suggest that added MP changes the nucleation behavior of fcc phases within the sample from a heterogeneous process to a more homogeneous distribution of nucleated species. MP and DX also stabilize the micelle lattices, allowing them to persevere at higher temperatures. We observed the unusual result that the presence of DX caused the primary peaks of the structure factor to be suppressed, while preserving the higher order peaks. The primary peaks reappeared at the highest temperatures tested.« less

The Rock Elm meteorite impact structure, Wisconsin: Geology and shock-metamorphic effects in quartz

USGS Publications Warehouse

French, B.M.; Cordua, W.S.; Plescia, J.B.

2004-01-01

The Rock Elm structure in southwest Wisconsin is an anomalous circular area of highly deformed rocks, ???6.5 km in diameter, located in a region of virtually horizontal undeformed sedimentary rocks. Shock-produced planar microstructures (PMs) have been identified in quartz grains in several lithologies associated with the structure: sandstones, quartzite pebbles, and breccia. Two distinct types of PMs are present: P1 features, which appear identical to planar fractures (PFs or cleavage), and P2 features, which are interpreted as possible incipient planar deformation features (PDFs). The latter are uniquely produced by the shock waves associated with meteorite impact events. Both types of PMs are oriented parallel to specific crystallographic planes in the quartz, most commonly to c(0001), ??112??2, and r/z101??1. The association of unusual, structurally deformed strata with distinct shock-produced microdeformation features in their quartz-bearing rocks establishes Rock Elm as a meteorite impact structure and supports the view that the presence of multiple parallel cleavages in quartz may be used independently as a criterion for meteorite impact. Preliminary paleontological studies indicate a minimum age of Middle Ordovician for the Rock Elm structure. A similar age estimate (450-400 Ma) is obtained independently by combining the results of studies of the general morphology of complex impact structures with estimated rates of sedimentation for the region. Such methods may be applicable to dating other old and deeply eroded impact structures formed in sedimentary target rocks.

Diverse microbially induced sedimentary structures from 1 Ga lakes of the Diabaig Formation, Torridon Group, northwest Scotland

NASA Astrophysics Data System (ADS)

Callow, Richard H. T.; Battison, Leila; Brasier, Martin D.

2011-08-01

The siliciclastic lacustrine rocks of the ~ 1000 Ma Diabaig Formation, northwest Scotland, contain a remarkable diversity of macroscopic structures on bedding planes that can be compared with various kinds of microbially induced sedimentary structures (MISS). Field sedimentological investigations, combined with laboratory analysis of bedding planes and petrographic study of thin sections have allowed us to characterise a range of depositional environments and document the spectrum of biological structures. MISS are reported from frequently subaerial environments, through commonly submerged facies, and down to permanently sub-wavebase settings. Palaeoenvironmental conditions (water depth, exposure, hydrodynamic energy) control the distribution of MISS within these facies. This demonstrates that mat-forming microbial communities were arguably well adapted to low light levels or periodic exposure. Some MISS from the Diabaig Formation are typical of Precambrian microbial mats, including reticulate fabrics and 'old elephant skin' textures. In addition to these, a number of new and unusual fabrics of putative microbial origin are described, including linear arrays of ridges and grooves (cf. 'Arumberia') and discoidal structures that are comparable with younger Ediacaran fossils such as Beltanelliformis. These observations indicate that benthic microbial ecosystems were thriving in freshwater lake systems ~ 1000 Ma, and indicate how microbially induced sedimentary structures may be applied as facies indicators for Proterozoic lacustrine environments. The discovery of structures closely resembling Ediacaran fossils (cf. Beltanelliformis) also serves to highlight the difficulty of interpreting simple discoidal bedding plane structures as metazoan fossils.

Death in the "microwave oven": A form of execution by carbonization.

PubMed

Durão, Carlos; Machado, Marcos P; Daruge Júnior, Eduardo

2015-08-01

Death in the "microwave oven" has nothing to do with microwaves energy. It is the jargon name given to a criminal form of execution by carbonization that has been adopted by drug dealers in Rio de Janeiro (Brazil). The goal is to torture and intimidate victims, in an attempt of corpse occultation and to make identification harder or impossible. This paper brings to attention of the forensic international community an unusual and very cruel form of execution as a way to document these situations. Copyright © 2015. Published by Elsevier Ireland Ltd.

A Case of Unusual Clitoromegaly.

PubMed

Wooi Ch'ng, Tong; Umpaichitra, Vatcharapan

2018-05-03

Mild degree of clitoromegaly can be associated with patient with polycystic ovarian syndrome (PCOS). We describe an unusually significant clitoromegaly in a patient with PCOS. An 18-year old non-obese female referred for clitoromegaly. Her genitalia exam showed significant clitoral enlargement with a well-formed glans, clitoris measured at 35 mm for length and 10 mm for width. Pelvic ultrasound showed left ovarian cyst. Testosterone level ranged from 28.8 to 64.1 ng/dl (normal: 8.4-48.1 ng/dl) with normal sex hormone binding globulin. Other ovarian hormones were in acceptable ranges. This case demonstrates the coexistence of significant clitoromegaly, PCOS, and non-functioning ovarian cyst. Copyright © 2018. Published by Elsevier Inc.

Establishing an unusual cell type: How to make a dikaryon

PubMed Central

Kruzel, Emilia K.; Hull, Christina M.

2010-01-01

Summary The dikaryons of basidiomycete fungi represent an unusual cell type required for complete sexual development. Dikaryon formation occurs via the activities of cell type-specific homeodomain transcription factors, which form regulatory complexes to establish the dikaryotic state. Decades of classical genetic and cell biological studies in mushrooms have provided a foundation for more recent molecular studies in the pathogenic species Ustilago maydis and Cryptococcus neoformans. Studies in these systems have revealed novel mechanisms of regulation that function downstream of classic homeodomain complexes to ensure that dikaryons are established and propagated. Comparisons of these dikaryon-specific networks promise to reveal the nature of regulatory network evolution and the adaptations responsible for driving complex eukaryotic development. PMID:21036099

Cemento-ossifying fibroma of mandible: An unusual case report and review of literature.

PubMed

Mohapatra, Mounabati; Banushree, C S; Nagarajan, K; Pati, Debashish

2015-01-01

The term ossifying fibroma (OF) has recently been included under fibro-osseous lesions. Cemento-OF (COF) is a benign neoplasm that arises from the periodontal membrane which contains multipotential cells that are capable of forming cementum, lamellar bone and fibrous tissue. These tumors occur in the third and fourth decades of life with a predilection for women. The mandible is more commonly involved than the maxilla. This lesion has caused considerable controversy regarding the use of terminology, origin and diagnostic criteria. This article describes an unusual case of COF presenting as unilocular lytic lesion of mandible in a 38-year-old male patient with review of literature.

Cemento-ossifying fibroma of mandible: An unusual case report and review of literature

PubMed Central

Mohapatra, Mounabati; Banushree, CS; Nagarajan, K; Pati, Debashish

2015-01-01

The term ossifying fibroma (OF) has recently been included under fibro-osseous lesions. Cemento-OF (COF) is a benign neoplasm that arises from the periodontal membrane which contains multipotential cells that are capable of forming cementum, lamellar bone and fibrous tissue. These tumors occur in the third and fourth decades of life with a predilection for women. The mandible is more commonly involved than the maxilla. This lesion has caused considerable controversy regarding the use of terminology, origin and diagnostic criteria. This article describes an unusual case of COF presenting as unilocular lytic lesion of mandible in a 38-year-old male patient with review of literature. PMID:26980975