Interpretation of Ferroan Anorthosite Ages and Implications for the Lunar Magma Ocean

NASA Technical Reports Server (NTRS)

Neal, C. R.; Draper, D. S.

2017-01-01

Ferroan Anorthosites (FANs) are considered to have purportedly crystallized directly from the lunar magma ocean (LMO) as a flotation crust. LMO modeling suggests that such anorthosites started to form only after greater than 70 percent of the LMO had crystallized. Recent age dates for FANs have questioned this hypothesis as they span too large of an age range. This means a younger age for the Moon-forming giant impact or the LMO hypothesis is flawed. However, FANs are notoriously difficult to age-date using the isochron method. We have proposed a mechanism for testing the LMO hypothesis through using plagioclase trace element abundances to calculate equilibrium liquids and compare them with LMO crystallization models. We now examine the petrography of the samples that have Sm-Nd (Samarium-Neodymium) age dates (Rb-Sr (Rubidium-Strontium) isotopic systematics may have been disturbed) and propose a relative way to age date FANs.

Origins of carbonate spherulites: Implications for Brazilian Aptian pre-salt reservoir

NASA Astrophysics Data System (ADS)

Chafetz, Henry; Barth, Jennifer; Cook, Megan; Guo, Xuan; Zhou, Jie

2018-03-01

Spherulites, spherical to elliptical allochems composed of crystals radiating from a common core, investigated from a variety of depositional settings, e.g., hot springs, ambient water temperature geyser, tufa, and caliche, are all composed of a fine-grained nucleus made-up of carbonate encrusted bacterial bodies, biofilms, and/or EPS and surrounded by a cortex of radiating crystals of either aragonite or calcite. The microbes and their by-products in the nucleus induced the precipitation of carbonate, overcoming the inhibition to initiate crystal formation. The enveloping radiating crystals comprising aragonitic cortices tended to grow abiotically producing well-formed euhedral crystals with a paucity of included bacterial fossils. Whereas those cortical crystals made-up of calcite commonly contained bacterial fossils, indicating that the bacterial colonies contributed to the calcitic cortical crystal precipitation. Similar spherulites form a thick, widespread accumulation in the Aptian Pre-Salt lacustrine deposits in the Campos Basin, offshore Brazil. As with the travertine, tufa, and caliche spherulites, the Pre-Salt spherulites most likely initiated carbonate precipitation around bacterial colonies and/or their bioproducts, probably while afloat in a lacustrine water column before settling to the water-sediment interface. Absence of inter-spherulite sediment and the spherulite-to-spherulite compaction indicate that cortical crystal growth continued while the spherulites were at the sediment-water interface rather than displacively within a sediment.

Purification, crystallization and preliminary X-ray diffraction of human S100A15

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

Boeshans, Karen M.; Wolf, Ronald; Voscopoulos, Christopher

2006-05-01

S100 proteins are differentially expressed during epithelial cell maturation, tumorigenesis and inflammation. The novel human S100A15 protein has been cloned, expressed, purified and crystallized in two crystal forms, a triclinic and a monoclinic form, which diffract to 1.7 and 2.0 Å, respectively. Human S100A15 is a novel member of the S100 family of EF-hand calcium-binding proteins and was recently identified in psoriasis, where it is significantly upregulated in lesional skin. The protein is implicated as an effector in calcium-mediated signal transduction pathways. Although its biological function is unclear, the association of the 11.2 kDa S100A15 with psoriasis suggests that itmore » contributes to the pathogenesis of the disease and could provide a molecular target for therapy. To provide insight into the function of S100A15, the protein was crystallized to visualize its structure and to further the understanding of how the many similar calcium-binding mediator proteins in the cell distinguish their cognate target molecules. The S100A15 protein has been cloned, expressed and purified to homogeneity and produced two crystal forms. Crystals of form I are triclinic, with unit-cell parameters a = 33.5, b = 44.3, c = 44.8 Å, α = 71.2, β = 68.1, γ = 67.8° and an estimated two molecules in the asymmetric unit, and diffract to 1.7 Å resolution. Crystals of form II are monoclinic, with unit-cell parameters a = 82.1, b = 33.6, c = 52.2 Å, β = 128.2° and an estimated one molecule in the asymmetric unit, and diffract to 2.0 Å resolution. This structural analysis of the human S100A15 will further aid in the phylogenic comparison between the other members of the S100 protein family, especially the highly homologous paralog S100A7.« less

Crystallization and preliminary crystallographic studies of human kallikrein 7, a serine protease of the multigene kallikrein family

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

Fernández, Israel S.; Ständker, Ludger; Hannover Medical School, Center of Pharmacology, 30625 Hannover

2007-08-01

The cloning, expression, purification and crystallization of recombinant human kallikrein 7, directly synthesized in the active form in E. coli, is described. Diffraction data were collected to 2.8 Å resolution from native crystals. Human kallikreins are a group of serine proteases of high sequence homology whose genes are grouped as a single cluster at chromosome 19. Although the physiological roles of kallikreins are generally still unknown, members of the kallikrein family have been clearly implicated in pathological situations such as cancer and psoriasis. Human kallikrein 7 (hK7) has been shown to be involved in pathological keratinization, psoriasis and ovarian cancer.more » In order to gain insight into the molecular structure of this protein, hK7 was crystallized after recombinant production in its folded and active form using a periplasmic secretion vector in Escherichia coli. The crystals belonged to the rhombohedral space group H32 and diffracted to 2.8 Å. The phase problem was solved by molecular replacement using the mouse kallikrein-related protein neuropsin. Completion of the model and structure refinement are under way.« less

EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Lad, R. A.

1975-01-01

An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

Crystal structure of N-{ N-[ N-acetyl-( S)-leucyl]-( S)-leucyl}norleucinal (ALLN), an inhibitor of proteasome

DOE PAGES

Czerwinski, Andrzej; Basava, Channa; Dauter, Miroslawa; ...

2015-03-01

The title compound, C 20H 37N 3O 4, also known by the acronym ALLN, is a tripeptidic inhibitor of the proteolytic activity of the proteasomes, enzyme complexes implicated in several neurodegenerative diseases and other disorders, including cancer. Thus, the crystal structure of ALLN, solved from synchrotron radiation diffraction data, revealed the molecules in extended conformation of the backbone and engaging all peptide N and O atoms in intermolecular hydrogen bonds forming an infinite antiparallel β-sheet.

Expression, purification, crystallization and preliminary X-ray diffraction analysis of the VP8* sialic acid-binding domain of porcine rotavirus strain OSU

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

Zhang, Yang-De, E-mail: zhangyd1960@yahoo.com.cn; Li, Hao; Liu, Hui

2007-02-01

Porcine rotavirus strain OSU VP8* domain has been expressed, purified and crystallized. X-ray diffraction data from different crystal forms of the VP8* domain have been collected to 2.65 and 2.2 Å resolution, respectively. The rotavirus outer capsid spike protein VP4 is utilized in the process of rotavirus attachment to and membrane penetration of host cells. VP4 is cleaved by trypsin into two domains: VP8* and VP5*. The VP8* domain is implicated in initial interaction with sialic acid-containing cell-surface carbohydrates and triggers subsequent virus invasion. The VP8* domain from porcine OSU rotavirus was cloned and expressed in Escherichia coli. Different crystalmore » forms (orthorhombic P2{sub 1}2{sub 1}2{sub 1} and tetragonal P4{sub 1}2{sub 1}2) were harvested from two distinct crystallization conditions. Diffraction data have been collected to 2.65 and 2.2 Å resolution and the VP8*{sub 65–224} structure was determined by molecular replacement.« less

Two conformational states of the membrane-associated Bacillus thuringiensis Cry4Ba {delta}-endotoxin complex revealed by electron crystallography: Implications for toxin-pore formation

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

Ounjai, Puey; Laboratory of Molecular Biophysics and Structural Biochemistry, Institute of Molecular Biology and Genetics, Mahidol University, Salaya Campus, Nakornpathom 73170; Unger, Vinzenz M.

The insecticidal nature of Cry {delta}-endotoxins produced by Bacillus thuringiensis is generally believed to be caused by their ability to form lytic pores in the midgut cell membrane of susceptible insect larvae. Here we have analyzed membrane-associated structures of the 65-kDa dipteran-active Cry4Ba toxin by electron crystallography. The membrane-associated toxin complex was crystallized in the presence of DMPC via detergent dialysis. Depending upon the charge of the adsorbed surface, 2D crystals of the oligomeric toxin complex have been captured in two distinct conformations. The projection maps of those crystals have been generated at 17 A resolution. Both complexes appeared tomore » be trimeric; as in one crystal form, its projection structure revealed a symmetrical pinwheel-like shape with virtually no depression in the middle of the complex. The other form revealed a propeller-like conformation displaying an obvious hole in the center region, presumably representing the toxin-induced pore. These crystallographic data thus demonstrate for the first time that the 65-kDa activated Cry4Ba toxin in association with lipid membranes could exist in at least two different trimeric conformations, conceivably implying the closed and open states of the pore.« less

Nonclassical crystallization in vivo et in vitro (II): Nanogranular features in biomimetic minerals disclose a general colloid-mediated crystal growth mechanism.

PubMed

Rodríguez-Navarro, Carlos; Ruiz-Agudo, Encarnación; Harris, Joe; Wolf, Stephan E

2016-11-01

Recent research has shown that biominerals and their biomimetics (i) typically form via an amorphous precursor phase, and (ii) commonly display a nanogranular texture. Apparently, these two key features are closely related, underlining the fact that the formation of biominerals and their biomimetics does not necessarily follow classical crystallization routes, and leaves a characteristic nanotextural imprint which may help to disclose their origins and formation mechanisms. Here we present a general overview of the current theories and models of nonclassical crystallization and their applicability for the advance of our current understanding of biomineralization and biomimetic mineralization. We pay particular attention to the link between nonclassical crystallization routes and the resulting nanogranular textures of biomimetic CaCO 3 mineral structures. After a general introductory section, we present an overview of classical nucleation and crystal growth theories and their limitations. Then, we introduce the Ostwald's step rule as a general framework to explain nonclassical crystallization. Subsequently, we describe nonclassical crystallization routes involving stable prenucleation clusters, dense liquid and solid amorphous precursor phases, as well as current nonclassical crystal growth models. The latter include oriented attachment, mesocrystallization and the new model based on the colloidal growth of crystals via attachment of amorphous nanoparticles. Biomimetic examples of nanostructured CaCO 3 minerals formed via these nonclassical routes are presented which help us to show that colloid-mediated crystal growth can be regarded as a wide-spread growth mechanism. Implications of these observations for the advance in the current understanding on the formation of biomimetic materials and biominerals are finally outlined. Copyright © 2016 Elsevier Inc. All rights reserved.

Electronic structure of lead pyrophosphate

NASA Astrophysics Data System (ADS)

Suewattana, Malliga; Singh, David

2007-03-01

Lead Pyrophosphate Pb2P2O7 is of interest for potential radiation detection applications and use in long term waste storage. It forms in triclinic P1 crystals and can also be grown as glasses. We performed electronic structure calculations using the crystal structure which determined by Mullica et. al (J. Solid State Chem (1986)) using x-ray diffraction and found large forces on atoms suggesting that the refined atomic positions were not fully correct. Here we report first principles structure relaxation and a revised crystal structure for this compound. We analyze the resulting structure using pair distribution functions and discuss the implications for the electronic properties. This work was supported by DOE NA22 and the Office of Naval Research.

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

NASA Astrophysics Data System (ADS)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo and Co because Fe-rich MSS is absent. The concentrations of Sn and Pb, which are incompatible with Fe-rich MSS, are highest in magnetite that formed from the fractionated Cu-rich liquid. At subsolidus temperatures, ilmenite exsolved from titanomagnetite whereas Al-spinel exsolved from the cores of some magnetite, locally redistributing the trace elements. However, during laser ablation ICP-MS analysis of these Fe-oxides both the magnetite and its exsolution products are ablated so that the analysis represents the original magmatic composition of the Fe-oxide that crystallized from the sulfide melt.

Erratum: Evolution of precipitate morphology during heat treatment and its implications for the superconductivity in K x F e 1.6 + y S e 2 single crystals [Phys. Rev. B 86 , 144507 (2012)

DOE PAGES

Liu, Y.; Xing, Q.; Dennis, K. W.; ...

2015-08-14

In this article, we study the relationship between precipitate morphology and superconductivity in K xFe 1.6+ySe 2 single crystals grown by self-flux method. Scanning electron microscopy (SEM) measurements revealed that the superconducting phase forms a network in the samples quenched above iron vacancy order-disorder transition temperature T s, whereas it aggregates into micrometer-sized rectangular bars and aligns as disconnected chains in the furnace-cooled samples.

Cloning, expression, purification, crystallization and preliminary X-ray diffraction analysis of the VP8* carbohydrate-binding protein of the human rotavirus strain Wa

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

Kraschnefski, Mark J.; Scott, Stacy A.; Holloway, Gavan

2005-11-01

The carbohydrate-binding component (VP8*{sub 64–223}) of the human Wa rotavirus spike protein has been overexpressed in E. coli, purified and crystallized in two different crystal forms. X-ray diffraction data have been collected that have enabled determination of the Wa VP8*{sub 64–223} structure by molecular replacement. Rotaviruses exhibit host-specificity and the first crystallographic information on a rotavirus strain that infects humans is reported here. Recognition and attachment to host cells, leading to invasion and infection, is critically linked to the function of the outer capsid spike protein of the rotavirus particle. In some strains the VP8* component of the spike proteinmore » is implicated in recognition and binding of sialic-acid-containing cell-surface carbohydrates, thereby enabling infection by the virus. The cloning, expression, purification, crystallization and initial X-ray diffraction analysis of the VP8* core from human Wa rotavirus is reported. Two crystal forms (trigonal P3{sub 2}21 and monoclinic P2{sub 1}) have been obtained and X-ray diffraction data have been collected, enabling determination of the VP8*{sub 64–223} structure by molecular replacement.« less

The Crystal Structure of the Escherichia coli Autoinducer-2 Processing Protein LsrF

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

Diaz, Z.; Xavier, K; Miller, S

2009-01-01

Many bacteria produce and respond to the quorum sensing signal autoinducer-2 (AI-2). Escherichia coli and Salmonella typhimurium are among the species with the lsr operon, an operon containing AI-2 transport and processing genes that are up regulated in response to AI-2. One of the Lsr proteins, LsrF, has been implicated in processing the phosphorylated form of AI-2. Here, we present the structure of LsrF, unliganded and in complex with two phospho-AI-2 analogues, ribose-5-phosphate and ribulose-5-phosphate. The crystal structure shows that LsrF is a decamer of (??)8-barrels that exhibit a previously unseen N-terminal domain swap and have high structural homology withmore » aldolases that process phosphorylated sugars. Ligand binding sites and key catalytic residues are structurally conserved, strongly implicating LsrF as a class I aldolase.« less

A functional role of Rv1738 in Mycobacterium tuberculosis persistence suggested by racemic protein crystallography.

PubMed

Bunker, Richard D; Mandal, Kalyaneswar; Bashiri, Ghader; Chaston, Jessica J; Pentelute, Bradley L; Lott, J Shaun; Kent, Stephen B H; Baker, Edward N

2015-04-07

Protein 3D structure can be a powerful predictor of function, but it often faces a critical roadblock at the crystallization step. Rv1738, a protein from Mycobacterium tuberculosis that is strongly implicated in the onset of nonreplicating persistence, and thereby latent tuberculosis, resisted extensive attempts at crystallization. Chemical synthesis of the L- and D-enantiomeric forms of Rv1738 enabled facile crystallization of the D/L-racemic mixture. The structure was solved by an ab initio approach that took advantage of the quantized phases characteristic of diffraction by centrosymmetric crystals. The structure, containing L- and D-dimers in a centrosymmetric space group, revealed unexpected homology with bacterial hibernation-promoting factors that bind to ribosomes and suppress translation. This suggests that the functional role of Rv1738 is to contribute to the shutdown of ribosomal protein synthesis during the onset of nonreplicating persistence of M. tuberculosis.

Understanding Singlet and Triplet Excitons in Acene Crystals from First Principles

NASA Astrophysics Data System (ADS)

Rangel Gordillo, Tonatiuh; Sharifzadeh, Sahar; Kronik, Leeor; Neaton, Jeffrey

2014-03-01

Singlet fission, a process in which two triplet excitons are formed from a singlet exciton, has the potential to increase the solar cell efficiencies above 100%. Efficient singlet fission has been reported in larger acene crystals, such as tetracene and pentacene, in part attributable to their low-lying triplet energies. In this work, we use many-body perturbation theory within the GW approximation and the Bethe-Salpeter equation approach to compute quasiparticle gaps, low-lying singlet and and triplet excitations, and optical absorption spectra across the entire acene family of crystals, from benzene to hexacene. We closely examine the degree of localization and charge-transfer character of the low-lying singlets and triplets, and their sensitivity to crystal environment, and discuss implications for the efficiency of singlet fission in this systems. This work supported by DOE and computational resources provided by NERSC.

String-like cooperative motion in homogeneous melting

PubMed Central

Zhang, Hao; Khalkhali, Mohammad; Liu, Qingxia; Douglas, Jack F.

2013-01-01

Despite the fundamental nature and practical importance of melting, there is still no generally accepted theory of this ubiquitous phenomenon. Even the earliest simulations of melting of hard discs by Alder and Wainwright indicated the active role of collective atomic motion in melting and here we utilize molecular dynamics simulation to determine whether these correlated motions are similar to those found in recent studies of glass-forming (GF) liquids and other condensed, strongly interacting, particle systems. We indeed find string-like collective atomic motion in our simulations of “superheated” Ni crystals, but other observations indicate significant differences from GF liquids. For example, we observe neither stretched exponential structural relaxation, nor any decoupling phenomenon, while we do find a boson peak, findings that have strong implications for understanding the physical origin of these universal properties of GF liquids. Our simulations also provide a novel view of “homogeneous” melting in which a small concentration of interstitial defects exerts a powerful effect on the crystal stability through their initiation and propagation of collective atomic motion. These relatively rare point defects are found to propagate down the strings like solitons, driving the collective motion. Crystal integrity remains preserved when the permutational atomic motions take the form of ring-like atomic exchanges, but a topological transition occurs at higher temperatures where the rings open to form linear chains similar in geometrical form and length distribution to the strings of GF liquids. The local symmetry breaking effect of the open strings apparently destabilizes the local lattice structure and precipitates crystal melting. The crystal defects are thus not static entities under dynamic conditions, such as elevated temperatures or material loading, but rather are active agents exhibiting a rich nonlinear dynamics that is not addressed in conventional “static” defect melting models. PMID:23556789

String-like cooperative motion in homogeneous melting.

PubMed

Zhang, Hao; Khalkhali, Mohammad; Liu, Qingxia; Douglas, Jack F

2013-03-28

Despite the fundamental nature and practical importance of melting, there is still no generally accepted theory of this ubiquitous phenomenon. Even the earliest simulations of melting of hard discs by Alder and Wainwright indicated the active role of collective atomic motion in melting and here we utilize molecular dynamics simulation to determine whether these correlated motions are similar to those found in recent studies of glass-forming (GF) liquids and other condensed, strongly interacting, particle systems. We indeed find string-like collective atomic motion in our simulations of "superheated" Ni crystals, but other observations indicate significant differences from GF liquids. For example, we observe neither stretched exponential structural relaxation, nor any decoupling phenomenon, while we do find a boson peak, findings that have strong implications for understanding the physical origin of these universal properties of GF liquids. Our simulations also provide a novel view of "homogeneous" melting in which a small concentration of interstitial defects exerts a powerful effect on the crystal stability through their initiation and propagation of collective atomic motion. These relatively rare point defects are found to propagate down the strings like solitons, driving the collective motion. Crystal integrity remains preserved when the permutational atomic motions take the form of ring-like atomic exchanges, but a topological transition occurs at higher temperatures where the rings open to form linear chains similar in geometrical form and length distribution to the strings of GF liquids. The local symmetry breaking effect of the open strings apparently destabilizes the local lattice structure and precipitates crystal melting. The crystal defects are thus not static entities under dynamic conditions, such as elevated temperatures or material loading, but rather are active agents exhibiting a rich nonlinear dynamics that is not addressed in conventional "static" defect melting models.

Functional Implications of Photosystem II Crystal Formation in Photosynthetic Membranes*

PubMed Central

Tietz, Stefanie; Puthiyaveetil, Sujith; Enlow, Heather M.; Yarbrough, Robert; Wood, Magnus; Semchonok, Dmitry A.; Lowry, Troy; Li, Zhirong; Jahns, Peter; Boekema, Egbert J.; Lenhert, Steven; Niyogi, Krishna K.; Kirchhoff, Helmut

2015-01-01

The structural organization of proteins in biological membranes can affect their function. Photosynthetic thylakoid membranes in chloroplasts have the remarkable ability to change their supramolecular organization between disordered and semicrystalline states. Although the change to the semicrystalline state is known to be triggered by abiotic factors, the functional significance of this protein organization has not yet been understood. Taking advantage of an Arabidopsis thaliana fatty acid desaturase mutant (fad5) that constitutively forms semicrystalline arrays, we systematically test the functional implications of protein crystals in photosynthetic membranes. Here, we show that the change into an ordered state facilitates molecular diffusion of photosynthetic components in crowded thylakoid membranes. The increased mobility of small lipophilic molecules like plastoquinone and xanthophylls has implications for diffusion-dependent electron transport and photoprotective energy-dependent quenching. The mobility of the large photosystem II supercomplexes, however, is impaired, leading to retarded repair of damaged proteins. Our results demonstrate that supramolecular changes into more ordered states have differing impacts on photosynthesis that favor either diffusion-dependent electron transport and photoprotection or protein repair processes, thus fine-tuning the photosynthetic energy conversion. PMID:25897076

Crystalline Silicates in Comets: Modeling Irregularly-Shaped Forsterite Crystals and Its Implications on Condensation Conditions

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean S.

2011-01-01

Crystalline silicates in comets are a product of the condensation in the hot inner regions (T > or approx. equals 1400 K [1]) of our proto-planetary disk or annealing at somewhat lower temperatures (T > or approx. equals 1000-1200 K) [2, 3, 4] in shocks coupled with disk evolutionary processes that include radial transport of crystals from their formation locations out to the cold outer regions where comet nuclei formed. The grain shape of forsterite (crystals) could be indicative of their formation pathways at high temperatures through vapor-solid condensation or at lower temperatures through vapor-liquid-solid formation and growth [5, 6, 7]. Experiments demonstrate that crystals that formed from a rapidly cooled highly supersaturated silicate vapor are characterized by bulky, platy, columnar/needle and droplet shapes for values of temperature and supersaturation, T and sigma, of 1000-1450 C and < 97, 700-1000 C and 97-161, 580-820 C and 131-230, and <500 C and > 230, respectively [7]. The experimental columnar/needle shapes, which form by vapor-liquid-solid at lower temperatures (<820 C), are extended stacks of plates, where the extension is not correlated with an axial direction: columnar/needles may be extended in the c-axis or a-axis direction, can change directions, and/or are off-kilter or a bit askew extending in a combination of the a- and c-axis direction.

Solid-state transformations in the β-form of chlorpropamide on cooling to 100 K.

PubMed

Drebushchak, Tatiana N; Drebushchak, Valeri A; Boldyreva, Elena V

2011-04-01

A single-crystal X-ray diffraction study of the effect of cooling down to 100 K on the β-form of chlorpropamide, 4-chloro-N-(propylaminocarbonyl)benzenesulfonamide, has revealed reversible phase transitions at ∼257 K and between 150 and 125 K: β (Pbcn, Z' = 1) ⇔ β(II) (P2/c, Z' = 2) ⇔ β(III) (P2/n, a' = 2a, Z' = 4); the sequence corresponds to cooling. Despite changes in the space group and number of symmetry-independent molecules, the volume per molecule changes continuously in the temperature range 100-300 K. The phase transition at ∼257 K is accompanied by non-merohedral twinning, which is preserved on further cooling and through the second phase transition, but the original single crystal does not crack. DSC (differential scanning calorimetry) and X-ray powder diffraction investigations confirm the phase transitions. Twinning disappears on heating as the reverse transformations take place. The second phase transition is related to a change in conformation of the alkyl tail from trans to gauche in 1/4 of the molecules, regularly distributed in the space. Possible reasons for the increase in Z' upon cooling are discussed in comparison to other reported examples of processes (crystallization, phase transitions) in which organic crystals with Z' > 1 have been formed. Implications for pharmaceutical applications are discussed. © 2011 International Union of Crystallography

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

NASA Technical Reports Server (NTRS)

Day, Delbert E.; Ray, Chandra S.

1999-01-01

The following list summarizes the most important results that have been consistently reported for glass forming melts in microgravity: (1) Glass formation is enhanced for melts prepared in space; (2) Glasses prepared in microgravity are more chemically homogeneous and contain fewer and smaller chemically heterogeneous regions than identical glasses prepared on earth; (3) Heterogeneities that are deliberately introduced such as Pt particles are more uniformly distributed in a glass melted in space than in a glass melted on earth; (4) Glasses prepared in microgravity are more resistant to crystallization and have a higher mechanical strength and threshold energy for radiation damage; and (5) Glasses crystallized in space have a different microstructure, finer grains more uniformly distributed, than equivalent samples crystallized on earth. The preceding results are not only scientifically interesting, but they have considerable practical implications. These results suggest that the microgravity environment is advantageous for developing new and improved glasses and glass-ceramics that are difficult to prepare on earth. However, there is no suitable explanation at this time for why a glass melted in microgravity will be more chemically homogeneous and more resistant to crystallization than a glass melted on earth. A fundamental investigation of melt homogenization, nucleation, and crystal growth processes in glass forming melts in microgravity is important to understanding these consistently observed, but yet unexplained results. This is the objective of the present research. A lithium disilicate (Li2O.2SiO2) glass will be used for this investigation, since it is a well studied system, and the relevant thermodynamic and kinetic parameters for nucleation and crystal growth at 1-g are available. The results from this research are expected to improve our present understanding of the fundamental mechanism of nucleation and crystal growth in melts and liquids, and to lead improvements in glass processing technology on earth, with the potential for creating new high performance glasses and glass-ceramics.

Nucleation and growth of crystals under cirrus and polar stratospheric cloud conditions

NASA Technical Reports Server (NTRS)

Hallett, John; Queen, Brian; Teets, Edward; Fahey, James

1995-01-01

Laboratory studies examine phase changes of hygroscopic substances which occur as aerosol in stratosphere and troposphere (sodium chloride, ammonium sulfate, ammonium bisulfate, nitric acid, sulfuric acid), under controlled conditions, in samples volume 1 to 10(exp -4) ml. Crystallization of salts from supersaturated solutions is examined by slowly evaporating a solution drop on a substrate, under controlled relative humidity, until self nucleation occurs; controlled nucleation of ice in a mm capillary U-tube gives a measured ice crystallization velocity at known supercooling. Two states of crystallization occur for regions where hydrates exist. It is inferred that all of the materials readily exist as supersaturated/supercooled solutions; the degree of metastability appears to be slightly enhanced by inclusion of aircraft produced soot. The crystallization velocity is taken as a measure of viscosity. Results suggest an approach to a glass transition at high molality, supersaturation and/or supercooling within the range of atmospheric interest. It is hypothesized that surface reactions occur more readily on solidified particles - either crystalline or glass, whereas volume reactions are more important on droplets with sufficiently low viscosity and volume diffusivity. Implications are examined for optical properties of such particles in the atmosphere. In a separate experiment, crystal growth was examined in a modified thermal vapor diffusion chamber over the range of cirrus temperature (-30 to -70 C) and under controlled supersaturation and air pressure. The crystals grew at a velocity of 1-2 microns/s, thickness 60-70 micron, in the form of thin column crystals. Design criteria are given for a system to investigate particle growth down to -100 C, (PSC temperatures) where nitric acid particles can be grown under similar control and in the form of hydrate crystals.

Didanosine polymorphism in a supercritical antisolvent process.

PubMed

Bettini, R; Menabeni, R; Tozzi, R; Pranzo, M B; Pasquali, I; Chierotti, M R; Gobetto, R; Pellegrino, L

2010-04-01

Solid-state properties of active ingredients are crucial in pharmaceutical development owing to their significant clinical and economical implications. In the present work we investigated the solid-state properties and the solubility in water of didanosine, DDI, re-crystallized from a dimethylsulfoxide solution using supercritical CO(2) as an antisolvent (SAS process) for comparison with the commercially available drug product. We also applied modern solid-state NMR (SS NMR) techniques, namely 2D (1)H DQ CRAMPS (Combined Rotation And Multiple Pulse Spectroscopy) and (1)H-(13)C on- and off-resonance CP (cross polarization) FSLG-HETCOR experiments, known for providing reliable information about (1)H-(1)H and (1)H-(13)C intra- and intermolecular proximities, in order to address polymorphism issues arising from the crystallization of a new form in the supercritical process. A new polymorph of didanosine was obtained from the supercritical antisolvent process and characterized by means of 1D and 2D multinuclear ((1)H, (13)C, (15)N) SS NMR. The particle size of the new crystal phase was reduced by varying the antisolvent density through a pressure increase. The structural differences between the commercial product and the SAS re-crystallized DDI are highlighted by X-ray diffractometry and well described by solid-state NMR. The carbon C6 (13)C chemical shift suggests that both commercial and re-crystallized didanosine samples are in the enol form. The analysis of homo- and heteronuclear proximities obtained by means of 2D NMR experiments shows that commercial and SAS re-crystallized DDI possess very similar molecular conformation and hydrogen bond network, but different packing. The new polymorph proved to be a metastable form at ambient conditions, showing higher solubility in water and lower stability to mechanical stress. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

C-type lectin domain family 12, member A: A common denominator in Behçet's syndrome and acute gouty arthritis.

PubMed

Oğuz, Ali Kemal; Yılmaz, Seda; Akar, Nejat; Özdağ, Hilal; Gürler, Aysel; Ateş, Aşkın; Oygür, Çağdaş Şahap; Kılıçoğlu, Sibel Serin; Demirtaş, Selda

2015-08-01

C-type lectin domain family 12, member A (CLEC12A) is a C-type lectin-like pattern recognition receptor capable of recognizing monosodium urate crystals. Monosodium urate crystals, the causative agents of gout are also among the danger-associated molecular patterns reflecting cellular injury/cell death. In response to monosodium urate crystals, CLEC12A effectively inhibits granulocyte and monocyte/macrophage functions and hence acts as a negative regulator of inflammation. Behçet's syndrome and gout are autoinflammatory disorders sharing certain pathological (neutrophilic inflammation), clinical (exaggerated response to monosodium urate crystals) and therapeutic (colchicine) features. We propose the hypothesis that decreased expression of CLEC12A is a common denominator in the hyperinflammatory responses observed in Behçet's syndrome and gout. Major lines of evidence supporting this hypothesis are: (1) Downregulation/deficiency of CLEC12A is associated with hyperinflammatory responses. (2) CLEC12A polymorphisms with functional and clinical implications have been documented in other inflammatory diseases. (3) Colchicine, a fundamental therapeutic agent used both in Behçet's syndrome and gout is shown to oppose the downregulation of CLEC12A. (4) Behçet's syndrome and gout are characterized by a hyperinflammatory response to monosodium urate crystals and other than gout, Behçet's syndrome is the only inflammatory condition exhibiting this exaggerated response. (5) Genomewide linkage and association studies of Behçet's syndrome collectively point to 12p12-13, the chromosomal region harboring CLEC12A. (6) Patients with severe forms of Behçet's syndrome underexpress CLEC12A with respect to patients with mild forms of the disease. If supported by well-designed, rigorous experiments, the forementioned hypothesis pertinent to CLEC12A will carry important implications for therapy, designing experimental models, and uncovering immunopathogenic mechanisms in Behçet's syndrome and gout. Copyright © 2015 Elsevier Ltd. All rights reserved.

Implications of the Homogeneous Nucleation Barrier for Top-Down Crystallization in Mercury's Core

NASA Astrophysics Data System (ADS)

Huguet, L.; Hauck, S. A.; Van Orman, J. A.; Jing, Z.

2018-05-01

Crystallization of solids in planetary cores depends both on ambient temperatures falling below the liquidus and on the ability to nucleate crystal growth. We discuss the implications of the nucleation barrier for thermal evolution of Mercury's core.

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

NASA Technical Reports Server (NTRS)

Day, Delbert E.; Ray, Chandra S.

2001-01-01

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on Earth (1 g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on Earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials.

A new strategy of transforming pharmaceutical crystal forms.

PubMed

Tian, Jian; Dalgarno, Scott J; Atwood, Jerry L

2011-02-09

The robust nature of network materials allows them to (for example) respond to external stimuli such as pressure, temperature, light, or gas/solvent adsorption and desorption. There is difficulty in retaining long-range order in purely molecular organic solids, due to weak intermolecular interactions such as van der Waals forces. Here, we show gas-induced transformations of the well-known pharmaceuticals clarithromycin and lansoprazole. For clarithromycin, the stimulus is capable of converting the kinetic solvate and guest-free crystal forms to the commercial thermodynamically stable polymorph with a huge saving in energy cost relative to industrially employed methods. The synthesis of the marketing form of lansoprazole involves a solvate that readily decomposes and that is stirred in water, filtered, and dried intensively. Our method readily circumvents such synthetic problems and transforms the sensitive solvate to the marketed drug substance with ease. Such expedient transformations hold great implications for the pharmaceutical industry in general when considering the ease of transformation and mild conditions employed.

Nanocrystallography measurements of early stage synthetic malaria pigment

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

Dilanian, Ruben A.; Streltsov, Victor; Coughlan, Hannah D.

The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data.more » If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.« less

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

Dilanian, Ruben A.; Streltsov, Victor; Coughlan, Hannah D.

The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data.more » If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.« less

Nanocrystallography measurements of early stage synthetic malaria pigment

DOE PAGES

Dilanian, Ruben A.; Streltsov, Victor; Coughlan, Hannah D.; ...

2017-09-28

The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data.more » If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.« less

Timing of mantle overturn during magma ocean solidification

NASA Astrophysics Data System (ADS)

Boukaré, C.-E.; Parmentier, E. M.; Parman, S. W.

2018-06-01

Solidification of magma oceans (MOs) formed early in the evolution of planetary bodies sets the initial condition for their evolution on much longer time scales. Ideal fractional crystallization would generate an unstable chemical stratification that subsequently overturns to form a stably stratified mantle. The simplest model of overturn assumes that cumulates remain immobile until the end of MO solidification. However, overturning of cumulates and thermal convection during solidification may act to reduce this stratification and introduce chemical heterogeneity on scales smaller than the MO thickness. We explore overturning of cumulates before the end of MO crystallization and the possible consequences for mantle structure and composition. In this model, increasingly dense iron-rich layers, crystallized from the overlying residual liquid MO, are deposited on a thickening cumulate layer. Overturn during solidification occurs if the dimensionless parameter, Rc, measuring the ratio of the MO time of crystallization τMO to the timescale associated with compositional overturn τov = μ / ΔρgH exceeds a threshold value. If overturn did not occur until after solidification, this implies that the viscosity of the solidified mantle must have been sufficiently high (possibly requiring efficient melt extraction from the cumulate) for a given rate of solidification. For the lunar MO, possible implications for the generation of the Mg-suites and mare basalt are suggested.

Crystallographic studies of the Anthrax lethal toxin. Annual report

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

Frederick, C.A.

1996-07-01

The lethal form of Anthrax results from the inhalation of anthrax spores. Death is primarily due to the effects of the lethal toxin (Protective Antigen (PA) + Lethal Factor) from the causative agent, Bacillus anthracis. All the Anthrax vaccines currently in use or under development contain or produce PA, the major antigenic component of anthrax toxin, and there is a clear need for an improved vaccine for human use. In the previous report we described the first atomic resolution structure of PA, revealing that the molecule is composed largely of beta-sheets organized into four domains. This information can be usedmore » in the design. of recombinant PA vaccines. In this report we describe additional features of the full-length PA molecule derived from further crystallographic refinement and careful examination of the structure. We compare two crystal forms of PA grown at different pH values and discuss the functional implications. A complete definition of the function of each domain must await the crystal structure of the PA63 heptamer. We have grown crystals of the heptamer under both detergent and detergent-free conditions, and made substantial progress towards the crystal structure. The mechanism of anthrax intoxication in the light of our results is reviewed.« less

Scattering of charge and spin excitations and equilibration of a one-dimensional Wigner crystal

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

Matveev, K. A.; Andreev, A. V.; Klironomos, A. D.

2014-07-01

We study scattering of charge and spin excitations in a system of interacting electrons in one dimension. At low densities, electrons form a one-dimensional Wigner crystal. To a first approximation, the charge excitations are the phonons in the Wigner crystal, and the spin excitations are described by the Heisenberg model with nearest-neighbor exchange coupling. This model is integrable and thus incapable of describing some important phenomena, such as scattering of excitations off each other and the resulting equilibration of the system. We obtain the leading corrections to this model, including charge-spin coupling and the next-nearest-neighbor exchange in the spin subsystem.more » We apply the results to the problem of equilibration of the one-dimensional Wigner crystal and find that the leading contribution to the equilibration rate arises from scattering of spin excitations off each other. We discuss the implications of our results for the conductance of quantum wires at low electron densities« less

The 1983 hydraulic jump in Crystal Rapid: implications for river- running and geomorphic evolution in the Grand Canyon.

USGS Publications Warehouse

Kieffer, S.W.

1985-01-01

At Crystal Creek, a debris fan was emplaced in 1966, constricting the channel of the Colorado River to about 0.25 of its upstream width between 1967 and 1983, forming a major rapid. The hydraulics of Crystal Creek rapid are described, and an analysis is presented to support the hypothesis that the major wave in the rapid was a normal wave (one type of hydraulic jump). Hydraulic jumps rarely occur in natural river channels with erodible beds, but one was present at Crystal Rapid because of the unusually severe constriction of the Colorado River by the 1966 debris fan. A quantitative model for river debris fan shapes is proposed and is used to estimate prehistoric flood levels from the observed constrictions: the 0.5 value of river constriction found at the more mature debris fans in the Grand Canyon suggests that peak flood discharges of approximately 11 320 m3/s have occurred. -from Author

Lattice rotation vortex observed between polar nanoregions in relaxor-ferroelectric (1-x)Pb(Zn1/3Nb2/3) O3-xPbTiO3 single crystal

NASA Astrophysics Data System (ADS)

Shao, Yu-Tsun; Zuo, Jian-Min

Domain walls (DWs) play a critical role in determining the polarization switching behavior in relaxor-based ferroelectric crystals. The domains in relaxor-ferroelectric crystals consist of polar nanoregions (PNRs) and their interface is poorly understood. Here, we report an energy-filtered (EF-) scanning convergent beam electron diffraction (SCBED) study for the identification of PNRs and determination of their interface. With the aid of electro dynamical diffraction simulation, nanometer-sized PNRs having monoclinic Pm (MC) symmetry in single crystal PZN- 8%PT were identified. Lattice rotation vortices having an average radius of 7 nm at the 50° DWs were revealed by maps of crystal orientations, domain configurations, symmetry breaking. Such measurements suggest the merging of 2D and 1D topological defects, with implications for domain-switching mechanisms in relaxor ferroelectric crystals. The interplay between polarization, charge, and strain degrees of freedom suggests a complex landscape of topological defects in ferroelectrics that may be explored for a new form of nanoscale ferroelectric devices. Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign.

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

Czerwinski, Andrzej; Basava, Channa; Dauter, Miroslawa

The title compound, C 20H 37N 3O 4, also known by the acronym ALLN, is a tripeptidic inhibitor of the proteolytic activity of the proteasomes, enzyme complexes implicated in several neurodegenerative diseases and other disorders, including cancer. Thus, the crystal structure of ALLN, solved from synchrotron radiation diffraction data, revealed the molecules in extended conformation of the backbone and engaging all peptide N and O atoms in intermolecular hydrogen bonds forming an infinite antiparallel β-sheet.

High chloride content calcium silicate glasses.

PubMed

Chen, Xiaojing; Karpukhina, Natalia; Brauer, Delia S; Hill, Robert G

2017-03-08

Chloride is known to volatilize from silicate glass melts and until now, only a limited number of studies on oxychloride silicate glasses have been reported. In this paper we have synthesized silicate glasses that retain large amounts of CaCl 2 . The CaCl 2 has been added to the calcium metasilicate composition (CaO·SiO 2 ). Glasses were produced via a melt quench route and an average of 70% of the chloride was retained after melting. Up to 31.6 mol% CaCl 2 has been successfully incorporated into these silicate glasses without the occurrence of crystallization. 29 Si MAS-NMR spectra showed the silicon being present mainly as a Q 2 silicate species. This suggests that chloride formed Cl-Ca(n) species, rather than Si-Cl bonds. Upon increasing the CaCl 2 content, the T g reduced markedly from 782 °C to 370 °C. Glass density and glass crystallization temperature decreased linearly with an increase in the CaCl 2 content. However, both linear regressions revealed a breakpoint at a CaCl 2 content just below 20 mol%. This might be attributed to a significant change in the structure and is also correlated with the nature of the crystallizing phases formed upon heat treatment. The glasses with less than 19.2 mol% CaCl 2 crystallized to wollastonite, whilst the compositions with CaCl 2 content equal to or greater than 19.2 mol% are thought to crystallize to CaCl 2 . In practice, the crystallization of CaCl 2 could not occur until the crystallization temperature fell below the melting point of CaCl 2 . The implications of the results along with the high chloride retention are discussed.

Influence of pH, particle size and crystal form on dissolution behaviour of engineered nanomaterials.

PubMed

Avramescu, M-L; Rasmussen, P E; Chénier, M; Gardner, H D

2017-01-01

Solubility is a critical component of physicochemical characterisation of engineered nanomaterials (ENMs) and an important parameter in their risk assessments. Standard testing methodologies are needed to estimate the dissolution behaviour and biodurability (half-life) of ENMs in biological fluids. The effect of pH, particle size and crystal form on dissolution behaviour of zinc metal, ZnO and TiO 2 was investigated using a simple 2 h solubility assay at body temperature (37 °C) and two pH conditions (1.5 and 7) to approximately frame the pH range found in human body fluids. Time series dissolution experiments were then conducted to determine rate constants and half-lives. Dissolution characteristics of investigated ENMs were compared with those of their bulk analogues for both pH conditions. Two crystal forms of TiO 2 were considered: anatase and rutile. For all compounds studied, and at both pH conditions, the short solubility assays and the time series experiments consistently showed that biodurability of the bulk analogues was equal to or greater than biodurability of the corresponding nanomaterials. The results showed that particle size and crystal form of inorganic ENMs were important properties that influenced dissolution behaviour and biodurability. All ENMs and bulk analogues displayed significantly higher solubility at low pH than at neutral pH. In the context of classification and read-across approaches, the pH of the dissolution medium was the key parameter. The main implication is that pH and temperature should be specified in solubility testing when evaluating ENM dissolution in human body fluids, even for preliminary (tier 1) screening.

Crystal-rich lava dome extrusion during vesiculation: An experimental study

NASA Astrophysics Data System (ADS)

Pistone, Mattia; Whittington, Alan G.; Andrews, Benjamin J.; Cottrell, Elizabeth

2017-11-01

Lava dome-forming eruptions represent a common eruptive style and a major hazard at numerous active volcanoes worldwide. The extrusion mechanics of crystal-rich lava domes and the influence of volatiles on the transition from viscous to brittle behaviour during lava dome extrusion remain unclear. Understanding how gas exsolution and crystallinity control effusive versus explosive eruption behaviour is essential. Here, we present new experimental results on the rheology of synthesised, crystal-rich (50 to 80 vol% quartz crystals), hydrous (4.2 wt% H2O in the glass) dacite samples, which vesiculate from 5 to 27 vol% gas bubbles at high temperatures (from glass transition temperature to 797 °C) during deformation conducted in a parallel plate viscometer (constant stress at 0.63-0.64 MPa, and variable strain-rates ranging from 8.32·10- 8 to 3.58·10- 5 s- 1). The experiments reproduce certain aspects of lava dome deformation in volcanic conduits during vesiculation of the residual melt, instigated in the experiments by increasing temperature. During gas exsolution (i.e. nucleation and growth of gas-pressurised bubbles) and volume inflation, we find that the rheological lubrication of the system during deformation is strongly dictated by the initial crystallinity. At crystal contents < 60 vol%, gas bubbles form and coalesce during expansion and viscous deformation, favouring strain localisation and gas permeability within shear bands, which control the overall sample rheology. At crystallinities of 60 to 70 vol%, gas exsolution generates pressurisation (i.e. pore pressure increase) within the bubbles trapped in the solid crystal clusters, and embryonic formation of microscopic fractures through melt and crystals drives the system to a brittle behaviour. At higher crystallinity (80 vol%) vesiculation leads to large pressurisation, which then triggers extensive brittle fragmentation. Through macroscopic fractures, outgassing determines the rheological stalling of the system. In the light of these results we propose a rheological description of crystal-rich lava dome mechanics. The contrasting experimental behaviours at different crystallinities have implications for the style of slow-ascending dome-forming eruptions. All other factors being equal, our experiments suggest that crystal-poor magmas will undergo efficient outgassing, reducing the potential for an explosive eruption. Conversely, crystal-rich magmas may experience limited outgassing and larger gas overpressures during vesiculation, therefore increasing the potential for an explosive eruption.

Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

NASA Technical Reports Server (NTRS)

Hazen, R. M.; Filley, T. R.; Goodfriend, G. A.

2001-01-01

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Interleukin-6 and chondrocyte mineralisation act in tandem to promote experimental osteoarthritis.

PubMed

Nasi, Sonia; So, Alexander; Combes, Christèle; Daudon, Michel; Busso, Nathalie

2016-07-01

Basic calcium phosphate (BCP) crystal and interleukin 6 (IL-6) have been implicated in osteoarthritis (OA). We hypothesise that these two factors may be linked in a reciprocal amplification loop which leads to OA. Primary murine chondrocytes and human cartilage explants were incubated with hydroxyapatite (HA) crystals, a form of BCP, and the modulation of cytokines and matrix-degrading enzymes assayed. The ability of IL-6 to stimulate chondrocyte calcification was assessed in vitro. The mechanisms underlying the effects of HA on chondrocytes were investigated using chemical inhibitors, and the pathways mediating IL-6-induced calcification characterised by quantifying the expression of genes involved in chondrocyte mineralisation. The role of calcification in vivo was studied in the meniscectomy model of murine OA (MNX), and the link between IL-6 and cartilage degradation investigated by histology. In chondrocytes, BCP crystals stimulated IL-6 secretion, further amplified in an autocrine loop, through signalling pathways involving Syk and PI3 kinases, Jak2 and Stat3 molecules. Exogenous IL-6 promoted calcium-containing crystal formation and upregulation of genes involved in calcification: the pyrophosphate channel Ank, the calcium channel Annexin5 and the sodium/phosphate cotransporter Pit-1. Treatment of chondrocytes with IL-6 inhibitors significantly inhibited IL-6-induced crystal formation. In meniscectomised mice, increasing deposits of BCP crystals were observed around the joint and correlated with cartilage degradation and IL-6 expression. Finally, BCP crystals induced proteoglycan loss and IL-6 expression in human cartilage explants, which were reduced by an IL-6 inhibitor. BCP crystals and IL-6 form a positive feedback loop leading to OA. Targeting calcium-containing crystal formation and/or IL-6 are promising therapeutic strategies in OA. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/

Crystal structure of cbbF from Zymomonas mobilis and its functional implication

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

Hwang, Hyo-Jeong; Park, Suk-Youl; Kim, Jeong-Sun, E-mail: jsunkim@chonnam.ac.kr

2014-02-28

Highlights: • The crystal structure of one cbbF from Zymomonas mobilis was revealed. • Scores of residues form two secondary structures with a non-polar protruded residue. • It exists as a dimeric form in solution. - Abstract: A phosphate group at the C1-atom of inositol-monophosphate (IMP) and fructose-1,6-bisphosphate (FBP) is hydrolyzed by a phosphatase IMPase and FBPase in a metal-dependent way, respectively. The two enzymes are almost indiscernible from each other because of their highly similar sequences and structures. Metal ions are bound to residues on the β1- and β2-strands and one mobile loop. However, FBP has another phosphate andmore » FBPases exist as a higher oligomeric state, which may discriminate FBPases from IMPases. There are three genes annotated as FBPases in Zymomonas mobilis, termed also cbbF (ZmcbbF). The revealed crystal structure of one ZmcbbF shows a globular structure formed by five stacked layers. Twenty-five residues in the middle of the sequence form an α-helix and a β-strand, which occupy one side of the catalytic site. A non-polar Leu residue among them is protruded to the active site, pointing out unfavorable access of a bulky charged group to this side. In vitro assays have shown its dimeric form in solution. Interestingly, two β-strands of β1 and β2 are disordered in the ZmcbbF structure. These data indicate that ZmcbbF might structurally belong to IMPase, and imply that its active site would be reorganized in a yet unreported way.« less

Crystallization of probucol from solution and the glassy state.

PubMed

Kawakami, Kohsaku; Ohba, Chie

2017-01-30

Crystallization of probucol (PBL) from both solution and glassy solid state was investigated. In the crystallization study from solution, six solvents and three methods, i.e., evaporation, addition of a poor solvent, and cooling on ice, were used to obtain various crystal forms. In addition to common two crystal forms (forms I and II), two further forms (forms III and cyclohexane-solvate) were found in this study, and their thermodynamic relationships were determined. Forms I and II are likely to be enantiotropically related with thermodynamic transition temperature below 5°C. Isothermal crystallization studies revealed that PBL glass initially crystallized into form III between 25 and 50°C, and then transformed to form I. The isothermal crystallization appears to be a powerful option to find uncommon crystal forms. The crystallization of PBL was identified to be pressure controlled, thus the physical stability of PBL glass is higher than that of typical compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Crystal Structures of T Cell Receptor (Beta) Chains Related to Rheumatoid Arthritis

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

Li,H.; van Vranken, S.; Zhao, Y.

The crystal structures of the V{beta}17+ {beta} chains of two human T cell receptors (TCRs), originally derived from the synovial fluid (SF4) and tissue (C5-1) of a patient with rheumatoid arthritis (RA), have been determined in native (SF4) and mutant (C5-1{sub F104{yields}Y/C187{yields}S}) forms, respectively. These TCR {beta} chains form homo-dimers in solution and in crystals. Structural comparison reveals that the main-chain conformations in the CDR regions of the C5-1 and SF4 V{beta}17 closely resemble those of a V{beta}17 JM22 in a bound form; however, the CDR3 region shows different conformations among these three V{beta}17 structures. At the side-chain level, conformationalmore » differences were observed at the CDR2 regions between our two ligand-free forms and the bound JM22 form. Other significant differences were observed at the V{beta} regions 8-12, 40-44, and 82-88 between C5-1/SF4 and JM22 V{beta}17, implying that there is considerable variability in the structures of very similar {beta} chains. Structural alignments also reveal a considerable variation in the V{beta}-C{beta} associations, and this may affect ligand recognition. The crystal structures also provide insights into the structure basis of T cell recognition of Mycoplasma arthritidis mitogen (MAM), a superantigen that may be implicated in the development of human RA. Structural comparisons of the V{beta} domains of known TCR structures indicate that there are significant similarities among V{beta} regions that are MAM-reactive, whereas there appear to be significant structural differences among those V{beta} regions that lack MAM-reactivity. It further reveals that CDR2 and framework region (FR) 3 are likely to account for the binding of TCR to MAM.« less

Laboratory and field studies of stratospheric aerosols: Phase changes under high supersaturation

NASA Technical Reports Server (NTRS)

Hallet, John

1991-01-01

It is well known that water in the form of isolated small droplets supercool as much as 40 C below their equilibrium melting point. Solutions similarly supercool (with respect to water) and supersaturate (with respect of the solute). Experiments are described in which bulk solutions typical of atmospheric aerosols (nitric acid, sulfuric acid, and hydrates; ammonium sulfate; ammonium bisulfate; sodium chloride) are supercooled and/or supersaturated and nucleated to initiate crystal growth. Supersaturation of 300 percent is readily attainable, with linear growth of crystals increasing roughly as (supercooling/supersaturation)sup 2. The implication of the experiments is that the situation of metastability in polar stratosphere clouds is very likely, with nucleation only occuring under a high degree of supercooling or supersaturation.

Drug-polymer interactions at water-crystal interfaces and implications for crystallization inhibition: molecular dynamics simulations of amphiphilic block copolymer interactions with tolazamide crystals.

PubMed

Gao, Yi; Olsen, Kenneth W

2015-07-01

A diblock copolymer, poly(ethylene glycol)-block-poly(lactic acid) (PEG-b-PLA), modulates the crystal growth of tolazamide (TLZ), resulting in a crystal morphology change from needles to plates in aqueous media. To understand this crystal surface drug-polymer interaction, we conducted molecular dynamics simulations on crystal surfaces of TLZ in water containing PEG-b-PLA. A 130-ns simulation of the polymer in a large water box was run before initiating 50 ns simulations with each of the crystal surfaces. The simulations demonstrated differentiated drug-polymer interactions that are consistent with experimental studies. Interaction of PEG-b-PLA with the (001) face occurred more rapidly (≤10 ns) and strongly (total interaction energy of -121.1 kJ/mol/monomer) than that with the (010) face (∼35 ns, -85.4 kJ/mol/monomer). There was little interaction with the (100) face. Hydrophobic and van der Waals (VDW) interactions were the dominant forces, accounting for more than 90% of total interaction energies. It suggests that polymers capable of forming strong hydrophobic and VDW interactions might be more effective in inhibiting crystallization of poorly water-soluble and hydrophobic drugs in aqueous media (such as gastrointestinal fluid) than those with hydrogen-bonding capacities. Such in-depth analysis and understanding facilitate the rational selection of polymers in designing supersaturation-based enabling formulations. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Crystallization and Colloidal Stabilization of Ca(OH)2 in the Presence of Nopal Juice (Opuntia ficus indica): Implications in Architectural Heritage Conservation.

PubMed

Rodriguez-Navarro, Carlos; Ruiz-Agudo, Encarnacion; Burgos-Cara, Alejandro; Elert, Kerstin; Hansen, Eric F

2017-10-17

Hydrated lime (Ca(OH) 2 ) is a vernacular art and building material produced following slaking of CaO in water. If excess water is used, a slurry, called lime putty, forms, which has been the preferred craftsman selection for formulating lime mortars since Roman times. A variety of natural additives were traditionally added to the lime putty to improve its quality. The mucilaginous juice extracted from nopal cladodes has been and still is used as additive incorporated in the slaking water for formulation of lime mortars and plasters, both in ancient Mesoamerica and in the USA Southwest. Little is known on the ultimate effects of this additive on the crystallization and microstructure of hydrated lime. Here, we show that significant changes in habit and size of portlandite crystals occur following slaking in the presence of nopal juice as well as compositionally similar citrus pectin. Both additives contain polysaccharides made up of galacturonic acid and neutral sugar residues. The carboxyl (and hydroxyl) functional groups present in these residues and in their alkaline degradation byproducts, which are deprotonated at the high pH (12.4) produced during lime slaking, strongly interact with newly formed Ca(OH) 2 crystals acting in two ways: (a) as nucleation inhibitors, promoting the formation of nanosized crystals, and (b) as habit modifiers, favoring the development of planar habit following their adsorption onto positively charged (0001) Ca(OH) 2 faces. Adsorption of polysaccharides on Ca(OH) 2 crystals prevents the development of large particles, resulting in a very reactive, nanosized portlandite slurry. It also promotes steric stabilization, which limits aggregation, thus enhancing the colloidal nature of the lime putty. Overall, these effects are very favorable for the preparation of highly plastic lime mortars with enhanced properties.

Phase transitions of antibiotic clarithromycin forms I, IV and new form VII crystals.

PubMed

Ito, Masataka; Shiba, Rika; Watanabe, Miteki; Iwao, Yasunori; Itai, Shigeru; Noguchi, Shuji

2018-06-01

Metastable crystal form I of the antibiotic clarithromycin has a pharmaceutically valuable characteristic that its crystalline phase transition can be applied for its sustained release from tablets. The phase transition of form I was investigated in detail by single crystal and powder X-ray analyses, dynamic vapor sorption analysis and thermal analysis. The single crystal structure of form I revealed that form I was not an anhydrate crystal but contained a partially occupied water molecule in the channel-like void space. Dynamic vapor sorption (DVS) analysis demonstrated that form I crystals reversibly sorbed water molecules in two steps when the relative humidity (RH) increased and finally transited to hydrate form IV at 95% RH. DVS analysis also showed that when the RH decreased form IV crystals lost water molecules at 40% RH and transited to the newly identified anhydrate crystal form VII. Form VII reversibly transited to form IV at lower RH than form I, suggesting that form I is more suitable for manufacturing a sustained-release tablet of CAM utilizing the crystalline phase transition. Copyright © 2018 Elsevier B.V. All rights reserved.

Crystals and crystallization in oil-in-water emulsions: implications for emulsion-based delivery systems.

PubMed

McClements, David Julian

2012-06-15

Many bioactive components intended for oral ingestion (pharmaceuticals and nutraceuticals) are hydrophobic molecules with low water-solubilities and high melting points, which poses considerable challenges to the formulation of oral delivery systems. Oil-in-water emulsions are often suitable vehicles for the encapsulation and delivery of this type of bioactive component. The bioactive component is usually dissolved in a carrier lipid phase by either dilution and/or heating prior to homogenization, and then the carrier lipid and water phases are homogenized to form an emulsion consisting of small oil droplets dispersed in water. The successful development of this kind of emulsion-based delivery system depends on a good understanding of the influence of crystals on the formation, stability, and properties of emulsions. This review article addresses the physicochemical phenomena associated with the encapsulation, retention, crystallization, release, and absorption of hydrophobic bioactive components within emulsions. This knowledge will be useful for the rational formulation of effective emulsion-based delivery systems for oral delivery of crystalline hydrophobic bioactive components in the food, health care, and pharmaceutical industries. Copyright © 2012 Elsevier B.V. All rights reserved.

On cooperative effects and aggregation of GNNQQNY and NNQQNY peptides

NASA Astrophysics Data System (ADS)

Nochebuena, Jorge; Ireta, Joel

2015-10-01

Some health disturbances like neurodegenerative diseases are associated to the presence of amyloids. GNNQQNY and NNQQNY peptides are considered as prototypical examples for studying the formation of amyloids. These exhibit quite different aggregation behaviors despite they solely differ in size by one residue. To get insight into the reasons for such difference, we have examined association energies of aggregates (parallel β-sheets, fibril-spines, and crystal structures) from GNNQQNY and NNQQY using density functional theory. As we found that GNNQQNY tends to form a zwitterion in the crystal structure, we have investigated the energetics of parallel β-sheets and fibril-spines in the canonical and zwitterionic states. We found that the formation of GNNQQNY aggregates is energetically more favored than the formation of the NNQQNY ones. We show that the latter is connected to the network of hydrogen bonds formed by each aggregate. Moreover, we found that the formation of some NNQQNY aggregates is anticooperative, whereas cooperative with GNNQQNY. These results have interesting implications for deciphering the factors determining peptide aggregation propensities.

Molecular packing in virus crystals: geometry, chemistry, and biology.

PubMed

Natarajan, P; Johnson, J E

1998-01-01

An automated procedure was developed to determine the geometrical and chemical interactions of crystalline virus particles using the crystal parameters, particle position, orientation, and atomic coordinates for an icosahedral asymmetric unit. Two applications of the program are reported: (1) An analysis of a novel pseudo-rhombohedral (R32) symmetry present in the monoclinic crystal lattices of both Nodamura Virus (NOV) and Coxsackie virus B3 (CVB3). The study shows that in both cases the interactions between particles is substantially increased by minor deviations from exact R32 symmetry and that only particles with the proper ratio of dimensions along twofold and fivefold symmetry axes (such as southern bean mosaic virus) can achieve comparable buried surface area in the true R32 space group. (2) An attempt was made to correlate biological function with remarkably conserved interparticle contact regions found in different crystal forms of three members of the nodavirus family, NOV, Flock House Virus (FHV), and Black Beetle Virus (BBV). Mutational evidence implicates the quasi-threefold region on the viral surface in receptor binding in nodaviruses and this region is dominant in particle contacts in all three virus crystals. Examination of particle contacts in numerous crystal structures of viruses in the picornavirus super-family showed that portions of the capsid surface known to interact with a receptor or serve as an epitope for monoclonal antibodies frequently stabilize crystal contacts.

Neutron Structure of Human Carbonic Anhydrase II: Implications for Proton Transfer†

PubMed Central

Fisher, S. Zoë; Kovalevsky, Andrey Y.; Domsic, John F.; Mustyakimov, Marat; McKenna, Robert; Silverman, David N.; Langan, Paul A.

2010-01-01

Human carbonic anhydrase II (HCA II) catalyzes the reversible hydration of carbon dioxide to form bicarbonate and a proton. Despite many high-resolution X-ray crystal structures, mutagenesis, and kinetic data, the structural details of the active site, especially the proton transfer pathway, are unclear. A large HCA II crystal was prepared at pH 9.0 and subjected to vapor H–D exchange to replace labile hydrogens with deuteriums. Neutron diffraction studies were conducted at the Protein Crystallography Station at Los Alamos National Laboratory. The structure to 2.0 Å resolution reveals several interesting active site features: (1) the Zn-bound solvent appearing to be predominantly a D2O molecule, (2) the orientation and hydrogen bonding pattern of solvent molecules in the active site cavity, (3) the side chain of His64 being unprotonated (neutral) and predominantly in an inward conformation pointing toward the zinc, and (4) the phenolic side chain of Tyr7 appearing to be unprotonated. The implications of these details are discussed, and a proposed mechanism for proton transfer is presented. PMID:20025241

Crystal Structure of a UDP-glucose-specific Glycosyltransferase from a Mycobacterium Species

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

Fulton, Zara; McAlister, Adrian; Wilce, Matthew C.J.

2008-10-24

Glycosyltransferases (GTs) are a large and ubiquitous family of enzymes that specifically transfer sugar moieties to a range of substrates. Mycobacterium tuberculosis contains a large number of GTs, many of which are implicated in cell wall synthesis, yet the majority of these GTs remain poorly characterized. Here, we report the high resolution crystal structures of an essential GT (MAP2569c) from Mycobacterium avium subsp. paratuberculosis (a close homologue of Rv1208 from M. tuberculosis) in its apo- and ligand-bound forms. The structure adopted the GT-A fold and possessed the characteristic DXD motif that coordinated an Mn{sup 2+} ion. Atypical of most GTsmore » characterized to date, MAP2569c exhibited specificity toward the donor substrate, UDP-glucose. The structure of this ligated complex revealed an induced fit binding mechanism and provided a basis for this unique specificity. Collectively, the structural features suggested that MAP2569c may adopt a 'retaining' enzymatic mechanism, which has implications for the classification of other GTs in this large superfamily.« less

Influence of substrate mineralogy on bacterial mineralization of calcium carbonate: implications for stone conservation.

PubMed

Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-06-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

Exploring the salt–cocrystal continuum with solid-state NMR using natural-abundance samples: implications for crystal engineering

PubMed Central

Rajput, Lalit; Banik, Manas; Yarava, Jayasubba Reddy; Joseph, Sumy; Pandey, Manoj Kumar

2017-01-01

There has been significant recent interest in differentiating multicomponent solid forms, such as salts and cocrystals, and, where appropriate, in determining the position of the proton in the X—H⋯A—Y X −⋯H—A +—Y continuum in these systems, owing to the direct relationship of this property to the clinical, regulatory and legal requirements for an active pharmaceutical ingredient (API). In the present study, solid forms of simple cocrystals/salts were investigated by high-field (700 MHz) solid-state NMR (ssNMR) using samples with naturally abundant 15N nuclei. Four model compounds in a series of prototypical salt/cocrystal/continuum systems exhibiting {PyN⋯H—O—}/{PyN+—H⋯O−} hydrogen bonds (Py is pyridine) were selected and prepared. The crystal structures were determined at both low and room temperature using X-ray diffraction. The H-atom positions were determined by measuring the 15N—1H distances through 15N-1H dipolar interactions using two-dimensional inversely proton-detected cross polarization with variable contact-time (invCP-VC) 1H→15N→1H experiments at ultrafast (νR ≥ 60–70 kHz) magic angle spinning (MAS) frequency. It is observed that this method is sensitive enough to determine the proton position even in a continuum where an ambiguity of terminology for the solid form often arises. This work, while carried out on simple systems, has implications in the pharmaceutical industry where the salt/cocrystal/continuum condition of APIs is considered seriously. PMID:28875033

Exploring the salt-cocrystal continuum with solid-state NMR using natural-abundance samples: implications for crystal engineering.

PubMed

Rajput, Lalit; Banik, Manas; Yarava, Jayasubba Reddy; Joseph, Sumy; Pandey, Manoj Kumar; Nishiyama, Yusuke; Desiraju, Gautam R

2017-07-01

There has been significant recent interest in differentiating multicomponent solid forms, such as salts and cocrystals, and, where appropriate, in determining the position of the proton in the X -H⋯ A - Y X - ⋯H- A + - Y continuum in these systems, owing to the direct relationship of this property to the clinical, regulatory and legal requirements for an active pharmaceutical ingredient (API). In the present study, solid forms of simple cocrystals/salts were investigated by high-field (700 MHz) solid-state NMR (ssNMR) using samples with naturally abundant 15 N nuclei. Four model compounds in a series of prototypical salt/cocrystal/continuum systems exhibiting {PyN⋯H-O-}/{PyN + -H⋯O - } hydrogen bonds (Py is pyridine) were selected and prepared. The crystal structures were determined at both low and room temperature using X-ray diffraction. The H-atom positions were determined by measuring the 15 N- 1 H distances through 15 N- 1 H dipolar interactions using two-dimensional inversely proton-detected cross polarization with variable contact-time (invCP-VC) 1 H→ 15 N→ 1 H experiments at ultrafast (ν R ≥ 60-70 kHz) magic angle spinning (MAS) frequency. It is observed that this method is sensitive enough to determine the proton position even in a continuum where an ambiguity of terminology for the solid form often arises. This work, while carried out on simple systems, has implications in the pharmaceutical industry where the salt/cocrystal/continuum condition of APIs is considered seriously.

Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

PubMed Central

Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

2012-01-01

The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

Measurement of the intrinsic variability within protein crystals: implications for sample-evaluation and data-collection strategies.

PubMed

Bowler, Michael G; Bowler, Matthew W

2014-01-01

The advent of micro-focused X-ray beams has led to the development of a number of advanced methods of sample evaluation and data collection. In particular, multiple-position data-collection and helical oscillation strategies are now becoming commonplace in order to alleviate the problems associated with radiation damage. However, intra-crystal and inter-crystal variation means that it is not always obvious on which crystals or on which region or regions of a crystal these protocols should be performed. For the automation of this process for large-scale screening, and to provide an indication of the best strategy for data collection, a metric of crystal variability could be useful. Here, measures of the intrinsic variability within protein crystals are presented and their implications for optimal data-collection strategies are discussed.

Physicochemical and crystal structure analyses of the antidiabetic agent troglitazone.

PubMed

Kobayashi, Katsuhiro; Fukuhara, Hiroshi; Hata, Tadashi; Sekine, Akiko; Uekusa, Hidehiro; Ohashi, Yuji

2003-07-01

The antidiabetic agent troglitazone has two asymmetric carbons located at the chroman ring and the thiazolidine ring and is produced as a mixture of equal amounts of four optical isomers, 2R-5S, 2S-5R, 2R-5R, and 2S-5S. The crystalline powdered drug substance consists of two diastereomer pairs, 2R-5R/2S-5S and 2R-5S/2S-5R. There are many types of crystals obtained from various crystallization conditions. The X-ray structure analysis and the physicochemical analyses of troglitazone were performed. The solvated crystals of the 2R-5R/2S-5S pair were crystallized from several solutions: methanol, ethanol, acetonitrile, and dichloromethane. The ratio of solvent and troglitazone was 1 : 2 (L1/2-form). The monohydrate crystals were obtained from aqueous acetone solution (L1-form). On the other hand, only an anhydrate crystal of the 2R-5S/2S-5R pair was crystallized from various solutions (H0-form). The dihydrous mixed crystal (MA2-form) was obtained from a mixture of the two diastereomer pairs of 2R-5R/2S-5S and 2R-5S/2S-5R in equal amounts by the slow evaporation of aqueous acetone solution. The crystal structure of the MA2-form is similar to the H0-form. When the MA2 crystal was kept under low humidity, it was converted into the dehydrated form (MA0-form) with retention of the single crystal form. The structure of the MA0-form is isomorphous to the H0-form. The MA2-form was converted into the MA0-form and vice versa with retention of the single crystal under low and high humidity, respectively. The crystallization and storage conditions of the drug substances were successfully analyzed.

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

Jones, B.; Renault, R.W.

Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The wallsmore » of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.« less

DENTAL ENAMEL FORMATION AND IMPLICATIONS FOR ORAL HEALTH AND DISEASE.

PubMed

Lacruz, Rodrigo S; Habelitz, Stefan; Wright, J Timothy; Paine, Michael L

2017-07-01

Dental enamel is the hardest and most mineralized tissue in extinct and extant vertebrate species and provides maximum durability that allows teeth to function as weapons and/or tools as well as for food processing. Enamel development and mineralization is an intricate process tightly regulated by cells of the enamel organ called ameloblasts. These heavily polarized cells form a monolayer around the developing enamel tissue and move as a single forming front in specified directions as they lay down a proteinaceous matrix that serves as a template for crystal growth. Ameloblasts maintain intercellular connections creating a semi-permeable barrier that at one end (basal/proximal) receives nutrients and ions from blood vessels, and at the opposite end (secretory/apical/distal) forms extracellular crystals within specified pH conditions. In this unique environment, ameloblasts orchestrate crystal growth via multiple cellular activities including modulating the transport of minerals and ions, pH regulation, proteolysis, and endocytosis. In many vertebrates, the bulk of the enamel tissue volume is first formed and subsequently mineralized by these same cells as they retransform their morphology and function. Cell death by apoptosis and regression are the fates of many ameloblasts following enamel maturation, and what cells remain of the enamel organ are shed during tooth eruption, or are incorporated into the tooth's epithelial attachment to the oral gingiva. In this review, we examine key aspects of dental enamel formation, from its developmental genesis to the ever-increasing wealth of data on the mechanisms mediating ionic transport, as well as the clinical outcomes resulting from abnormal ameloblast function. Copyright © 2017 the American Physiological Society.

DDA Computations of Porous Aggregates with Forsterite Crystals: Effects of Crystal Shape and Crystal Mass Fraction

NASA Technical Reports Server (NTRS)

Wooden, Diane H.; Lindsay, Sean S.; Harker, David; Woodward, Charles; Kelley, Michael S.; Kolokolova, Ludmilla

2015-01-01

Porous aggregate grains are commonly found in cometary dust samples and are needed to model cometary IR spectral energy distributions (SEDs). Models for thermal emissions from comets require two forms of silicates: amorphous and crystalline. The dominant crystal resonances observed in comet SEDs are from Forsterite (Mg2SiO4). The mass fractions that are crystalline span a large range from 0.0 < or = fcrystal < or = 0.74. Radial transport models that predict the enrichment of the outer disk (>25 AU at 1E6 yr) by inner disk materials (crystals) are challenged to yield the highend-range of cometary crystal mass fractions. However, in current thermal models, Forsterite crystals are not incorporated into larger aggregate grains but instead only are considered as discrete crystals. A complicating factor is that Forsterite crystals with rectangular shapes better fit the observed spectral resonances in wavelength (11.0-11.15 microns, 16, 19, 23.5, 27, and 33 microns), feature asymmetry and relative height (Lindley et al. 2013) than spherically or elliptically shaped crystals. We present DDA-DDSCAT computations of IR absorptivities (Qabs) of 3 micron-radii porous aggregates with 0.13 < or = fcrystal < or = 0.35 and with polyhedral-shaped Forsterite crystals. We can produce crystal resonances with similar appearance to the observed resonances of comet Hale- Bopp. Also, a lower mass fraction of crystals in aggregates can produce the same spectral contrast as a higher mass fraction of discrete crystals; the 11micron and 23 micron crystalline resonances appear amplified when crystals are incorporated into aggregates composed otherwise of spherically shaped amorphous Fe-Mg olivines and pyroxenes. We show that the optical properties of a porous aggregate is not linear combination of its monomers, so aggregates need to be computed. We discuss the consequence of lowering comet crystal mass fractions by modeling IR SEDs with aggregates with crystals, and the implications for radial transport models of our protoplanetary disk.

Competition between monomeric and dimeric crystals in schematic models for globular proteins.

PubMed

Fusco, Diana; Charbonneau, Patrick

2014-07-17

Advances in experimental techniques and in theoretical models have improved our understanding of protein crystallization. However, they have also left open questions regarding the protein phase behavior and self-assembly kinetics, such as why (nearly) identical crystallization conditions can sometimes result in the formation of different crystal forms. Here, we develop a patchy particle model with competing sets of patches that provides a microscopic explanation of this phenomenon. We identify different regimes in which one or two crystal forms can coexist with a low-density fluid. Using analytical approximations, we extend our findings to different crystal phases, providing a general framework for treating protein crystallization when multiple crystal forms compete. Our results also suggest different experimental routes for targeting a specific crystal form, and for reducing the dynamical competition between the two forms, thus facilitating protein crystal assembly.

The crystal structure of the C45S mutant of annelid Arenicola marina peroxiredoxin 6 supports its assignment to the mechanistically typical 2-Cys subfamily without any formation of toroid-shaped decamers

PubMed Central

Smeets, Aude; Loumaye, Eléonore; Clippe, André; Rees, Jean-François; Knoops, Bernard; Declercq, Jean-Paul

2008-01-01

The peroxiredoxins (PRDXs) define a superfamily of thiol-dependent peroxidases able to reduce hydrogen peroxide, alkyl hydroperoxides, and peroxynitrite. Besides their cytoprotective antioxidant function, PRDXs have been implicated in redox signaling and chaperone activity, the latter depending on the formation of decameric high-molecular-weight structures. PRDXs have been mechanistically divided into three major subfamilies, namely typical 2-Cys, atypical 2-Cys, and 1-Cys PRDXs, based on the number and position of cysteines involved in the catalysis. We report the structure of the C45S mutant of annelid worm Arenicola marina PRDX6 in three different crystal forms determined at 1.6, 2.0, and 2.4 Å resolution. Although A. marina PRDX6 was cloned during the search of annelid homologs of mammalian 1-Cys PRDX6s, the crystal structures support its assignment to the mechanistically typical 2-Cys PRDX subfamily. The protein is composed of two distinct domains: a C-terminal domain and an N-terminal domain exhibiting a thioredoxin fold. The subunits are associated in dimers compatible with the formation of intersubunit disulfide bonds between the peroxidatic and the resolving cysteine residues in the wild-type enzyme. The packing of two crystal forms is very similar, with pairs of dimers associated as tetramers. The toroid-shaped decamers formed by dimer association and observed in most typical 2-Cys PRDXs is not present. Thus, A. marina PRDX6 presents structural features of typical 2-Cys PRDXs without any formation of toroid-shaped decamers, suggesting that it should function more like a cytoprotective antioxidant enzyme or a modulator of peroxide-dependent cell signaling rather than a molecular chaperone. PMID:18359859

Noncovalent Polymerization of Mesogens Crystallizes Lysozyme: Correlation between Nonamphiphilic Lyotropic Liquid Crystal Phase and Protein Crystal Formation

PubMed Central

Simon, Karen A.; Shetye, Gauri S.; Englich, Ulrich; Wu, Lei; Luk, Yan-Yeung

2011-01-01

Crystallization of proteins is important for fundamental studies and biopharmaceutical development but remains largely an empirical science. Here, we report the use of organic salts that can form a class of unusual non-amphiphilic lyotropic liquid crystals to crystallize the protein lysozyme. Certain non-amphiphilic organic molecules with fused aromatic rings and two charges can assemble into stable thread-like noncovalent polymers that may further form liquid crystal phases in water, traditionally termed chromonic liquid crystals. Using five of these mesogenic molecules as additives to induce protein crystallization, we discover that molecules that can form liquid crystal phases in water are highly effective at inducing the crystal formation of lysozyme, even at concentrations significantly lower than that required for forming liquid crystal phases. This result reveals an example of inducing protein crystallization by the molecular assembly of the additives, and is consistent with a new mechanism by which the strong hydration of an assembly process provides a gradual means to compete for the water molecules to enable solvated proteins to form crystals. PMID:21786812

Seeding for sirtuins: microseed matrix seeding to obtain crystals of human Sirt3 and Sirt2 suitable for soaking

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

Rumpf, Tobias; Gerhardt, Stefan; Einsle, Oliver, E-mail: einsle@biochemie.uni-freiburg.de

2015-11-18

In the present study, microseed matrix seeding was successfully applied to obtain a large number of crystals of the human sirtuin isotypes Sirt2 and Sirt3. These crystals appeared predictably in diverse crystallization conditions, diffracted to a higher resolution than reported in the literature and were subsequently used to study the protein–ligand interactions of two indole inhibitors. Sirtuins constitute a family of NAD{sup +}-dependent enzymes that catalyse the cleavage of various acyl groups from the ∊-amino group of lysines. They regulate a series of cellular processes and their misregulation has been implicated in various diseases, making sirtuins attractive drug targets. Tomore » date, only a few sirtuin modulators have been reported that are suitable for cellular research and their development has been hampered by a lack of structural information. In this work, microseed matrix seeding (MMS) was used to obtain crystals of human Sirt3 in its apo form and of human Sirt2 in complex with ADP ribose (ADPR). Crystal formation using MMS was predictable, less error-prone and yielded a higher number of crystals per drop than using conventional crystallization screening methods. The crystals were used to solve the crystal structures of apo Sirt3 and of Sirt2 in complex with ADPR at an improved resolution, as well as the crystal structures of Sirt2 in complex with ADPR and the indoles EX527 and CHIC35. These Sirt2–ADPR–indole complexes unexpectedly contain two indole molecules and provide novel insights into selective Sirt2 inhibition. The MMS approach for Sirt2 and Sirt3 may be used as the basis for structure-based optimization of Sirt2/3 inhibitors in the future.« less

Structure of N-acetyl-[beta]-D-glucosaminidase (GcnA) from the Endocarditis Pathogen Streptococcus gordonii and its Complex with the Mechanism-based Inhibitor NAG-thiazoline

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

Langley, David B.; Harty, Derek W.S.; Jacques, Nicholas A.

2008-09-17

The crystal structure of GcnA, an N-acetyl-{beta}-D-glucosaminidase from Streptococcus gordonii, was solved by multiple wavelength anomalous dispersion phasing using crystals of selenomethionine-substituted protein. GcnA is a homodimer with subunits each comprised of three domains. The structure of the C-terminal {alpha}-helical domain has not been observed previously and forms a large dimerization interface. The fold of the N-terminal domain is observed in all structurally related glycosidases although its function is unknown. The central domain has a canonical ({beta}/{alpha}){sub 8} TIM-barrel fold which harbours the active site. The primary sequence and structure of this central domain identifies the enzyme as a familymore » 20 glycosidase. Key residues implicated in catalysis have different conformations in two different crystal forms, which probably represent active and inactive conformations of the enzyme. The catalytic mechanism for this class of glycoside hydrolase, where the substrate rather than the enzyme provides the cleavage-inducing nucleophile, has been confirmed by the structure of GcnA complexed with a putative reaction intermediate analogue, N-acetyl-{beta}-D-glucosamine-thiazoline. The catalytic mechanism is discussed in light of these and other family 20 structures.« less

The crystal structure of xanthine oxidoreductase during catalysis: Implications for reaction mechanism and enzyme inhibition

PubMed Central

Okamoto, Ken; Matsumoto, Koji; Hille, Russ; Eger, Bryan T.; Pai, Emil F.; Nishino, Takeshi

2004-01-01

Molybdenum is widely distributed in biology and is usually found as a mononuclear metal center in the active sites of many enzymes catalyzing oxygen atom transfer. The molybdenum hydroxylases are distinct from other biological systems catalyzing hydroxylation reactions in that the oxygen atom incorporated into the product is derived from water rather than molecular oxygen. Here, we present the crystal structure of the key intermediate in the hydroxylation reaction of xanthine oxidoreductase with a slow substrate, in which the carbon–oxygen bond of the product is formed, yet the product remains complexed to the molybdenum. This intermediate displays a stable broad charge–transfer band at ≈640 nm. The crystal structure of the complex indicates that the catalytically labile Mo—OH oxygen has formed a bond with a carbon atom of the substrate. In addition, the Mo⋕S group of the oxidized enzyme has become protonated to afford Mo—SH on reduction of the molybdenum center. In contrast to previous assignments, we find this last ligand at an equatorial position in the square-pyramidal metal coordination sphere, not the apical position. A water molecule usually seen in the active site of the enzyme is absent in the present structure, which probably accounts for the stability of this intermediate toward ligand displacement by hydroxide. PMID:15148401

Near-liquidus growth of feldspar spherulites in trachytic melts: 3D morphologies and implications in crystallization mechanisms

NASA Astrophysics Data System (ADS)

Arzilli, Fabio; Mancini, Lucia; Voltolini, Marco; Cicconi, Maria Rita; Mohammadi, Sara; Giuli, Gabriele; Mainprice, David; Paris, Eleonora; Barou, Fabrice; Carroll, Michael R.

2015-02-01

The nucleation and growth processes of spherulitic alkali feldspar have been investigated in this study through X-ray microtomography and electron backscatter diffraction (EBSD) data. Here we present the first data on Shape Preferred Orientation (SPO) and Crystal Preferred Orientation (CPO) of alkali feldspar within spherulites. The analysis of synchrotron X-ray microtomography and EBSD datasets allowed us to study the morphometric characteristics of spherulites in trachytic melts in quantitative fashion, highlighting the three-dimensional shape, preferred orientation, branching of lamellae and crystal twinning, providing insights about the nucleation mechanism involved in the crystallization of the spherulites. The nucleation starts with a heterogeneous nucleus (pre-existing crystal or bubble) and subsequently it evolves forming "bow tie" morphologies, reaching radially spherulitic shapes in few hours. Since each lamella within spherulite is also twinned, these synthetic spherulites cannot be considered as single nuclei but crystal aggregates originated by heterogeneous nucleation. A twin boundary may have a lower energy than general crystal-crystal boundaries and many of the twinned grains show evidence of strong local bending which, combined with twin plane, creates local sites for heterogeneous nucleation. This study shows that the growth rates of the lamellae (10- 6-10- 7 cm/s) in spherulites are either similar or slightly higher than that for single crystals by up to one order of magnitude. Furthermore, the highest volumetric growth rates (10- 11-10- 12 cm3/s) show that the alkali feldspar within spherulites can grow fast reaching a volumetric size of ~ 10 μm3 in 1 s.

Polymer-Induced Heteronucleation for Protein Single Crystal Growth: Structural Elucidation of Bovine Liver Catalase and Concanavalin A Forms

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

Foroughi, Leila M.; Kang, You-Na; Matzger, Adam J.

Obtaining single crystals for X-ray diffraction remains a major bottleneck in structural biology; when existing crystal growth methods fail to yield suitable crystals, often the target rather than the crystallization approach is reconsidered. Here we demonstrate that polymer-induced heteronucleation, a powerful technique that has been used for small molecule crystallization form discovery, can be applied to protein crystallization by optimizing the heteronucleant composition and crystallization formats for crystallizing a wide range of protein targets. Applying these advances to two benchmark proteins resulted in dramatically increased crystal size, enabling structure determination, for a half century old form of bovine liver catalasemore » (BLC) that had previously only been characterized by electron microscopy, and the discovery of two new forms of concanavalin A (conA) from the Jack bean and accompanying structural elucidation of one of these forms.« less

Orthopyroxene oikocrysts in the MG1 chromitite layer of the Bushveld Complex: implications for cumulate formation and recrystallisation

NASA Astrophysics Data System (ADS)

Kaufmann, Felix E. D.; Vukmanovic, Zoja; Holness, Marian B.; Hecht, Lutz

2018-02-01

Two typical mineral textures of the MG 1 chromitite of the Bushveld Complex, South Africa, were observed; one characterised by abundant orthopyroxene oikocrysts, and the other by coarse-grained granular chromitite with only minor amounts of interstitial material. Oikocrysts form elongate clusters of several crystals aligned parallel to the layering, and typically have subhedral, almost chromite-free, core zones containing remnants of olivine. The core zones are surrounded by poikilitic aureoles overgrowing euhedral to subhedral chromite chadacrysts. Chromite grains show no preferred crystal orientation, whereas orthopyroxene grains forming clusters commonly share the same crystallographic orientation. Oikocryst core zones have lower Mg# and higher concentrations of incompatible trace elements compared to their poikilitic aureoles. Core zones are relatively enriched in REE compared to a postulated parental magma (B1) and did not crystallise in equilibrium with the surrounding minerals, whereas the composition of the poikilitic orthopyroxene is consistent with growth from the B1 magma. These observations cannot be explained by the classic cumulus and post-cumulus models of oikocryst formation. Instead, we suggest that the oikocryst core zones in the MG1 chromitite layer formed by peritectic replacement of olivine primocrysts by reaction with an upwards-percolating melt enriched in incompatible trace elements. Poikilitic overgrowth on oikocryst core zones occurred in equilibrium with a basaltic melt of B1 composition near the magma-crystal mush interface. Finally, adcumulus crystallisation followed by grain growth resulted in the surrounding granular chromitite.

WAXS studies of the structural diversity of hemoglobin in solution.

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

Makowski, L.; Bardhan, J.; Gore, D.

2011-01-01

Specific ligation states of hemoglobin are, when crystallized, capable of taking on multiple quaternary structures. The relationship between these structures, captured in crystal lattices, and hemoglobin structure in solution remains uncertain. Wide-angle X-ray solution scattering (WAXS) is a sensitive probe of protein structure in solution that can distinguish among similar structures and has the potential to contribute to these issues. We used WAXS to assess the relationships among the structures of human and bovine hemoglobins in different liganded forms in solution. WAXS data readily distinguished among the various forms of hemoglobins. WAXS patterns confirm some of the relationships among hemoglobinmore » structures that have been defined through crystallography and NMR and extend others. For instance, methemoglobin A in solution is, as expected, nearly indistinguishable from HbCO A. Interestingly, for bovine hemoglobin, the differences between deoxy-Hb, methemoglobin and HbCO are smaller than the corresponding differences in human hemoglobin. WAXS data were also used to assess the spatial extent of structural fluctuations of various hemoglobins in solution. Dynamics has been implicated in allosteric control of hemoglobin, and increased dynamics has been associated with lowered oxygen affinity. Consistent with that notion, WAXS patterns indicate that deoxy-Hb A exhibits substantially larger structural fluctuations than HbCO A. Comparisons between the observed WAXS patterns and those predicted on the basis of atomic coordinate sets suggest that the structures of Hb in different liganded forms exhibit clear differences from known crystal structure.« less

Genetic implications of the trace element distribution pattern in the upper knox carbonate rocks, copper ridge district, East Tennessee

NASA Astrophysics Data System (ADS)

Churnet, Habte G.; Misra, Kula C.

1981-11-01

The Lower Ordovician, Upper Knox Group rocks (the Kingsport and Mascot formations) in the Copper Ridge district consist predominantly of fine-grained dolostones, medium and coarser grained dolostones, and limestones. Dolomite crystals of medium and coarser grained dolostones show up to eight cathodoluminescent zones of variable width and intensity. Electron microprobe analyses indicate that the zoning is related to variation in Fe/Mn ratios, the brighter luminescent zones corresponding to lower ratios. Superposed on this growth zoning is a compositional zoning characterized by a general increase in Fe from core to rim of individual dolomite crystals. Field and petrographic studies (Churnet, 1979; Churnet et al., 1981) indicate that the fine-grained dolostones formed in supratidal to upper intratidal environments, whereas the precursor lime muds of the limestones as well as of the medium and coarser grained dolostones formed in shallow subtidal to lower intertidal environments. The large areal extent of the dolostones must have required a regionally abundant source of Mg such as marine water. Yet, both limestones and dolostones have low Na and Sr contents suggestive of their formation in solutions more dilute than normal marine water. It is proposed that the fine-grained dolostones formed by aggradation of initially very fine-grained dolostones in presence of fresh water, and that the limestones stabilized and the medium and coarser grained dolostones formed in environments of mixed marine and fresh waters. Considered in the light of ordering of partition coefficients, such a mixing model can account for the observed correlation pattern of trace elements (especially, SMn and SrFe) as well as the Fe distribution in the zoned dolomite crystals. Variation of the partition coefficient of Mn due to fluctuations in the relative proportions of fresh and marine waters in the diagenetic solution may explain the different Fe/Mn ratios observed in the growth zones (luminescence bands) of zoned dolomite crystals.

Preliminary crystallographic studies of four crystal forms of serum albumin

NASA Technical Reports Server (NTRS)

Carter, D. C.; Chang, B.; Ho, J. X.; Keeling, K.; Krishnasami, Z.

1994-01-01

Several crystal forms of serum albumin suitable for three-dimensional structure determination have been grown. These forms include crystals of recombinant and wild-type human serum albumin, baboon serum albumin, and canine serum albumin. The intrinsic limits of X-ray diffraction for these crystals are in the range 0.28-0.22 nm. Two of the crystal forms produced from human and canine albumin include incorporated long-chain fatty acids. Molecular replacement experiments have been successfully conducted on each crystal form using the previously determined atomic coordinates of human serum albumin illustrating the conserved tertiary structure.

Copper Benzenetricarboxylate Metal-Organic Framework Nucleation Mechanisms on Metal Oxide Powders and Thin Films formed by Atomic Layer Deposition.

PubMed

Lemaire, Paul C; Zhao, Junjie; Williams, Philip S; Walls, Howard J; Shepherd, Sarah D; Losego, Mark D; Peterson, Gregory W; Parsons, Gregory N

2016-04-13

Chemically functional microporous metal-organic framework (MOF) crystals are attractive for filtration and gas storage applications, and recent results show that they can be immobilized on high surface area substrates, such as fiber mats. However, fundamental knowledge is still lacking regarding initial key reaction steps in thin film MOF nucleation and growth. We find that thin inorganic nucleation layers formed by atomic layer deposition (ALD) can promote solvothermal growth of copper benzenetricarboxylate MOF (Cu-BTC) on various substrate surfaces. The nature of the ALD material affects the MOF nucleation time, crystal size and morphology, and the resulting MOF surface area per unit mass. To understand MOF nucleation mechanisms, we investigate detailed Cu-BTC MOF nucleation behavior on metal oxide powders and Al2O3, ZnO, and TiO2 layers formed by ALD on polypropylene substrates. Studying both combined and sequential MOF reactant exposure conditions, we find that during solvothermal synthesis ALD metal oxides can react with the MOF metal precursor to form double hydroxy salts that can further convert to Cu-BTC MOF. The acidic organic linker can also etch or react with the surface to form MOF from an oxide metal source, which can also function as a nucleation agent for Cu-BTC in the mixed solvothermal solution. We discuss the implications of these results for better controlled thin film MOF nucleation and growth.

Magnesium content within the skeletal architecture of the coral Montastraea faveolata: locations of brucite precipitation and implications to fine-scale data fluctuations

USGS Publications Warehouse

Buster, N.A.; Holmes, C.W.

2006-01-01

Small portions of coral cores were analyzed using a high-resolution laser ablation inductively coupled plasma mass spectrometer (LA ICP-MS) to determine the geochemical signatures within and among specific skeletal structures in the large framework coral, Montastraea faveolata. Vertical transects were sampled along three parallel skeletal structures: endothecal (septal flank), corallite wall, and exothecal (costal flank) areas. The results demonstrate that trace element levels varied among the three structures. Magnesium (Mg) varied among adjacent structures and was most abundant within the exothecal portion of the skeleton. Scanning electron microscopy (SEM) revealed the presence of hexagonal crystals forming thick discs, pairs or doublets of individual crystals, and rosettes in several samples. High Mg within these crystals was confirmed with energy dispersive spectroscopy (EDS), infrared spectrometry, and LA ICP-MS. The chemical composition is consistent with the mineral brucite [Mg(OH2)]. These crystals are located exclusively in the exothecal area of the skeleton, are often associated with green endolithic algae, and are commonly associated with increased Mg levels found in the adjacent corallite walls. Although scattered throughout the exothecal, the brucite crystals are concentrated within green bands where levels of Mg increase substantially relative to other portions of the skeleton. The presence and locations of high-Mg crystals may explain the fine-scale fluctuations in Mg data researchers have been questioning for years.

Crystallization and X-ray diffraction of crystals formed in water-plasticized amorphous lactose.

PubMed

Jouppila, K; Kansikas, J; Roos, Y H

1998-01-01

Effects of storage time and relative humidity on crystallization and crystal forms produced from amorphous lactose were investigated. Crystallization was observed from time-dependent loss of sorbed water and increasing intensities of peaks in X-ray diffraction patterns. The rate of crystallization increased with increasing storage relative humidity. Lactose crystallized mainly as alpha-lactose monohydrate and anhydrous crystals with alpha- and beta-lactose in a molar ratio of 5:3. The results suggested that the crystal form was defined by the early nucleation process. The crystallization data are important in modeling of crystallization phenomena and prediction of stability of lactose-containing food and pharmaceutical materials.

Kinetics of Nucleation and Crystal Growth in Glass Forming Melts in Microgravity

NASA Technical Reports Server (NTRS)

Day, Delbert E.; Ray, Chandra S.

2003-01-01

This flight definition project has the specific objective of investigating the kinetics of nucleation and crystal growth in high temperature inorganic oxide, glass forming melts in microgravity. It is related to one1 of our previous NASA projects that was concerned with glass formation for high temperature containerless melts in microgravity. The previous work culminated in two experiments which were conducted aboard the space shuttle in 1983 and 1985 and which consisted of melting (at 1500 C) and cooling levitated 6 to 8 mm diameter spherical samples in a Single Axis Acoustic Levitator (SAAL) furnace. Compared to other types of materials, there have been relatively few experiments, 6 to 8, conducted on inorganic glasses in space. These experiments have been concerned with mass transport (alkali diffusion), containerless melting, critical cooling rate for glass formation, chemical homogeneity, fiber pulling, and crystallization of glass forming melts. One of the most important and consistent findings in all of these experiments has been that the glasses prepared in microgravity are more resistant to crystallization (better glass former) and more chemically homogeneous than equivalent glasses made on earth (1g). The chemical composition of the melt appears relatively unimportant since the same general results have been reported for oxide, fluoride and chalcogenide melts. These results for space-processed glasses have important implications, since glasses with a higher resistance to crystallization or higher chemical homogeneity than those attainable on earth can significantly advance applications in areas such as fiber optics communications, high power laser glasses, and other photonic devices where glasses are the key functional materials. The classical theories for nucleation and crystal growth for a glass or melt do not contain any parameter that is directly dependent upon the g-value, so it is not readily apparent why glasses prepared in microgravity should be more resistant to crystallization than equivalent glasses prepared on earth. Similarly, the gravity-driven convection in a fluid melt is believed to be the primary force field that is responsible for melt homogenization on earth. Thus, it is not obvious why a glass prepared in space, where gravity-driven convection is ideally absent, would be more chemically homogeneous than a glass identically prepared on earth. The primary objective of the present research is to obtain experimental data for the nucleation rate and crystal growth rate for a well characterized silicate melt (lithium disilicate) processed entirely in space (low gravity) and compare these rates with the nucleation and crystal growth rates for a similar glass prepared identically on earth (1g).

Thermal oxidation of single crystal aluminum antimonide and materials having the same

DOEpatents

Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.

2012-12-25

In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.

Effect of local structures on crystallization in deeply undercooled metallic glass-forming liquids

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

Jiang, S. Q.; Li, M. Z., E-mail: maozhili@ruc.edu.cn; Wu, Z. W.

2016-04-21

The crystallization mechanism in deeply undercooled ZrCu metallic glass-forming liquids was investigated via molecular dynamics simulations. It was found that the crystallization process is mainly controlled by the growth of crystal nuclei formed by the BCC-like atomic clusters, consistent with experimental speculations. The crystallization rate is found to relate to the number of growing crystal nuclei in the crystallization process. The crystallization rate in systems with more crystal nuclei is significantly hindered by the larger surface fractions of crystal nuclei and their different crystalline orientations. It is further revealed that in the crystallization in deeply undercooled regions, the BCC-like crystalmore » nuclei are formed from the inside of the precursors formed by the FCC-like atomic clusters, and growing at the expense of the precursors. Meanwhile, the precursors are expanding at the expense of the outside atomic clusters. This process is consistent with the so-called Ostwald step rule. The atomic structures of metallic glasses are found to have significant impact on the subsequent crystallization process. In the Zr{sub 85}Cu{sub 15} system, the stronger spatial correlation of Cu atoms could hinder the crystallization processes in deeply undercooled regions.« less

An Investigation into the Polymorphism and Crystallization of Levetiracetam and the Stability of its Solid Form.

PubMed

Xu, Kailin; Xiong, Xinnuo; Guo, Liuqi; Wang, Lili; Li, Shanshan; Tang, Peixiao; Yan, Jin; Wu, Di; Li, Hui

2015-12-01

Levetiracetam (LEV) crystals were prepared using different solvents at different temperatures. The LEV crystals were systematically characterized by X-ray powder diffraction (XRPD) and morphological analysis. The results indicated that many kinds of crystal habits exist in a solid form of LEV. To investigate the effects of LEV concentration, crystallization temperature, and crystallization type on crystallization and solid phase transformation of LEV, multiple methods were performed for LEV aqueous solution to determine if a new solid form exists in solid-state LEV. However, XRPD data demonstrate that the LEV solid forms possess same spatial arrangements that are similar to the original solid form. This result indicates that the LEV concentration, crystallization temperature, and crystallization type in aqueous solution have no influence on the crystallization and solid phase transformation of LEV. Moreover, crystallization by sublimation, melt cooling, and quench cooling, as well as mechanical effect, did not result in the formation of new LEV solid state. During melt cooling, the transformation of solid form LEV is a direct process from melting amorphous phase to the original LEV crystal phase, and the conversion rate is very quick. In addition, stability investigation manifested that LEV solid state is very stable under various conditions. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Structural modulation of factor VIIa by full-length tissue factor (TF1-263): implication of novel interactions between EGF2 domain and TF.

PubMed

Prasad, Ramesh; Sen, Prosenjit

2018-02-01

Tissue factor (TF)-mediated factor VII (FVII) activation and a subsequent proteolytic TF-FVIIa binary complex formation is the key step initiating the coagulation cascade, with implications in various homeostatic and pathologic scenarios. TF binding allosterically modifies zymogen-like free FVIIa to its highly catalytically active form. As a result of unresolved crystal structure of the full-length TF 1-263 -FVIIa binary complex and free FVIIa, allosteric alterations in FVIIa following its binding to full-length TF and the consequences of these on function are not entirely clear. The present study aims to map and identify structural alterations in FVIIa and TF resulting from full-length TF binding to FVIIa and the key events responsible for enhanced FVIIa activity in coagulation. We constructed the full-length TF 1-263 -FVIIa membrane bound complex using computational modeling and subjected it to molecular dynamics (MD) simulations. MD simulations showed that TF alters the structure of each domain of FVIIa and these combined alterations contribute to enhanced TF-FVIIa activity. Detailed, domain-wise investigation revealed several new non-covalent interactions between TF and FVIIa that were not found in the truncated soluble TF-FVIIa crystal structure. The structural modulation of each FVIIa domain imparted by TF indicated that both inter and intra-domain communication is crucial for allosteric modulation of FVIIa. Our results suggest that these newly formed interactions can provide additional stability to the protease domain and regulate its activity profile by governing catalytic triad (CT) orientation and localization. The unexplored newly formed interactions between EGF2 and TF provides a possible explanation for TF-induced allosteric activation of FVIIa.

Influence of pH and method of crystallization on the solid physical form of indomethacin.

PubMed

Dubbini, Alessandra; Censi, Roberta; Martena, Valentina; Hoti, Ela; Ricciutelli, Massimo; Malaj, Ledjan; Di Martino, Piera

2014-10-01

The purpose of this study was to investigate the effect of pH and method of crystallization on the solid physical form of indomethacin (IDM). IDM, a non steroidal anti-inflammatory drug poorly soluble in water, underwent two different crystallization methods: crystallization by solvent evaporation under reduced pressure at 50.0°C (method A), and crystallization by cooling of solution from 50.0 to 5.0°C (method B). In both cases, several aqueous ethanolic solutions of IDM of different pHs were prepared. pHs were adjusted by adding acidic solutions (HCl 2M) or alkali (NaOH or NH4OH 2M) to an aqueous ethanolic solution of IDM. Thus, several batches were recovered after crystallization. The chemical stability of IDM was verified through (1)H NMR and mass spectroscopy (FIA-ESI-MS), that revealed that IDM degraded in strong alkali media (pH ≥ 12). Crystals obtained under different crystallization conditions at pHs of 1.0, 4.5, 7.0, 8.0, 10.0 and chemically stable were thus characterized for crystal habit by scanning electron microscopy, for thermal behaviour by differential scanning calorimetry, and thermogravimetry, and for solid state by X-ray powder diffractometry. Under the Method A, IDM always crystallized into pure metastable alpha form when solutions were acidified or alkalized respectively with HCl and NH4OH. On the contrary, in presence of NaOH, IDM crystallized under a mixture of alpha and sodium trihydrate form, because the presence of the sodium counter ion orientates the crystallization towards the formation of the trihydrate salt. Under the method B, at pH of 1.0, IDM crystallized under the alpha form; at pH 4.5, IDM crystallized under the form alpha in presence of some nuclei of gamma form; at pH 7.0, 8.0, and 10.0 for NH4OH, IDM crystallized under the most stable polymorph gamma form, whereas in presence of NaOH, a mix of alpha, and salt forms was formed whatever the pH of the solution. Copyright © 2014 Elsevier B.V. All rights reserved.

The protein folds as platonic forms: new support for the pre-Darwinian conception of evolution by natural law.

PubMed

Denton, Michael J; Marshall, Craig J; Legge, Michael

2002-12-07

Before the Darwinian revolution many biologists considered organic forms to be determined by natural law like atoms or crystals and therefore necessary, intrinsic and immutable features of the world order, which will occur throughout the cosmos wherever there is life. The search for the natural determinants of organic form-the celebrated "Laws of Form"-was seen as one of the major tasks of biology. After Darwin, this Platonic conception of form was abandoned and natural selection, not natural law, was increasingly seen to be the main, if not the exclusive, determinant of organic form. However, in the case of one class of very important organic forms-the basic protein folds-advances in protein chemistry since the early 1970s have revealed that they represent a finite set of natural forms, determined by a number of generative constructional rules, like those which govern the formation of atoms or crystals, in which functional adaptations are clearly secondary modifications of primary "givens of physics." The folds are evidently determined by natural law, not natural selection, and are "lawful forms" in the Platonic and pre-Darwinian sense of the word, which are bound to occur everywhere in the universe where the same 20 amino acids are used for their construction. We argue that this is a major discovery which has many important implications regarding the origin of proteins, the origin of life and the fundamental nature of organic form. We speculate that it is unlikely that the folds will prove to be the only case in nature where a set of complex organic forms is determined by natural law, and suggest that natural law may have played a far greater role in the origin and evolution of life than is currently assumed.

Site specific mineral composition and microstructure of human supra-gingival dental calculus.

PubMed

Hayashizaki, Junko; Ban, Seiji; Nakagaki, Haruo; Okumura, Akihiko; Yoshii, Saori; Robinson, Colin

2008-02-01

Dental calculus has been implicated in the aetiology of several periodontal conditions. Its prevention and removal are therefore desirable clinical goals. While it is known that calculus is very variable in chemical composition, crystallinity and crystallite size little is known about site specific variability within a dentition and between individuals. With this in mind, a study was undertaken to investigate the comparative site specific nature and composition of human dental supra-gingival dental calculus obtained from 66 male patients visiting for their dental check-up using fluorescent X-ray spectroscopy, X-ray diffractometry and Fourier transform infrared spectroscopy. The supra-gingival dental calculus formed on the lingual surfaces of lower anterior teeth and the buccal surfaces of upper molar teeth were classified into four types based on calcium phosphate phases present. There was significant difference in composition of the crystal phase types between lower and upper teeth (p<0.01). There was no significant difference in crystal size between dental calculus on anterior or molar teeth of all samples. The degree of crystallinity of dental calculus formed on the upper molar teeth was higher than that formed on the lower anterior teeth (p<0.01). The CO(3)(2-) contents in dental calculus formed on the lower anterior teeth were higher than on upper molar teeth (p<0.05) which might explain the difference in crystallinity. Magnesium and Si contents and Ca:P ratio on the other hand showed no significant difference between lower and upper teeth. It was concluded that the crystal phases, crystallinity and CO(3)(2-) contents of human dental supra-gingival dental calculus is related to its location in the mouth.

Effect of Multiple Alloying Elements on the Glass-Forming Ability, Thermal Stability, and Crystallization Behavior of Zr-Based Alloys

NASA Astrophysics Data System (ADS)

Bazlov, A. I.; Tsarkov, A. A.; Ketov, S. V.; Suryanarayana, C.; Louzguine-Luzgin, D. V.

2018-02-01

Effect of multiple alloying elements on the glass-forming ability, thermal stability, and crystallization behavior of Zr-based glass-forming alloys were studied in the present work. We investigated the effect of complete or partial substitution of Ti and Ni with similar early and late transition metals, respectively, on the glass-forming ability and crystallization behavior of the Zr50Ti10Cu20Ni10Al10 alloy. Poor correlation was observed between different parameters indicating the glass-forming ability and the critical size of the obtained glassy samples. Importance of the width of the crystallization interval is emphasized. The kinetics of primary crystallization, i.e., the rate of nucleation and rate of growth of the nuclei of primary crystals is very different from that of the eutectic alloys. Thus, it is difficult to estimate the glass-forming ability only on the basis of the empirical parameters not taking into account the crystallization behavior and the crystallization interval.

Crystal Structure of Dengue Virus Type 1 Envelope Protein in the Postfusion Conformation and Its Implications for Membrane Fusion

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

Nayak, Vinod; Dessau, Moshe; Kucera, Kaury

Dengue virus relies on a conformational change in its envelope protein, E, to fuse the viral lipid membrane with the endosomal membrane and thereby deliver the viral genome into the cytosol. We have determined the crystal structure of a soluble fragment E (sE) of dengue virus type 1 (DEN-1). The protein is in the postfusion conformation even though it was not exposed to a lipid membrane or detergent. At the domain I-domain III interface, 4 polar residues form a tight cluster that is absent in other flaviviral postfusion structures. Two of these residues, His-282 and His-317, are conserved in flavivirusesmore » and are part of the 'pH sensor' that triggers the fusogenic conformational change in E, at the reduced pH of the endosome. In the fusion loop, Phe-108 adopts a distinct conformation, forming additional trimer contacts and filling the bowl-shaped concavity observed at the tip of the DEN-2 sE trimer.« less

Crystal Structure of Dengue Type 1 Envelope Protein in the Postfusion Conformation and its Implication for Receptor Binding, Membrane Fusion and Antibody Recognition

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

Nayak, V.; Dessau, M; Kucera, K

Dengue virus relies on a conformational change in its envelope protein, E, to fuse the viral lipid membrane with the endosomal membrane and thereby deliver the viral genome into the cytosol. We have determined the crystal structure of a soluble fragment E (sE) of dengue virus type 1 (DEN-1). The protein is in the postfusion conformation even though it was not exposed to a lipid membrane or detergent. At the domain I-domain III interface, 4 polar residues form a tight cluster that is absent in other flaviviral postfusion structures. Two of these residues, His-282 and His-317, are conserved in flavivirusesmore » and are part of the pH sensor that triggers the fusogenic conformational change in E, at the reduced pH of the endosome. In the fusion loop, Phe-108 adopts a distinct conformation, forming additional trimer contacts and filling the bowl-shaped concavity observed at the tip of the DEN-2 sE trimer.« less

Structures of Saccharomyces cerevisiae D-arabinose dehydrogenase Ara1 and its complex with NADPH: implications for cofactor-assisted substrate recognition.

PubMed

Hu, Xiao-Qian; Guo, Peng-Chao; Ma, Jin-Di; Li, Wei-Fang

2013-11-01

The primary role of yeast Ara1, previously mis-annotated as a D-arabinose dehydrogenase, is to catalyze the reduction of a variety of toxic α,β-dicarbonyl compounds using NADPH as a cofactor at physiological pH levels. Here, crystal structures of Ara1 in apo and NADPH-complexed forms are presented at 2.10 and 2.00 Å resolution, respectively. Ara1 exists as a homodimer, each subunit of which adopts an (α/β)8-barrel structure and has a highly conserved cofactor-binding pocket. Structural comparison revealed that induced fit upon NADPH binding yielded an intact active-site pocket that recognizes the substrate. Moreover, the crystal structures combined with computational simulation defined an open substrate-binding site to accommodate various substrates that possess a dicarbonyl group.

Drug crystallization - implications for topical and transdermal delivery.

PubMed

Hadgraft, Jonathan; Lane, Majella E

2016-06-01

Crystallization of actives in skin following topical application was suggested by studies in the 1950s and 1960s but is poorly understood. In contrast, the problem of crystallization of actives on skin and in transdermal formulations has been known for many years. With respect to crystallization in skin, this review describes early reports of a skin 'reservoir' and possible reasons underlying its genesis. Techniques to study crystallization on and in skin and in transdermal patches are outlined. The role of the vehicle in skin delivery is emphasised. Studies which have investigated permeation from crystalline particles are described. Approaches to limit crystallization of actives are discussed. Using supersaturation and antinuclean polymers, control of crystal size is possible; controlled release from crystals is also employed in transdermal patches. Drug crystallization has significant implications for topical and transdermal delivery. Approaches have been developed to counteract the issue for transdermal patches but crystallization in and on the skin for other formulations remains unresolved. Greater knowledge of residence time of excipients and their interaction with skin at the molecular level is critical in order to address the problem. This will lay the foundations for better design of topical/transdermal formulations.

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

Bolotin, B. M., E-mail: bolotin70@yandex.ru; Mikhlina, Ya. A.; Arkhipova, S. A.

The crystal and molecular structures of two crystal forms (pale yellow form 1 and yellow form 2) of N-[2-(4-oxo-4H-benzo[d][1,3]oxazin-2-yl)phenyl]naphthalene-2-sulfonamide (Orlyum White 520T), which is an organic luminophore with an anomalously high Stokes shift, were determined. Crystal 2 is a solvate with para-xylene. Crystal 1 is a solvent-free form. The molecular geometry in crystal 1 differs from that in 2 only in the orientation of the SO{sub 2}Ar substituent. The bond-length distribution in the planar moiety of the molecule in crystal 1 is virtually identical to that in 2, but the bonds in the NH-SO{sub 2}Ar-bearing benzene ring in crystal 1more » are systematically longer than the corresponding bonds in crystal 2. This fact can be attributed to the crystal-packing effects. In 2 the molecules form stacked dimers with {pi}-stacking interactions between two planar conjugated tricyclic systems. The charge transfer in this system accounts for the intensification of the color of these crystals and the observed difference in the optical properties of 1 and 2.« less

Photonic time crystals.

PubMed

Zeng, Lunwu; Xu, Jin; Wang, Chengen; Zhang, Jianhua; Zhao, Yuting; Zeng, Jing; Song, Runxia

2017-12-07

When space (time) translation symmetry is spontaneously broken, the space crystal (time crystal) forms; when permittivity and permeability periodically vary with space (time), the photonic crystal (photonic time crystal) forms. We proposed the concept of photonic time crystal and rewritten the Maxwell's equations. Utilizing Finite Difference Time Domain (FDTD) method, we simulated electromagnetic wave propagation in photonic time crystal and photonic space-time crystal, the simulation results show that more intensive scatter fields can obtained in photonic time crystal and photonic space-time crystal.

A Model for the Thermal and Chemical Evolution of the Moon's Interior: Implications for the Onset of Mare Volcanism

NASA Technical Reports Server (NTRS)

Hess, Paul C.; Parmentier, E. M.

1995-01-01

Crystallization of the lunar magma ocean creates a chemically stratified Moon consisting of an anorthositic crust and magma ocean cumulates overlying the primitive lunar interior. Within the magma ocean cumulates the last liquids to crystallize form dense, ilmenite-rich cumulates that contain high concentrations of incompatible radioactive elements. The underlying olivine-orthopyroxene cumulates are also stratified with later crystallized, denser, more Fe-rich compositions at the top. This paper explores the chemical and thermal consequences of an internal evolution model accounting for the possible role of these sources of chemical buoyancy. Rayleigh-Taylor instability causes the dense ilmenite-rich cumulate layer and underlying Fe-rich cumulates to sink toward the center of the Moon, forming a dense lunar core. After this overturn, radioactive heating within the ilmenite-rich cumulate core heats the overlying mantle, causing it to melt. In this model, the source region for high-TiO2 mare basalts is a convectively mixed layer above the core-mantle boundary which would contain small and variable amounts of admixed ilmenite and KREEP. This deep high-pressure melting, as required for mare basalts, occurs after a reasonable time interval to explain the onset of mare basalt volcanism if the content of radioactive elements in the core and the chemical density gradients above the core are sufficiently high but within a range of values that might have been present in the Moon. Regardless of details implied by particular model parameters, gravitational overturn driven by the high density of magma ocean Fe-rich cumulates should concentrate high-TiO2 mare basalt sources, and probably a significant fraction of radioactive heating, toward the center of the Moon. This will have important implications for both the thermal evolution of the Moon and for mare basalt genesis.

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

Kish, Kevin; McDonnell, Patricia A.; Goldfarb, Valentina

Protein tyrosine phosphatase {gamma} is a membrane-bound receptor and is designated RPTP{gamma}. RPTP{gamma} and two mutants, RPTP{gamma}(V948I, S970T) and RPTP{gamma}(C858S, S970T), were recombinantly expressed and purified for X-ray crystallographic studies. The purified enzymes were crystallized using the hanging-drop vapor-diffusion method. Crystallographic data were obtained from several different crystal forms in the absence and the presence of inhibitor. In this paper, a description is given of how three different crystal forms were obtained that were used with various ligands. An orthorhombic crystal form and a trigonal crystal form were obtained both with and without ligand, and a monoclinic crystal form wasmore » only obtained in the presence of a particularly elaborated inhibitor.« less

Analysis of stochastic crystallization in micron-sized droplets of undercooled liquid l-arabitol.

PubMed

Guinet, Yannick; Carpentier, Laurent; Paccou, Laurent; Derollez, Patrick; Hédoux, Alain

2016-11-29

Kinetics of isothermal crystallization of l-arabitol were analyzed from the undercooled liquid state within micron-sized droplets from micro-Raman spectroscopy. This study reveals that crystallization slightly above T g is controlled by stochastic heterogeneous nucleation inherent to the droplet size. Microscopic Raman investigations performed in droplets give the unique opportunity to analyze the pure metastable Form II of l-arabitol. It was found that Form II is characterized by a molecular packing more compact than that of the stable Form I, inherent to strong intermolecular hydrogen bonding. Kinetics laws obtained by analyzing several droplets at different temperatures, reveal the transient character of Form II, quasi systematically detected during the crystallization process of form I. Form II appears as the first step of crystallization prior to successive short-living metastable states which is necessary to achieve a complete crystallization in Form I. It was found that the kinetics of conversion between the metastable states (Form II) into Form I is dependent on the amount of strong hydrogen bonding distinctive of Form II. Copyright © 2016 Elsevier Ltd. All rights reserved.

Growth and defects of explosives crystals

NASA Astrophysics Data System (ADS)

Cady, H. H.

Large single crystals of PETN, RDX, and TNT can be grown easily from evaporating ethyl acetate solutions. The crystals all share a similar type of defect that may not be commonly recognized. The defect generates conical faces, ideally mosaic crystals, and may account for the 'polymorphs' of TNT and detonator grades of PETN. TATB crystals manufactured by the amination of trichlorotrinitrobenzene in dry toluene entrain two forms of ammonium chloride. One of these forms causes 'worm holes' in the TATB crystals that may be the reason for its unusually low failure diameters. Strained HMX crystals form mechanical twins that can spontaneously revert back to the untwinned form when the straining force is removed. Large strains or temperatures above 100 C lock in the mechanical twins.

Effect of surfactants or a water soluble polymer on the crystal transition of clarithromycin during a wet granulation process.

PubMed

Nozawa, Kenji; Iwao, Yasunori; Noguchi, Shuji; Itai, Shigeru

2015-11-10

To generate products containing a stable form of clarithromycin (CAM) (form II) regardless of the initial crystal form of CAM or type of granulation solvent, the effects of five surfactants, or a water-soluble polymer (macrogol 400) were determined on the crystal transition of CAM. The metastable form (form I) was kneaded with water, after adding surfactants, or a water-soluble polymer. Form II was also kneaded with ethanol, after adding the same additives. The resulting samples were analyzed by powder X-ray diffraction. Form I was completely converted to form II by a wet granulation using water with additives bearing polyoxyethylene chains such as polysorbate 80 (PS80), polyoxyl 40 stearate or macrogol 400. The granulation of the form II using ethanol with these additives did not result in a crystal transition to form I. Furthermore, CAM tablets were manufactured using granules with PS80, and these crystal forms and dissolution behaviors were investigated. As a result, the wet granulation of CAM with PS80 gave CAM tablets containing only form II and PS80 did not have any adverse effects on tablet characteristics. Therefore, these data suggests that the crystal form of CAM can be controlled to be form II using a wet granulation process with additives bearing polyoxyethylene chains regardless of the initial crystal form of CAM or type of granulation solvent. Copyright © 2015 Elsevier B.V. All rights reserved.

Crystallization and crystal manipulation of a steric chaperone in complex with its lipase substrate

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

Pauwels, Kris, E-mail: krpauwel@vub.ac.be; Loris, Remy; Vandenbussche, Guy

2005-08-01

Crystals of the lipase of B. glumae in complex with its specific foldase were obtained in two forms. Crystallization, crystal manipulation and preliminary X-ray diffraction analysis are described. Bacterial lipases that are secreted via the type II secretion pathway require a lipase-specific foldase in order to obtain their native and biologically active conformation in the periplasmic space. The lipase–foldase complex from Burkholderia glumae (319 and 333 residues, respectively) was crystallized in two crystal forms. One crystal form belongs to space group P3{sub 1}21 (P3{sub 2}21), with unit-cell parameters a = b = 122.3, c = 98.2 Å. A procedure ismore » presented which improved the diffraction of these crystals from ∼5 to 2.95 Å. For the second crystal form, which belonged to space group C2 with unit-cell parameters a = 183.0, b = 75.7, c = 116.6 Å, X-ray data were collected to 1.85 Å.« less

Unraveling Complexity in the Solid Form Screening of a Pharmaceutical Salt: Why so Many Forms? Why so Few?

PubMed Central

2017-01-01

The solid form landscape of 5-HT2a antagonist 3-(4-(benzo[d]isoxazole-3-yl)piperazin-1-yl)-2,2-dimethylpropanoic acid hydrochloride (B5HCl) proved difficult to establish. Many crystalline materials were produced by solid form screening, but few forms readily grew high quality crystals to afford a clear picture or understanding of the solid form landscape. Careful control of crystallization conditions, a range of experimental methods, computational modeling of solvate structures, and crystal structure prediction were required to see potential arrangements of the salt in its crystal forms. Structural diversity in the solid form landscape of B5HCl was apparent in the layer structures for the anhydrate polymorphs (Forms I and II), dihydrate and a family of solvates with alcohols. The alcohol solvates, which provided a distinct packing from the neat forms and the dihydrate, form layers with conserved hydrogen bonding between B5HCl and the solvent, as well as stacking of the aromatic rings. The ability of the alcohol hydrocarbon moieties to efficiently pack between the layers accounted for the difficulty in growing some solvate crystals and the inability of other solvates to crystallize altogether. Through a combination of experiment and computation, the crystallization problems, form stability, and desolvation pathways of B5HCl have been rationalized at a molecular level. PMID:29018305

New Form Discovery for the Analgesics Flurbiprofen and Sulindac Facilitated by Polymer-Induced Heteronucleation

PubMed Central

GRZESIAK, ADAM L.; MATZGER, ADAM J.

2008-01-01

The selection and discovery of new crystalline forms is a longstanding issue in solid-state chemistry of critical importance because of the effect molecular packing arrangement exerts on materials properties. Polymer-induced heteronucleation has recently been developed as a powerful approach to discover and control the production of crystal modifications based on the insoluble polymer heteronucleant added to the crystallization solution. The selective nucleation and discovery of new crystal forms of the well-studied pharmaceuticals flurbiprofen (FBP) and sulindac (SUL) has been achieved utilizing this approach. For the first time, FBP form III was produced in bulk quantities and its crystal structure was also determined. Furthermore, a novel 3:2 FBP:H2O phase was discovered that nucleates selectively from only a few polymers. Crystallization of SUL in the presence of insoluble polymers facilitated the growth of form I single crystals suitable for structure determination. Additionally, a new SUL polymorph (form IV) was discovered by this method. The crystal forms of FBP and SUL are characterized by Raman and FTIR spectroscopies, X-ray diffraction, and differential scanning calorimetry. PMID:17567888

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

NASA Technical Reports Server (NTRS)

Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

1993-01-01

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

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

Crystallization and initial X-ray diffraction studies of scaffolding protein (gp7) of bacteriophage ϕ29

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

Badasso, Mohammed O., E-mail: badas001@umn.edu; Anderson, Dwight L.; Department of Oral Science, University of Minnesota, Minneapolis, MN 55455

2005-04-01

ϕ29 bacteriophage scaffolding protein (gp7) has been overproduced in E. coli, purified, crystallized and characterized by X-ray diffraction. Two distinct crystal forms were obtained and a diffraction data set was collected to 1.8 Å resolution. The Bacillus subtilis bacteriophage ϕ29 scaffolding protein (gp7) has been crystallized by the hanging-drop vapour-diffusion method at 293 K. Two new distinct crystal forms that both differed from a previously crystallized and solved scaffolding protein were grown under the same conditions. Form I belongs to the primitive tetragonal space group P4{sub 1}2{sub 1}2, with unit-cell parameters a = b = 77.13, c = 37.12 Å.more » Form II crystals exhibit an orthorhombic crystal form, with space group C222 and unit-cell parameters a = 107.50, b = 107. 80, c = 37.34 Å. Complete data sets have been collected to 1.78 and 1.80 Å for forms I and II, respectively, at 100 K using Cu Kα X-rays from a rotating-anode generator. Calculation of a V{sub M} value of 2.46 Å{sup 3} Da{sup −1} for form I suggests the presence of one molecule in the asymmetric unit, corresponding to a solvent content of 50.90%, whereas form II has a V{sub M} of 4.80 Å{sup 3} Da{sup −1} with a solvent content of 48.76% and two molecules in the asymmetric unit. The structures of both crystal forms are being determined by the molecular-replacement method using the coordinates of the published crystal structure of gp7.« less

Solid-state characterization of mefenamic acid.

PubMed

Panchagnula, Ramesh; Sundaramurthy, Prakash; Pillai, Omathanu; Agrawal, Shrutidevi; Raj, Yasvanth Ashok

2004-04-01

The purpose of this study was to characterize mefenamic acid (MA) from commercial samples and samples crystallized from different solvents. Various techniques used for characterization included microscopy (hot stage microscopy, scanning electron microscopy), intrinsic dissolution rate, differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffractometry (pXRD). The commercial samples varied in their crystal habit, thermal behavior, and intrinsic dissolution rate. It was found that the commercial samples were polymorphic Form I, which converted to Form II on heating in a DSC pan. Similarly, compression in an intrinsic dissolution rate (IDR) press resulted in the conversion of Form I to Form II. On the other hand, the samples recrystallized from different solvents under varying conditions yielded different crystal habits. Stirring and degree of supersaturation significantly influenced the crystal habit in all the solvents used in the study. Samples crystallized from ethanol and tetrahydrofuran yielded Form I, which behaved similarly to the commercial samples (M1 and M3). Recrystallization from ethyl acetate at a fast cooling rate yielded Form I, which on melting crystallized to Form II. The form I crystallized from ethyl acetate by fast cooling converted partially to form II on storing at ambient conditions. Forms I and II of MA were enantiotropically related. The results demonstrate the variable material characteristics of the commercial samples of MA and the influence of the crystallizing conditions on the formation of the polymorphs. Copyright 2004 Wiley-Liss, Inc. and the American Pharmacists Association.

Synthesis and Structural Features of [4,4'-Diisopropoxyester-2,2'-bipyridine], [Dichloro(4,4'-diisopropoxyester-2,2'-bi-pyridine)-platinum(ii)] and Its Dichloromethane Solvated Pseudo-Polymorph: Versatile Supramolecular Interactions

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

Browning, Charles; Nesterov, Vladimir N.; Wang, Xiaoping

We report that the organic ligand 4,4'-diisopropoxyester-2,2'-bipyridine, C 18H 20N 2O 4 (1), crystallizes in the triclinic crystal system P-1 and the molecule occupies a special position in the unit cell. In the crystal, molecules form stacks with partial overlapping of the pyridine rings. The Pt(II) dichloro complex of 1 crystallizes from a mixture of ethanol/hexane and from dichloromethane to form orange and yellow crystals, respectively. The orange non-solvated crystals of the (bipyridine)(dichloro)platinum(II) complex C 18H 20N 2O 4PtCl 2 (2) crystallize in the triclinic crystal system P-1 as well with two independent molecules in the unit cell. In themore » crystal packing, molecules form two types of dimers with Pt1 ··· Pt1A and Pt2···Pt2A distances of 3.478 and 5.186 angstrom respectively. The yellow crystals, as a solvated pseudo-polymorph C 18H 20N 2O 4PtCl 2·1.5 CH 2Cl 2 (3) also crystallize in the triclinic crystal system P-1 with two independent molecules in the unit cell. In the crystal packing, molecules form Pt2 ···Pt1 ···Pt1A ···Pt2A intermolecular contacts with alternating distances 3.501 and 3.431 angstrom, respectively, forming infinite chains. Graphical Abstract The dichloro(bipyridine)platinum complex, dichloro(4,4'-diisopropoxyester-2,2'-bipyridine)platinum(II), forms single crystals as a stable non-solvated form and a solvated polymorph with dramatically different supramolecular structure and short contacts.« less

Synthesis and Structural Features of [4,4'-Diisopropoxyester-2,2'-bipyridine], [Dichloro(4,4'-diisopropoxyester-2,2'-bi-pyridine)-platinum(ii)] and Its Dichloromethane Solvated Pseudo-Polymorph: Versatile Supramolecular Interactions

DOE PAGES

Browning, Charles; Nesterov, Vladimir N.; Wang, Xiaoping; ...

2015-06-03

We report that the organic ligand 4,4'-diisopropoxyester-2,2'-bipyridine, C 18H 20N 2O 4 (1), crystallizes in the triclinic crystal system P-1 and the molecule occupies a special position in the unit cell. In the crystal, molecules form stacks with partial overlapping of the pyridine rings. The Pt(II) dichloro complex of 1 crystallizes from a mixture of ethanol/hexane and from dichloromethane to form orange and yellow crystals, respectively. The orange non-solvated crystals of the (bipyridine)(dichloro)platinum(II) complex C 18H 20N 2O 4PtCl 2 (2) crystallize in the triclinic crystal system P-1 as well with two independent molecules in the unit cell. In themore » crystal packing, molecules form two types of dimers with Pt1 ··· Pt1A and Pt2···Pt2A distances of 3.478 and 5.186 angstrom respectively. The yellow crystals, as a solvated pseudo-polymorph C 18H 20N 2O 4PtCl 2·1.5 CH 2Cl 2 (3) also crystallize in the triclinic crystal system P-1 with two independent molecules in the unit cell. In the crystal packing, molecules form Pt2 ···Pt1 ···Pt1A ···Pt2A intermolecular contacts with alternating distances 3.501 and 3.431 angstrom, respectively, forming infinite chains. Graphical Abstract The dichloro(bipyridine)platinum complex, dichloro(4,4'-diisopropoxyester-2,2'-bipyridine)platinum(II), forms single crystals as a stable non-solvated form and a solvated polymorph with dramatically different supramolecular structure and short contacts.« less

Multiple plagioclase crystal populations identified by crystal size distribution and in situ chemical data: Implications for timescales of magma chamber processes associated with the 1915 eruption of Lassen Peak, CA

USGS Publications Warehouse

Salisbury, M.J.; Bohrson, W.A.; Clynne, M.A.; Ramos, F.C.; Hoskin, P.

2008-01-01

Products of the 1915 Lassen Peak eruption reveal evidence for a magma recharge-magma mixing event that may have catalyzed the eruption and from which four compositional members were identified: light dacite, black dacite, andesitic inclusion, and dark andesite. Crystal size distribution, textural, and in situ chemical (major and trace element and Sr isotope) data for plagioclase from these compositional products define three crystal populations that have distinct origins: phenocrysts (long axis > 0??5 mm) that typically have core An contents between 34 and 36 mol %, microphenocrysts (long axis between 0??1 and 0??5 mm) that have core An contents of 66-69, and microlites (long axis < 0??1 mm) with variable An core contents from 64 to 52. Phenocrysts are interpreted to form in an isolated dacitic magma chamber that experienced slow cooling. Based on textural, compositional, and isotopic data for the magma represented by the dacitic component, magma recharge was not an important process until just prior to the 1915 eruption. Average residence times for phenocrysts are in the range of centuries to millennia. Microphenocrysts formed in a hybrid layer that resulted from mixing between end-member reservoir dacite and recharge magma of basaltic andesite composition. High thermal contrast between the two end-member magmas led to relatively high degrees of undercooling, which resulted in faster crystal growth rates and acicular and swallowtail crystal habits. Some plagioclase phenocrysts from the dacitic chamber were incorporated into the hybrid layer and underwent dissolution-precipitation, seen in both crystal textures and rim compositions. Average microphenocryst residence times are of the order of months. Microlites may have formed in response to decompression and/ or syn-eruptive degassing as magma ascended from the chamber through the volcanic conduit. Chemical distinctions in plagioclase microlite An contents reveal that melt of the dark andesite was more mafic than the melt of the other three compositions. We suggest that mixing of an intruding basaltic andesite and reservoir dacite before magma began ascending in the conduit allowed formation of a compositionally distinct microlite population. Melt in the other three products was more evolved because it had undergone differentiation during the months following initial mixing; as a consequence, melt and microlites among these three products have similar compositions. The results of this study highlight the integrated use of crystal size distribution, textural, and in situ chemical data in identifying distinct crystal populations and linking these populations to the thermal and chemical characteristics of complex magma bodies. ?? The Author 2008. Published by Oxford University Press. All rights reserved.

Solubility behavior of lamivudine crystal forms in recrystallization solvents.

PubMed

Jozwiakowski, M J; Nguyen, N A; Sisco, J M; Spancake, C W

1996-02-01

Lamivudine can be obtained as acicular crystals (form I, 0.2 hydrate) from water or methanol and as bipyramidal crystals (form II, nonsolvated) from many nonaqueous solvents. Form II is thermodynamically favored in the solid state (higher melting point and greater density than form I) at ambient relative humidities. Solubility measurements on both forms versus solvent and temperature was used to determine whether entropy or enthalpy was the driving force for solubility. Solution calorimetry data indicated that form I is favored (less soluble) in all solvents studied on the basis of enthalpy alone. In higher alcohols and other organic solvents, form I has a larger entropy of solution than form II, which compensates for the enthalpic factors and results in physical stability for form II in these systems. The metastable crystal form solubility at 25 degrees C was estimated to be 1.2-2.3 times as high as the equilibrium solubility of the stable form, depending on the temperature, solvent, and crystal form. Binary solvent studies showed that > 18-20% water must be present in ethanol to convert the excess solid to form I at equilibrium.

Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

NASA Technical Reports Server (NTRS)

Nadarajah, Arunan

1996-01-01

Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

Effects of storage time and temperature on pH, specific gravity, and crystal formation in urine samples from dogs and cats.

PubMed

Albasan, Hasan; Lulich, Jody P; Osborne, Carl A; Lekcharoensuk, Chalermpol; Ulrich, Lisa K; Carpenter, Kathleen A

2003-01-15

To determine effects of storage temperature and time on pH and specific gravity of and number and size of crystals in urine samples from dogs and cats. Randomized complete block design. 31 dogs and 8 cats. Aliquots of each urine sample were analyzed within 60 minutes of collection or after storage at room or refrigeration temperatures (20 vs 6 degrees C [68 vs 43 degrees F]) for 6 or 24 hours. Crystals formed in samples from 11 of 39 (28%) animals. Calcium oxalate (CaOx) crystals formed in vitro in samples from 1 cat and 8 dogs. Magnesium ammonium phosphate (MAP) crystals formed in vitro in samples from 2 dogs. Compared with aliquots stored at room temperature, refrigeration increased the number and size of crystals that formed in vitro; however, the increase in number and size of MAP crystals in stored urine samples was not significant. Increased storage time and decreased storage temperature were associated with a significant increase in number of CaOx crystals formed. Greater numbers of crystals formed in urine aliquots stored for 24 hours than in aliquots stored for 6 hours. Storage time and temperature did not have a significant effect on pH or specific gravity. Urine samples should be analyzed within 60 minutes of collection to minimize temperature- and time-dependent effects on in vitro crystal formation. Presence of crystals observed in stored samples should be validated by reevaluation of fresh urine.

Visualization of exciton transport in ordered and disordered molecular solids.

PubMed

Akselrod, Gleb M; Deotare, Parag B; Thompson, Nicholas J; Lee, Jiye; Tisdale, William A; Baldo, Marc A; Menon, Vinod M; Bulović, Vladimir

2014-04-16

Transport of nanoscale energy in the form of excitons is at the core of photosynthesis and the operation of a wide range of nanostructured optoelectronic devices such as solar cells, light-emitting diodes and excitonic transistors. Of particular importance is the relationship between exciton transport and nanoscale disorder, the defining characteristic of molecular and nanostructured materials. Here we report a spatial, temporal and spectral visualization of exciton transport in molecular crystals and disordered thin films. Using tetracene as an archetype molecular crystal, the imaging reveals that exciton transport occurs by random walk diffusion, with a transition to subdiffusion as excitons become trapped. By controlling the morphology of the thin film, we show that this transition to subdiffusive transport occurs at earlier times as disorder is increased. Our findings demonstrate that the mechanism of exciton transport depends strongly on the nanoscale morphology, which has wide implications for the design of excitonic materials and devices.

Interface Properties of Atomic-Layer-Deposited Al2O3 Thin Films on Ultraviolet/Ozone-Treated Multilayer MoS2 Crystals.

PubMed

Park, Seonyoung; Kim, Seong Yeoul; Choi, Yura; Kim, Myungjun; Shin, Hyunjung; Kim, Jiyoung; Choi, Woong

2016-05-11

We report the interface properties of atomic-layer-deposited Al2O3 thin films on ultraviolet/ozone (UV/O3)-treated multilayer MoS2 crystals. The formation of S-O bonds on MoS2 after low-power UV/O3 treatment increased the surface energy, allowing the subsequent deposition of uniform Al2O3 thin films. The capacitance-voltage measurement of Au-Al2O3-MoS2 metal oxide semiconductor capacitors indicated n-type MoS2 with an electron density of ∼10(17) cm(-3) and a minimum interface trap density of ∼10(11) cm(-2) eV(-1). These results demonstrate the possibility of forming a high-quality Al2O3-MoS2 interface by proper UV/O3 treatment, providing important implications for their integration into field-effect transistors.

Preliminary petrographic description and geologic implications of the Apollo 17 Station 7 boulder consortium samples

USGS Publications Warehouse

Chao, E.C.T.; Minkin, J.A.; Thompson, C.L.

1974-01-01

Preliminary petrographic description and mineral composition of four hand samples (77135, 77115, 77075 and 77215) are presented. 77135, 77115, and 77075 all crystallized from fragment-laden melts; they are similar in textures but differ in grain size. 77135 and 77115 are pigeonite feldspathic basalts. On the basis of geologic and petrographic evidence, 77115 and 77075 are related; they formed, cooled, and consolidated before being engulfed in the vesicular 77135. The impact or igneous origin of the melts from which these rocks crystallized cannot be determined. 77215 is a shocked, strongly sheared and granulated microbreccia consisting of three major lithologies dominated by mineral clasts of orthopyroxene and calcic plagioclase. The orthopyroxene clasts contain coarse exsolved blebs of augite, suggesting a deep-seated origin. The major, minor, and trace element compositions of 77135, 77115, and 77075 are in general similar. They represent a major highland rock type, perhaps more important than anorthosites. ?? 1974.

What we know about Mars (but otherwise wouldn't) if it is the shergottite parent body

NASA Technical Reports Server (NTRS)

Mcsween, H. Y., Jr.

1985-01-01

The evidence that some meteorites may actually be samples of fairly large solar system bodies, specifically the moon and the planet Mars was presented. The proposed martian meteorites, called shergottites are igneous rocks that crystallized from molten magmas. Their crystallization ages are much too young to have formed by internal melting within small asteroids, and the unusual chemical composition of gases trapped when these rocks were severely shocked matches that of the martin atmosphere measured by Viking. The implications of these samples for martian evolution was discussed and suggested, that if Mars is the shergottite parent body, the martian interior is much more like that of the earth than has been previously thought. Shergottites explain presence of small magnetic field indicate that volatileement concentratins in Mars should be similar to the Earth, and explain the great lengths of volcanic flows on the martian surface.

Structure of the measles virus hemagglutinin bound to its cellular receptor SLAM.

PubMed

Hashiguchi, Takao; Ose, Toyoyuki; Kubota, Marie; Maita, Nobuo; Kamishikiryo, Jun; Maenaka, Katsumi; Yanagi, Yusuke

2011-02-01

Measles virus, a major cause of childhood morbidity and mortality worldwide, predominantly infects immune cells using signaling lymphocyte activation molecule (SLAM) as a cellular receptor. Here we present crystal structures of measles virus hemagglutinin (MV-H), the receptor-binding glycoprotein, in complex with SLAM. The MV-H head domain binds to a β-sheet of the membrane-distal ectodomain of SLAM using the side of its β-propeller fold. This is distinct from attachment proteins of other paramyxoviruses that bind receptors using the top of their β-propeller. The structure provides templates for antiviral drug design, an explanation for the effectiveness of the measles virus vaccine, and a model of the homophilic SLAM-SLAM interaction involved in immune modulations. Notably, the crystal structures obtained show two forms of the MV-H-SLAM tetrameric assembly (dimer of dimers), which may have implications for the mechanism of fusion triggering.

Sixty years from discovery to solution: crystal structure of bovine liver catalase form III

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

Foroughi, Leila M.; Kang, You-Na; Matzger, Adam J.

2012-03-27

The crystallization and structural characterization of bovine liver catalase (BLC) has been intensively studied for decades. Forms I and II of BLC have previously been fully characterized using single-crystal X-ray diffraction. Form III has previously been analyzed by electron microscopy, but owing to the thinness of this crystal form an X-ray crystal structure had not been determined. Here, the crystal structure of form III of BLC is presented in space group P212121, with unit-cell parameters a = 68.7, b = 173.7, c = 186.3 {angstrom}. The asymmetric unit is composed of the biological tetramer, which is packed in a tetrahedronmore » motif with three other BLC tetramers. This higher resolution structure has allowed an assessment of the previously published electron-microscopy studies.« less

Small molecule inhibitors of mesotrypsin from a structure-based docking screen

DOE PAGES

Kayode, Olumide; Huang, Zunnan; Soares, Alexei S.; ...

2017-05-02

PRSS3/mesotrypsin is an atypical isoform of trypsin, the upregulation of which has been implicated in promoting tumor progression. To date there are no mesotrypsin-selective pharmacological inhibitors which could serve as tools for deciphering the pathological role of this enzyme, and could potentially form the basis for novel therapeutic strategies targeting mesotrypsin. A virtual screen of the Natural Product Database (NPD) and Food and Drug Administration (FDA) approved Drug Database was conducted by high-throughput molecular docking utilizing crystal structures of mesotrypsin. Twelve high-scoring compounds were selected for testing based on lowest free energy docking scores, interaction with key mesotrypsin active sitemore » residues, and commercial availability. Diminazene (C1D22956468), along with two similar compounds presenting the bis-benzamidine substructure, was validated as a competitive inhibitor of mesotrypsin and other human trypsin isoforms. Diminazene is the most potent small molecule inhibitor of mesotrypsin reported to date with an inhibitory constant (K i) of 3.6±0.3 pM. Diminazene was subsequently co-crystalized with mesotrypsin and the crystal structure was solved and refined to 1.25 Å resolution. This high resolution crystal structure can now offer a foundation for structure-guided efforts to develop novel and potentially more selective mesotrypsin inhibitors based on similar molecular substructures.« less

Small molecule inhibitors of mesotrypsin from a structure-based docking screen

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

Kayode, Olumide; Huang, Zunnan; Soares, Alexei S.

PRSS3/mesotrypsin is an atypical isoform of trypsin, the upregulation of which has been implicated in promoting tumor progression. To date there are no mesotrypsin-selective pharmacological inhibitors which could serve as tools for deciphering the pathological role of this enzyme, and could potentially form the basis for novel therapeutic strategies targeting mesotrypsin. A virtual screen of the Natural Product Database (NPD) and Food and Drug Administration (FDA) approved Drug Database was conducted by high-throughput molecular docking utilizing crystal structures of mesotrypsin. Twelve high-scoring compounds were selected for testing based on lowest free energy docking scores, interaction with key mesotrypsin active sitemore » residues, and commercial availability. Diminazene (C1D22956468), along with two similar compounds presenting the bis-benzamidine substructure, was validated as a competitive inhibitor of mesotrypsin and other human trypsin isoforms. Diminazene is the most potent small molecule inhibitor of mesotrypsin reported to date with an inhibitory constant (K i) of 3.6±0.3 pM. Diminazene was subsequently co-crystalized with mesotrypsin and the crystal structure was solved and refined to 1.25 Å resolution. This high resolution crystal structure can now offer a foundation for structure-guided efforts to develop novel and potentially more selective mesotrypsin inhibitors based on similar molecular substructures.« less

Characterization and evaluation of miconazole salts and cocrystals for improved physicochemical properties.

PubMed

Tsutsumi, Shunichirou; Iida, Motoo; Tada, Norio; Kojima, Takashi; Ikeda, Yukihiro; Moriwaki, Toshiya; Higashi, Kenjirou; Moribe, Kunikazu; Yamamoto, Keiji

2011-12-15

Miconazole salts and cocrystals were studied to improve the physicochemical properties of miconazole. Maleate, hemifumarate, and hemisuccinate were prepared and characterized by powder X-ray diffractometry, differential scanning calorimetry, and single crystal X-ray diffractometry. The intrinsic dissolution rate and stability of each miconazole crystal form were compared to those of freebase and nitrate to evaluate the optimal crystal form. Crystal structure analysis indicated that maleate was a salt formed by proton transfer from the acid to the imidazole group of miconazole. Hemifumarate and hemisuccinate were determined to be cocrystals formed by hydrogen bonding between the acids and the base in their crystal lattices. Intrinsic dissolution tests showed that the formation of salts and cocrystals improved the dissolution rate of miconazole. Stability tests of preliminary formulations prepared with each crystal form indicated that maleate and hemifumarate were unstable at 80°C and generated a specific degraded product, i.e., a Michael adduct, between miconazole and the acids. Hemisuccinate had a superior intrinsic dissolution rate and stability, and is thus considered a promising crystal form of miconazole. Copyright © 2011 Elsevier B.V. All rights reserved.

Re-awakening Magmatic Systems: The Mechanics of an Open-system Event

NASA Astrophysics Data System (ADS)

Bergantz, George; Burgisser, Alain; Schleicher, Jillian

2016-04-01

The re-awakening of magmatic systems requires new magma input, which often induces mixing with a resident magma existing as a crystal-rich mush. This is expressed by complex phenocryst populations, many of which preserve evidence of multiple episodes of recycling. The unlocking and mobilization of these resident mushes conditions the progress of re-awakening, however their processes are poorly understood. Crystal-rich but mobile systems, dominated by their granular mechanics, are not satisfactorily explained from either fluid or solid-like models. We will present a generalizing framework for describing the mechanics of crystal-rich mushes based on the notion of force chains. Force chains arise from crystal-crystal contacts and describe the highly non-uniform way that stress is transmitted in a crystal-rich mush. Using CFD-DEM simulations that resolve crystal-scale mechanics, we will show how the populations of crystal mush force chains and their spatial fabric change during an open-system event. We will show how the various forms of dissipation, such as: fluid drag, particle-fluid drag, particle normal and shear lubrication, and contact friction, jointly contribute to the processes of magma mush unlocking, mobilization and fabric formation. We will also describe non-intuitive constitutive behavior such as non-local and non-affine deformation as well as complex, rheological transitions from continuous to discontinuous shear thickening as a function of the dimensionless shear rate. One implication of this is that many of the commonly-invoked postulates about magma behavior such as lock-up at a critical crystallinity and suspension rheology, are better understood from a micro-physical (crystal-scale) perspective as a combination of far-field geometrical controls, local frictional thickening and shear jamming, each with distinct time scales. This kind of crystal-based unifying framework can simultaneously recover diverse processes such as strain-localization, shear-induced dilatency, and help to identify the volumes of resident magma re-mobilized during magma system re-awakening.

Is it Possible to have the Similar Unit Cell in Crystals of Different form from the same Macromolecule? (A Case Study of Ribosome Crystals)

NASA Technical Reports Server (NTRS)

Karpova, E. A.; Rose, M. Franklin (Technical Monitor)

2000-01-01

Three different types of ribosome crystals were grown by the vapor diffusion technique in hanging drops as described in (1,2). The ribosome is a large asymmetric RNA-protein complex (2.3 million Da), which is protein syntheses machinery of the cell. In this poster we would like to discuss the features of ribosome crystallization. Ribosomes were purified from the thermophilic bacteria Thermus thermophilus by centrifugation (3). Three types of crystals (needle, flat tetragonal and tetragonal-like pyramid) can be grown from the same solution; furthermore, in the same drop using 10-15% 2-methyl-2,4- pentanediol as a precipitant. The crystals appeared in 5-48 hours. The crystals were stable and can co-exist in solution over long period of time. The kinetics of appearance of different crystal forms was different: first the needle crystals were grown, then the tetragonal, and finally the tetragonal pyramids. Later studies of the process of ribosome crystal growth depending on supersaturation showed that low supersaturation results in the appearance of tetragonal plates or tetragonal-like pyramids. An electron microscopy study, together with computer modeling, has shown that crystals of different forms have a high probability of having the same unit cell parameters. According to these experiments the following conclusion can be dranvn: the level of supersaturation of the macromolecule in a crystallizing solution is one of the major factors for forming three-dimensional crystals convenient for X-rays diffraction analysis. From the same macromolecule solution, crystals of different forms can be grown at approximately the same conditions by varying the concentration of macromolecule in the solution. Ion-macromolecule and water-macromolecule interactions, apparently, play the main role in the formation of the unit cell of the crystals.

Million-year melt-presence in monotonous intermediate magma for a volcanic-plutonic assemblage in the Central Andes: Contrasting histories of crystal-rich and crystal-poor super-sized silicic magmas

NASA Astrophysics Data System (ADS)

Kaiser, Jason F.; de Silva, Shanaka; Schmitt, Axel K.; Economos, Rita; Sunagua, Mayel

2017-01-01

The melt-present lifetime of super-sized monotonous intermediate magmas that feed supereruptions and end life as granodioritic plutons is investigated using zircon chronochemistry. These data add to the ongoing discussion on magma assembly rates and have implications for how continental batholiths are built. Herein, we estimate ∼1.1 Ma of continuous melt presence before and after the climactic caldera-forming 2.89 ± 0.01 Ma (2σ error) Pastos Grandes Ignimbrite (PGI) supereruption (∼1500 km3 of magma) in the Andes of southwest Bolivia. Zircon crystallization in PGI pumice and lava from the faulted Southern Postcaldera Dome span ∼0.7 Ma prior to the climactic eruption and formation of the eponymous caldera, whereas younger, unfaulted Postcaldera Dome lavas (termed Northern and Middle) and a granodioritic plutonic clast within the products of a Pleistocene eruption indicate a further ∼0.4 Ma of post-climactic zircon crystallization. Bulk-rock compositions as well as zircon thermometry and geochemistry indicate the presence of homogeneous dacitic magma before and after the climactic eruption, but a trend to zircon crystallization at higher temperatures and from less evolved melts is seen for post-climactic zircon. We propose a model in which a large volume of crystal-rich dacite magma was maintained above solidus temperatures by periodic andesitic recharge that is chemically invisible in the erupted components. The climactic caldera-forming eruption vented the upper portions of the magma system zircon was saturated. Zircon in postcaldera lavas indicate that residual magma from this system remained locally viable for eruption at least for some time after the caldera-forming event. Subsequently, deeper "remnant" dacite magma previously outside the zone of zircon saturation rose to shallower levels to re-establish hydraulic and isostatic equilibrium where zircon crystallization commenced anew, and drove more resurgent volcanism and uplift. The same magma crystallized as a granodiorite pluton which was sampled as xenoliths in much later volcanic events. Over the ∼1.1 Ma zircon crystallization history for the PGI, postcaldera lavas and xenoliths, the melt remained in an ∼100-150 °C temperature window as indicated by Ti-in-zircon thermometry. Although chemical trends are consistent with zircon crystallization at variable temperatures, there is no secular cooling, but rather a thermal rejuvenation following the 2.89 Ma PGI eruption. As such these data provide a "low and slow" temporal constraint for models for the pre-eruptive lifetimes of mushy magma in contrast to the "rapid" mobilization of crystal-poor silicic magmas, consistent with a model where the latter are incubated within the former and extracted rapidly prior to eruption. The thermal and chemical monotony of crystal-rich dacites throughout a caldera cycle connotes conditions where near-eutectic melt can be maintained in near-surface magma reservoirs for an extended period of time if the subvolcanic magma reservoir is sufficiently large so that hotter and initially zircon-undersaturated magma can replenish shallow magma vented in a supereruption.

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

Jones, B.; Renaut, R.W.

Skeletal crystals are hollow crystals that develop because their outer walls grow before their cores. The presence of skeletal crystals of calcite (three types--trigonal prisms, hexagonal prisms, and plates) and trona in hot (> 90 C) spring deposits in New Zealand (Waikite Springs and Ohaaki Pool) and Kenya (Lorusio hot springs) shows that they can form in natural sedimentary regimes. Analysis of samples from these deposits shows that this crystal morphology develops under disequilibrium conditions that are unrelated to a specific environmental or diagenetic setting. Skeletal crystals transform into solid crystals when subsequent precipitation fills their hollow cores. In somemore » cases, this may involve precipitation of crystalline material that has a sieve-like texture. In other examples, the skeletal crystal provides a framework upon which other materials can be precipitated. Walls in the skeletal trigonal calcite prisms from Waikite Springs are formed of subcrystals that mimic the shape of the parent crystal. Similarly, plate-like skeletal crystals from Lorusio are formed of densely packed subcrystals that are < 0.5 {micro}m long. Conversely, the walls of the skeletal hexagonal calcite crystals from Ohaaki Pool and the skeletal trona crystals from Lorusio are not formed of subcrystals. Recognition of skeletal crystals is important because they represent growth that follows the reverse pattern of normal growth. Failure to recognize that crystal growth followed the skeletal motif may lead to false interpretations concerning the growth of a crystal.« less

Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

PubMed Central

Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

2011-01-01

Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

Discovery of black dye crystal structure polymorphs: Implications for dye conformational variation in dye-sensitized solar cells

DOE PAGES

Cole, Jacqueline M.; Low, Kian Sing; Gong, Yun

2015-11-24

Here, we present the discovery of a new crystal structure polymorph (1) and pseudopolymorph (2) of the Black Dye, one of the world’s leading dyes for dye-sensitized solar cells, DSSCs (10.4% device performance efficiency). This reveals that Black Dye molecules can adopt multiple low-energy conformers. This is significant since it challenges existing models of the Black Dye···TiO 2 adsorption process that renders a DSSC working electrode; these have assumed a single molecular conformation that refers to the previously reported Black Dye crystal structure (3). The marked structural differences observed between 1, 2, and 3 make the need for modeling multiplemore » conformations more acute. Additionally, the ordered form of the Black Dye (1) provides a more appropriate depiction of its anionic structure, especially regarding its anchoring group and NCS bonding descriptions. The tendency toward NCS ligand isomerism, evidenced via the disordered form 2, has consequences for electron injection and electron recombination in Black Dye embedded DSSC devices. Dyes 2 and 3 differ primarily by the absence or presence of a solvent of crystallization, respectively; solvent environment effects on the dye are thereby elucidated. This discovery of multiple Black Dye conformers from diffraction, with atomic-level definition, complements recently reported nanoscopic evidence for multiple dye conformations existing at a dye···TiO 2 interface, for a chemically similar DSSC dye; those results emanated from imaging and spectroscopy, but were unresolved at the submolecular level. Taken together, these findings lead to the general notion that multiple dye conformations should be explicitly considered when modeling dye···TiO 2 interfaces in DSSCs, at least for ruthenium-based dye complexes.« less

New insights into the origin of ladder dikes: Implications for punctuated growth and crystal accumulation in the Cathedral Peak granodiorite

NASA Astrophysics Data System (ADS)

Wiebe, R. A.; Jellinek, A. M.; Hodge, K. F.

2017-04-01

Ladder dikes are steep tabular bodies, typically a meter or less thick, composed of moderately dipping, concave upward, alternating dark (i.e. schlieren) and light bands oriented roughly perpendicular to the ladder dike margins. These structures occur widely but sparsely in granitic rocks and are found prominently in the Cathedral Peak granodiorite (CPG) of the Tuolumne Intrusive suite. Previous studies have interpreted that ladder dikes form as a result of processes including the downward flow of crystal mush in cracks within strong crystal mush or by upward flow in steep tubes that migrate within a strong crystal mush. Our new observations indicate that ladder dikes formed by downward flow of crystal mush in troughs or valleys, in a manner potentially comparable to trough bands in mafic layered intrusions. Extensions of the schlieren outward and upward away from the ladder dike margins into the host granite demonstrate that the host granite was deposited as mounds on both sides at the same time as the ladder dikes. Ladder dikes, therefore, record lateral flows of crystal mush on a magma chamber floor. Vertical exposures suggest these flows are on the order of ten meters thick. Some steep exposures on granite domes indicate multiple ladder dikes (and flows) over a stratigraphic height of 80-100 m. Later (stratigraphically higher) flows commonly deform and erode the top of an earlier flow, and granitic material rich in K-feldspar megacrysts has locally engulfed large blocks of ladder dikes, demonstrating that the megacrysts were also transported in flows. Flows in the CPG are directed away from the center of the pluton toward the western and eastern margins and apparently spread along a strong crystal mush floor and into a rheologically complex CPG magma. Whereas established dynamical models for spreading (single phase) gravity currents with simple and complex rheologies explain the elongate geometry, spacing and orientation of the tabular bodies, the origin and character of the downward flows required to explain the trough band schlieren structures is challenging. However, an intermittent and progressive deposition of trough bands, consistent with field observations, is potentially explained if the two-phase (crystals and melt) dynamics governing the response of the CPG magma to a new injection are considered.

Recovering and recycling uranium used for production of molybdenum-99

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

Reilly, Sean Douglas; May, Iain; Copping, Roy

A processes for recycling uranium that has been used for the production of molybdenum-99 involves irradiating a solution of uranium suitable for forming fission products including molybdenum-99, conditioning the irradiated solution to one suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina. Another process involves irradiation of a solid target comprising uranium, forming an acidic solution from the irradiated targetmore » suitable for inducing the formation of crystals of uranyl nitrate hydrates, then forming the crystals and a supernatant and then separating the crystals from the supernatant, thus using the crystals as a source of uranium for recycle. Molybdenum-99 is recovered from the supernatant using an adsorbent such as alumina.« less

Growth, Characterization and Applications of Beta-Barium Borate and Related Crystals

DTIC Science & Technology

1993-10-31

Crystal symmetry determines the form of the second order polarization tensor. The second order polarizability tensor is defined by the piezoelectric...cold finger. A temperature oscillation technique1 I was used to limit the number of nuclei formed . These experiments typically yielded thin crystal...statistically sampled to determine the optimal seeding orientation. % was reasoned that the large crystal plates were formed from nucleii which had a favorable

Expression, purification, crystallization and preliminary X-ray diffraction analysis of an essential lipoprotein implicated in cell-wall biosynthesis in Mycobacteria

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

Marland, Zara; Beddoe, Travis; Zaker-Tabrizi, Leyla

2005-12-01

A lipoprotein implicated in mycobacterial cell-wall biosynthesis, LpqW, was expressed in E. coli. Crystals were obtained that diffracted to 2.4 Å resolution. Mycobacterium tuberculosis is a renewed cause of devastation in the developing world. Critical to the success of this re-emerging pathogen is its unusual waxy cell wall, which is rich in rare components including lipoarabinomannan (LAM) and its precursors, the phosphatidylinositol mannosides (PIMs). Balanced synthesis of these related glycolipids is intrinsic to both cell-wall integrity and virulence in M. tuberculosis and presents a promising, albeit poorly defined, therapeutic target. Here, the expression, purification and crystallization of an essential 600-amino-acidmore » lipoprotein, LpqW, implicated in this process are reported. Crystals of LpqW were grown using 20–24%(w/v) PEG 4000, 8–16%(v/v) 2-propanol, 100 mM sodium citrate pH 5.5 and 10 mM DTT. A complete data set was collected at 2.4 Å using synchrotron radiation on a crystal belonging to space group C222, with unit-cell parameters a = 188.57, b = 312.04, c = 104.15 Å. Structure determination is under way.« less

Influence of moisture on the crystal forms of niclosamide obtained from acetone and ethyl acetate.

PubMed

Manek, Rahul V; Kolling, William M

2004-03-04

The purpose of this study was to elucidate the formation of crystal hydrates of niclosamide and to delineate the effect of relative humidity on the crystal forms obtained from acetone and ethyl acetate. Recrystallization of niclosamide was performed in the presence and absence of moisture. Two hydrates and their corresponding anhydrates were isolated. The hydrates obtained by the process of recrystallization from acetone (Form I) and that obtained from ethyl acetate (Form II) were classified based on differences in their dehydration profile, crystal structure, shape, and morphology. Crystals obtained in the absence of moisture were unstable, and when exposed to the laboratory atmosphere transformed to their corresponding hydrates. Differential scanning calorimetry thermograms indicate that Form I changes to an anhydrate at temperatures below 100 degrees C, while Form II dehydrates in a stepwise manner above 140 degrees C. This finding was further confirmed by thermogravimetric analysis. Dehydration of Form II was accompanied by a loss of structural integrity, demonstrating that water molecules play an important role in maintaining its crystal structure. Form I, Form II, and the anhydrate of Form II showed no significant moisture sorption over the entire range of relative humidity. Although the anhydrate of Form I did not show any moisture uptake at low humidity, it converted to the monohydrate at elevated relative humidity (>95%). All forms could be interconverted depending on the solvent and humidity conditions.

Precipitation of ikaite crystals in Antarctic marine sediments: implications from pore water geochemistry

NASA Astrophysics Data System (ADS)

Lu, Z.; Kennedy, H.; Rickaby, R. E.; Georg, B.; Shaw, S.; Lennie, A.; Pancost, R. D.

2008-12-01

Ikaite is a calcium carbonate hexahydrate (CaCO3•6H20) considered to be stable only at low temperatures. It has been found in form of tufa tower at locations where alkaline water mixes with water masses enriched in calcium (e.g. Ikka Fjord, Mono Lake). Large euhedral single crystals of ikaite were also recovered in marine sediments, associated with organic matter degradation, anaerobic oxidation of methane (AOM) and sulfate reduction. The hydration water in the ikaite crystals were demonstrated to record the oxygen isotope composition of the water from which they precipitated. Such a characteristic may allow using ikaite to reconstruct the ice volume in the past. For this purpose, the controls on its precipitation in the sediment column need to be investigated which is the main goal of this study. U.S. Antarctica Program cruise NBP0703 collected two cores with ikaite crystals at Antarctica Peninsula (Bransfield Strait and Firth of Tay). We determined major cation/anion concentrations, dissolved inorganic carbon (DIC) and δ13C composition of DIC in the pore waters in these two cores. Strong organic matter degradation or AOM in both cores results in quick consumption of sulfate in shallow part of the cores (SMT at around 3m).Rapid build-up of DIC is accompanied by the sharp decrease of dissolved calcium in the top 5m. Large variations were observed in δ13CDIC values (-20‰ to +13‰). The δ13C of ikaite in two cores were distinctive from each other (-19‰ and +4‰) corresponding to the DIC pools at different depths. The down core saturation state of the ikaite was modeled in PHREEQC based on the pore water chemistry, and the results are consistent with carbon isotope data, suggesting that these large crystals very likely formed within a narrow depth interval and a short time period (given high sedimentation rates of 0.5-1 cm/yr in this area).

The origin of plagioclase phenocrysts in basalts from continental monogenetic volcanoes of the Kaikohe-Bay of Islands field, New Zealand: implications for magmatic assembly and ascent

NASA Astrophysics Data System (ADS)

Coote, Alisha; Shane, Phil; Stirling, Claudine; Reid, Malcolm

2018-02-01

Late Quaternary, porphyritic basalts erupted in the Kaikohe-Bay of Islands area, New Zealand, provide an opportunity to explore the crystallization and ascent history of small volume magmas in an intra-continental monogenetic volcano field. The plagioclase phenocrysts represent a diverse crystal cargo. Most of the crystals have a rim growth that is compositionally similar to groundmass plagioclase ( An65) and is in equilibrium with the host basalt rock. The rims surround a resorbed core that is either less calcic ( An20-45) or more calcic (> An70), having crystallized in more differentiated or more primitive melts, respectively. The relic cores, particularly those that are less calcic (< An45), have 87Sr/86Sr ratios that are either mantle-like ( 0.7030) or crustal-like ( 0.7040 to 0.7060), indicating some are antecrysts formed in melts fractionated from plutonic basaltic forerunners, while others are true xenocrysts from greywacke basement and/or Miocene arc volcanics. It is envisaged that intrusive basaltic forerunners produced a zone where various degrees of crustal assimilation and fractional crystallization occurred. The erupted basalts represent mafic recharge of this system, as indicated by the final crystal rim growths around the entrained antecrystic and xenocrystic cargo. The recharge also entrained cognate gabbros that occur as inclusions, and produced mingled groundmasses. Multi-stage magmatic ascent and interaction is indicated, and is consistent with the presence of a partial melt body in the lower crust detected by geophysical methods. This crystallization history contrasts with traditional concepts of low-flux basaltic systems where rapid ascent from the mantle is inferred. From a hazards perspective, the magmatic system inferred here increases the likelihood of detecting eruption precursor phenomena such as seismicity, degassing and surface deformation.

Late Diagenetic Cements in the Murray Formation, Gale Crater, Mars: Implications for Postdepositional Fluid Flow

NASA Astrophysics Data System (ADS)

Kah, L. C.; Kronyak, R. E.; Van Beek, J.; Nachon, M.; Mangold, N.; Thompson, L. M.; Wiens, R. C.; Grotzinger, J. P.; Schieber, J.

2015-12-01

The Murray formation in its type section at Pahrump Hills, consists of approximately 14 meters of recessive-weathering mudstone interbedded with decimeter-scale cross-bedded sandstone in the upper portions of the exposed section. Mudstone textures vary from massive, to poorly laminated, to well laminated. Unusual 3-dimensional crystal clusters and dendrites occur in the lowermost part of the section and are erosionally resistant with respect to the host rock. Crystal clusters consist of elongate lathes that occur within individual blocks of the fractured substrate. Individual lathes show tabular morphologies with a pseudo-rectangular cross-section and the three dimensional morphology of the crystal clusters cross-cut host rock lamination with little or no deformation. Dendritic structures are typically larger and show predominantly planar growth aligned with bedding planes. Individual lathes within the dendrites are elongate and pseudo-rectangular in cross-section. Unlike crystal clusters, dendritic morphologies appear to nucleate at bedrock fractures and near mineralized veins. Here we show evidence that crystal clusters and dendrites are post-depositional, potentially burial diagenetic features. Association of features with through-going fractures suggests that fractures may have been a primary transport pathway for ions responsible for dendrite growth. Even where dendrites do not occur, enhanced cementation suggests that fluids permeated the rock matrix. We suggest that growth of clusters proceeded as inter-particle crystal growth, wherein mineral growth within inter-particle spaces resulted in cementation and porosity loss, with little further effect on the rock matrix. Crystal clusters and dendrites are most likely to form when mineral saturation states are highest, for instance with initial intrusion of fracture-borne fluids and mixing with ambient pore fluids, and thus emphasize the importance of fractures in ion transport during late diagenesis.

Purification, crystallization and preliminary X-ray diffraction analysis of aspartate semialdehyde dehydrogenase (Rv3708c) from Mycobacterium tuberculosis

PubMed Central

Vyas, Rajan; Kumar, Vijay; Panjikar, Santosh; Karthikeyan, Subramanian; Kishan, K. V. Radha; Tewari, Rupinder; Weiss, Manfred S.

2008-01-01

Aspartate semialdehyde dehydrogenase from Mycobacterium tuberculosis (Asd, ASADH, Rv3708c), which is the second enzyme in the lysine/homoserine-biosynthetic pathways, has been expressed heterologously in Escherichia coli. The enzyme was purified using affinity and gel-filtration chromatographic techniques and crystallized in two different crystal forms. Preliminary diffraction data analysis suggested the presence of up to four monomers in the asymmetric unit of the orthorhombic crystal form A and of one or two monomers in the cubic crystal form B. PMID:18323599

Self-powdering and nonlinear optical domain structures in ferroelastic β‧-Gd2(MoO4)3 crystals formed in glass

NASA Astrophysics Data System (ADS)

Tsukada, Y.; Honma, T.; Komatsu, T.

2009-08-01

Ferroelastic β'-Gd 2(MoO 4) 3, (GMO), crystals are formed through the crystallization of 21.25Gd 2O 3-63.75MoO 3-15B 2O 3 glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50-500 μm spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called "self-powdering phenomenon during crystallization" in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and a spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO 4) 2- tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals.

Solid-state properties and crystallization behavior of PHA-739521 polymorphs.

PubMed

Sun, Changquan Calvin

2006-08-17

PHA-739521 is an experimental compound that exhibits polymorphism. The two anhydrous crystal forms, I and II, are characterized using powder X-ray diffractometry, thermal analyses, moisture sorption gravimetry. Both Forms I and II are non-hygroscopic and are stable to compaction pressure. The melting temperature is about 152 degrees C for Form I and 168 degrees C for Form II. Forms I and II are enantiotropically related where Form I is more stable below a transition temperature of approximately 70 degrees C. Crystallization behavior of this compound from solutions and during heating is also studied. Information obtained is used to design an appropriate crystallization process to successfully manufacture desired polymorph at large scale.

Method of making macrocrystalline or single crystal semiconductor material

NASA Technical Reports Server (NTRS)

Shlichta, P. J. (Inventor); Holliday, R. J. (Inventor)

1986-01-01

A macrocrystalline or single crystal semiconductive material is formed from a primary substrate including a single crystal or several very large crystals of a relatively low melting material. This primary substrate is deposited on a base such as steel or ceramic, and it may be formed from such metals as zinc, cadmium, germanium, aluminum, tin, lead, copper, brass, magnesium silicide, or magnesium stannide. These materials generally have a melting point below about 1000 C and form on the base crystals the size of fingernails or greater. The primary substrate has an epitaxial relationship with a subsequently applied layer of material, and because of this epitaxial relationship, the material deposited on the primary substrate will have essentially the same crystal size as the crystals in the primary substrate. If required, successive layers are formed, each of a material which has an epitaxial relationship with the previously deposited layer, until a layer is formed which has an epitaxial relationship with the semiconductive material. This layer is referred to as the epitaxial substrate, and its crystals serve as sites for the growth of large crystals of semiconductive material. The primary substrate is passivated to remove or otherwise convert it into a stable or nonreactive state prior to deposition of the seconductive material.

Photonic crystal devices formed by a charged-particle beam

DOEpatents

Lin, Shawn-Yu; Koops, Hans W. P.

2000-01-01

A photonic crystal device and method. The photonic crystal device comprises a substrate with at least one photonic crystal formed thereon by a charged-particle beam deposition method. Each photonic crystal comprises a plurality of spaced elements having a composition different from the substrate, and may further include one or more impurity elements substituted for spaced elements. Embodiments of the present invention may be provided as electromagnetic wave filters, polarizers, resonators, sources, mirrors, beam directors and antennas for use at wavelengths in the range from about 0.2 to 200 microns or longer. Additionally, photonic crystal devices may be provided with one or more electromagnetic waveguides adjacent to a photonic crystal for forming integrated electromagnetic circuits for use at optical, infrared, or millimeter-wave frequencies.

Trace element distribution in mineral separates of the Allende inclusions and their genetic implications

NASA Technical Reports Server (NTRS)

Nagasawa, H.; Blanchard, D. P.; Jacobs, J. W.; Brannon, J. C.; Philpotts, J. A.; Onuma, N.

1977-01-01

Concentrations of the rare earth elements (REE), Sc, Co, Fe, Zn, Ir, Na, and Cr were determined for mineral separates of the coarseand fine-grained types (group I and II) of the Allende inclusions. These data in combination with other data suggest that the minerals in the coarse-grained inclusions (group I) crystallized in a closed system with respect to refractory elements although a totally molten stage is precluded. The data also indicate that fine-grained (group II) inclusions were formed by condensation from a super-cooled nebular gas; REE-rich clinopyroxene and spinel were formed earlier than REE-poor sodalite and nepheline. In addition, pre-existing Mg isotope anomalies in the coarse-grained inclusions must have been erased during the heating stage.

Positrons as interface-sensitive probes of polar semiconductor heterostructures

NASA Astrophysics Data System (ADS)

Makkonen, I.; Snicker, A.; Puska, M. J.; Mäki, J.-M.; Tuomisto, F.

2010-07-01

Group-III nitrides in their wurtzite crystal structure are characterized by large spontaneous polarization and significant piezoelectric contributions in heterostructures formed of these materials. Polarization discontinuities in polar heterostructures grown along the (0001) direction result in huge built-in electric fields on the order of megavolt per centimeter. We choose the III-nitride heterostructures as archetypal representatives of polar heterostructures formed of semiconducting or insulating materials and study the behavior of positrons in these structures using first-principles electronic-structure theory supported by positron annihilation experiments for bulk systems. The strong electric fields drive positrons close to interfaces, which is clearly seen in the predicted momentum distributions of annihilating electron-positron pairs as changes relative to the constituent bulk materials. Implications of the effect to positron defect studies of polar heterostructures are addressed.

Crystallization and preliminary crystallographic analysis of latent, active and recombinantly expressed aurone synthase, a polyphenol oxidase, from Coreopsis grandiflora

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

Molitor, Christian; Mauracher, Stephan Gerhard; Rompel, Annette, E-mail: annette.rompel@univie.ac.at

2015-05-22

Latent and active aurone synthase purified from petals of C. grandiflora (cgAUS1) were crystallized. The crystal quality of recombinantly expressed latent cgAUS1 was significantly improved by co-crystallization with the polyoxotungstate Na{sub 6}[TeW{sub 6}O{sub 24}] within the liquid–liquid phase-separation zone. Aurone synthase (AUS), a member of a novel group of plant polyphenol oxidases (PPOs), catalyzes the oxidative conversion of chalcones to aurones. Two active cgAUS1 (41.6 kDa) forms that differed in the level of phosphorylation or sulfation as well as the latent precursor form (58.9 kDa) were purified from the petals of Coreopsis grandiflora. The differing active cgAUS1 forms and themore » latent cgAUS1 as well as recombinantly expressed latent cgAUS1 were crystallized, resulting in six different crystal forms. The active forms crystallized in space groups P2{sub 1}2{sub 1}2{sub 1} and P12{sub 1}1 and diffracted to ∼1.65 Å resolution. Co-crystallization of active cgAUS1 with 1,4-resorcinol led to crystals belonging to space group P3{sub 1}21. The crystals of latent cgAUS1 belonged to space group P12{sub 1}1 and diffracted to 2.50 Å resolution. Co-crystallization of recombinantly expressed pro-AUS with the hexatungstotellurate(VI) salt Na{sub 6}[TeW{sub 6}O{sub 24}] within the liquid–liquid phase separation zone significantly improved the quality of the crystals compared with crystals obtained without hexatungstotellurate(VI)« less

Polymorph selection: the role of nucleation, crystal growth and molecular modeling.

PubMed

Erdemir, Deniz; Lee, Alfred Y; Myerson, Allan S

2007-11-01

Solution crystallization is an important separation and purification process used in the chemical, pharmaceutical and food industries. The quality of a crystalline product is generally judged by four main criteria: purity, crystal habit, particle size and solid form. Consistent production of the desired polymorph is crucial as the unanticipated emergence of a different crystal form may have severe consequences. Thus, the selection of a solid-state form for a crystalline product is vital and is ultimately based on knowledge of the properties of the other polymorphs. This review discusses the role of nucleation, crystal growth and molecular modeling on polymorphism in molecular crystals. Examples are presented demonstrating how the first two factors can govern the appearance of a particular crystalline form, and how the latter factor can be used as a tool for understanding polymorphism.

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

Aoki, Ken-ichi; Tanaka, Nobutada, E-mail: ntanaka@pharm.showa-u.ac.jp; Ishikura, Shuhei

Pig heart carbonyl reductase has been crystallized in the presence of NADPH. Diffraction data have been collected using synchrotron radiation. Pig heart carbonyl reductase (PHCR), which belongs to the short-chain dehydrogenase/reductase (SDR) family, has been crystallized by the hanging-drop vapour-diffusion method. Two crystal forms (I and II) have been obtained in the presence of NADPH. Form I crystals belong to the tetragonal space group P4{sub 2}, with unit-cell parameters a = b = 109.61, c = 94.31 Å, and diffract to 1.5 Å resolution. Form II crystals belong to the tetragonal space group P4{sub 1}2{sub 1}2, with unit-cell parameters amore » = b = 120.10, c = 147.00 Å, and diffract to 2.2 Å resolution. Both crystal forms are suitable for X-ray structure analysis at high resolution.« less

Screening and Characterization of Hydrate Forms of T-3256336, a Novel Inhibitor of Apoptosis (IAP) Protein Antagonist.

PubMed

Takeuchi, Shoko; Kojima, Takashi; Hashimoto, Kentaro; Saito, Bunnai; Sumi, Hiroyuki; Ishikawa, Tomoyasu; Ikeda, Yukihiro

2015-01-01

Different crystal packing of hydrates from anhydrate crystals leads to different physical properties, such as solubility and stability. Investigation of the potential of varied hydrate formation, and understanding the stability in an anhydrous/hydrate system, are crucial to prevent an undesired transition during the manufacturing process and storage. Only one anhydrous form of T-3256336, a novel inhibitor of apoptosis (IAP) protein antagonist, was discovered during synthesis, and no hydrate form has been identified. In this study, we conducted hydrate screening such as dynamic water vapor sorption/desorption (DVS), and the slurry experiment, and characterized the solid-state properties of anhydrous/hydrate forms to determine the most desirable crystalline form for development. New hydrate forms, both mono-hydrate and hemi-hydrate forms, were discovered as a result of this hydrate screening. The characterization of two new hydrate forms was conducted, and the anhydrous form was determined to be the most desirable development form of T-3256336 in terms of solid-state stability. In addition, the stability of the anhydrous form was investigated using the water content and temperature controlled slurry experiment to obtain the desirable crystal form in the crystallization process. The water content regions of the stable phase of the desired form, the anhydrous form, were identified for the cooling crystallization process.

Sm-Nd systematics of lunar ferroan anorthositic suite rocks: Constraints on lunar crust formation

NASA Astrophysics Data System (ADS)

Boyet, Maud; Carlson, Richard W.; Borg, Lars E.; Horan, Mary

2015-01-01

We have measured Sm-Nd systematics, including the short-lived 146Sm-142Nd chronometer, in lunar ferroan anorthositic suite (FAS) whole rocks (15415, 62236, 62255, 65315, 60025). At least some members of the suite are thought to be primary crystallization products formed by plagioclase flotation during crystallization of the lunar magma ocean (LMO). Most of these samples, except 62236, have not been exposed to galactic cosmic rays for a long period and thus require minimal correction to their 142Nd isotope composition. These samples all have measured deficits in 142Nd relative to the JNdi-1 terrestrial standard in the range -45 to -21 ppm. The range is -45 to -15 ppm once the 62236 142Nd/144Nd ratio is corrected from neutron-capture effects. Analyzed FAS samples do not define a single isochron in either 146Sm-142Nd or 147Sm-143Nd systematics, suggesting that they either do not have the same crystallization age, come from different sources, or have suffered isotopic disturbance. Because the age is not known for some samples, we explore the implications of their initial isotopic compositions for crystallization ages in the first 400 Ma of solar system history, a timing interval that covers all the ages determined for the ferroan anorthositic suite whole rocks as well as different estimates for the crystallization of the LMO. 62255 has the largest deficit in initial 142Nd and does not appear to have followed the same differentiation path as the other FAS samples. The large deficit in 142Nd of FAN 62255 may suggest a crystallization age around 60-125 Ma after the beginning of solar system accretion. This result provides essential information about the age of the giant impact forming the Moon. The initial Nd isotopic compositions of FAS samples can be matched either with a bulk-Moon with chondritic Sm/Nd ratio but enstatite-chondrite-like initial 142Nd/144Nd (e.g. 10 ppm below modern terrestrial), or a bulk-Moon with superchondritic Sm/Nd ratio and initial 142Nd/144Nd similar to ordinary chondrites.

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

Boyet, Maud; Carlson, Richard W.; Borg, Lars E.

Here, we have measured Sm–Nd systematics, including the short-lived 146Sm– 142Nd chronometer, in lunar ferroan anorthositic suite (FAS) whole rocks (15415, 62236, 62255, 65315, 60025). At least some members of the suite are thought to be primary crystallization products formed by plagioclase flotation during crystallization of the lunar magma ocean (LMO). Most of these samples, except 62236, have not been exposed to galactic cosmic rays for a long period and thus require minimal correction to their 142Nd isotope composition. These samples all have measured deficits in 142Nd relative to the JNdi-1 terrestrial standard in the range –45 to –21 ppm.more » The range is –45 to –15 ppm once the 62236 142Nd/ 144Nd ratio is corrected from neutron-capture effects. Analyzed FAS samples do not define a single isochron in either 146Sm– 142Nd or 147Sm– 143Nd systematics, suggesting that they either do not have the same crystallization age, come from different sources, or have suffered isotopic disturbance. Because the age is not known for some samples, we explore the implications of their initial isotopic compositions for crystallization ages in the first 400 Ma of solar system history, a timing interval that covers all the ages determined for the ferroan anorthositic suite whole rocks as well as different estimates for the crystallization of the LMO. 62255 has the largest deficit in initial 142Nd and does not appear to have followed the same differentiation path as the other FAS samples. The large deficit in 142Nd of FAN 62255 may suggest a crystallization age around 60–125 Ma after the beginning of solar system accretion. This result provides essential information about the age of the giant impact forming the Moon. The initial Nd isotopic compositions of FAS samples can be matched either with a bulk-Moon with chondritic Sm/Nd ratio but enstatite-chondrite-like initial 142Nd/ 144Nd (e.g. 10 ppm below modern terrestrial), or a bulk-Moon with superchondritic Sm/Nd ratio and initial 142Nd/ 144Nd similar to ordinary chondrites.« less

Sm-Nd systematics of lunar ferroan anorthositic suite rocks: Constraints on lunar crust

DOE PAGES

Boyet, Maud; Carlson, Richard W.; Borg, Lars E.; ...

2014-09-28

Here, we have measured Sm–Nd systematics, including the short-lived 146Sm– 142Nd chronometer, in lunar ferroan anorthositic suite (FAS) whole rocks (15415, 62236, 62255, 65315, 60025). At least some members of the suite are thought to be primary crystallization products formed by plagioclase flotation during crystallization of the lunar magma ocean (LMO). Most of these samples, except 62236, have not been exposed to galactic cosmic rays for a long period and thus require minimal correction to their 142Nd isotope composition. These samples all have measured deficits in 142Nd relative to the JNdi-1 terrestrial standard in the range –45 to –21 ppm.more » The range is –45 to –15 ppm once the 62236 142Nd/ 144Nd ratio is corrected from neutron-capture effects. Analyzed FAS samples do not define a single isochron in either 146Sm– 142Nd or 147Sm– 143Nd systematics, suggesting that they either do not have the same crystallization age, come from different sources, or have suffered isotopic disturbance. Because the age is not known for some samples, we explore the implications of their initial isotopic compositions for crystallization ages in the first 400 Ma of solar system history, a timing interval that covers all the ages determined for the ferroan anorthositic suite whole rocks as well as different estimates for the crystallization of the LMO. 62255 has the largest deficit in initial 142Nd and does not appear to have followed the same differentiation path as the other FAS samples. The large deficit in 142Nd of FAN 62255 may suggest a crystallization age around 60–125 Ma after the beginning of solar system accretion. This result provides essential information about the age of the giant impact forming the Moon. The initial Nd isotopic compositions of FAS samples can be matched either with a bulk-Moon with chondritic Sm/Nd ratio but enstatite-chondrite-like initial 142Nd/ 144Nd (e.g. 10 ppm below modern terrestrial), or a bulk-Moon with superchondritic Sm/Nd ratio and initial 142Nd/ 144Nd similar to ordinary chondrites.« less

Implications of Chirality of Drugs and Excipients in Physical Pharmacy.

NASA Astrophysics Data System (ADS)

Duddu, Sarma P.

1993-01-01

The interactions of enantiomers of a chiral drug with other chemical entities, which may lead to changes and stereoselective differences in the physicochemical properties of the drug, were investigated. The various interactions described below employed ephedrine, pseudoephedrine and some of their salts, and to a minor extent, propranolol hydrochloride. The interaction of ephedrinium or pseudoephedrinium with the achiral anion, salicylate, yielded crystalline salts with the notable exception of homochiral ephedrine. Racemic ephedrinium salicylate exists as a centrosymmetric crystal (P2_1/n) whereas racemic pseudoephedrinium salicylate is a mixture of homochiral crystals (P2 _1). The inability of ephedrinium to exist as a homochiral salicylate salt is attributed to a high energy conformation of the ephedrinium cation, following conformational analysis. Arising from conformationally favorable interactions, the crystallization of racemic ephedrinium salicylate from aqueous solutions was utilized to improve the enantiomeric purity of a partially resolved mixture of ephedrine from 60% to 82% in one crystallization step. Interaction of the opposite enantiomers of ephedrine and pseudoephedrine in the solid, liquid, solution and vapor state produced the respective racemic compounds. The formation of racemic ephedrine in the solid state as predominantly second order (k = 392 mol^{-1} hr^{-1}), probably mediated by the vapor phase. The formation of racemic pseudoephedrine was predominantly diffusion-controlled in the solid state via an intermediate non-crystalline phase. The interaction with traces of the opposite enantiomer during crystallization of (RS)-(-)-ephedrinium 2-naphthalenesulfonate and (SS)-(+)-pseudoephedrinium salicylate changed pharmaceutically important solid state properties, including dissolution rate. Uptake of the enantiomeric impurity was measured by a new, sensitive HPLC method. The enantiomeric impurity, at mole fractions <= 0.0027 greatly increased the lattice disorder, i.e. entropy, measured calorimetrically. The release of propranolol hydrochloride from a sustained-release matrix containing HPMC and racemic propranolol hydrochloride was stereoselective, though variable, suggesting a differential interaction of the two enantiomers with the hydrated chiral matrix. Thus, the interaction of a chiral drug with other chemical entities leads to significant, interpretable changes in the physicochemical properties of the drug, which may have important implications in the design and development of reliable and effective solid dosage forms.

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life.

PubMed

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D; Sears, S Kelly; Hesse, Reinhard; Vali, Hojatollah

2012-06-01

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

Formation of replicating saponite from a gel in the presence of oxalate: implications for the formation of clay minerals in carbonaceous chondrites and the origin of life

USGS Publications Warehouse

Schumann, Dirk; Hartman, Hyman; Eberl, Dennis D.; Sears, S. Kelly; Hesse, Reinhard; Vali, Hojatollah

2012-01-01

The potential role of clay minerals in the abiotic origin of life has been the subject of ongoing debate for the past several decades. At issue are the clay minerals found in a class of meteorites known as carbonaceous chondrites. These clay minerals are the product of aqueous alteration of anhydrous mineral phases, such as olivine and orthopyroxene, that are often present in the chondrules. Moreover, there is a strong correlation in the occurrence of clay minerals and the presence of polar organic molecules. It has been shown in laboratory experiments at low temperature and ambient pressure that polar organic molecules, such as the oxalate found in meteorites, can catalyze the crystallization of clay minerals. In this study, we show that oxalate is a robust catalyst in the crystallization of saponite, an Al- and Mg-rich, trioctahedral 2:1 layer silicate, from a silicate gel at 60°C and ambient pressure. High-resolution transmission electron microscopy analysis of the saponite treated with octadecylammonium (n(C)=18) cations revealed the presence of 2:1 layer structures that have variable interlayer charge. The crystallization of these differently charged 2:1 layer silicates most likely occurred independently. The fact that 2:1 layer silicates with variable charge formed in the same gel has implications for our understanding of the origin of life, as these 2:1 clay minerals most likely replicate by a mechanism of template-catalyzed polymerization and transmit the charge distribution from layer to layer. If polar organic molecules like oxalate can catalyze the formation of clay-mineral crystals, which in turn promote clay microenvironments and provide abundant adsorption sites for other organic molecules present in solution, the interaction among these adsorbed molecules could lead to the polymerization of more complex organic molecules like RNA from nucleotides on early Earth.

Mechanochemical synthesis of N-salicylidene­aniline: thermosalient effect of polymorphic crystals

PubMed Central

Mittapalli, Sudhir; Sravanakumar Perumalla, D.

2017-01-01

Polymorphs of the dichloro derivative of N-salicylideneaniline exhibit mechanical responses such as jumping (Forms I and III) and exploding (Form II) in its three polymorphs. The molecules are connected via the amide N—H⋯O dimer synthon and C—Cl⋯O halogen bond in the three crystal structures. A fourth high-temperature Form IV was confirmed by variable-temperature single-crystal X-ray diffraction at 180°C. The behaviour of jumping exhibited by the polymorphic crystals of Forms I and III is due to the layered sheet morphology and the transmission of thermal stress in a single direction, compared with the corrugated sheet structure of Form II such that heat dissipation is more isotropic causing blasting. The role of weak C—Cl⋯O interactions in the thermal response of molecular crystals is discussed. PMID:28512571

Monomer structure of a hyperthermophilic β-glucosidase mutant forming a dodecameric structure in the crystal form

PubMed Central

Nakabayashi, Makoto; Kataoka, Misumi; Watanabe, Masahiro; Ishikawa, Kazuhiko

2014-01-01

One of the β-glucosidases from Pyrococcus furiosus (BGLPf) is found to be a hyperthermophilic tetrameric enzyme that can degrade cellooligosaccharides. Recently, the crystal structures of the tetrameric and dimeric forms were solved. Here, a new monomeric form of BGLPf was constructed by removing the C-terminal region of the enzyme and its crystal structure was solved at a resolution of 2.8 Å in space group P1. It was discovered that the mutant enzyme forms a unique dodecameric structure consisting of two hexameric rings in the asymmetric unit of the crystal. Under biological conditions, the mutant enzyme forms a monomer. This result helps explain how BGLPf has attained its oligomeric structure and thermostability. PMID:25005077

Morphology of diesel soot residuals from supercooled water droplets and ice crystals: Implications for optical properties

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

China, Swarup; Kulkarni, Gourihar; Scarnato, Barbara V.

Freshly emitted soot particles are fractal-like aggregates, but atmospheric processing often transforms their morphology. Morphology of soot particles plays an important role in determining their optical properties, life cycle and hence their effect on Earth’s radiative balance. However, little is known about the morphology of soot particles that participated in cold cloud processes. Here we report results from laboratory experiments that simulate cold cloud processing of diesel soot particles by allowing them to form supercooled droplets and ice crystals at -20 and -40°C, respectively. Electron microscopy revealed that soot residuals from ice crystals were more compact (roundness~0.55) than those frommore » supercooled droplets (roundness ~0.45), while nascent soot particles were the least compact (roundness~0.41). Optical simulations using the discrete dipole approximation showed that the more compact structure enhances soot single scattering albedo by a factor up to 1.4, thereby reducing the top-of-the-atmosphere direct radiative forcing by ~63%. Lastly, these results underscore that climate models should consider the morphological evolution of soot particles due to cold cloud processing to improve the estimate of direct radiative forcing of soot.« less

Morphology of diesel soot residuals from supercooled water droplets and ice crystals: Implications for optical properties

DOE PAGES

China, Swarup; Kulkarni, Gourihar; Scarnato, Barbara V.; ...

2015-11-01

Freshly emitted soot particles are fractal-like aggregates, but atmospheric processing often transforms their morphology. Morphology of soot particles plays an important role in determining their optical properties, life cycle and hence their effect on Earth’s radiative balance. However, little is known about the morphology of soot particles that participated in cold cloud processes. Here we report results from laboratory experiments that simulate cold cloud processing of diesel soot particles by allowing them to form supercooled droplets and ice crystals at -20 and -40°C, respectively. Electron microscopy revealed that soot residuals from ice crystals were more compact (roundness~0.55) than those frommore » supercooled droplets (roundness ~0.45), while nascent soot particles were the least compact (roundness~0.41). Optical simulations using the discrete dipole approximation showed that the more compact structure enhances soot single scattering albedo by a factor up to 1.4, thereby reducing the top-of-the-atmosphere direct radiative forcing by ~63%. Lastly, these results underscore that climate models should consider the morphological evolution of soot particles due to cold cloud processing to improve the estimate of direct radiative forcing of soot.« less

Two distinct crystallization processes in supercooled liquid

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

Tane, Masakazu, E-mail: mtane@sanken.osaka-u.ac.jp; Kimizuka, Hajime; Ichitsubo, Tetsu

2016-05-21

Using molecular dynamics simulations we show that two distinct crystallization processes, depending on the temperature at which crystallization occurs, appear in a supercooled liquid. As a model for glass-forming materials, an Al{sub 2}O{sub 3} model system, in which both the glass transition and crystallization from the supercooled liquid can be well reproduced, is employed. Simulations in the framework of an isothermal-isobaric ensemble indicate that the calculated time-temperature-transformation curve for the crystallization to γ(defect spinel)-Al{sub 2}O{sub 3} exhibited a typical nose shape, as experimentally observed in various glass materials. During annealing above the nose temperature, the structure of the supercooled liquidmore » does not change before the crystallization, because of the high atomic mobility (material transport). Thus, the crystallization is governed by the abrupt crystal nucleation, which results in the formation of a stable crystal structure. In contrast, during annealing below the nose temperature, the structure of the supercooled liquid gradually changes before the crystallization, and the formed crystal structure is less stable than that formed above the nose temperature, because of the restricted material transport.« less

Effect of supersaturation on L-glutamic acid polymorphs under droplet-based microchannels

NASA Astrophysics Data System (ADS)

Jiang, Nan; Wang, Zhanzhong; Dang, Leping; Wei, Hongyuan

2016-07-01

Supersaturation is an important controlling factor for crystallization process and polymorphism. Droplet-based microchannels and conventional crystallization were used to investigate polymorphs of L-gluatamic acid in this work. The results illustrate that it is easy to realize the accurate and rapid control of the crystallization temperature in the droplets, which is especially beneficial to heat and mass transfer during crystallization. It is also noted that higher degree of supersaturation favors the nucleation of α crystal form, while lower degree of supersaturation favors the nucleation of β crystal form under droplet-based microchannels for L-gluatamic acid. In addition, there is a different nucleation behavior to be found under droplet-based microchannels both for the β form and α form of L-glutamic acid. This new finding can provide important insight into the development and design of investigation meanings for drug polymorph.

Crystallization, X-ray diffraction analysis and SIRAS/molecular-replacenent phasing of three crystal forms of Anabaena sensory rhodopsin transducer

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

Vogeley, Lutz; Luecke, Hartmut, E-mail: hudel@uci.edu

2006-04-01

Crystals of Anabaena sensory rhodopsin transducer, the transducer for the cyanobacterial photosensor Anabaena sensory rhodopsin, obtained in the space groups P4, C2 and P2{sub 1}2{sub 1}2{sub 1} diffract to 1.8, 2.1 and 2.0 Å, respectively. Phases for these crystal forms were obtained by SIRAS phasing using an iodide quick-soak derivative (P4) and molecular replacement (C2 and P2{sub 1}2{sub 1}2{sub 1}). Anabaena sensory rhodopsin transducer (ASRT) is a 14.7 kDa soluble signaling protein associated with the membrane-embedded light receptor Anabaena sensory rhodopsin (ASR) from Anabaena sp., a freshwater cyanobacterium. Crystals of ASRT were obtained in three different space groups, P4, C2more » and P2{sub 1}2{sub 1}2{sub 1}, which diffract to 1.8, 2.1 and 2.0 Å, respectively. Phases for one of these crystal forms (P4) were obtained by SIRAS phasing using an iodide quick-soak derivative and a partial model was built. Phases for the remaining crystal forms were obtained by molecular replacement using the partial model from the P4 crystal form.« less

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.

Symmetrical polyhedra (simple crystal forms) as orbits of noncrystallographic point symmetry groups

NASA Astrophysics Data System (ADS)

Ovsetsina, T. I.; Chuprunov, E. V.

2017-09-01

Simple crystal forms are analyzed as the orbits of noncrystallographic point symmetry groups on a set of smooth or structured ("hatched") planes of crystal space. Polyhedra with symmetrically equivalent faces, obtained using noncrystallographic point symmetry groups, are considered. All possible versions of simple forms for all noncrystallographic groups are listed in a unified table.

The spatial coherence function in scanning transmission electron microscopy and spectroscopy.

PubMed

Nguyen, D T; Findlay, S D; Etheridge, J

2014-11-01

We investigate the implications of the form of the spatial coherence function, also referred to as the effective source distribution, for quantitative analysis in scanning transmission electron microscopy, and in particular for interpreting the spatial origin of imaging and spectroscopy signals. These questions are explored using three different source distribution models applied to a GaAs crystal case study. The shape of the effective source distribution was found to have a strong influence not only on the scanning transmission electron microscopy (STEM) image contrast, but also on the distribution of the scattered electron wavefield and hence on the spatial origin of the detected electron intensities. The implications this has for measuring structure, composition and bonding at atomic resolution via annular dark field, X-ray and electron energy loss STEM imaging are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Biogenic twinned crystals exhibiting unique morphological symmetry

NASA Astrophysics Data System (ADS)

Hirsch, Anna; Gur, Dvir; Palmer, Ben; Addadi, Lia; Leiserowitz, Leslie; Kronik, Leeor

Guanine crystals are widely used in nature as components of multilayer reflectors. Organisms control the size, morphology, and arrangement of these crystals, to obtain a variety of optical ''devices''. The reflection systems found in the lens of the scallop eye and in the copepod cuticle are unique in that the multilayered reflectors are tiled together to form a contiguous packed array. In the former, square crystals are tiled to form a reflecting mirror. In the latter, hexagonal crystals are closely packed to produce brilliant colors. Based on electron diffraction, morphology considerations, and density functional theory, these crystals were shown to possess similar monoclinic crystal symmetry, which we have previously identified as different from that of synthetic anhydrous guanine. However, the crystals are different in that multiple twinning about the {012} and the {011} crystallographic planes results in square and hexagonal morphology, respectively. This is a unique example where controlled twinning is used as a strategy to form a morphology with higher symmetry than that of the underlying crystal, allowing for tilling that facilitates optical functionality.

Real-time molecular scale observation of crystal formation.

PubMed

Schreiber, Roy E; Houben, Lothar; Wolf, Sharon G; Leitus, Gregory; Lang, Zhong-Ling; Carbó, Jorge J; Poblet, Josep M; Neumann, Ronny

2017-04-01

How molecules in solution form crystal nuclei, which then grow into large crystals, is a poorly understood phenomenon. The classical mechanism of homogeneous crystal nucleation proceeds via the spontaneous random aggregation of species from liquid or solution. However, a non-classical mechanism suggests the formation of an amorphous dense phase that reorders to form stable crystal nuclei. So far it has remained an experimental challenge to observe the formation of crystal nuclei from five to thirty molecules. Here, using polyoxometallates, we show that the formation of small crystal nuclei is observable by cryogenic transmission electron microscopy. We observe both classical and non-classical nucleation processes, depending on the identity of the cation present. The experiments verify theoretical studies that suggest non-classical nucleation is the lower of the two energy pathways. The arrangement in just a seven-molecule proto-crystal matches the order found by X-ray diffraction of a single bulk crystal, which demonstrates that the same structure was formed in each case.

Growth of silicon carbide crystals on a seed while pulling silicon crystals from a melt

NASA Technical Reports Server (NTRS)

Ciszek, T. F.; Schwuttke, G. H. (Inventor)

1979-01-01

A saturated solution of silicon and an element such as carbon having a segregation coefficient less than unity is formed by placing a solid piece of carbon in a body of molten silicon having a temperature differential decreasing toward the surface. A silicon carbide seed crystal is disposed on a holder beneath the surface of the molten silicon. As a rod or ribbon of silicon is slowly pulled from the melt, a supersaturated solution of carbon in silicon is formed in the vicinity of the seed crystal. Excess carbon is emitted from the solution in the form of silicon carbide which crystallizes on the seed crystal held in the cool region of the melt.

Morphology and solubility of multiple crystal forms of Taka-amylase A

NASA Astrophysics Data System (ADS)

Ninomiya, Kumiko; Yamamoto, Tenyu; Oheda, Tadashi; Sato, Kiyotaka; Sazaki, Gen; Matsuura, Yoshiki

2001-01-01

An α-amylase originating from a mold Aspergillus oryzae, Taka-amylase A (Mr of 52 kDa, pI of 3.8), has been purified to an electrophoretically single band grade. Crystallization behaviors were investigated using ammonium sulfate and polyethleneglycol 8000 as precipitants. The variations in the morphology of the crystals obtained with changing crystallization parameters are described. Five apparently different crystal forms were obtained, and their morphology and crystallographic data have been determined. Solubility values of four typical forms were measured using a Michelson-type two-beam interferometer. The results of these experiments showed that this protein can be a potentially interesting and useful model for crystal growth study with a gram-amount availability of pure protein sample.

Shaped nanocrystal particles and methods for making the same

DOEpatents

Alivisatos, A Paul [Oakland, CA; Scher, Erik C [Menlo Park, CA; Manna, Liberato [Berkeley, CA

2011-11-22

Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

Shaped nanocrystal particles and methods for making the same

DOEpatents

Alivisatos, A. Paul; Scher, Erik C; Manna, Liberato

2013-12-17

Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

Shaped nanocrystal particles and methods for working the same

DOEpatents

Alivisatos, A. Paul; Sher, Eric C.; Manna, Liberato

2007-12-25

Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

Shaped Nonocrystal Particles And Methods For Making The Same

DOEpatents

Alivisatos, A. Paul; Scher, Erik C.; Manna, Liberato

2005-02-15

Shaped nanocrystal particles and methods for making shaped nanocrystal particles are disclosed. One embodiment includes a method for forming a branched, nanocrystal particle. It includes (a) forming a core having a first crystal structure in a solution, (b) forming a first arm extending from the core having a second crystal structure in the solution, and (c) forming a second arm extending from the core having the second crystal structure in the solution.

Self-powdering and nonlinear optical domain structures in ferroelastic beta'-Gd{sub 2}(MoO{sub 4}){sub 3} crystals formed in glass

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

Tsukada, Y.; Honma, T.; Komatsu, T., E-mail: komatsu@mst.nagaokaut.ac.j

Ferroelastic beta'-Gd{sub 2}(MoO{sub 4}){sub 3}, (GMO), crystals are formed through the crystallization of 21.25Gd{sub 2}O{sub 3}-63.75MoO{sub 3}-15B{sub 2}O{sub 3} glass (mol%), and two scientific curious phenomena are observed. (1) GMO crystals formed in the crystallization break into small pieces with a triangular prism or pyramid shape having a length of 50-500 {mu}m spontaneously during the crystallizations in the inside of an electric furnace, not during the cooling in air after the crystallization. This phenomenon is called 'self-powdering phenomenon during crystallization' in this paper. (2) Each self-powdered GMO crystal grain shows a periodic domain structure with different refractive indices, and amore » spatially periodic second harmonic generation (SHG) depending on the domain structure is observed. It is proposed from polarized micro-Raman scattering spectra and the azimuthal dependence of second harmonic intensities that GMO crystals are oriented in each crystal grain and the orientation of (MoO{sub 4}){sup 2-} tetrahedra in GMO crystals changes periodically due to spontaneous strains in ferroelastic GMO crystals. - Graphical abstract: This figure shows the polarized optical photograph at room temperature for a particle (piece) obtained by a heat treatment of the glass at 590 deg. C for 2 h in an electric furnace in air. This particle was obtained through the self-powdering behavior in the crystallization of glass. The periodic domain structure is observed. Ferroelastic beta'-Gd{sub 2}(MoO{sub 4}){sub 3} crystals are formed in the particle, and second harmonic generations are detected, depending on the domain structure.« less

Crystallization and preliminary crystallographic analysis of an aminoglycoside kinase from Legionella pneumophila

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

Lemke, Christopher T.; Hwang, Jiyoung; Xiong, Bing

2005-06-01

Two crystal forms of the antibiotic resistance enzyme APH(9)-Ia from L. pneumophila are reported. 9-Aminoglycoside phosphotransferase type Ia [APH(9)-Ia] is a resistance factor in Legionella pneuemophila, the causative agent of legionnaires’ disease. It is responsible for providing intrinsic resistance to the antibiotic spectinomycin. APH(9)-Ia phosphorylates one of the hydroxyl moieties of spectinomycin in an ATP-dependent manner, abolishing the antibiotic properties of this drug. Here, the crystallization and preliminary X-ray studies of this enzyme in two crystal forms is reported. One of the these crystal forms provides diffraction data to a resolution of 1.7 Å.

Reactions of atomic oxygen with the chlorate ion and the perchlorate ion

NASA Astrophysics Data System (ADS)

Anan'ev, Vladimir; Miklin, Mikhail; Kriger, Ludmila

2014-06-01

The reactions of the chlorate ion with atomic oxygen formed under photolysis of the nitrate ion introduced to potassium chlorate crystal by co-crystallization were studied by optical and infrared absorption spectroscopy. The perchlorate ion was found to form in solids as product of addition reaction of singlet atomic oxygen, formed under dissociation of the peroxynitrite ion - the product of isomerization of the excited nitrate ion. Triplet atomic oxygen does not react with the chlorate ion. The atomic oxygen formed under photolysis of the nitrate ion introduced to potassium perchlorate crystal by co-crystallization does not react with the perchlorate ion.

The use of trimethylamine N-oxide as a primary precipitating agent and related methylamine osmolytes as cryoprotective agents for macromolecular crystallography

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

Marshall, Haley; Venkat, Murugappan; Hti Lar Seng, Nang San

2012-01-01

The stabilizing osmolyte trimethylamine N-oxide (TMAO) is shown to be an efficient primary precipitant for protein crystal growth. In addition to TMAO, two other methylamine osmolytes, sarcosine and betaine, are shown to be effective cryoprotective agents for protein crystal cooling. Both crystallization and cryoprotection are often bottlenecks for high-resolution X-ray structure determination of macromolecules. Methylamine osmolytes are known stabilizers of protein structure. One such osmolyte, trimethylamine N-oxide (TMAO), has seen occasional use as an additive to improve macromolecular crystal quality and has recently been shown to be an effective cryoprotective agent for low-temperature data collection. Here, TMAO and the relatedmore » osmolytes sarcosine and betaine are investigated as primary precipitating agents for protein crystal growth. Crystallization experiments were undertaken with 14 proteins. Using TMAO, seven proteins crystallized in a total of 13 crystal forms, including a new tetragonal crystal form of trypsin. The crystals diffracted well, and eight of the 13 crystal forms could be effectively cryocooled as grown with TMAO as an in situ cryoprotective agent. Sarcosine and betaine produced crystals of four and two of the 14 proteins, respectively. In addition to TMAO, sarcosine and betaine were effective post-crystallization cryoprotective agents for two different crystal forms of thermolysin. Precipitation reactions of TMAO with several transition-metal ions (Fe{sup 3+}, Co{sup 2+}, Cu{sup 2+} and Zn{sup 2+}) did not occur with sarcosine or betaine and were inhibited for TMAO at lower pH. Structures of proteins from TMAO-grown crystals and from crystals soaked in TMAO, sarcosine or betaine were determined, showing osmolyte binding in five of the 12 crystals tested. When an osmolyte was shown to bind, it did so near the protein surface, interacting with water molecules, side chains and backbone atoms, often at crystal contacts.« less

A flow-free droplet-based device for high throughput polymorphic crystallization.

PubMed

Yang, Shih-Mo; Zhang, Dapeng; Chen, Wang; Chen, Shih-Chi

2015-06-21

Crystallization is one of the most crucial steps in the process of pharmaceutical formulation. In recent years, emulsion-based platforms have been developed and broadly adopted to generate high quality products. However, these conventional approaches such as stirring are still limited in several aspects, e.g., unstable crystallization conditions and broad size distribution; besides, only simple crystal forms can be produced. In this paper, we present a new flow-free droplet-based formation process for producing highly controlled crystallization with two examples: (1) NaCl crystallization reveals the ability to package saturated solution into nanoliter droplets, and (2) glycine crystallization demonstrates the ability to produce polymorphic crystallization forms by controlling the droplet size and temperature. In our process, the saturated solution automatically fills the microwell array powered by degassed bulk PDMS. A critical oil covering step is then introduced to isolate the saturated solution and control the water dissolution rate. Utilizing surface tension, the solution is uniformly packaged in the form of thousands of isolating droplets at the bottom of each microwell of 50-300 μm diameter. After water dissolution, individual crystal structures are automatically formed inside the microwell array. This approach facilitates the study of different glycine growth processes: α-form generated inside the droplets and γ-form generated at the edge of the droplets. With precise temperature control over nanoliter-sized droplets, the growth of ellipsoidal crystalline agglomerates of glycine was achieved for the first time. Optical and SEM images illustrate that the ellipsoidal agglomerates consist of 2-5 μm glycine clusters with inner spiral structures of ~35 μm screw pitch. Lastly, the size distribution of spherical crystalline agglomerates (SAs) produced from microwells of different sizes was measured to have a coefficient variation (CV) of less than 5%, showing crystal sizes can be precisely controlled by microwell sizes with high uniformity. This new method can be used to reliably fabricate monodispersed crystals for pharmaceutical applications.

Solvent effects on the crystal growth structure and morphology of the pharmaceutical dirithromycin

NASA Astrophysics Data System (ADS)

Wang, Yuan; Liang, Zuozhong

2017-12-01

Solvent effects on the crystal structure and morphology of pharmaceutical dirithromycin molecules were systematically investigated using both experimental crystallization and theoretical simulation. Dirithromycin is one of the new generation of macrolide antibiotics with two polymorphic forms (Form I and Form II) and many solvate forms. Herein, six solvates of the dirithromycin, including acetonitrile, acetonitrile/water, acetone, 1-propanol, N,N-dimethylformamide (DMF) and cyclohexane, were studied. Experimentally, we crystallized the dirithromycin molecules in different solvents by the solvent evaporating method and measured the crystal structures with the X-ray diffraction (XRD). We compared these crystal structures of dirithromycin solvates and analyzed the solvent property-determined structure evolution. The solvents have a strong interaction with the dirithromycin molecule due to the formation of inter-molecular interactions (such as the hydrogen bonding and close contacts (sum of vdW radii)). Theoretically, we calculated the ideal crystal habit based on the solvated structures with the attachment growth (AE) model. The predicted morphologies and aspect ratios of dirithromycin solvates agree well with the experimental results. This work could be helpful to better understand the structure and morphology evolution of solvates controlled by solvents and guide the crystallization of active pharmaceutical ingredients in the pharmaceutical industry.

Polymorphism of Alprazolam (Xanax): a review of its crystalline phases and identification, crystallographic characterization, and crystal structure of a new polymorph (form III).

PubMed

de Armas, Héctor Novoa; Peeters, Oswald M; Van den Mooter, Guy; Blaton, Norbert

2007-05-01

A new polymorphic form of Alprazolam (Xanax), 8-chloro-1-methyl-6-phenyl-4H-[1,2,4]triazolo-[4,3-alpha][1,4]benzodiazepine, C(17)H(13)ClN(4), has been investigated by means of X-ray powder diffraction (XRPD), single crystal X-ray diffraction, and differential scanning calorimetry (DSC). This polymorphic form (form III) was obtained during DSC experiments after the exothermic recrystallization of the melt of form I. The crystal unit cell dimensions for form III were determined from diffractometer methods. The monoclinic unit cell found for this polymorph using XRPD after indexing the powder diffractogram was confirmed by the cell parameters obtained from single crystal X-ray diffractometry on a crystal isolated from the DSC pans. The single crystal unit cell parameters are: a = 28.929(9), b = 13.844(8), c = 7.361(3) angstroms, beta = 92.82(3) degrees , V = 2944(2) angstroms(3), Z = 8, space group P2(1) (No.4), Dx = 1.393 Mg/m(3). The structure obtained from single crystal X-ray diffraction was used as initial model for Rietveld refinement on the powder diffraction data of form III. The temperature phase transformations of alprazolam were also studied using high temperature XRPD. A review of the different phases available in the Powder Diffraction File (PDF) database for this drug is described bringing some clarification and corrections. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association.

Crystal-contact engineering to obtain a crystal form of the Kelch domain of human Keap1 suitable for ligand-soaking experiments.

PubMed

Hörer, Stefan; Reinert, Dirk; Ostmann, Katja; Hoevels, Yvette; Nar, Herbert

2013-06-01

Keap1 is a substrate adaptor protein for a Cul3-dependent ubiquitin ligase complex and plays an important role in the cellular response to oxidative stress. It binds Nrf2 with its Kelch domain and thus triggers the ubiquitinylation and degradation of Nrf2. Oxidative stress prevents the degradation of Nrf2 and leads to the activation of cytoprotective genes. Therefore, Keap1 is an attractive drug target in inflammatory diseases. The support of a medicinal chemistry effort by structural research requires a robust crystallization system in which the crystals are preferably suited for performing soaking experiments. This facilitates the generation of protein-ligand complexes in a routine and high-throughput manner. The structure of human Keap1 has been described previously. In this crystal form, however, the binding site for Nrf2 was blocked by a crystal contact. This interaction was analysed and mutations were introduced to disrupt this crystal contact. One double mutation (E540A/E542A) crystallized in a new crystal form in which the binding site for Nrf2 was not blocked and was accessible to small-molecule ligands. The crystal structures of the apo form of the mutated Keap1 Kelch domain (1.98 Å resolution) and of the complex with an Nrf2-derived peptide obtained by soaking (2.20 Å resolution) are reported.

Suppressed Release of Clarithromycin from Tablets by Crystalline Phase Transition of Metastable Polymorph Form I.

PubMed

Fujiki, Sadahiro; Watanabe, Narumi; Iwao, Yasunori; Noguchi, Shuji; Mizoguchi, Midori; Iwamura, Takeru; Itai, Shigeru

2015-08-01

The pharmaceutical properties of clarithromycin (CAM) tablets containing the metastable form I of crystalline CAM were investigated. Although the dissolution rate of form I was higher than that of stable form II, the release of CAM from form I tablet was delayed. Disintegration test and liquid penetration test showed that the disintegration of the tablet delayed because of the slow penetration of an external solution into form I tablet. Investigation by scanning electron microscopy revealed that the surface of form I tablet was covered with fine needle-shaped crystals following an exposure to the external solution. These crystals were identified as form IV crystals by powder X-ray diffraction. The phenomenon that CAM releases from tablet was inhibited by fine crystals spontaneously formed on the tablet surface could be applied to the design of sustained-release formulation systems with high CAM contents by minimizing the amount of functional excipients. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

Observation of interstitial molecular hydrogen in clathrate hydrates.

PubMed

Grim, R Gary; Barnes, Brian C; Lafond, Patrick G; Kockelmann, Winfred A; Keen, David A; Soper, Alan K; Hiratsuka, Masaki; Yasuoka, Kenji; Koh, Carolyn A; Sum, Amadeu K

2014-09-26

The current knowledge and description of guest molecules within clathrate hydrates only accounts for occupancy within regular polyhedral water cages. Experimental measurements and simulations, examining the tert-butylamine + H2 + H2O hydrate system, now suggest that H2 can also be incorporated within hydrate crystal structures by occupying interstitial sites, that is, locations other than the interior of regular polyhedral water cages. Specifically, H2 is found within the shared heptagonal faces of the large (4(3)5(9)6(2)7(3)) cage and in cavities formed from the disruption of smaller (4(4)5(4)) water cages. The ability of H2 to occupy these interstitial sites and fluctuate position in the crystal lattice demonstrates the dynamic behavior of H2 in solids and reveals new insight into guest-guest and guest-host interactions in clathrate hydrates, with potential implications in increasing overall energy storage properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ring-shaped architecture of RecR: implications for its role in homologous recombinational DNA repair

PubMed Central

Lee, Byung Il; Kim, Kyoung Hoon; Park, Soo Jeong; Eom, Soo Hyun; Song, Hyun Kyu; Suh, Se Won

2004-01-01

RecR, together with RecF and RecO, facilitates RecA loading in the RecF pathway of homologous recombinational DNA repair in procaryotes . The human Rad52 protein is a functional counterpart of RecFOR. We present here the crystal structure of RecR from Deinococcus radiodurans (DR RecR). A monomer of DR RecR has a two-domain structure: the N-terminal domain with a helix–hairpin–helix (HhH) motif and the C-terminal domain with a Cys4 zinc-finger motif, a Toprim domain and a Walker B motif. Four such monomers form a ring-shaped tetramer of 222 symmetry with a central hole of 30−35 Å diameter. In the crystal, two tetramers are concatenated, implying that the RecR tetramer is capable of opening and closing. We also show that DR RecR binds to both dsDNA and ssDNA, and that its HhH motif is essential for DNA binding. PMID:15116069

NPAS1-ARNT and NPAS3-ARNT crystal structures implicate the bHLH-PAS family as multi-ligand binding transcription factors

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

Wu, Dalei; Su, Xiaoyu; Potluri, Nalini

Here, the neuronal PAS domain proteins NPAS1 and NPAS3 are members of the basic helix-loop-helix-PER-ARNT-SIM (bHLH-PAS) family, and their genetic deficiencies are linked to a variety of human psychiatric disorders including schizophrenia, autism spectrum disorders and bipolar disease. NPAS1 and NPAS3 must each heterodimerize with the aryl hydrocarbon receptor nuclear translocator (ARNT), to form functional transcription complexes capable of DNA binding and gene regulation. Here we examined the crystal structures of multi-domain NPAS1-ARNT and NPAS3-ARNT-DNA complexes, discovering each to contain four putative ligand-binding pockets. Through expanded architectural comparisons between these complexes and HIF-1α-ARNT, HIF-2α-ARNT and CLOCK-BMAL1, we show the widermore » mammalian bHLH-PAS family is capable of multi-ligand-binding and presents as an ideal class of transcription factors for direct targeting by small-molecule drugs.« less

NPAS1-ARNT and NPAS3-ARNT crystal structures implicate the bHLH-PAS family as multi-ligand binding transcription factors

DOE PAGES

Wu, Dalei; Su, Xiaoyu; Potluri, Nalini; ...

2016-10-26

Here, the neuronal PAS domain proteins NPAS1 and NPAS3 are members of the basic helix-loop-helix-PER-ARNT-SIM (bHLH-PAS) family, and their genetic deficiencies are linked to a variety of human psychiatric disorders including schizophrenia, autism spectrum disorders and bipolar disease. NPAS1 and NPAS3 must each heterodimerize with the aryl hydrocarbon receptor nuclear translocator (ARNT), to form functional transcription complexes capable of DNA binding and gene regulation. Here we examined the crystal structures of multi-domain NPAS1-ARNT and NPAS3-ARNT-DNA complexes, discovering each to contain four putative ligand-binding pockets. Through expanded architectural comparisons between these complexes and HIF-1α-ARNT, HIF-2α-ARNT and CLOCK-BMAL1, we show the widermore » mammalian bHLH-PAS family is capable of multi-ligand-binding and presents as an ideal class of transcription factors for direct targeting by small-molecule drugs.« less

Structural insight into arginine methylation by the mouse protein arginine methyltransferase 7: a zinc finger freezes the mimic of the dimeric state into a single active site.

PubMed

Cura, Vincent; Troffer-Charlier, Nathalie; Wurtz, Jean Marie; Bonnefond, Luc; Cavarelli, Jean

2014-09-01

Protein arginine methyltransferase 7 (PRMT7) is a type III arginine methyltransferase which has been implicated in several biological processes such as transcriptional regulation, DNA damage repair, RNA splicing, cell differentiation and metastasis. PRMT7 is a unique but less characterized member of the family of PRMTs. The crystal structure of full-length PRMT7 from Mus musculus refined at 1.7 Å resolution is described. The PRMT7 structure is composed of two catalytic modules in tandem forming a pseudo-dimer and contains only one AdoHcy molecule bound to the N-terminal module. The high-resolution crystal structure presented here revealed several structural features showing that the second active site is frozen in an inactive state by a conserved zinc finger located at the junction between the two PRMT modules and by the collapse of two degenerated AdoMet-binding loops.

Crystal water as the mol-ecular glue for obtaining different co-crystal ratios: the case of gallic acid tris-caffeine hexa-hydrate.

PubMed

Vella-Zarb, L; Baisch, U

2018-04-01

The crystal structure of the hexa-hydrate co-crystal of gallic acid and caffeine, C 7 H 6 O 5 ·3C 8 H 10 N 4 O 2 ·6H 2 O or GAL3CAF·6H 2 O , is a remarkable example of the importance of hydrate water acting as structural glue to facilitate the crystallization of two components of different stoichiometries and thus to compensate an imbalance of hydrogen-bond donors and acceptors. The water mol-ecules provide the additional hydrogen bonds required to form a crystalline solid. Whereas the majority of hydrogen bonds forming the inter-molecular network between gallic acid and caffeine are formed by crystal water, only one direct classical hydrogen bond between two mol-ecules is formed between the carb-oxy-lic oxygen of gallic acid and the carbonyl oxygen of caffeine with d ( D ⋯ A ) = 2.672 (2) Å. All other hydrogen bonds either involve crystal water or utilize protonated carbon atoms as donors.

Crystallization and preliminary X-ray analysis of a protease inhibitor from the latex of Carica papaya

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

Azarkan, Mohamed; Garcia-Pino, Abel; Dibiani, Rachid

2006-12-01

The Kunitz-type trypsin/chymotrypsin inhibitor isolated from C. papaya latex has been crystallized using the hanging-drop vapour-diffusion method. Two different crystal forms are observed, diffracting to 2.6 and 1.7 Å. A Kunitz-type protease inhibitor purified from the latex of green papaya (Carica papaya) fruits was crystallized in the presence and absence of divalent metal ions. Crystal form I, which is devoid of divalent cations, diffracts to a resolution of 2.6 Å and belongs to space group P3{sub 1} or P3{sub 2}. This crystal form is a merohedral twin with two molecules in the asymmetric unit and unit-cell parameters a = bmore » = 74.70, c = 78.97 Å. Crystal form II, which was grown in the presence of Co{sup 2+}, diffracts to a resolution of 1.7 Å and belongs to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 44.26, b = 81.99, c = 140.89 Å.« less

Metabolic activity of microorganisms in evaporites

NASA Technical Reports Server (NTRS)

Rothschild, L. J.; Giver, L. J.; White, M. R.; Mancinelli, R. L.

1994-01-01

Crystalline salt is generally considered so hostile to most forms of life that it has been used for centuries as a preservative. Here, we present evidence that prokaryotes inhabiting a natural evaporite crust of halite and gypsum are metabolically active while inside the evaporite for at least 10 months. In situ measurements demonstrated that some of these "endoevaporitic" microorganisms (probably the cyanobacterium Synechococcus Nageli) fixed carbon and nitrogen. Denitrification was not observed. Our results quantified the slow microbial activity that can occur in salt crystals. Implications of this study include the possibility that microorganisms found in ancient evaporite deposits may have been part of an evaporite community.

Cutin and suberin monomers are membrane perturbants.

PubMed

Douliez, Jean-Paul

2004-03-15

The interaction between cutin and suberin monomers, i.e., omega -hydroxylpalmitic acid, alpha, omega -hexadecanedioic acid, alpha, omega --hexadecanediol, 12-hydroxylstearic acid, and phospholipid vesicles biomimicking the lipid structure of plant cell membranes has been studied by optical and transmission electron microscopy, quasielastic light scattering, differential scanning calorimetry, and (31)P solid-state NMR. Monomers were shown to penetrate model membranes until a molar ratio of 30%, modulating their gel to fluid-phase transition, after which monomer crystals also formed in solution. These monomers induced a decrease of the phospholipid vesicle size from several micrometers to about 300 nm. The biological implications of these findings are discussed.

Structure of deformed silicon and implications for low cost solar cells

NASA Technical Reports Server (NTRS)

Mardesich, N.; Leipold, M. H.; Turner, G. B.; Digges, T. G., Jr.

1978-01-01

The microstructure and minority carrier lifetime of silicon were investigated in uniaxially compressed silicon samples. The objective of the investigation was to determine if it is feasible to produce silicon solar cells from sheet formed by high temperature rolling. The initial structure of the silicon samples ranged from single crystal to fine-grained polycrystals. The samples had been deformed at strain rates of 0.1 to 8.5/sec and temperatures of 1270-1380 C with subsequent annealing at 1270-1380 C. The results suggest that high temperature rolling of silicon to produce sheet for cells of high efficiency is not practical.

Effect of method of crystallization on the IV-III and IV-II polymorphic transitions of ammonium nitrate.

PubMed

Vargeese, Anuj A; Joshi, Satyawati S; Krishnamurthy, V N

2009-01-15

A study has been undertaken on the effect of crystallization method on the IV<-->III transition of ammonium nitrate (AN). AN is crystallized in three different ways, viz. recrystallization, evaporative crystallization and melt crystallization. When the samples were crystallized from saturated aqueous solution, ideal crystals were formed, which behaved differently from the crystals formed from the other methods. The DTA examination of the crystals showed that the crystals have different transition behaviour. The moisture uptake of the samples determined were found to have influenced by the mode of crystallization. The samples were further analyzed by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The present study showed that the parameters like thermal history, number of previous transformations and moisture content have a very negligible influence on the IV<-->III transition of AN as compared to the method of crystallization.

Comparative analysis of anti-polyglutamine Fab crystals grown on Earth and in microgravity.

PubMed

Owens, Gwen E; New, Danielle M; Olvera, Alejandra I; Manzella, Julia Ashlyn; Macon, Brittney L; Dunn, Joshua C; Cooper, David A; Rouleau, Robyn L; Connor, Daniel S; Bjorkman, Pamela J

2016-10-01

Huntington's disease is one of nine neurodegenerative diseases caused by a polyglutamine (polyQ)-repeat expansion. An anti-polyQ antigen-binding fragment, MW1 Fab, was crystallized both on Earth and on the International Space Station, a microgravity environment where convection is limited. Once the crystals returned to Earth, the number, size and morphology of all crystals were recorded, and X-ray data were collected from representative crystals. The results generally agreed with previous microgravity crystallization studies. On average, microgravity-grown crystals were 20% larger than control crystals grown on Earth, and microgravity-grown crystals had a slightly improved mosaicity (decreased by 0.03°) and diffraction resolution (decreased by 0.2 Å) compared with control crystals grown on Earth. However, the highest resolution and lowest mosaicity crystals were formed on Earth, and the highest-quality crystal overall was formed on Earth after return from microgravity.

Comparative analysis of anti-polyglutamine Fab crystals grown on Earth and in microgravity

PubMed Central

Owens, Gwen E.; New, Danielle M.; Olvera, Alejandra I.; Manzella, Julia Ashlyn; Macon, Brittney L.; Dunn, Joshua C.; Cooper, David A.; Rouleau, Robyn L.; Connor, Daniel S.; Bjorkman, Pamela J.

2016-01-01

Huntington’s disease is one of nine neurodegenerative diseases caused by a polyglutamine (polyQ)-repeat expansion. An anti-polyQ antigen-binding fragment, MW1 Fab, was crystallized both on Earth and on the International Space Station, a microgravity environment where convection is limited. Once the crystals returned to Earth, the number, size and morphology of all crystals were recorded, and X-ray data were collected from representative crystals. The results generally agreed with previous microgravity crystallization studies. On average, microgravity-grown crystals were 20% larger than control crystals grown on Earth, and microgravity-grown crystals had a slightly improved mosaicity (decreased by 0.03°) and diffraction resolution (decreased by 0.2 Å) compared with control crystals grown on Earth. However, the highest resolution and lowest mosaicity crystals were formed on Earth, and the highest-quality crystal overall was formed on Earth after return from microgravity. PMID:27710941

Three-dimensional crystals of ribosomes and their subunits from eu- and archaebacteria.

PubMed

Glotz, C; Müssig, J; Gewitz, H S; Makowski, I; Arad, T; Yonath, A; Wittmann, H G

1987-11-01

Ordered three-dimensional crystals of 70S ribosomes as well as of 30S and 50S ribosomal subunits from various bacteria (E. coli, Bacillus stearothermophilus, Thermus thermophilus and Halobacterium marismortui) have been grown by vapour diffusion in hanging drops using mono- and polyalcohols. A new compact crystal form of 50S subunits has been obtained, and it is suitable for crystallographic studies at medium resolution. In addition, from one crystal form large crystals could be grown in X-ray capillaries. In all cases the crystals were obtained from functionally active ribosomal particles, and the particles from dissolved crystals retained their integrity and biological activity.

Correlative microscopy of the constituents of a dinosaur rib fossil and hosting mudstone: Implications on diagenesis and fossil preservation.

PubMed

Kim, Jung-Kyun; Kwon, Yong-Eun; Lee, Sang-Gil; Kim, Chang-Yeon; Kim, Jin-Gyu; Huh, Min; Lee, Eunji; Kim, Youn-Joong

2017-01-01

We have applied correlative microscopy to identify the key constituents of a dorsal rib fossil from Koreanosaurus boseongensis and its hosting mudstone discovered at the rich fossil site in Boseong, South Korea, to investigate the factors that likely contributed to diagenesis and the preservation of fossil bone. Calcite and illite were the commonly occurring phases in the rib bone, hosting mudstone, and the boundary region in-between. The boundary region may have contributed to bone preservation once it fully formed by acting as a protective shell. Fluorapatite crystals in the rib bone matrix signified diagenetic alteration of the original bioapatite crystals. While calcite predominantly occupied vascular channels and cracks, platy illite crystals widely occupied miniscule pores throughout the bone matrix. Thorough transmission electron microscopy (TEM) study of illite within the bone matrix indicated the solid-state transformation of 1M to 2M without composition change, which was more evident from the lateral variation of 1M to 2M within the same layer. The high level of lattice disordering of 2M illite suggested an early stage of 1M to 2M transformation. Thus, the diagenetic alteration of both apatite and illite crystals within the bone matrix may have increased its overall density, as the preferred orientation of apatite crystals from moderate to strong degrees was evident despite the poor preservation of osteohistological features. The combined effects of rapid burial, formation of a boundary region, and diagenesis of illite and apatite within the bone matrix may have contributed to the rib bone preservation.

Quartz crystal microbalance (QCM) with immobilized protein receptors: comparison of response to ligand binding for direct protein immobilization and protein attachment via disulfide linker.

PubMed

Baltus, Ruth E; Carmon, Kendra S; Luck, Linda A

2007-03-27

Results from an investigation of the frequency response resulting from ligand binding for a genetically engineered hormone-binding domain of the alpha-estrogen receptor immobilized to a piezoelectric quartz crystal are reported. Two different approaches were used to attach a genetically altered receptor to the gold electrode on the quartz surface: (1) the mutant receptor containing a single solvent-exposed cysteine was directly attached to the crystal via a sulfur to gold covalent bond, forming a self-assembled protein monolayer, and (2) the N-terminal histidine-tagged end was utilized to attach the receptor via a 3,3-dithiobis[N-(5-amino-5-carboxypentyl)propionamide-N',N'-diacetic acid] linker complexed with nickel. Previous studies have shown that these engineered constructs bind 17beta-estradiol and are fully functional. Exposure of the receptor directly attached to the piezoelectric crystal to the known ligand 17beta-estradiol resulted in a measurable frequency response, consistent with a change in conformation of the receptor with ligand binding. However, no response was observed when the receptor immobilized via the linker was exposed to the same ligand. The presence of the linker between the quartz surface and the protein receptor does not allow the crystal to sense the conformational change in the receptor that occurs with ligand binding. These results illustrate that the immobilization strategy used to bind the receptor to the sensor platform is key to eliciting an appropriate response from this biosensor. This study has important implications for the development of QCM-based sensors using protein receptors.

Crystallization from microemulsions ? a novel method for the preparation of new crystal forms of aspartame

NASA Astrophysics Data System (ADS)

Füredi-Milhofer, Helga; Garti, N.; Kamyshny, A.

1999-03-01

Solubilization and crystallization of the artificial sweetener aspartame (APM), in water/isooctane microemulsions stabilized with sodium diisooctyl sulfosuccinate (AOT) has been investigated. The amount of aspartame that could be solubilized depended primarily on the amount of surfactant and on the temperature. The maximum AOT/aspartame molar ratio at the w/o interface is shown to be 6.2 at 25°C. It was concluded that the dipeptide is located at the w/o interface interspersed between surfactant molecules and that it acts as a cosurfactant. A new crystal form, APM III, was obtained by cooling of hot w/isooctane/AOT microemulsions containing solubilized aspartame. The new crystal form exhibits a distinct X-ray diffraction powder pattern, as well as changes in the FTIR spectra, thermogravimetric and DSC patterns. H-NMR spectra of APM III dissolved in D 2O were identical to the spectrum of commercial aspartame recorded under the same conditions. The new crystal form has greatly improved dissolution kinetics.

Location of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg white lysozyme from salt solutions. Previous studies employing X-ray crystallography had found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystal grown in bromide and chloride solutions. Five possible anion binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four of these sites corresponded to four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion binding sites in lysozyme remain unchanged, even when different anions and different crystal forms of lysozyme are employed.

Locations of Bromide Ions in Tetragonal Lysozyme Crystals

NASA Technical Reports Server (NTRS)

Lim, Kap; Nadarajah, Arunan; Forsythe, Elizabeth L.; Pusey, Marc L.

1998-01-01

Anions have been shown to play a dominant role in the crystallization of chicken egg-white lysozyme from salt solutions. Previous studies employing X-ray crystallography have found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystals grown in bromide and chloride solutions. Five possible anion-binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four further sites were found which corresponded to the four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion-binding sites in lysozyme remain unchanged even when different anions and different crystal forms of lysozyme are employed.

Process for Forming a High Temperature Single Crystal Canted Spring

NASA Technical Reports Server (NTRS)

DeMange, Jeffrey J (Inventor); Ritzert, Frank J (Inventor); Nathal, Michael V (Inventor); Dunlap, Patrick H (Inventor); Steinetz, Bruce M (Inventor)

2017-01-01

A process for forming a high temperature single crystal canted spring is provided. In one embodiment, the process includes fabricating configurations of a rapid prototype spring to fabricate a sacrificial mold pattern to create a ceramic mold and casting a canted coiled spring to form at least one canted coil spring configuration based on the ceramic mold. The high temperature single crystal canted spring is formed from a nickel-based alloy containing rhenium using the at least one coil spring configuration.

Calderas and magma reservoirs

NASA Astrophysics Data System (ADS)

Cashman, Katharine V.; Giordano, Guido

2014-11-01

Large caldera-forming eruptions have long been a focus of both petrological and volcanological studies; petrologists have used the eruptive products to probe conditions of magma storage (and thus processes that drive magma evolution), while volcanologists have used them to study the conditions under which large volumes of magma are transported to, and emplaced on, the Earth's surface. Traditionally, both groups have worked on the assumption that eruptible magma is stored within a single long-lived melt body. Over the past decade, however, advances in analytical techniques have provided new views of magma storage regions, many of which provide evidence of multiple melt lenses feeding a single eruption, and/or rapid pre-eruptive assembly of large volumes of melt. These new petrological views of magmatic systems have not yet been fully integrated into volcanological perspectives of caldera-forming eruptions. Here we explore the implications of complex magma reservoir configurations for eruption dynamics and caldera formation. We first examine mafic systems, where stacked-sill models have long been invoked but which rarely produce explosive eruptions. An exception is the 2010 eruption of Eyjafjallajökull volcano, Iceland, where seismic and petrologic data show that multiple sills at different depths fed a multi-phase (explosive and effusive) eruption. Extension of this concept to larger mafic caldera-forming systems suggests a mechanism to explain many of their unusual features, including their protracted explosivity, spatially variable compositions and pronounced intra-eruptive pauses. We then review studies of more common intermediate and silicic caldera-forming systems to examine inferred conditions of magma storage, time scales of melt accumulation, eruption triggers, eruption dynamics and caldera collapse. By compiling data from large and small, and crystal-rich and crystal-poor, events, we compare eruptions that are well explained by simple evacuation of a zoned magma chamber (termed the Standard Model by Gualda and Ghiorso, 2013) to eruptions that are better explained by tapping multiple, rather than single, melt lenses stored within a largely crystalline mush (which we term complex magma reservoirs). We then discuss the implications of magma storage within complex, rather than simple, reservoirs for identifying magmatic systems with the potential to produce large eruptions, and for monitoring eruption progress under conditions where successive melt lenses may be tapped. We conclude that emerging views of complex magma reservoir configurations provide exciting opportunities for re-examining volcanological concepts of caldera-forming systems.

In situ 3D topographic and shape analysis by synchrotron radiation X-ray microtomography for crystal form identification in polymorphic mixtures

PubMed Central

Yin, Xian-Zhen; Xiao, Ti-Qiao; Nangia, Ashwini; Yang, Shuo; Lu, Xiao-Long; Li, Hai-Yan; Shao, Qun; He, You; York, Peter; Zhang, Ji-Wen

2016-01-01

Polymorphism denotes the existence of more than one crystal structure of a substance, and great practical and theoretical interest for the chemical and pharmaceutical industries. In many cases, it is challenging to produce a pure crystal form and establish a sensitive detection method for the identification of crystal form in a mixture of polymorphs. In this study, an accurate and sensitive method based on synchrotron radiation X-ray computed microtomography (SR-μCT) was devised to identify the polymorphs of clopidogrel bisulphate (CLP). After 3D reconstruction, crystal particles were extracted and dozens of structural parameters were calculated. Whilst, the particle shapes of the two crystal forms were all irregular, the surface of CLP II was found to be rougher than CLP I. In order to classify the crystal form based on the quantitative morphological property of particles, Volume Bias Percentage based on Surface Smoothing (VBP) was defined and a new method based on VBP was successfully developed, with a total matching rate of 99.91% for 4544 particles and a lowest detectable limit of 1%. More important for the mixtures in solid pharmaceutical formulations, the interference of excipients can be avoided, a feature cannot achieved by other available analytical methods. PMID:27097672

Highly robust crystalsome via directed polymer crystallization at curved liquid/liquid interface

PubMed Central

Wang, Wenda; Qi, Hao; Zhou, Tian; Mei, Shan; Han, Lin; Higuchi, Takeshi; Jinnai, Hiroshi; Li, Christopher Y.

2016-01-01

Lipids and amphiphilic block copolymers spontaneously self-assemble in water to form a plethora of micelles and vesicles. They are typically fluidic in nature and often mechanically weak for applications such as drug delivery and gene therapeutics. Mechanical properties of polymeric materials could be improved by forming crystalline structures. However, most of the self-assembled micelles and vesicles have curved surfaces and precisely tuning crystallization within a nanoscale curved space is challenging, as the curved geometry is incommensurate with crystals having three-dimensional translational symmetry. Herein, we report using a miniemulsion crystallization method to grow nanosized, polymer single-crystal-like capsules. We coin the name crystalsome to describe this unique structure, because they are formed by polymer lamellar crystals and their structure mimics liposomes and polymersomes. Using poly(L-lactic acid) (PLLA) as the model polymer, we show that curved water/p-xylene interface formed by the miniemulsion process can guide the growth of PLLA single crystals. Crystalsomes with the size ranging from ∼148 nm to over 1 μm have been formed. Atomic force microscopy measurement demonstrate a two to three orders of magnitude increase in bending modulus compared with conventional polymersomes. We envisage that this novel structure could shed light on investigating spherical crystallography and drug delivery. PMID:26837260

Effect of milling conditions on solid-state amorphization of glipizide, and characterization and stability of solid forms.

PubMed

Xu, Kailin; Xiong, Xinnuo; Zhai, Yuanming; Wang, Lili; Li, Shanshan; Yan, Jin; Wu, Di; Ma, Xiaoli; Li, Hui

2016-09-10

In this study, the amorphization of glipizide was systematically investigated through high-energy ball milling at different temperatures. The results of solid-state amorphization through milling indicated that glipizide underwent direct crystal-to-glass transformation at 15 and 25°C and crystal-to-glass-to-crystal conversion at 35°C; hence, milling time and temperature had significant effects on the amorphization of glipizide, which should be effectively controlled to obtain totally amorphous glipizide. Solid forms of glipizide were detailedly characterized through analyses of X-ray powder diffraction, morphology, thermal curves, vibrational spectra, and solid-state nuclear magnetic resonance. The physical stability of solid forms was investigated under different levels of relative humidity (RH) at 25°C. Forms I and III are kinetically stable and do not form any new solid-state forms at various RH levels. By contrast, Form II is kinetically unstable, undergoing direct glass-to-crystal transformation when RH levels higher than 32.8%. Therefore, stability investigation indicated that Form II should be stored under relatively dry conditions to prevent rapid crystallization. High temperatures can also induce the solid-state transformation of Form II; the conversion rate increased with increasing temperature. Copyright © 2016 Elsevier B.V. All rights reserved.

Effect of water on self-assembled tubules in β-sitosterol + γ-oryzanol-based organogels

NASA Astrophysics Data System (ADS)

den Adel, Ruud; Heussen, Patricia C. M.; Bot, Arjen

2010-10-01

Mixtures of β-sitosterol and γ-oryzanol form a network in triglyceride oil that may serve as an alternative to the network of small crystallites of triglycerides occurring in regular oil structuring. The present x-ray diffraction study investigates the relation between the crystal forms of the individual compounds and the mixture in oil, water and emulsion. β-Sitosterol and γ-oryzanol form normal crystals in oil, in water, or in emulsions. The crystals are sensitive to the presence of water. The mixture of β-sitosterol + γ-oryzanol forms crystals in water and emulsions that can be traced back to the crystals of the pure compounds. Only in oil, a completely different structure emerges in the mixture of β-sitosterol + γ-oryzanol, which bears no relation to the structures that are formed by both individual compounds, and which can be identified as a self-assembled tubule (diameter 7.2±0.1 nm, wall thickness 0.8±0.2 nm).

Salt or cocrystal of salt? Probing the nature of multicomponent crystal forms with infrared spectroscopy

NASA Astrophysics Data System (ADS)

da Silva, Cameron Capeletti; Guimarães, Freddy Fernandes; Ribeiro, Leandro; Martins, Felipe Terra

2016-10-01

The recognition of the nature of a multicomponent crystal form (solvate, salt, cocrystal or cocrystal of salt) is of great importance for pharmaceutical industry because it is directly related to the performance of a pharmaceutical ingredient, since there is interdependence between the structure, its energy and its physical properties. In this context, here we have identified the nature of multicomponent crystal forms of the anti-HIV drug lamivudine with mandelic acid through infrared spectroscopy. These investigated crystal forms were the known S-mandelic acid cocrystal of lamivudine R-mandelate trihydrate (1), a cocrystal of salt, and lamivudine R-mandelate (2), a salt. This approach also supports the identification and distinction of both ionized and unionized forms of mandelic acid in the infrared spectrum of 1. In this way, infrared spectroscopy can be useful to distinguish a cocrystal of salt from either salt or cocrystal forms. In the course of this study, for the first time we have also characterized and determined the crystal structure of R-mandelic acid cocrystal of sodium R-mandelate (3).

Crystallization of Chicken Egg White Lysozyme from Sulfate Salts

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth; Pusey, Marc

1998-01-01

It has been "known" that chicken egg white lysozyme does not crystallize from sulfate, particularly ammonium sulfate, salts, but instead gives amorphous precipitates. This has been the basis of several studies using lysozyme comparing macromolecule crystal nucleation and amorphous precipitation. Recently Ries-Kautt et al (Acta Cryst D50, (1994) 366) have shown that purified isoionic CEWL could be crystallized from low concentrations of sulfate at basic pH, and we subsequently showed that in fact CEWL could be purified in both the tetragonal and orthorhombic forms using ammonium sulfate over the pH range 4.0 to 7.8 (Acta Cryst D53, (1997) 795). We have now extended these observations to include a range of common sulfate salts, specifically sodium, potassium, rubidium, magnesium, and manganese sulfates. In all cases but the manganese sulfates both the familiar tetragonal and orthorhombic forms were obtained, with unit cell dimensions close to those known for the "classic" sodium chloride crystallized forms. Manganese sulfate has only yielded orthorhombic crystals to date. All crystallizations were carried out using low (typically less than or equal to 6 M) salt and high (greater than approximately 90 mg/ml) protein concentrations. As with ammonium sulfate, the tetragonal - orthorhombic phase shift appears to be a function of both the temperature and the protein concentration, with higher temperatures and concentrations favoring the orthorhombic and lower the tetragonal form. The phase change range is somewhat reduced for the sulfate salts, depending upon conditions being typically between approximately 15 - 20 C. Both the magnesium and manganese sulfates gave crystals at salt concentrations over 0.6 M as well, with magnesium sulfate giving a very slowly nucleating and growing hexagonal form. A triclinic crystal form, characterized by aggressively small crystals (typically 0.1 mm in size) has been occasionally obtained from ammonium sulfate. Finally, preliminary spot solubility determinations have suggested that in some cases the solubility increases with increasing salt concentrations.

Four crystal forms of a Bence-Jones protein

PubMed Central

Makino, Debora L.; Henschen-Edman, Agnes H.; McPherson, Alexander

2005-01-01

Four crystal forms have been grown and characterized by X-ray diffraction of a Bence-Jones protein collected from the urine of a multiple myeloma patient more than 40 years ago. Closely related tetragonal and orthorhombic forms belonging to space groups P43212 and P212121, with unit-cell parameters a = b = 68.7, c = 182.1 and a = 67.7, b = 69.4, c = 87.3 Å, diffract to 1.5 and 1.9 Å, respectively. Two closely related trigonal forms, both belonging to space group P3121 with unit-cell parameters a = b = 154.3 Å but differing by a doubling of the c axis, one 46.9 Å and the other 94.0 Å, diffract to 2.9 and 2.6 Å resolution, respectively. The trigonal crystal of short c-axis length shows a positive indication of twinning. The trigonal crystal of longer c axis, which appeared only after eight months of incubation at room temperature, is likely to be composed of proteolytically degraded molecules and unlike the other crystal forms contains two entire Bence-Jones dimers in the asymmetric unit. This latter crystal form may shed some light on the formation of fibrils common to certain storage diseases. PMID:16508097

Purification, crystallization and preliminary crystallographic study of low oxygen-affinity haemoglobin from cat (Felis silvestris catus) in two different crystal forms.

PubMed

Balasubramanian, M; Moorthy, Pon Sathya; Neelagandan, K; Ponnuswamy, M N

2009-03-01

Haemoglobin is a metalloprotein which plays a major role in the transportation of oxygen from the lungs to tissues and of carbon dioxide back to the lungs. The present work reports the preliminary crystallographic study of low oxygen-affinity haemoglobin from cat in different crystal forms. Cat blood was collected, purified by anion-exchange chromatography and crystallized in two different conditions by the hanging-drop vapour-diffusion method under unbuffered low-salt and buffered high-salt concentrations using PEG 3350 as a precipitant. Intensity data were collected using MAR345 and MAR345dtb image-plate detector systems. Cat haemoglobin crystallizes in monoclinic and orthorhombic crystal forms with one and two whole biological molecules (alpha(2)beta(2)), respectively, in the asymmetric unit.

Aqueous trifluorethanol solutions simulate the environment of DNA in the crystalline state.

PubMed

Kypr, J; Chládková, J; Zimulová, M; Vorlícková, M

1999-09-01

We took 28 fragments of DNA whose crystal structures were known and used CD spectroscopy to search for conditions stabilising the crystal structures in solution. All 28 fragments switched into their crystal structures in 60-80% aqueous trifluorethanol (TFE) to indicate that the crystals affected the conformation of DNA like the concentrated TFE. The fragments crystallising in the B-form also underwent cooperative TFE-induced changes that took place within the wide family of B-form structures, suggesting that the aqueous and crystal B-forms differed as well. Spermine and magnesium or calcium cations, which were contained in the crystallisation buffers, promoted or suppressed the TFE-induced changes of several fragments to indicate that the crystallisation agents can decide which of the possible structures is adopted by the DNA fragment in the crystal.

Engineering calcium oxalate crystal formation in Arabidopsis

USDA-ARS?s Scientific Manuscript database

Many plants accumulate crystals of calcium oxalate. Just how these crystals form remains unknown. To gain insight into the mechanisms regulating calcium oxalate crystal formation, a crystal engineering approach was initiated utilizing the non-crystal accumulating plant, Arabidopsis. The success of t...

The role of cocrystals in pharmaceutical science.

PubMed

Shan, Ning; Zaworotko, Michael J

2008-05-01

Pharmaceutical cocrystals, a subset of a long known but little-studied class of compounds, represent an emerging class of crystal forms in the context of pharmaceutical science. They are attractive to pharmaceutical scientists because they can significantly diversify the number of crystal forms that exist for a particular active pharmaceutical ingredient (API), and they can lead to improvements in physical properties of clinical relevance. In this article we address pharmaceutical cocrystals from the perspective of design (crystal engineering) and present a series of case studies that demonstrate how they can enhance the solubility, bioavailability, and/or stability of API crystal forms.

Fabrication of single crystal architecture in Sb-S-I glass: Transition from dot to line

DOE PAGES

Savytskii, Dmytro; Dierolf, Volkmar; Tamura, Nobumichi; ...

2017-12-08

We have investigated the occurrence of the sometimes observed grain boundaries, as initial seed is extended to form line in laser-fabricated single-crystal architecture in glass (SCAG). In particular, for Sb 2S 3 SCAG in Sb-S-I glass as a model system, grain boundaries are formed during the transition from laser-written initial seed dot to crystal line. Such grain boundaries during the growth of Sb 2S 3 crystals occur in 16SbI 3-84Sb 2S 3glass, whereas they are absent in Sb 2S 3 glass. We correlate this difference in tendency to form multiple grains with the relative glass forming ability i.e. the dynamicsmore » of nucleation and crystal growth as determined by differential scanning calorimetry (DSC). On the basis of this understanding, methods to minimize the appearance of grain boundaries in the transition region are suggested.« less

Fabrication of single crystal architecture in Sb-S-I glass: Transition from dot to line

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

Savytskii, Dmytro; Dierolf, Volkmar; Tamura, Nobumichi

We have investigated the occurrence of the sometimes observed grain boundaries, as initial seed is extended to form line in laser-fabricated single-crystal architecture in glass (SCAG). In particular, for Sb 2S 3 SCAG in Sb-S-I glass as a model system, grain boundaries are formed during the transition from laser-written initial seed dot to crystal line. Such grain boundaries during the growth of Sb 2S 3 crystals occur in 16SbI 3-84Sb 2S 3glass, whereas they are absent in Sb 2S 3 glass. We correlate this difference in tendency to form multiple grains with the relative glass forming ability i.e. the dynamicsmore » of nucleation and crystal growth as determined by differential scanning calorimetry (DSC). On the basis of this understanding, methods to minimize the appearance of grain boundaries in the transition region are suggested.« less

Methods for synthesizing microporous crystals and microporous crystal membranes

DOEpatents

Dutta, Prabir; Severance, Michael; Sun, Chenhu

2017-02-07

A method of making a microporous crystal material, comprising: a. forming a mixture comprising NaOH, water, and one or more of an aluminum source, a silicon source, and a phosphate source, whereupon the mixture forms a gel; b. heating the gel for a first time period, whereupon a first volume of water is removed from the gel and micoroporous crystal nuclei form, the nuclei having a framework; and c.(if a membrane is to be formed) applying the gel to a solid support seeded with microporous crystals having a framework that is the same as the framework of the nuclei; d. heating the gel for a second time period. during which a second volume of water is added to the gel; wherein the rate of addition of the second volume of water is between about 0.5 and about 2.0 fold the rate of removal of the first volume of water.

Polymorphs and polymorphic cocrystals of temozolomide.

PubMed

Babu, N Jagadeesh; Reddy, L Sreenivas; Aitipamula, Srinivasulu; Nangia, Ashwini

2008-07-07

Crystal polymorphism in the antitumor drug temozolomide (TMZ), cocrystals of TMZ with 4,4'-bipyridine-N,N'-dioxide (BPNO), and solid-state stability were studied. Apart from a known X-ray crystal structure of TMZ (form 1), two new crystalline modifications, forms 2 and 3, were obtained during attempted cocrystallization with carbamazepine and 3-hydroxypyridine-N-oxide. Conformers A and B of the drug molecule are stabilized by intramolecular amide N--HN(imidazole) and N--HN(tetrazine) interactions. The stable conformer A is present in forms 1 and 2, whereas both conformers crystallized in form 3. Preparation of polymorphic cocrystals I and II (TMZBPNO 1:0.5 and 2:1) were optimized by using solution crystallization and grinding methods. The metastable nature of polymorph 2 and cocrystal II is ascribed to unused hydrogen-bond donors/acceptors in the crystal structure. The intramolecularly bonded amide N-H donor in the less stable structure makes additional intermolecular bonds with the tetrazine C==O group and the imidazole N atom in stable polymorph 1 and cocrystal I, respectively. All available hydrogen-bond donors and acceptors are used to make intermolecular hydrogen bonds in the stable crystalline form. Synthon polymorphism and crystal stability are discussed in terms of hydrogen-bond reorganization.

Crystallization and preliminary X-ray diffraction studies of delta-toxin from Clostridium perfringens.

PubMed

Huyet, Jessica; Gilbert, Maryse; Popoff, Michel R; Basak, Ajit

2011-03-01

Clostridium perfringens is a Gram-positive anaerobic bacterium that is responsible for a wide range of diseases in humans and both wild and domesticated animals, including birds. C. perfringens is notable for its ability to produce a plethora of toxins, e.g. phospholipases C (alpha-toxin), pore-forming toxins (epsilon-toxin, beta-toxin and enterotoxin) and binary toxins (iota-toxin). Based on alpha-, beta-, epsilon- and iota-toxin production, the bacterium is classified into five different toxinotypes (A-E). Delta-toxin, which is a 32.6 kDa protein with 290 amino acids, is one of three haemolysins released by type C and possibly by type B strains of C. perfringens. This toxin is immunogenic and lytic to erythrocytes from the even-toed ungulates sheep, goats and pigs, and is cytotoxic to other cell types such as rabbit macrophages, human monocytes and blood platelets from goats, rabbits, guinea pigs and humans. The recombinant delta-toxin has been cloned, expressed, purified and crystallized in two different crystal forms by the hanging-drop vapour-diffusion method. Of these two different crystal forms, only the form II crystal diffracted to atomic resolution (dmin=2.4 Å), while the form I crystal diffracted to only 15 Å resolution. The form II crystals belonged to space group P2(1)2(1)2, with one molecule in the crystallographic asymmetric unit and unit-cell parameters a=49.66, b=58.48, c=112.93 Å.

TEM analysis of the initial stages of BaSO4 crystallization

NASA Astrophysics Data System (ADS)

Ruiz Agudo, Cristina; Putnis, Christine V.; Ruiz Agudo, Encarnación; Putnis, Andrew

2014-05-01

Barite scales in oilfields are formed by mixing of seawater with high SO42- content and formation water (high Ba2+ content) in the reservoir. Although barite precipitation has been widely studied, a lack of a complete understanding of the mechanisms of barite nucleation and growth at the early stages poses a problem in the development of preventive methods designed to reduce the damaging consequences associated with scale formation. A general strategy to reduce scale formation is the use of additives that act as inhibitors of barite precipitation. These scale inhibitors act by hampering and delaying nucleation and growth of barite and in most cases they modify the habit of the crystal. The performance of these inhibitors depends on numerous parameters, such as pH, temperature and concentration, and they can affect different stages of the precipitation process (e.g. blocking active growth sites at the surface, sequestering the scale-forming metal ion, influencing the type of amorphous phase or crystalline polymorph formed, as well as promoting solid-cluster formation (Gebauer et al., 2009)). In recent studies, the precipitation of several minerals, e.g. calcite (Gebauer et al., 2008), gypsum (Van Driessche et al., 2012), magnetite (Baumgartner et al., 2013) and iron oxyhydroxide (Li et. al 2012) has been shown to follow a non-classical crystallization process. Primary crystalline nanoparticles that coalesce after previous co-alignment, and amorphous and crystalline precursor phases have been observed in the crystallization processes of these minerals. The purpose of the present work was to gain a better understanding of the early stages of barium sulfate precipitation with the objective of obtaining fundamental knowledge that allows us to select the appropriate inhibitors for barite scale formation. With this aim, barite was precipitated by mixing BaCl2 and Na2SO4 solutions. The process was quenched with ethanol at different times and the particles obtained were observed ex-situ in a Transmission Electron Microscope. We found that barite precipitation involves the initial formation of nanometer-size (5-10 nm) particles that fuse in an oriented way to form larger particles. Two hierarchical levels of aggregation are observed: first, the aggregation of 5-10 nm particles to form larger, but still nanometer-sized (20-60 nm) particles. In a second stage, these latter particles aggregate to produce larger single crystals (200-500 nm). No evidence of an amorphous or crystalline precursor phase previous to crystalline barite was found. These results are of importance for the design of scale prevention methods, particularly in the choice of the most suitable scale inhibitor. Gebauer D., Cölfen H., Verch A. and Antonietti M. (2009) The multiple roles of additives in CaCO3 crystallization: a quantitative case study. Adv. Mater. 21, 435-439. Gebauer D., Völkel A. and Cölfen H. (2008) Stable prenucleation calcium carbonate clusters. Science 332, 1819-1822. Van Driessche A.E.S., Benning L.G., Rodriguez-Blanco J. D., Ossorio M., Bots P. and García-Ruiz J. M. (2012) The role and implications of bassanite as a stable precursor phase to gypsum precipitation. Science 336, 69-71. Baumgartner J., Dey A., Bomans P. H. H., Le Coadou C., Fratzl P., Sommerdijk N. A. J. M. and Faivre D. (2013) Nucleation and growth of magnetite from solution. Nature 12, 310-314. Li D., Nielsen M.H., Lee J.R.I, Frandsen C., Banfield J.F. and De Yoreo J.J.(2012) Direction-Specific Interactions Control Crystal Growth by Oriented Attachment. Science 336, 1014-1018.

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

Saturated fatty acids and fatty acid esters promote the polymorphic transition of clarithromycin metastable form I crystal.

PubMed

Watanabe, Miteki; Mizoguchi, Midori; Aoki, Hajime; Iwao, Yasunori; Noguchi, Shuji; Itai, Shigeru

2016-10-15

The phase transition of active pharmaceutical ingredients should be taken into account during manufacturing, processing- and storage, because different crystal forms lead to different physical properties of formulations. The phase transition of clarithromycin (CAM) metastable form I to stable form II was investigated on heating with additives such as fatty acids or fatty acid esters. Differential scanning calorimetry analyses revealed that when form I was heated with additives, the phase transition temperature of form I decreased close to the melting points of the additives. Powder X-ray diffraction analyses indicated the tentative presence of a non-crystalline component during the transition of form I to form II on heating with additives. These observations implied that CAM form I dissolved in the melted additives on heating and the dissolved CAM crystallized to form II. Reduction of transition temperatures in the presence of additives were also observed for the crystals of nifedipine form B and carbamazepine form III. These results suggested that the phenomena can be widely applicable for simultaneous crystalline phase transition and granulation using binder additives. Copyright © 2016 Elsevier B.V. All rights reserved.

Phase behavior and crystal structure of 3-(1-naphthyloxy)- and 3-(4-indolyloxy)-propane-1,2-diol, synthetic precursors of chiral drugs propranolol and pindolol

NASA Astrophysics Data System (ADS)

Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.; Fayzullin, Robert R.; Samigullina, Aida I.; Zakharychev, Dmitry V.

2013-08-01

Valuable precursors of popular chiral drugs propranolol and pindolol, 3-(1-naphthyloxy)-propane-1,2-diol 3 and 3-(4-indolyloxy)-propane-1,2-diol 4 were investigated by IR spectroscopy, DSC, and X-ray diffraction methods. Both compounds, crystallizing from enantiopure feed material, form "guaifenesin-like" crystal packing in which the classic H-bonded bilayers, framed in both sides by hydrophobic fragments of the molecules, acts as the basic crystal-forming motif. Diol 4 prone to spontaneous resolution and conserves its packing pattern crystallizing from racemate. Under the same conditions, diol 3 forms weakly stable solid racemic compound. Some reasons for such a behavior are identified and discussed.

Improving the dissolution and bioavailability of 6-mercaptopurine via co-crystallization with isonicotinamide.

PubMed

Wang, Jian-Rong; Yu, Xueping; Zhou, Chun; Lin, Yunfei; Chen, Chen; Pan, Guoyu; Mei, Xuefeng

2015-03-01

6-Mercaptopurine (6-MP) is a clinically important antitumor drug. The commercially available form was provided as monohydrate and belongs to BCS class II category. Co-crystallization screening by reaction crystallization method (RCM) and monitored by powder X-ray diffraction led to the discovery of a new co-crystal formed between 6-MP and isonicotinamide (co-crystal 1). Co-crystal 1 was thoroughly characterized by X-ray diffraction, FT-IR and Raman spectroscopy, and thermal analysis. Noticeably, the in vitro and in vivo studies revealed that co-crystal 1 possesses improved dissolution rate and superior bioavailability on animal model. Copyright © 2015 Elsevier Ltd. All rights reserved.

Salt-induced aggregation of lysozyme: Implications for crystal growth

NASA Technical Reports Server (NTRS)

Wilson, Lori J.

1994-01-01

Crystallization of proteins is a prerequisite for structural analysis by x-ray crystallography. While improvements in protein crystals have been obtained in microgravity onboard the U.S. Space Shuttle, attempts to improve the crystal growth process both on the ground and in space have been limited by our lack of understanding of the mechanisms involved. Almost all proteins are crystallized with the aid of a precipitating agent. Many of the common precipitating agents are inorganic salts. An understanding of the role of salts on the aggregation of protein monomers is the key to the elucidation of the mechanisms involved in protein crystallization. In order for crystallization to occur individual molecules must self-associate into aggregates. Detection and characterization of aggregates in supersaturated protein solutions is the first step in understanding salt-induced crystallization.

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

Rashin, Alexander A., E-mail: alexander-rashin@hotmail.com; Iowa State University, 112 Office and Lab Bldg, Ames, IA 50011-3020; Domagalski, Marcin J.

Conformational differences between myoglobin structures are studied. Most structural differences in whale myoglobin beyond the uncertainty threshold can be correlated with a few specific structural factors. There are always exceptions and a search for additional factors is needed. The results might have serious implications for biological insights from conformational differences. Validation of general ideas about the origins of conformational differences in proteins is critical in order to arrive at meaningful functional insights. Here, principal component analysis (PCA) and distance difference matrices are used to validate some such ideas about the conformational differences between 291 myoglobin structures from sperm whale, horsemore » and pig. Almost all of the horse and pig structures form compact PCA clusters with only minor coordinate differences and outliers that are easily explained. The 222 whale structures form a few dense clusters with multiple outliers. A few whale outliers with a prominent distortion of the GH loop are very similar to the cluster of horse structures, which all have a similar GH-loop distortion apparently owing to intermolecular crystal lattice hydrogen bonds to the GH loop from residues near the distal histidine His64. The variations of the GH-loop coordinates in the whale structures are likely to be owing to the observed alternative intermolecular crystal lattice bond, with the change to the GH loop distorting bonds correlated with the binding of specific ‘unusual’ ligands. Such an alternative intermolecular bond is not observed in horse myoglobins, obliterating any correlation with the ligands. Intermolecular bonds do not usually cause significant coordinate differences and cannot be validated as their universal cause. Most of the native-like whale myoglobin structure outliers can be correlated with a few specific factors. However, these factors do not always lead to coordinate differences beyond the previously determined uncertainty thresholds. The binding of unusual ligands by myoglobin, leading to crystal-induced distortions, suggests that some of the conformational differences between the apo and holo structures might not be ‘functionally important’ but rather artifacts caused by the binding of ‘unusual’ substrate analogs. The causes of P6 symmetry in myoglobin crystals and the relationship between crystal and solution structures are also discussed.« less

Structure of a new crystal form of human Hsp70 ATPase domain.

PubMed

Osipiuk, J; Walsh, M A; Freeman, B C; Morimoto, R I; Joachimiak, A

1999-05-01

Hsp70 proteins are highly conserved proteins induced by heat shock and other stress conditions. An ATP-binding domain of human Hsp70 protein has been crystallized in two major morphological forms at pH 7.0 in the presence of PEG 8000 and CaCl2. Both crystal forms belong to the orthorhombic space group P212121, but show no resemblance in unit-cell parameters. Analysis of the crystal structures for both forms shows a 1-2 A shift of one of the subdomains of the protein. This conformational change could reflect a 'natural' flexibility of the protein which might be relevant to ATP binding and may facilitate the interaction of other proteins with Hsp70 protein.

A Crystallization-Temperature Profile Through Paleo-Oceanic Crust (Wadi Gideah Transect, Oman Ophiolite): Application of the REE-in-Plagioclase-Clinopyroxene Partitioning Thermometer

NASA Astrophysics Data System (ADS)

Mueller, S.; Hasenclever, J.; Garbe-Schönberg, D.; Koepke, J.; Hoernle, K.

2017-12-01

The accretion mechanisms forming oceanic crust at fast spreading ridges are still under controversial discussion. Thermal, petrological, and geochemical observations predict different end-member models, i.e., the gabbro glacier and the sheeted sill model. They all bear implications for heat transport, temperature distribution, mode of crystallization and hydrothermal heat removal over crustal depth. In a typical MOR setting, temperature is the key factor driving partitioning of incompatible elements during crystallization. LA-ICP-MS data for co-genetic plagioclase and clinopyroxene in gabbros along a transect through the plutonic section of paleo-oceanic crust (Wadi Gideah Transect, Oman ophiolite) reveal that REE partitioning coefficients are relatively constant in the layered gabbro section but increase for the overlying foliated gabbros, with an enhanced offset towards HREEs. Along with a systematic enrichment of REE's with crustal height, these trends are consistent with a system dominated by in-situ crystallization for the lower gabbros and a change in crystallization mode for the upper gabbros. Sun and Liang (2017) used experimental REE partitioning data for calibrating a new REE-in-plagioclase-clinopyroxene thermometer that we used here for establishing the first crystallization-temperature depth profile through oceanic crust that facilitates a direct comparison with thermal models of crustal accretion. Our results indicate crystallization temperatures of about 1220±8°C for the layered gabbros and lower temperatures of 1175±8°C for the foliated gabbros and a thermal minimum above the layered-to-foliated gabbro transition. Our findings are consistent with a hybrid accretion model for the oceanic crust. The thermal minimum is assumed to represent a zone where the descending crystal mushes originating from the axial melt lens meet with mushes that have crystallized in situ. These results can be used to verify and test thermal models (e.g., Maclennan et al., 2004, Theissen-Krah et al., 2016) and their predictions for heat flow and temperature distribution in the crust. Maclennan, J., Hulme, T., & Singh, S. C. (2004), G3, 5(2). / Sun, C., & Liang, Y., (2017), CMP, 172(4). / Theissen-Krah, S., Rüpke, L. H., & Hasenclever, J. (2016), GRL, 43(3).

Method For Screening Microcrystallizations For Crystal Formation

DOEpatents

Santarsiero, Bernard D. , Stevens, Raymond C. , Schultz, Peter G. , Jaklevic, Joseph M. , Yegian, Derek T. , Cornell, Earl W. , Nordmeyer, Robert A.

2003-10-07

A method is provided for performing array microcrystallizations to determine suitable crystallization conditions for a molecule, the method comprising: forming an array of microcrystallizations, each microcrystallization comprising a drop comprising a mother liquor solution whose composition varies within the array and a molecule to be crystallized, the drop having a volume of less than 1 microliter; storing the array of microcrystallizations under conditions suitable for molecule crystals to form in the drops in the array; and detecting molecule crystal formation in the drops by taking images of the drops.

Refractory oxide hosts for a high power, broadly tunable laser with high quantum efficiency and method of making same

DOEpatents

Chen, Yok; Gonzalez, Roberto

1986-01-01

Refractory oxide crystals having high-quantum efficiency and high thermal stability for use as broadly tunable laser host materials. The crystals are formed by removing hydrogen from a single crystal of the oxide material to a level below about 10.sup.12 protons per cm.sup.3 and subsequently thermochemically reducing the oxygen content of the crystal to form sufficient oxygen anion vacancies so that short-lived F.sup.+ luminescence is produced when the crystal is optically excited.

Refractory oxide hosts for a high power, broadly tunable laser with high quantum efficiency and method of making same

DOEpatents

Chen, Yok; Gonzalez, R.

1985-07-03

Refractory oxide crystals having high-quantum efficiency and high thermal stability for use as broadly tunable laser host materials. The crystals are formed by removing hydrogen from a single crystal of the oxide material to a level below about 10/sup 12/ protons per cm/sup 3/ and subsequently thermochemically reducing the oxygen content of the crystal to form sufficient oxygen anion vacancies so that short-lived F/sup +/ luminescence is produced when the crystal is optically excited.

Cooperative dynamics in ultrasoft 2D crystals

NASA Astrophysics Data System (ADS)

Sprakel, Joris; van der Meer, Berend; Dijkstra, Marjolein; van der Gucht, Jasper

2015-03-01

The creation, annihilation, and diffusion of defects in crystal lattices play an important role during crystal melting and deformation. Although it is well understood how defects form and react when crystals are subjected to external stresses, it remains unclear how crystals cope with internal stresses. We report a study in which we create a highly localized internal stress, by means of optical tweezing, in a crystal formed from micrometer-sized colloidal spheres and directly observe how the solid reacts using microscopy. We find that, even though the excitation is highly localized, a collective dance of colloidal particles results; these collective modes take the form of closed rings or open-ended strings, depending on the sequence of events which nucleate the rearrangements. Surprisingly, we find from Brownian Dynamics simulations that these cooperative dynamics are thermally-activated modes inherent to the crystal, and can even occur through a single, sufficiently large thermal fluctuation, resulting in the irreversible displacement of 100s of particles from their lattice sites.

Chitosan-Assisted Crystallization and Film Forming of Perovskite Crystals through Biomineralization.

PubMed

Yang, Yang; Sun, Chen; Yip, Hin-Lap; Sun, Runcang; Wang, Xiaohui

2016-03-18

Biomimetic mineralization is a powerful approach for the synthesis of advanced composite materials with hierarchical organization and controlled structure. Herein, chitosan was introduced into a perovskite precursor solution as a biopolymer additive to control the crystallization and to improve the morphology and film-forming properties of a perovskite film by way of biomineralization. The biopolymer additive was able to control the size and morphology of the perovskite crystals and helped to form smooth films. The mechanism of chitosan-mediated nucleation and growth of the perovskite crystals was explored. As a possible application, the chitosan-perovskite composite film was introduced into a planar heterojunction solar cell and increased power conversion efficiency relative to that observed for the pristine perovskite film was achieved. The biomimetic mineralization method proposed in this study provides an alternative way of preparing perovskite crystals with well-controlled morphology and properties and extends the applications of perovskite crystals in photoelectronic fields, including planar-heterojunction solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of Authigenic Sulfates in Cold Dry Glaciers: Terrestrial and Planetary Implications of Sublimites

NASA Astrophysics Data System (ADS)

Massé, M.; Rondeau, B.; Ginot, P.; Schmitt, B.; Bourgeois, O.; Mitri, G.

2015-12-01

Salts are common on planetary surfaces, and sulfates have been widely observed on Earth, Mars (Gendrin et al., 2005) and on some of Jupiter's and Saturn's icy moons like Europa (Dalton et al., 2007). These minerals can form under a wide range of conditions, and the determination of sulfate formation processes can provide key elements for deciphering past planetary surface conditions. Most terrestrial sulfates form as evaporites in warm environments with high water/rock ratios, but these conditions are rarely encountered on other planets. Here we describe the formation of cryogenic sulfates in an extreme cold and dry environment: the Guanaco glacier located in the Chilean Andes (Fig.1a, Rabatel et al., 2011). Field analyses reveal that it is a cold-based glacier, its surface temperature remains below 0°C throughout the year, and ablation occurs mostly by sublimation. Ablation creates ice cliffs punctuated of pluricentimetric whitish, tapered crystals embedded in the ice (Fig.1b, c). By Raman and chemistry, they proved to be gypsum, covered by micrometric crystals of jarosite, halotrichite and native sulfur. The euhedral morphology of these soft minerals indicates that they are neoformed and have not been transported in the ice. This is supported by the absence of gypsum crystals in ice cores drilled through the glacier. We infer that the crystallization thus occurred at the glacier surface during ice sublimation and does not involve liquid water. To distinguish this original salt formation process from the more common evaporites, we name these minerals "sublimites". Though this formation process is uncommon and generates minor quantities of sulfates on Earth, it may be dominant on other bodies in the Solar System where sublimation is effective. Examples of planetary sublimites may include gypsum on the North Polar Cap of Mars (Massé et al., 2012), and other sulfates on icy moons where sublimation has been observed (Howard et al., 2008).

Fabrication and characterization of poly(L-lactic acid) gels induced by fibrous complex crystallization with solvents

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

Matsuda, Yasuhiro; Fukatsu, Akinobu; Wang, Yangyang

2014-01-01

Complex crystal induced gelation of poly(L-lactic acid) (PLLA) solutions was studied for a series of solvents, including N,N-dimethylformamide (DMF). By cooling the solutions prepared at elevated temperatures, PLLA gels were produced in solvents that induced complex crystals ( -crystals) with PLLA. Fibrous structure of PLLA in the gel with DMF was observed by polarizing optical microscopy, field emission electron microscopy, and atomic force microscopy. Upon heating, the crystal form of PLLA in the DMF gel changed from -crystal to a-crystal, the major crystal form in common untreated PLLA films, but the morphology and high elastic modulus of the gel remainedmore » until the a-crystal dissolved at higher temperature. In addition, a solvent exchanging method was developed, which allowed PLLA gels to be prepared in other useful solvents that do not induce -crystals without losing the morphology and mechanical properties.« less

Sent packing: protein engineering generates a new crystal form of Pseudomonas aeruginosa DsbA1 with increased catalytic surface accessibility

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

McMahon, Roisin M., E-mail: r.mcmahon1@uq.edu.au; Coinçon, Mathieu; Tay, Stephanie

The crystal structure of a P. aeruginosa DsbA1 variant is more suitable for fragment-based lead discovery efforts to identify inhibitors of this antimicrobial drug target. In the reported structures the active site of the protein can simultaneously bind multiple ligands introduced in the crystallization solution or via soaking. Pseudomonas aeruginosa is an opportunistic human pathogen for which new antimicrobial drug options are urgently sought. P. aeruginosa disulfide-bond protein A1 (PaDsbA1) plays a pivotal role in catalyzing the oxidative folding of multiple virulence proteins and as such holds great promise as a drug target. As part of a fragment-based lead discoverymore » approach to PaDsbA1 inhibitor development, the identification of a crystal form of PaDsbA1 that was more suitable for fragment-soaking experiments was sought. A previously identified crystallization condition for this protein was unsuitable, as in this crystal form of PaDsbA1 the active-site surface loops are engaged in the crystal packing, occluding access to the target site. A single residue involved in crystal-packing interactions was substituted with an amino acid commonly found at this position in closely related enzymes, and this variant was successfully used to generate a new crystal form of PaDsbA1 in which the active-site surface is more accessible for soaking experiments. The PaDsbA1 variant displays identical redox character and in vitro activity to wild-type PaDsbA1 and is structurally highly similar. Two crystal structures of the PaDsbA1 variant were determined in complex with small molecules bound to the protein active site. These small molecules (MES, glycerol and ethylene glycol) were derived from the crystallization or cryoprotectant solutions and provide a proof of principle that the reported crystal form will be amenable to co-crystallization and soaking with small molecules designed to target the protein active-site surface.« less

Impact of interaction range and curvature on crystal growth of particles confined to spherical surfaces.

PubMed

Paquay, Stefan; Both, Gert-Jan; van der Schoot, Paul

2017-07-01

When colloidal particles form a crystal phase on a spherical template, their packing is governed by the effective interaction between them and the elastic strain of bending the growing crystal. For example, if growth commences under appropriate conditions, and the isotropic crystal that forms reaches a critical size, growth continues via the incorporation of defects to alleviate elastic strain. Recently, it was experimentally found that, if defect formation is somehow not possible, the crystal instead continues growing in ribbons that protrude from the original crystal. Here we report on computer simulations in which we observe both the formation of ribbons at short interaction ranges and packings that incorporate defects if the interaction is longer-ranged. The ribbons only form above some critical crystal size, below which the nucleus is disk-shaped. We find that the scaling of the critical crystal size differs slightly from the one proposed in the literature, and we argue that this is because the actual morphology transition is caused by the competition between line tension and elastic stress, rather than the competition between chemical potential and elastic stress.

Impact of interaction range and curvature on crystal growth of particles confined to spherical surfaces

NASA Astrophysics Data System (ADS)

Paquay, Stefan; Both, Gert-Jan; van der Schoot, Paul

2017-07-01

When colloidal particles form a crystal phase on a spherical template, their packing is governed by the effective interaction between them and the elastic strain of bending the growing crystal. For example, if growth commences under appropriate conditions, and the isotropic crystal that forms reaches a critical size, growth continues via the incorporation of defects to alleviate elastic strain. Recently, it was experimentally found that, if defect formation is somehow not possible, the crystal instead continues growing in ribbons that protrude from the original crystal. Here we report on computer simulations in which we observe both the formation of ribbons at short interaction ranges and packings that incorporate defects if the interaction is longer-ranged. The ribbons only form above some critical crystal size, below which the nucleus is disk-shaped. We find that the scaling of the critical crystal size differs slightly from the one proposed in the literature, and we argue that this is because the actual morphology transition is caused by the competition between line tension and elastic stress, rather than the competition between chemical potential and elastic stress.

Charge Stabilized Crystalline Colloidal Arrays As Templates For Fabrication of Non-Close-Packed Inverted Photonic Crystals

PubMed Central

Bohn, Justin J.; Ben-Moshe, Matti; Tikhonov, Alexander; Qu, Dan; Lamont, Daniel N.

2010-01-01

We developed a straightforward method to form non close-packed highly ordered fcc direct and inverse opal silica photonic crystals. We utilize an electrostatically self assembled crystalline colloidal array (CCA) template formed by monodisperse, highly charged polystyrene particles. We then polymerize a hydrogel around the CCA (PCCA) and condense the silica to form a highly ordered silica impregnated (siPCCA) photonic crystal. Heating at 450 °C removes the organic polymer leaving a silica inverse opal structure. By altering the colloidal particle concentration we independently control the particle spacing and the wall thickness of the inverse opal photonic crystals. This allows us to control the optical dielectric constant modulation in order to optimize the diffraction; the dielectric constant modulation is controlled independently of the photonic crystal periodicity. These fcc photonic crystals are better ordered than typical close-packed photonic crystals because their self assembly utilizes soft electrostatic repulsive potentials. We show that colloidal particle size and charge polydispersity has modest impact on ordering, in contrast to that for close-packed crystals. PMID:20163800

Crystallization of aluminum hydroxide in the aluminum-air battery: Literature review, crystallizer design and results of integrated system tests

NASA Astrophysics Data System (ADS)

Maimoni, A.

1988-03-01

The literature on aluminum trihydroxide crystallization is reviewed and the implications of crystallization on the design and performance of the aluminum-air battery are illustrated. Results of research on hydrargillite crystallization under battery operating conditions at Alcoa Laboratories, Alcan Kingston Laboratories, and Lawrence Livermore National Laboratory are summarized and are applied to the design of an electrolyte management system using lamella settlers for clarification of the electrolyte and product separation. The design principles were validated in a series of experiments that, for the first time in the aluminum-air program, demonstrated continuous operation of an integrated system consisting of cells, crystallizer, and a product-removal system.

Solid-state characterization of nevirapine.

PubMed

Sarkar, Mahua; Perumal, O P; Panchagnula, R

2008-09-01

The purpose of this investigation is to characterize nevirapine from commercial samples and samples crystallized from different solvents under various conditions. The solid-state behavior of nevirapine samples was investigated using a variety of complementary techniques such as microscopy (optical, polarized, hot stage microscopy), differential scanning calorimeter, thermogravimetric analysis, Fourier transform infrared spectroscopy and powder X-ray diffractometry. The commercial samples of nevirapine had the same polymorphic crystalline form with an anhedral crystal habit. Intrinsic dissolution of nevirapine was similar for both the commercial batches. Powder dissolution showed pH dependency, with maximum dissolution in acidic pH and there was no significant effect of particle size. The samples recrystallized from different solvent systems with varying polarity yielded different crystal habits. Stirring and degrees of supersaturation influenced the size and shape of the crystals. The recrystallized samples did not produce any new polymorphic form, but weak solvates with varying crystal habit were produced. Recrystallized samples showed differences in the x-ray diffractograms. However, all the samples had the same internal crystal lattice as revealed from their similar melting points and heat of fusion. The intrinsic dissolution rate of recrystallized samples was lower than the commercial sample. It was found that the compression pressure resulted in desolvation and partial conversion of the crystal form. After compression, the recrystallized samples showed similar x-ray diffractograms to the commercial sample. Amorphous form showed slightly higher aqueous solubility than the commercial crystalline form.

Temperature dependent evolution of wrinkled single-crystal silicon ribbons on shape memory polymers.

PubMed

Wang, Yu; Yu, Kai; Qi, H Jerry; Xiao, Jianliang

2017-10-25

Shape memory polymers (SMPs) can remember two or more distinct shapes, and thus can have a lot of potential applications. This paper presents combined experimental and theoretical studies on the wrinkling of single-crystal Si ribbons on SMPs and the temperature dependent evolution. Using the shape memory effect of heat responsive SMPs, this study provides a method to build wavy forms of single-crystal silicon thin films on top of SMP substrates. Silicon ribbons obtained from a Si-on-insulator (SOI) wafer are released and transferred onto the surface of programmed SMPs. Then such bilayer systems are recovered at different temperatures, yielding well-defined, wavy profiles of Si ribbons. The wavy profiles are shown to evolve with time, and the evolution behavior strongly depends on the recovery temperature. At relatively low recovery temperatures, both wrinkle wavelength and amplitude increase with time as evolution progresses. Finite element analysis (FEA) accounting for the thermomechanical behavior of SMPs is conducted to study the wrinkling of Si ribbons on SMPs, which shows good agreement with experiment. Merging of wrinkles is observed in FEA, which could explain the increase of wrinkle wavelength observed in the experiment. This study can have important implications for smart stretchable electronics, wrinkling mechanics, stimuli-responsive surface engineering, and advanced manufacturing.

Crystal Structure of Arginase from Plasmodium falciparum and Implications for l-Arginine Depletion in Malarial Infection

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

Dowling, Daniel P.; Ilies, Monica; Olszewski, Kellen L.

The 2.15 {angstrom} resolution crystal structure of arginase from Plasmodium falciparum, the parasite that causes cerebral malaria, is reported in complex with the boronic acid inhibitor 2(S)-amino-6-boronohexanoic acid (ABH) (K{sub d} = 11 {micro}M). This is the first crystal structure of a parasitic arginase. Various protein constructs were explored to identify an optimally active enzyme form for inhibition and structural studies and to probe the structure and function of two polypeptide insertions unique to malarial arginase: a 74-residue low-complexity region contained in loop L2 and an 11-residue segment contained in loop L8. Structural studies indicate that the low-complexity region ismore » largely disordered and is oriented away from the trimer interface; its deletion does not significantly compromise enzyme activity. The loop L8 insertion is located at the trimer interface and makes several intra- and intermolecular interactions important for enzyme function. In addition, we also demonstrate that arg- Plasmodium berghei sporozoites show significantly decreased liver infectivity in vivo. Therefore, inhibition of malarial arginase may serve as a possible candidate for antimalarial therapy against liver-stage infection, and ABH may serve as a lead for the development of inhibitors.« less

Large single domain 123 material produced by seeding with single crystal rare earth barium copper oxide single crystals

DOEpatents

Todt, V.; Miller, D.J.; Shi, D.; Sengupta, S.

1998-07-07

A method of fabricating bulk YBa{sub 2}Cu{sub 3}O{sub x} where compressed powder oxides and/or carbonates of Y and Ba and Cu present in mole ratios to form YBa{sub 2}Cu{sub 3}O{sub x} are heated in the presence of a Nd{sub 1+x}Ba{sub 2{minus}x}Cu{sub 3}O{sub y} seed crystal to a temperature sufficient to form a liquid phase in the YBa{sub 2}Cu{sub 3}O{sub x} while maintaining the seed crystal solid. The materials are slowly cooled to provide a YBa{sub 2}Cu{sub 3}O{sub x} material having a predetermined number of domains between 1 and 5. Crack-free single domain materials can be formed using either plate shaped seed crystals or cube shaped seed crystals with a pedestal of preferential orientation material. 7 figs.

Large single domain 123 material produced by seeding with single crystal rare earth barium copper oxide single crystals

DOEpatents

Todt, Volker; Miller, Dean J.; Shi, Donglu; Sengupta, Suvankar

1998-01-01

A method of fabricating bulk YBa.sub.2 Cu.sub.3 O.sub.x where compressed powder oxides and/or carbonates of Y and Ba and Cu present in mole ratios to form YBa.sub.2 Cu.sub.3 O.sub.x are heated in the presence of a Nd.sub.1+x Ba.sub.2-x Cu.sub.3 O.sub.y seed crystal to a temperature sufficient to form a liquid phase in the YBa.sub.2 Cu.sub.3 O.sub.x while maintaining the seed crystal solid. The materials are slowly cooled to provide a YBa.sub.2 Cu.sub.3 O.sub.x material having a predetermined number of domains between 1 and 5. Crack-free single domain materials can be formed using either plate shaped seed crystals or cube shaped seed crystals with a pedestal of preferential orientation material.

Growth of zeolite crystals in the microgravity environment of space

NASA Technical Reports Server (NTRS)

Sacco, A., Jr.; Sand, L. B.; Collette, D.; Dieselman, K.; Crowley, J.; Feitelberg, A.

1986-01-01

Zeolites are hydrated, crystalline aluminosilicates with alkali and alkaling earth metals substituted into cation vacancies. Typically zeolite crystals are 3 to 8 microns. Larger cyrstals are desirable. Large zeolite crystals were produced (100 to 200 microns); however, they have taken restrictively long times to grow. It was proposed if the rate of nucleation or in some other way the number of nuclei can be lowered, fewer, larger crystals will be formed. The microgravity environment of space may provide an ideal condition to achieve rapid growth of large zeolite crystals. The objective of the project is to establish if large zeolite crystals can be formed rapidly in space.

Ultratight crystal packing of a 10 kDa protein

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

Trillo-Muyo, Sergio; Jasilionis, Andrius; Domagalski, Marcin J.

2013-03-01

The crystal structure of the C-terminal domain of a putative U32 peptidase from G. thermoleovorans is reported; it is one of the most tightly packed protein structures reported to date. While small organic molecules generally crystallize forming tightly packed lattices with little solvent content, proteins form air-sensitive high-solvent-content crystals. Here, the crystallization and full structure analysis of a novel recombinant 10 kDa protein corresponding to the C-terminal domain of a putative U32 peptidase are reported. The orthorhombic crystal contained only 24.5% solvent and is therefore among the most tightly packed protein lattices ever reported.

Formation of porous crystals via viscoelastic phase separation

NASA Astrophysics Data System (ADS)

Tsurusawa, Hideyo; Russo, John; Leocmach, Mathieu; Tanaka, Hajime

2017-10-01

Viscoelastic phase separation of colloidal suspensions can be interrupted to form gels either by glass transition or by crystallization. With a new confocal microscopy protocol, we follow the entire kinetics of phase separation, from homogeneous phase to different arrested states. For the first time in experiments, our results unveil a novel crystallization pathway to sponge-like porous crystal structures. In the early stages, we show that nucleation requires a structural reorganization of the liquid phase, called stress-driven ageing. Once nucleation starts, we observe that crystallization follows three different routes: direct crystallization of the liquid phase, the Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganized network, but crystals grow past it by direct condensation of the gas phase on their surface, driving liquid evaporation, and producing a network structure different from the original phase separation pattern. We argue that similar crystal-gel states can be formed in monatomic and molecular systems if the liquid phase is slow enough to induce viscoelastic phase separation, but fast enough to prevent immediate vitrification. This provides a novel pathway to form nanoporous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.

Occurrence of Tourmaline in Metasedimentary Rocks of the Isua Supracrustal Belt, Greenland: Implications for Ribose Stabilization in Hadean Marine Sediments.

PubMed

Mishima, Shinpei; Ohtomo, Yoko; Kakegawa, Takeshi

2016-06-01

Abiotic formation of RNA was important for the emergence of terrestrial life, but the acknowledged difficulties of generating and stabilizing ribose have often raised questions regarding how the first RNA might have formed. Previous researchers have proposed that borate could have stabilized ribose; however, the availability of borate on the early Earth has been the subject of intense debate. In order to examine whether borate was available on the early Earth, this study examined metasedimentary rocks from the Isua Supracrustal Belt. Garnet, biotite, and quartz comprise the major constituents of the examined rocks. Field relationships and the chemical compositions of the examined rocks suggest sedimentary origin. The present study found that garnet crystals contain a number of inclusions of tourmaline (a type of borosilicate mineral). All tourmaline crystals are Fe-rich and categorized as schorl. Both garnet and tourmaline often contain graphite inclusions and this close association of tourmaline with garnet and graphite has not been recognized previously. Garnet-biotite and graphite geothermometers suggest that the tourmaline in garnet experienced peak metamorphic conditions (~500 °C and 5 kbar). The mineralogical characteristics of the tourmaline and the whole rock composition indicate that the tourmaline formed authigenically in the sediment during diagenesis and/or early metamorphism. Clay minerals in modern sediments have the capability to adsorb and concentrate borate, which could lead to boron enrichment during diagenesis, followed by tourmaline formation under metamorphic conditions. Clay minerals, deposited on the early Archean seafloor, were the precursors of the garnet and biotite in the examined samples. The studied tourmaline crystals were most likely formed in the same way as modern tourmaline in marine sediments. Therefore, boron enrichment by clays must have been possible even during the early Archean. Thus, similar enrichment could have been possible during the Hadean, providing a stabilization agent for ribose.

Annual dynamics of halite precipitation in the Dead Sea: In situ observations and their geological implications

NASA Astrophysics Data System (ADS)

Sirota, Ido; enzel, Yehouda; Lensky, Nadav G.

2017-04-01

Layered halite sequences deposited in deep basins throughout the geological record. However, analogues of such sequences are commonly studied in sallow environments. Here we study active precipitation of halite layers from the only modern analog for deep, halite-precipitating basin, the hypersaline Dead Sea. In situ observations in the Dead Sea link seasonal thermohaline stratification, halite saturation, and the characteristics of the actively forming halite layers. The spatiotemporal evolution of halite precipitation in the Dead Sea was characterized by means of monthly observations of the i) lake thermohaline stratification (temperature, salinity, and density), ii) degree of halite saturation, and iii) textural evolution of the active halite deposits. We present the observed relationships between textural characteristics of layered halite deposits (i.e. grain size, consolidation, and roughness) and the degree of saturation, which in turn reflected the limnology and hydro-climatology. The lakefloor is divided into two principle environments: A deep, hypolimnetic and a shallow, epilimnetic lakefloor. In the deeper hypolimnetic lakefloor halite continuously precipitates with seasonal variations: (a) during summer, consolidated coarse halite crystals form rough surfaces under slight super-saturation. (b) During winter, unconsolidated, fine halite crystals form smooth seafloor deposits under high supersaturation. The observations also emphasize the thought regarding seasonal alternation of halite crystallization mechanism. The shallow epilimnetic lake floor is highly influenced by the seasonal temperature variations, and by intensive summer dissolution of part of the previous year's halite deposit which results in thin sequences with annual unconformities. This emphasizes the control of temperature seasonality on the precipitated halite layers characteristics. In addition, precipitation of halite in the hypolimnetic floor, on the expense of the dissolution of the epilimnetic floor, results in lateral focusing and thickening of halite deposit in the deeper part of the basin and thinning of the deposits in shallow marginal basins.

Aberrated surface soliton formation in a nonlinear 1D and 2D photonic crystal

PubMed Central

Lysak, Tatiana M.; Trykin, Evgenii M.

2018-01-01

We discuss a novel type of surface soliton—aberrated surface soliton—appearance in a nonlinear one dimensional photonic crystal and a possibility of this surface soliton formation in two dimensional photonic crystal. An aberrated surface soliton possesses a nonlinear distribution of the wavefront. We show that, in one dimensional photonic crystal, the surface soliton is formed at the photonic crystal boundary with the ambient medium. Essentially, that it occupies several layers at the photonic crystal boundary and penetrates into the ambient medium at a distance also equal to several layers, so that one can infer about light energy localization at the lateral surface of the photonic crystal. In the one dimensional case, the surface soliton is formed from an earlier formed soliton that falls along the photonic crystal layers at an angle which differs slightly from the normal to the photonic crystal face. In the two dimensional case, the soliton can appear if an incident Gaussian beam falls on the photonic crystal face. The influence of laser radiation parameters, optical properties of photonic crystal layers and ambient medium on the one dimensional surface soliton formation is investigated. We also discuss the influence of two dimensional photonic crystal configuration on light energy localization near the photonic crystal surface. It is important that aberrated surface solitons can be created at relatively low laser pulse intensity and for close values of alternating layers dielectric permittivity which allows their experimental observation. PMID:29558497

Shock Induced Chemistry: Application and Development of Ultrafast Nonlinear Probes of the Energy Dynamics of Molecules in Solids

DTIC Science & Technology

1988-01-01

crystal and in a mixed crystal. The mixed crystal data was taken with resonance enhancement by the pentacene .. ... 7 Accesiw, r)re 0IE r)) NiS cR4~ IE~) D...observations as well as their implications about the nature of the coupling of a localized defect to the bulk modes of the crystal have been analyzed [7...matter systems, in addition to phonon induced fluctuations of local mechanical properties, there can be much slower timescale structural evolution

Can computed crystal energy landscapes help understand pharmaceutical solids?

PubMed Central

Price, Sarah L.; Braun, Doris E.; Reutzel-Edens, Susan M.

2017-01-01

Computational crystal structure prediction (CSP) methods can now be applied to the smaller pharmaceutical molecules currently in drug development. We review the recent uses of computed crystal energy landscapes for pharmaceuticals, concentrating on examples where they have been used in collaboration with industrial-style experimental solid form screening. There is a strong complementarity in aiding experiment to find and characterise practically important solid forms and understanding the nature of the solid form landscape. PMID:27067116

DNA-guided nanoparticle assemblies

DOEpatents

Gang, Oleg; Nykypanchuk, Dmytro; Maye, Mathew; van der Lelie, Daniel

2013-07-16

In some embodiments, DNA-capped nanoparticles are used to define a degree of crystalline order in assemblies thereof. In some embodiments, thermodynamically reversible and stable body-centered cubic (bcc) structures, with particles occupying <.about.10% of the unit cell, are formed. Designs and pathways amenable to the crystallization of particle assemblies are identified. In some embodiments, a plasmonic crystal is provided. In some aspects, a method for controlling the properties of particle assemblages is provided. In some embodiments a catalyst is formed from nanoparticles linked by nucleic acid sequences and forming an open crystal structure with catalytically active agents attached to the crystal on its surface or in interstices.

Recrystallization of puerarin using the supercritical fluid antisolvent process

NASA Astrophysics Data System (ADS)

Li, Y.; Yang, D. J.; Zhou, W.; Chen, S. B.; Chen, S. L.

2012-02-01

The purpose of this study was to investigate the influence of supercritical fluid (SCF) processing on the polymorphism of puerarin (Pur), a poorly soluble drug. The gas anti-solvent (GAS) technique was used to crystalize the drug in different conditions. The samples were analyzed by scanning electron microscopy and laser granulometry for changes in the habitus and particle size. The solid state was studied by X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR) and melting point determination. Finally, the dissolution and solubility tests were carried out. It was attested that compared with the commercial Pur in Crystal form I, at the optimum and most of conditions, Pur changed into crystal form II with more orderly and pure appearances. At the concentration of 60 mg/ml and at the solvent of methanol, two other new crystal forms (named form III and form IV) were produced. It was demonstrated that the particles mean diameter, size distribution and morphology can be strongly controlled through the manipulation of the process parameters and more importantly, Pur in the new crystal forms, which were not reported before with better physico-chemical properties could be produced by recrystalization by GAS.

Grain-scale investigations of deformation heterogeneities in aluminum alloys

NASA Astrophysics Data System (ADS)

Güler, Baran; Şimşek, Ülke; Yalçınkaya, Tuncay; Efe, Mert

2018-05-01

The anisotropic deformation of Aluminum alloys at micron scale exhibits localized deformation, which has negative implications on the macroscale mechanical and forming behavior. The scope of this work is twofold. Firstly, micro-scale deformation heterogeneities affecting forming behavior of aluminum alloys is investigated through experimental microstructure analysis at large strains and various strain paths. The effects of initial texture, local grain misorientation, and strain paths on the strain localizations are established. In addition to uniaxial tension condition, deformation heterogeneities are also investigated under equibiaxial tension condition to determine the strain path effects on the localization behavior. Secondly, the morphology and the crystallographic data obtained from the experiments is transferred to Abaqus software, in order to predict both macroscopic response and the microstructure evolution though crystal plasticity finite element simulations. The model parameters are identified through the comparison with experiments and the capability of the model to capture real material response is discussed as well.

Barium bioaccumulation by bacterial biofilms and implications for Ba cycling and use of Ba proxies.

PubMed

Martinez-Ruiz, Francisca; Jroundi, Fadwa; Paytan, Adina; Guerra-Tschuschke, Isabel; Abad, María Del Mar; González-Muñoz, María Teresa

2018-04-24

Ba proxies have been broadly used to reconstruct past oceanic export production. However, the precise mechanisms underlying barite precipitation in undersaturated seawater are not known. The link between bacterial production and particulate Ba in the ocean suggests that bacteria may play a role. Here we show that under experimental conditions marine bacterial biofilms, particularly extracellular polymeric substances (EPS), are capable of bioaccumulating Ba, providing adequate conditions for barite precipitation. An amorphous P-rich phase is formed at the initial stages of Ba bioaccumulation, which evolves into barite crystals. This supports that in high productivity regions where large amounts of organic matter are subjected to bacterial degradation, the abundant EPS would serve to bind the necessary Ba and form nucleation sites leading to barite precipitation. This also provides new insights into barite precipitation and opens an exciting field to explore the role of EPS in mineral precipitation in the ocean.

Crystallization of multiple forms of bovine seminal ribonuclease in the liganded and unliganded state

NASA Astrophysics Data System (ADS)

Sica, F.; Adinolfi, S.; Berisio, R.; De Lorenzo, C.; Mazzarella, L.; Piccoli, R.; Vitagliano, L.; Zagari, A.

1999-01-01

Bovine seminal ribonuclease (BS-RNase) is an intriguing homodimeric enzyme which exists as two conformational isomers, characterized by distinct catalytic and biological properties, referred to as M×M and M=M. Reduction of inter-chain disulfide bridges produces a stable monomeric derivative (M) which is still active. This paper reports the screening and optimization of crystallization conditions for growing single diffraction-quality crystals for the various BS-RNase forms. The crystallization trials were performed using both the vapor diffusion and microbatch methods. The M×M dimer was crystallized in the free form from polyethylene glycol (PEG) 4000 at pH 8.5 and as a complex with the substrate analog uridylyl(2'- 5')guanosine (UpG) from an unbuffered ammonium sulfate (AS) solution. These two crystal types diffract X-rays to 2.5 and 1.9 Å resolution, respectively. Two different crystal types were obtained both for the M=M dimer and for the monomeric derivative. (M=M)a crystals, grown from PEG 4000 (8% w/v) at pH 5.6, diffract X-rays to 4.0 Å. At higher PEG concentration (15% w/v) a different crystal type was obtained, (M=M)b, which showed a better diffraction limit (2.5 Å). For the monomer, type (M)a and (M)b crystals, diffracting X-rays to 2.5 Å resolution, were obtained from AS at pH 6.5 and from PEG 4000 at pH 8.5, respectively. A comparison with previously crystallized forms of the dimer M×M and its complexes with uridylyl(2'-5')adenosine and 2'-deoxycytidylyl(3'-5')-2'-deoxyadenosine is also presented. The three-dimensional structure analysis of (M×M)·UpG and (M=M)b is in progress.

The solid state of rebamipide: preparation, characterization, and dissolution.

PubMed

Jeon, Seong Hyeon; Sohn, Young Taek

2016-04-01

Rebamipide is marketed as a peptic ulcer agent under the trade name Mucosta(R). The objective of this work was to investigate the existence of polymorphs and pseudopolymorphs of rebamipide. Two crystal forms of rebamipide were isolated by recrystallization and characterized by differential thermal analysis (DTA), thermogravimetric analysis (TG), powder X-ray diffractometry, infrared spectrometry, and nuclear magnetic resonance. The DTA curve of Form 1 showed one endothermic peak at 305.2 °C, and that of Form 2 showed one endothermic peak at 307.3 °C. The TG curve of Form 1 showed a single weight loss at 305.2 °C, which corresponded to melting. The TG curve of Form 2 also showed a single weight loss at 307.3 °C, which corresponded to melting. The melting point of Form 2 was higher than that of Form 1. In the dissolution studies in pH 6.8 buffer at 37 ± 0.5 °C, the two crystal forms showed no significant differences in dissolution. After 3 months of storage at 0, 52, and 95% RH, the two crystal forms were not transformed. After milling with a Specamill for 2 h, the two crystal forms were not transformed.

Solid state of CG-400549, a novel FabI inhibitor: characterization, dissolution, transformation.

PubMed

Kim, Bo-Yeon; Sohn, Young-Taek

2011-05-01

The polymorphic and pseudopolymorphic forms of CG-400549, a novel FabI inhibitor with potent in vivo activity were prepared and characterized by differential scanning calorimetry (DSC), powder X-ray diffractometry (PXRD) and thermogravimetric analysis (TG). Seven crystal forms of CG-400549, one anhydrate and six solvates, have been isolated by recrystallization and the DSC and PXRD patterns of the seven crystal forms of CG-400549 were different respectively. The dissolution patterns of these seven crystal forms of CG-400549 were studied and they showed significant differences in the dissolution rate. After storage of 1 month at 0% RH (silica gel, 20°C), 52% RH (saturated solution of Na(2)Cr(2)O(7)2H(2)O/20°C) and 95% RH (saturated solution of Na(2)HPO(4)/20°C), all crystal forms were not transformed.

Crystallization over the liquid layer

NASA Astrophysics Data System (ADS)

Bogonosov, K. A.; Maksimovskii, S. N.

2013-04-01

In this article, a new phenomenon of high-speed crystallization of metals in a low-temperature plasma formed as a result of the effect of a short laser pulse is considered. The mechanism of the way the reaction occurs on the surface of the melt formed under the effect of the laser pulse on an amorphous substrate is described. The main factors affecting the crystallization process are described. Primary attention is paid to laminar convection and the latent heat of crystallization.

Crystallization of human estrogenic 17β-hydroxysteroid dehydrogenase under microgravity

NASA Astrophysics Data System (ADS)

Zhu, Dao-Wei; Zhou, Ming; Mao, Ying; Labrie, Fernand; Lin, Sheng-Xiang

1995-11-01

Human 17β-hydroxysteroid dehydrogenase has been crystallized on the ground in the complex form with NADP + and a complete data set of the crystal was primarily collected at 2.9 Å [D.-W. Zhu, X. Lee, R. Breton, D. Ghosh, W. Pangborn, W.L. Duax and S.-X. Lin, J. Mol. Biol. 234 (1993) 242]. To eliminate multiseeding, formation of multicrystals and to obtain higher quality crystals, we carried out the crystallization aboard the Russian MIR space station and crystals were recovered in January, 1994. Crystals of the enzyme were formed in 9 of the total 12 sitting drops in the space mission, in the presence of NADP + or estradiol. This is a first attempt of crystallization of a membrane-associated protein under microgravity in the presence of a detergent. The space experiments showed better results in nucleation number, crystal size and morphology than the ground ones, obtaining crystals diffracting to resolutions between 2.5-2.7 Å. The too early ground mixing has limited a more important improvement of the crystallization.

Supercritical fluid crystallization of griseofulvin: crystal habit modification with a selective growth inhibitor.

PubMed

Jarmer, Daniel J; Lengsfeld, Corinne S; Anseth, Kristi S; Randolph, Theodore W

2005-12-01

Poly (sebacic anhydride) (PSA) was used as a growth inhibitor to selectively modify habit of griseofulvin crystals formed via the Precipitation with a compressed-fluid antisolvent (PCA) process. PSA and griseofulvin were coprecipitated within a PCA injector, which provided efficient mixing between the solution and compressed antisolvent process streams. Griseofulvin crystal habit was modified from acicular to bipyramidal when the mass ratio of PSA/griseofulvin in the solution feed stream was

Cloning, preparation and preliminary crystallographic studies of penicillin V acylase autoproteolytic processing mutants

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

Chandra, P. Manish; Brannigan, James A., E-mail: jab@ysbl.york.ac.uk; Prabhune, Asmita

The production, crystallization and characterization of three inactive mutants of penicillin V acylase from B. sphaericus in their respective precursor and processed forms are reported. The space groups are different for the native enzyme and the mutants. The crystallization of three catalytically inactive mutants of penicillin V acylase (PVA) from Bacillus sphaericus in precursor and processed forms is reported. The mutant proteins crystallize in different primitive monoclinic space groups that are distinct from the crystal forms for the native enzyme. Directed mutants and clone constructs were designed to study the post-translational autoproteolytic processing of PVA. The catalytically inactive mutants willmore » provide three-dimensional structures of precursor PVA forms, plus open a route to the study of enzyme–substrate complexes for this industrially important enzyme.« less

Sponge-like nanoporous single crystals of gold

PubMed Central

Khristosov, Maria Koifman; Bloch, Leonid; Burghammer, Manfred; Kauffmann, Yaron; Katsman, Alex; Pokroy, Boaz

2015-01-01

Single crystals in nature often demonstrate fascinating intricate porous morphologies rather than classical faceted surfaces. We attempt to grow such crystals, drawing inspiration from biogenic porous single crystals. Here we show that nanoporous single crystals of gold can be grown with no need for any elaborate fabrication steps. These crystals are found to grow following solidification of a eutectic composition melt that forms as a result of the dewetting of nanometric thin films. We also present a kinetic model that shows how this nano-porous single-crystalline structure can be obtained, and which allows the potential size of the porous single crystal to be predicted. Retaining their single-crystalline nature is due to the fact that the full crystallization process is faster than the average period between two subsequent nucleation events. Our findings clearly demonstrate that it is possible to form single-crystalline nano porous metal crystals in a controlled manner. PMID:26554856

Nematic order-disorder state transition in a liquid crystal analogue formed by oriented and migrating amoeboid cells

NASA Astrophysics Data System (ADS)

Kemkemer, R.; Teichgräber, V.; Schrank-Kaufmann, S.; Kaufmann, D.; Gruler, H.

2000-10-01

In cell culture, liquid crystal analogues are formed by elongated, migrating, and interacting amoeboid cells. An apolar nematic liquid crystal analogue is formed by different cell types like human melanocytes (=pigment cells of the skin), human fibroblasts (=connective tissue cells), human osteoblasts (=bone cells), human adipocytes (=fat cells), etc. The nematic analogue is quite well described by i) a stochastic machine equation responsible for cell orientation and ii) a self-organized extracellular guiding signal, E_2, which is proportional to the orientational order parameter as well as to the cell density. The investigations were mainly made with melanocytes. The transition to an isotropic state analogue can be accomplished either by changing the strength of interaction (e.g. variation of the cell density) or by influencing the cellular machinery by an externally applied signal: i) An isotropic gaseous state analogue is observed at low cell density (ρ < 110melanocytes/mm^2) and a nematic liquid crystal state analogue at higher cell density. ii) The nematic state analogue disappears if the bipolar shaped melanocytes are forced to become a star-like shape (induced by colchicine or staurosporine). The analogy between nematic liquid crystal state analogue formed by elongated, migrating and interacting cells and the nematic liquid crystal phase formed by interacting elongated molecules is discussed.

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

Venkadesh, S.; Mandal, P.K.; Gautham, N., E-mail: n_gautham@hotmail.com

Highlights: {yields} This is the first crystal structure of a four-way junction with sticky ends. {yields} Four junction structures bind to each other and form a rhombic cavity. {yields} Each rhombus binds to others to form 'infinite' 2D tiles. {yields} This is an example of bottom-up fabrication of a DNA nano-lattice. -- Abstract: We report here the crystal structure of the partially self-complementary decameric sequence d(CGGCGGCCGC), which self assembles to form a four-way junction with sticky ends. Each junction binds to four others through Watson-Crick base pairing at the sticky ends to form a rhombic structure. The rhombuses bind tomore » each other and form two dimensional tiles. The tiles stack to form the crystal. The crystal diffracted in the space group P1 to a resolution of 2.5 A. The junction has the anti-parallel stacked-X conformation like other junction structures, though the formation of the rhombic net noticeably alters the details of the junction geometry.« less

Development of a New Class of Drugs To Inhibit All Forms of Androgen Receptor in Castration Resistant Prostate Cancers

DTIC Science & Technology

2016-10-01

ARdbd-DNA crystals and may represent a new crystal form. Key outcome 2: We have carried out followup crystallization screening operations with... Chiang , Y.T., Sharma, A., Peacock, J.W., Wang, W., Cherkasov, A., Rennie, P.S., Gleave, M.E., and Ong, C.J. (2016) Androgen Receptor transcriptionally

Inexpensive Electrooptic Experiments on Liquid Crystal Displays.

ERIC Educational Resources Information Center

Ciferno, Thomas M.; And Others

1995-01-01

Describes the construction and use of an electrooptic apparatus that can be incorporated into the classroom to test liquid crystal displays (LCDs) and introduce students to experiments of an applied physics nature with very practical implications. Presents experiments that give students hands-on experience with technologies of current interest to…

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

Wurzburg, Beth A; Jardetzky, Theodore S; Stanford)

The structure of immunoglobulin E (IgE)-Fc 3-4 has been solved in three new crystal forms, providing 13 snapshots of the Fc conformation and revealing a diverse range of open-closed motions among subunit chains and dimers. A more detailed analysis of the open-to-closed motion of IgE-Fc 3-4 was possible with so many structures, and the new structures allow a more thorough examination of the flexibility of IgE-Fc and its implications for receptor binding. The existence of a hydrophobic pocket at the elbow region of the Fc appears to be conformation dependent and suggests a means of regulating the IgE-Fc conformation (andmore » potentially receptor binding) with small molecules.« less

Poly(acrylic acid) to induce competitive crystallization of a theophylline/oxalic acid cocrystal and a theophylline polymorph

NASA Astrophysics Data System (ADS)

Jang, Jisun; Kim, Il Won

2016-01-01

Polymeric additives to induce competitive crystallization of pharmaceutical compounds were explored. A cocrystal of theophylline and oxalic acid was used as a model system, and poly(acrylic acid), poly(caprolactone), and poly(ethylene glycol) were the additives. The cocrystal formation was selectively hindered with addition of poly(acrylic acid). First the size of the cocrystals were reduced, and eventually the cocrystallization was inhibited to generate neat theophylline crystals. The theophylline crystals were of a distinctively different crystal structure from known polymorphs, based on powder X-ray diffraction. They were also obtained in nanoscale size, when millimeter-scale crystals formed without poly(acrylic acid). Polymeric additives that could form specific interactions with crystallizing compounds seem to be useful tools for the phase and size control of pharmaceutical crystals.

Study of crystallization mechanisms of Fe nanoparticle

NASA Astrophysics Data System (ADS)

Kien, P. H.; Trang, G. T. T.; Hung, P. K.

2017-06-01

In this paper, the nanoparticle (NP) Fe was investigated by means of molecular dynamics simulation. The crystallization mechanism was studied through the time evolution of crystal cluster and potential energies of different atom types. The simulation shows that the NP was crystallized into bcc crystal structure when it was annealed at 900 K for long times. At early stage of the annealing, small nuclei form in different places of NP and dissolve for short times. After long times some nuclei form and gather nearby which create the stable clusters in the core of NP. After that the crystal clusters grow in the direction to cover the core and then to spread into the surface of NP. Analyzing the energies of different type atoms, we found that the crystal growth is originated from specific atomic arrangement in the boundary region of crystal clusters.

Crystal Structures of Apo and Liganded 4-Oxalocrotonate Decarboxylase Uncover a Structural Basis for the Metal-Assisted Decarboxylation of a Vinylogous β-Keto Acid.

PubMed

Guimarães, Samuel L; Coitinho, Juliana B; Costa, Débora M A; Araújo, Simara S; Whitman, Christian P; Nagem, Ronaldo A P

2016-05-10

The enzymes in the catechol meta-fission pathway have been studied for more than 50 years in several species of bacteria capable of degrading a number of aromatic compounds. In a related pathway, naphthalene, a toxic polycyclic aromatic hydrocarbon, is fully degraded to intermediates of the tricarboxylic acid cycle by the soil bacteria Pseudomonas putida G7. In this organism, the 83 kb NAH7 plasmid carries several genes involved in this biotransformation process. One enzyme in this route, NahK, a 4-oxalocrotonate decarboxylase (4-OD), converts 2-oxo-3-hexenedioate to 2-hydroxy-2,4-pentadienoate using Mg(2+) as a cofactor. Efforts to study how 4-OD catalyzes this decarboxylation have been hampered because 4-OD is present in a complex with vinylpyruvate hydratase (VPH), which is the next enzyme in the same pathway. For the first time, a monomeric, stable, and active 4-OD has been expressed and purified in the absence of VPH. Crystal structures for NahK in the apo form and bonded with five substrate analogues were obtained using two distinct crystallization conditions. Analysis of the crystal structures implicates a lid domain in substrate binding and suggests roles for specific residues in a proposed reaction mechanism. In addition, we assign a possible function for the NahK N-terminal domain, which differs from most of the other members of the fumarylacetoacetate hydrolase superfamily. Although the structural basis for metal-dependent β-keto acid decarboxylases has been reported, this is the first structural report for that of a vinylogous β-keto acid decarboxylase and the first crystal structure of a 4-OD.

Struvite formation and decomposition characteristics for ammonia and phosphorus recovery: A review of magnesium-ammonia-phosphate interactions.

PubMed

Tansel, Berrin; Lunn, Griffin; Monje, Oscar

2018-03-01

Struvite (MgNH 4 PO 4 ·6H 2 O) forms in aqueous systems with high ammonia and phosphate concentrations. However, conditions that result into struvite formation are highly dependent on the ionic compositions, temperature, pH, and ion speciation characteristics. The primary ions involved in struvite formation have complex interactions and can form different crystals depending on the ionic levels, pH and temperature. Struvite as well as struvite analogues (with substitution of monovalent cations for NH 4 + or divalent cations for Mg 2+ ) as well as other crystals can form simultaneously and result in changes in crystal morphology during crystal growth. This review provides the results from experimental and theoretical studies on struvite formation and decomposition studies. Characteristics of NH 4 + or divalent cations for Mg 2+ were evaluated in comparison to monovalent and divalent ions for formation of struvite and its analogues. Struvite crystals forming in wastewater systems are likely to contain crystals other than struvite due to ionic interactions, pH changes, temperature effects and clustering of ions during nucleation and crystal growth. Decomposition of struvite occurs following a series of reactions depending on the rate of heating, temperature and availability of water during heating. Copyright © 2017 Elsevier Ltd. All rights reserved.

The closo-Si{sub 12}C{sub 12} molecule from cluster to crystal: A theoretical prediction

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

Duan, Xiaofeng F., E-mail: xiaofeng.duan@wpafb.af.mil, E-mail: larry.burggraf@us.af.mil; Air Force Institute of Technology, Wright-Patterson Air Force Base, Ohio 45433; Burggraf, Larry W., E-mail: xiaofeng.duan@wpafb.af.mil, E-mail: larry.burggraf@us.af.mil

2016-03-21

The structure of closo-Si{sub 12}C{sub 12} is unique among stable Si{sub n}C{sub m} isomers (n, m > 4) because of its high symmetry, π–π stacking of C{sub 6} rings and unsaturated silicon atoms at symmetrical peripheral positions. Dimerization potential surfaces reveal various dimerization reactions that form between two closo-Si{sub 12}C{sub 12} molecules through Si–Si bonds at unsaturated Si atoms. As a result the closo-Si{sub 12}C{sub 12} molecule is capable of polymerization to form stable 1D polymer chains, 2D crystal layers, and 3D crystals. 2D crystal structures formed by side-side polymerization satisfy eight Si valences on each monomer without large distortionmore » of the monomer structure. 3D crystals are formed by stacking 2D structures in the Z direction, preserving registry of C{sub 6} rings in monomer moiety.« less

Crystallization of the C-terminal domain of the addiction antidote CcdA in complex with its toxin CcdB

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

Buts, Lieven; De Jonge, Natalie; Loris, Remy, E-mail: reloris@vub.ac.be

2005-10-01

The CcdA C-terminal domain was crystallized in complex with CcdB in two crystal forms that diffract to beyond 2.0 Å resolution. CcdA and CcdB are the antidote and toxin of the ccd addiction module of Escherichia coli plasmid F. The CcdA C-terminal domain (CcdA{sub C36}; 36 amino acids) was crystallized in complex with CcdB (dimer of 2 × 101 amino acids) in three different crystal forms, two of which diffract to high resolution. Form II belongs to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 37.6, b = 60.5, c = 83.8 Å and diffracts to 1.8more » Å resolution. Form III belongs to space group P2{sub 1}, with unit-cell parameters a = 41.0, b = 37.9, c = 69.6 Å, β = 96.9°, and diffracts to 1.9 Å resolution.« less

Crystalline structures, thermal properties and crystallizing mechanism of polyamide 6 nanotubes in confined space

NASA Astrophysics Data System (ADS)

Li, Xiaoru; Peng, Zhi; Yang, Chao; Han, Ping; Song, Guojun; Cong, Longliang

2016-09-01

The polyamide 6 (PA6) nanotubes were prepared by infiltrating the anodic aluminum oxide templates with polymer solution. Crystalline regions in the nanotube walls were detected by high-resolution transmission electron microscopy (HRTEM). X-ray diffraction (XRD), Fast Fourier Transform (FFT) and differential scanning calorimetry (DSC) techniques were employed to investigate crystallization, crystal faces and thermodynamics. It was found that the crystals were transformed from α-form in bulk to γ-form in nanotubes. It was made a detailed analysis in this article. Moreover, schematic diagram for the crystallizing mechanism of PA6 nanotubes was given to explain PA6 molecules how to crystallize in the nano-pores.

Myotonic Dystrophy Type 1 RNA Crystal Structures Reveal Heterogeneous 1×1 Nucleotide UU Internal Loop Conformations⊥

PubMed Central

Kumar, Amit; Park, HaJeung; Fang, Pengfei; Parkesh, Raman; Guo, Min; Nettles, Kendall W.; Disney, Matthew D.

2011-01-01

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5′CUG/3′GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures are disclosed of a model DM1 triplet repeating construct, 5′r(UUGGGC(CUG)3GUCC)2, refined to 2.20 Å and 1.52 Å resolution. Here, differences in orientation of the 5′ dangling UU end between the two structures induce changes in the backbone groove width, which reveals that non-canonical 1×1 nucleotide UU internal loops can display an ensemble of pairing conformations. In the 2.20 Å structure, CUGa, the 5′UU forms one hydrogen-bonded pairs with a 5′UU of a neighboring helix in the unit cell to form a pseudo-infinite helix. The central 1×1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1×1 nucleotide UU internal loops each form a one hydrogen-bonded pair. In the 1.52 Å structure, CUGb, the 5′ UU dangling end is tucked into the major groove of the duplex. While the canonical paired bases show no change in base pairing, in CUGb the terminal 1×1 nucleotide UU internal loops form now two hydrogen-bonded pairs. Thus, the shift in major groove induced by the 5′UU dangling end alters non-canonical base patterns. Collectively, these structures indicate that 1×1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands. PMID:21988728

Myotonic dystrophy type 1 RNA crystal structures reveal heterogeneous 1 × 1 nucleotide UU internal loop conformations.

PubMed

Kumar, Amit; Park, HaJeung; Fang, Pengfei; Parkesh, Raman; Guo, Min; Nettles, Kendall W; Disney, Matthew D

2011-11-15

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5'CUG/3'GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures of a model DM1 triplet repeating construct, 5'r[UUGGGC(CUG)(3)GUCC](2), refined to 2.20 and 1.52 Å resolution are disclosed. Here, differences in the orientation of the 5' dangling UU end between the two structures induce changes in the backbone groove width, which reveals that noncanonical 1 × 1 nucleotide UU internal loops can display an ensemble of pairing conformations. In the 2.20 Å structure, CUGa, the 5' UU forms a one hydrogen-bonded pair with a 5' UU of a neighboring helix in the unit cell to form a pseudoinfinite helix. The central 1 × 1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1 × 1 nucleotide UU internal loops each form a one-hydrogen bond pair. In the 1.52 Å structure, CUGb, the 5' UU dangling end is tucked into the major groove of the duplex. While the canonically paired bases show no change in base pairing, in CUGb the terminal 1 × 1 nucleotide UU internal loops now form two hydrogen-bonded pairs. Thus, the shift in the major groove induced by the 5' UU dangling end alters noncanonical base patterns. Collectively, these structures indicate that 1 × 1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands.

Myotonic Dystrophy Type 1 RNA Crystal Structures Reveal Heterogeneous 1 × 1 Nucleotide UU Internal Loop Conformations

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

Kumar, Amit; Park, HaJeung; Fang, Pengfei

2012-03-27

RNA internal loops often display a variety of conformations in solution. Herein, we visualize conformational heterogeneity in the context of the 5'CUG/3'GUC repeat motif present in the RNA that causes myotonic dystrophy type 1 (DM1). Specifically, two crystal structures of a model DM1 triplet repeating construct, 5'r[{und UU}GGGC(C{und U}G){sub 3}GUCC]{sub 2}, refined to 2.20 and 1.52 {angstrom} resolution are disclosed. Here, differences in the orientation of the 5' dangling UU end between the two structures induce changes in the backbone groove width, which reveals that noncanonical 1 x 1 nucleotide UU internal loops can display an ensemble of pairing conformations.more » In the 2.20 {angstrom} structure, CUGa, the 5' UU forms a one hydrogen-bonded pair with a 5' UU of a neighboring helix in the unit cell to form a pseudoinfinite helix. The central 1 x 1 nucleotide UU internal loop has no hydrogen bonds, while the terminal 1 x 1 nucleotide UU internal loops each form a one-hydrogen bond pair. In the 1.52 {angstrom} structure, CUGb, the 5' UU dangling end is tucked into the major groove of the duplex. While the canonically paired bases show no change in base pairing, in CUGb the terminal 1 x 1 nucleotide UU internal loops now form two hydrogen-bonded pairs. Thus, the shift in the major groove induced by the 5' UU dangling end alters noncanonical base patterns. Collectively, these structures indicate that 1 x 1 nucleotide UU internal loops in DM1 may sample multiple conformations in vivo. This observation has implications for the recognition of this RNA, and other repeating transcripts, by protein and small molecule ligands.« less

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

Singh, Mahavir; Wang, Zhonghua; Cascio, Duilio

Shq1 is an essential protein involved in the early steps of biogenesis and assembly of H/ACA ribonucleoprotein particles (RNPs). Shq1 binds to dyskerin (Cbf5 in yeast) at an early step of H/ACA RNP assembly and is subsequently displaced by the H/ACA RNA. Shq1 contains an N-terminal CS and a C-terminal Shq1-specific domain (SSD). Dyskerin harbors many mutations associated with dyskeratosis congenita. Structures of yeast Shq1 SSD bound to Cbf5 revealed that only a subset of these mutations is in the SSD binding site, implicating another subset in the putative CS binding site. Here in this paper, we present the crystalmore » structure of human Shq1 CS (hCS) and the nuclear magnetic resonance (NMR) and crystal structures of hCS containing a serine substitution for proline 22 that is associated with some prostate cancers. The structure of hCS is similar to yeast Shq1 CS domain (yCS) and consists of two β-sheets that form an immunoglobulin-like β-sandwich fold. The N-terminal affinity tag sequence AHHHHHH associates with a neighboring protein in the crystal lattice to form an extra β-strand. Deletion of this tag was required to get spectra suitable for NMR structure determination, while the tag was required for crystallization. NMR chemical shift perturbation (CSP) experiments with peptides derived from putative CS binding sites on dyskerin and Cbf5 revealed a conserved surface on CS important for Cbf5/dyskerin binding. A HADDOCK (high-ambiguity-driven protein-protein docking) model of a Shq1-Cbf5 complex that defines the position of CS domain in the pre-H/ACA RNP was calculated using the CSP data.« less

Petrology and geochemistry of primitive lower oceanic crust from Pito Deep: Implications for the accretion of the lower crust at the Southern East Pacific Rise

USGS Publications Warehouse

Perk, N.W.; Coogan, L.A.; Karson, J.A.; Klein, E.M.; Hanna, H.D.

2007-01-01

A suite of samples collected from the uppermost part of the plutonic section of the oceanic crust formed at the southern East Pacific Rise and exposed at the Pito Deep has been examined. These rocks were sampled in situ by ROV and lie beneath a complete upper crustal section providing geological context. This is only the second area (after the Hess Deep) in which a substantial depth into the plutonic complex formed at the East Pacific Rise has been sampled in situ and reveals significant spatial heterogeneity in the plutonic complex. In contrast to the uppermost plutonic rocks at Hess Deep, the rocks studied here are generally primitive with olivine forsterite contents mainly between 85 and 88 and including many troctolites. The melt that the majority of the samples crystallized from was aggregated normal mid-ocean ridge basalt (MORB). Despite this high Mg# clinopyroxene is common despite model predictions that clinopyroxene should not reach the liquidus early during low-pressure crystallization of MORB. Stochastic modeling of melt crystallisation at various levels in the crust suggests that it is unlikely that a significant melt mass crystallized in the deeper crust (for example in sills) because this would lead to more evolved shallow level plutonic rocks. Similar to the upper plutonic section at Hess Deep, and in the Oman ophiolite, many samples show a steeply dipping, axis-parallel, magmatic fabric. This suggests that vertical magmatic flow is an important process in the upper part of the seismic low velocity zone beneath fast-spreading ridges. We suggest that both temporal and spatial (along-axis) variability in the magmatic and hydrothermal systems can explain the differences observed between the Hess Deep and Pito Deep plutonics. ?? Springer-Verlag 2007.

Structure and Interactions of the CS Domain of Human H/ACA RNP Assembly Protein Shq1

DOE PAGES

Singh, Mahavir; Wang, Zhonghua; Cascio, Duilio; ...

2014-12-29

Shq1 is an essential protein involved in the early steps of biogenesis and assembly of H/ACA ribonucleoprotein particles (RNPs). Shq1 binds to dyskerin (Cbf5 in yeast) at an early step of H/ACA RNP assembly and is subsequently displaced by the H/ACA RNA. Shq1 contains an N-terminal CS and a C-terminal Shq1-specific domain (SSD). Dyskerin harbors many mutations associated with dyskeratosis congenita. Structures of yeast Shq1 SSD bound to Cbf5 revealed that only a subset of these mutations is in the SSD binding site, implicating another subset in the putative CS binding site. Here in this paper, we present the crystalmore » structure of human Shq1 CS (hCS) and the nuclear magnetic resonance (NMR) and crystal structures of hCS containing a serine substitution for proline 22 that is associated with some prostate cancers. The structure of hCS is similar to yeast Shq1 CS domain (yCS) and consists of two β-sheets that form an immunoglobulin-like β-sandwich fold. The N-terminal affinity tag sequence AHHHHHH associates with a neighboring protein in the crystal lattice to form an extra β-strand. Deletion of this tag was required to get spectra suitable for NMR structure determination, while the tag was required for crystallization. NMR chemical shift perturbation (CSP) experiments with peptides derived from putative CS binding sites on dyskerin and Cbf5 revealed a conserved surface on CS important for Cbf5/dyskerin binding. A HADDOCK (high-ambiguity-driven protein-protein docking) model of a Shq1-Cbf5 complex that defines the position of CS domain in the pre-H/ACA RNP was calculated using the CSP data.« less

Structural Basis of Arc Binding to Synaptic Proteins: Implications for Cognitive Disease

DOE PAGES

Zhang, Wenchi; Wu, Jing; Ward, Matthew D.; ...

2015-04-09

Arc is a cellular immediate-early gene (IEG) that functions at excitatory synapses and is required for learning and memory. Here we report crystal structures of Arc subdomains that form a bi-lobar architecture remarkably similar to the capsid domain of human immunodeficiency virus (HIV) gag protein. Analysis indicates Arc originated from the Ty3/Gypsy retrotransposon family and was “domesticated” in higher vertebrates for synaptic functions. The Arc N-terminal lobe evolved a unique hydrophobic pocket that mediates intermolecular binding with synaptic proteins as resolved in complexes with TARPγ2 (Stargazin) and CaMKII peptides and is essential for Arc’s synaptic function. A consensus sequence formore » Arc binding identifies several additional partners that include genes implicated in schizophrenia. Arc N-lobe binding is inhibited by small chemicals suggesting Arc’s synaptic action may be druggable. Finally, these studies reveal the remarkable evolutionary origin of Arc and provide a structural basis for understanding Arc’s contribution to neural plasticity and disease.« less

Exsolution lamellae as fast diffusion pathways in rutile: implications for U-Pb thermochronology and Zr thermometry

NASA Astrophysics Data System (ADS)

Smye, A.; Seman, S.; Roberts, N. M. W.; Condon, D. J.; Davis, B.

2017-12-01

Geophysical processes impart characteristic thermal signatures to the lithosphere. Near-continuous thermal histories can be obtained from inversion of intracrystalline U-Pb age profiles in rutile and apatite provided that it can be shown that profile formed in response to Fickian-type diffusion. Here, we present the results of a combined LA-ICPMS and ID-TIMS U-Pb study on rutile grains from two garnet-bearing granulite xenoliths from a kimberlite in the Archean Slave province. Interpreted using numerical models, we show that the rutile U-Pb isotope systematics are consistent with slow-cooling following crystallization at 1.2 Ga, contemporaneous with the Mackenzie dike swarm. However, inversion of rutile U-Pb age gradients is complicated by the ubiquitous presence of ilmenite exsolution lamellae. We show that these lamellae act as fast diffusion pathways for Pb and High Field Strength Elements, including Zr. This has important implications for the use of rutile as a U-Pb themochronometer and as a single-phase thermometer.

Structural Basis of Arc Binding to Synaptic Proteins: Implications for Cognitive Disease

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

Zhang, Wenchi; Wu, Jing; Ward, Matthew D.

Arc is a cellular immediate-early gene (IEG) that functions at excitatory synapses and is required for learning and memory. Here we report crystal structures of Arc subdomains that form a bi-lobar architecture remarkably similar to the capsid domain of human immunodeficiency virus (HIV) gag protein. Analysis indicates Arc originated from the Ty3/Gypsy retrotransposon family and was “domesticated” in higher vertebrates for synaptic functions. The Arc N-terminal lobe evolved a unique hydrophobic pocket that mediates intermolecular binding with synaptic proteins as resolved in complexes with TARPγ2 (Stargazin) and CaMKII peptides and is essential for Arc’s synaptic function. A consensus sequence formore » Arc binding identifies several additional partners that include genes implicated in schizophrenia. Arc N-lobe binding is inhibited by small chemicals suggesting Arc’s synaptic action may be druggable. Finally, these studies reveal the remarkable evolutionary origin of Arc and provide a structural basis for understanding Arc’s contribution to neural plasticity and disease.« less

Structural Basis of Arc Binding to Synaptic Proteins: Implications for Cognitive Disease

PubMed Central

Zhang, Wenchi; Wu, Jing; Ward, Matthew D.; Yang, Sunggu; Chuang, Yang-An; Xiao, Meifang; Li, Ruojing; Leahy, Daniel J.; Worley, Paul F.

2015-01-01

SUMMARY Arc is a cellular immediate early gene (IEG) that functions at excitatory synapses and is required for learning and memory. We report crystal structures of Arc subdomains that form a bi-lobar architecture remarkably similar to the capsid domain of human immunodeficiency virus (HIV) gag protein. Analysis indicates Arc originated from the Ty3/Gypsy retrotransposon family and was “domesticated” in higher vertebrates for synaptic functions. The Arc N-terminal lobe evolved a unique hydrophobic pocket that mediates intermolecular binding with synaptic proteins as resolved in complexes with TARPγ2 (Stargazin) and CaMKII peptides, and is essential for Arc’s synaptic function. A consensus sequence for Arc binding identifies several additional partners that include genes implicated in schizophrenia. Arc N-lobe binding is inhibited by small chemicals suggesting Arc’s synaptic action may be druggable. These studies reveal the remarkable evolutionary origin of Arc and provide a structural basis for understanding Arc’s contribution to neural plasticity and disease. PMID:25864631

Functional implications from the Cid1 poly(U) polymerase crystal structure.

PubMed

Munoz-Tello, Paola; Gabus, Caroline; Thore, Stéphane

2012-06-06

In eukaryotes, mRNA degradation begins with poly(A) tail removal, followed by decapping, and the mRNA body is degraded by exonucleases. In recent years, the major influence of 3'-end uridylation as a regulatory step within several RNA degradation pathways has generated significant attention toward the responsible enzymes, which are called poly(U) polymerases (PUPs). We determined the atomic structure of the Cid1 protein, the founding member of the PUP family, in its UTP-bound form, allowing unambiguous positioning of the UTP molecule. Our data also suggest that the RNA substrate accommodation and product translocation by the Cid1 protein rely on local and global movements of the enzyme. Supplemented by point mutations, the atomic model is used to propose a catalytic cycle. Our study underlines the Cid1 RNA binding properties, a feature with critical implications for miRNAs, histone mRNAs, and, more generally, cellular RNA degradation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Drop deployment system for crystal growth apparatus

NASA Technical Reports Server (NTRS)

Rhodes, Percy (Inventor); Snyder, Robert S. (Inventor); Pusey, Marc L. (Inventor)

1990-01-01

A crystal growth apparatus is presented. It utilizes a vapor diffusion method for growing protein crystals, and particularly such an apparatus wherein a ball mixer is used to mix the fluids that form a drop within which crystals are grown. Particular novelty of this invention lies in utilizing a ball mixer to completely mix the precipitate and protein solutions prior to forming the drop. Additional novelty lies in details of construction of the vials, the fluid deployment system, and the fluid storage system of the preferred embodiment.

Influence of temperature on the rhombic shape of paracetamol molecular crystals

NASA Astrophysics Data System (ADS)

Belyaev, A. P.; Rubets, V. P.; Antipov, V. V.

2017-04-01

The method of differential scanning ellipsometry has been used to study the influence of heating on the rhombic shape of paracetamol molecular crystals. Rhombic molecular paracetamol crystals have been synthesized in vacuum from the vapor phase of paracetamol as a result of complex transformation, which includes a second-order transition that gives rise to a pretransition phase. It has been found that these crystals contain monoclinic nuclei, which favor the form I-to-form II polymorphic transformation during heating.

Expression, purification and preliminary X-ray diffraction studies of the transcriptional factor PyrR from Bacillus halodurans

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

Arreola, Rodrigo; Vega-Miranda, Anita; Gómez-Puyou, Armando

The gene-regulation factor PyrR from B. halodurans has been crystallized in two crystal forms. Preliminary crystallographic analysis showed that the protein forms tetramers in both space groups. The PyrR transcriptional regulator is widely distributed in bacteria. This RNA-binding protein is involved in the control of genes involved in pyrimidine biosynthesis, in which uridyl and guanyl nucleotides function as effectors. Here, the crystallization and preliminary X-ray diffraction analysis of two crystal forms of Bacillus halodurans PyrR are reported. One of the forms belongs to the monoclinic space group P2{sub 1} with unit-cell parameters a = 59.7, b = 87.4, c =more » 72.1 Å, β = 104.4°, while the other form belongs to the orthorhombic space group P22{sub 1}2{sub 1} with unit-cell parameters a = 72.7, b = 95.9, c = 177.1 Å. Preliminary X-ray diffraction data analysis and molecular-replacement solution revealed the presence of four and six monomers per asymmetric unit; a crystallographic tetramer is formed in both forms.« less

Saturated Monoglyceride Polymorphism and Gel Formation of Biodiesel Blends

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

Chupka, Gina; Fouts, Lisa; McCormick, Robert

Crystallization or gel formation of normal paraffins in diesel fuel under cold weather conditions leading to fuel filter clogging is a common problem. Cold weather operability of biodiesel (B100) and blends with diesel fuel presents additional complexity because of the presence of saturated monoglycerides (SMGs) and other relatively polar species. Currently, the cloud point measurement (a measure of when the first component crystallizes out of solution) is used to define the lowest temperature at which the fuel can be used without causing cold weather issues. While filter plugging issues have declined, there still remain intermittent unexpected problems above the cloudmore » point for biodiesel blends. Development of a fundamental understanding of how minor components in biodiesel crystallize, gel, and transform is needed in order to prevent these unexpected issues. We have found that SMGs, a low level impurity present in B100 from the production process, can crystallize out of solution and undergo a solvent-mediated polymorphic phase transformation to a more stable, less soluble form. This causes them to persist at temperatures above the cloud point once they have some out of solution. Additionally, we have found that SMGs can cause other more soluble, lower melting point minor components in the B100 to co-crystallize and come out of solution. Monoolein, another minor component from the production process is an unsaturated monoglyceride with a much lower melting point and higher solubility than SMGs. It is able to form a co-crystal with the SMGs and is found together with the SMGs on plugged filters we have analyzed in our laboratory. An observation of isolated crystals in the lab led us to believe that the SMGs may also be forming a gel-like network with components of the B100 and diesel fuel. During filtration experiments, we have noted that in some cases a solid layer of crystals forms and blocks the filter completely, while in other cases this does not occur. Because SMGs are polar and can form layered networks once a sufficient amount of crystals have come out of solution, we recently began investigating the ability of SMGs to form a gel network with fuel components as well as with other minor polar components in the fuel in order to obtain a fundamental understanding of the mechanism of formation. It has been well established that this type of phenomena occurs in sub-sea pipelines where a chief crystallizing component begins to crystallize out of solution. Once a sufficient amount of crystals exists, a volume spanning network of solid crystals can trap liquid crude oil and form a solid-like gel network. We are investigating whether this type of phenomena can occur with SMGs and both fatty acid methyl esters from the B100 and normal paraffins from diesel fuel. Additionally, SMGs are well known to incorporate water into their layered crystal structure. Water is often used to stabilize less stable polymorphic forms of SMGs, therefore water was another minor component of interest. Also of interest is glycerin which has been found on clogged filters in our laboratory.« less

Scanning electron microscope view of iron crystal growing on pyroxene crystal

NASA Technical Reports Server (NTRS)

1972-01-01

A scanning electron microscope photograph of a four-micron size iron crystal growing on a pyroxene crystal (calcium-magnesium-iron silicate) from the Apollo 15 Hadley-Apennino lunar landing site. The well developed crystal faces indicate that the crystal was formed from a hot vapor as the rock was cooling.

Effect of coccolith polysaccharides isolated from the coccolithophorid, Emiliania huxleyi, on calcite crystal formation in in vitro CaCO3 crystallization.

PubMed

Kayano, Keisuke; Saruwatari, Kazuko; Kogure, Toshihiro; Shiraiwa, Yoshihiro

2011-02-01

Marine coccolithophorids (Haptophyceae) produce calcified scales "coccoliths" which are composed of CaCO(3) and coccolith polysaccharides (CP) in the coccolith vesicles. CP was previously reported to be composed of uronic acids and sulfated residues, etc. attached to the polymannose main chain. Although anionic polymers are generally known to play key roles in biomineralization process, there is no experimental data how CP contributes to calcite crystal formation in the coccolithophorids. CP used was isolated from the most abundant coccolithophorid, Emiliania huxleyi. CaCO(3) crystallization experiment was performed on agar template layered onto a plastic plate that was dipped in the CaCO(3) crystallization solution. The typical rhombohedral calcite crystals were formed in the absence of CP. CaCO(3) crystals formed on the naked plastic plate were obviously changed to stick-like shapes when CP was present in the solution. EBSD analysis proved that the crystal is calcite of which c-axis was elongated. CP in the solution stimulated the formation of tabular crystals with flat edge in the agarose gel. SEM and FIB-TEM observations showed that the calcite crystals were formed in the gel. The formation of crystals without flat edge was stimulated when CP was preliminarily added in the gel. These observations suggest that CP has two functions: namely, one is to elongate the calcite crystal along c-axis and another is to induce tabular calcite crystal formation in the agarose gel. Thus, CP may function for the formation of highly elaborate species-specific structures of coccoliths in coccolithophorids.

Crystallization and preliminary X-ray crystallographic analysis of latent isoform PPO4 mushroom (Agaricus bisporus) tyrosinase

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

Mauracher, Stephan Gerhard; Molitor, Christian; Al-Oweini, Rami

Polyphenol oxidase 4 (PPO4) from the natural source A. bisporus was crystallized in its latent precursor form (pro-tyrosinase; Ser2–Thr565) using the 6-tungstotellurate(VI) salt Na{sub 6}[TeW{sub 6}O{sub 24}]·22H{sub 2}O as a crystallization additive. Tyrosinase exhibits catalytic activity for the ortho-hydroxylation of monophenols to diphenols as well as their subsequent oxidation to quinones. Owing to polymerization of these quinones, brown-coloured high-molecular-weight compounds called melanins are generated. The latent precursor form of polyphenol oxidase 4, one of the six tyrosinase isoforms from Agaricus bisporus, was purified to homogeneity and crystallized. The obtained crystals belonged to space group C121 (two molecules per asymmetric unit)more » and diffracted to 2.78 Å resolution. The protein only formed crystals under low-salt conditions using the 6-tungstotellurate(VI) salt Na{sub 6}[TeW{sub 6}O{sub 24}]·22H{sub 2}O as a co-crystallization agent.« less

Sodium chloride crystallization from thin liquid sheets, thick layers, and sessile drops in microgravity

NASA Astrophysics Data System (ADS)

Fontana, Pietro; Pettit, Donald; Cristoforetti, Samantha

2015-10-01

Crystallization from aqueous sodium chloride solutions as thin liquid sheets, 0.2-0.7 mm thick, with two free surfaces supported by a wire frame, thick liquid layers, 4-6 mm thick, with two free surfaces supported by metal frame, and hemispherical sessile drops, 20-32 mm diameter, supported by a flat polycarbonate surface or an initially flat gelatin film, were carried out under microgravity on the International Space Station (ISS). Different crystal morphologies resulted based on the fluid geometry: tabular hoppers, hopper cubes, circular [111]-oriented crystals, and dendrites. The addition of polyethylene glycol (PEG-3350) inhibited the hopper growth resulting in flat-faced surfaces. In sessile drops, 1-4 mm tabular hopper crystals formed on the free surface and moved to the fixed contact line at the support (polycarbonate or gelatin) self-assembling into a shell. Ring formation created by sessile drop evaporation to dryness was observed but with crystals 100 times larger than particles in terrestrially formed coffee rings. No hopper pyramids formed. By choosing solution geometries offered by microgravity, we found it was possible to selectively grow crystals of preferred morphologies.

Crystallization kinetics and molecular mobility of an amorphous active pharmaceutical ingredient: A case study with Biclotymol.

PubMed

Schammé, Benjamin; Couvrat, Nicolas; Malpeli, Pascal; Delbreilh, Laurent; Dupray, Valérie; Dargent, Éric; Coquerel, Gérard

2015-07-25

The present case study focuses on the crystallization kinetics and molecular mobility of an amorphous mouth and throat drug namely Biclotymol, through differential scanning calorimetry (DSC), temperature resolved X-ray powder diffraction (TR-XRPD) and hot stage microscopy (HSM). Kinetics of crystallization above the glass transition through isothermal and non-isothermal cold crystallization were considered. Avrami model was used for isothermal crystallization process. Non-isothermal cold crystallization was investigated through Augis and Bennett model. Differences between crystallization processes have been ascribed to a site-saturated nucleation mechanism of the metastable form, confirmed by optical microscopy images. Regarding molecular mobility, a feature of molecular dynamics in glass-forming liquids as thermodynamic fragility index m was determined through calorimetric measurements. It turned out to be around m=100, describing Biclotymol as a fragile glass-former for Angell's classification. Relatively long-term stability of amorphous Biclotymol above Tg was analyzed indirectly by calorimetric monitoring to evaluate thermodynamic parameters and crystallization behavior of glassy Biclotymol. Within eight months of storage above Tg (T=Tg+2°C), amorphous Biclotymol does not show a strong inclination to crystallize and forms a relatively stable glass. This case study, involving a multidisciplinary approach, points out the importance of continuing looking for stability predictors. Copyright © 2015 Elsevier B.V. All rights reserved.

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals

PubMed Central

Freeman, Colin L.; Gong, Xiuqing; Levenstein, Mark A.; Wang, Yunwei; Kulak, Alexander; Anduix‐Canto, Clara; Lee, Phillip A.; Li, Shunbo; Chen, Li; Christenson, Hugo K.

2017-01-01

Abstract As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg2+ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism. PMID:28767197

Crystallization of isoelectrically homogeneous cholera toxin

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

Spangler, B.D.; Westbrook, E.M.

1989-02-07

Past difficulty in growing good crystals of cholera toxin has prevented the study of the crystal structure of this important protein. The authors have determined that failure of cholera toxin to crystallize well has been due to its heterogeneity. They have now succeeded in overcoming the problem by isolating a single isoelectric variant of this oligomeric protein (one A subunit and five B subunits). Cholera toxin purified by their procedure readily forms large single crystals. The crystal form has been described previously. They have recorded data from native crystals of cholera toxin to 3.0-{angstrom} resolution with our electronic area detectors.more » With these data, they have found the orientation of a 5-fold symmetry axis within these crystals, perpendicular to the screw dyad of the crystal. They are now determining the crystal structure of cholera toxin by a combination of multiple heavy-atom isomorphous replacement and density modification techniques, making use of rotational 5-fold averaging of the B subunits.« less

Influence of additive L-phenylalanine on stabilization of metastable α-form of L-glutamic acid in cooling crystallization

NASA Astrophysics Data System (ADS)

Quang, Khuu Chau; Nhan, Le Thi Hong; Huyen, Trinh Thi Thanh; Tuan, Nguyen Anh

2017-09-01

The influence of additive amino acid L-phenylalanine on stabilization of metastable α-form of L-glutamic acid was investigated in cooling crystallization. The present study found that the additive L-phenylalanine could be used to stabilize the pure metastable α-form in L-glutamic acid crystallization, where the additive concentration of 0.05-0.1 (g/L) was sufficient to stabilize the 100% wt metastable α-form in solid product at L-glutamic acid concentration of 30-45 (g/L). Additionally, the present results indicated that the adsorption of additive L-phenylalanine on the (001) surface of α-form was more favorable than that of the β-form molecular, so the nucleation sites of stable β-form was occupied by additive molecular, which resulted in inhibition of nucleation and growth of β-form, allowing stabilization of metastable α-form.

Development of a New Class of Drugs to Inhibit All Forms of Androgen Receptor in Castration Resistant Prostate Cancers

DTIC Science & Technology

2016-10-01

previous rat ARdbd-DNA crystals and may represent a new crystal form. Key outcome 2: We have carried out followup crystallization screening...to VPC-14449 as a model drug to assist on other related projects. 1. Tam, K., Dalal, K., Hsing, M., Cheng, C.W., Chiang , Y.T., Sharma, A., Peacock

Development of a New Class of Drugs To Inhibit All Forms of Androgen Receptor in Castration Resistant Prostate Cancers

DTIC Science & Technology

2016-10-01

crystals and may represent a new crystal form. Key outcome 2: We have carried out followup crystallization screening operations with the ARdbd protein...related projects. 1. Tam, K., Dalal, K., Hsing, M., Cheng, C.W., Chiang , Y.T., Sharma, A., Peacock, J.W., Wang, W., Cherkasov, A., Rennie, P.S

A co-crystal between benzene and ethane: a potential evaporite material for Saturn’s moon Titan

PubMed Central

Maynard-Casely, Helen E.; Hodyss, Robert; Cable, Morgan L.; Vu, Tuan Hoang; Rahm, Martin

2016-01-01

Using synchrotron X-ray powder diffraction, the structure of a co-crystal between benzene and ethane formed in situ at cryogenic conditions has been determined, and validated using dispersion-corrected density functional theory calculations. The structure comprises a lattice of benzene molecules hosting ethane molecules within channels. Similarity between the intermolecular interactions found in the co-crystal and in pure benzene indicate that the C—H⋯π network of benzene is maintained in the co-crystal, however, this expands to accommodate the guest ethane molecules. The co-crystal has a 3:1 benzene:ethane stoichiometry and is described in the space group with a = 15.977 (1) Å and c = 5.581 (1) Å at 90 K, with a density of 1.067 g cm−3. The conditions under which this co-crystal forms identify it is a potential that forms from evaporation of Saturn’s moon Titan’s lakes, an evaporite material. PMID:27158505

The evolution of young silicic lavas at Medicine Lake Volcano, California: Implications for the origin of compositional gaps in calc-alkaline series lavas

USGS Publications Warehouse

Grove, T.L.; Donnelly-Nolan, J. M.

1986-01-01

At Medicine Lake Volcano, California, the compositional gap between andesite (57-62 wt.% SiO2) and rhyolite (73-74 wt.% SiO2) has been generated by fractional crystallization. Assimilation of silicic crust has also occurred along with fractionation. Two varieties of inclusions found in Holocene rhyolite flows, hornblende gabbros and aphyric andesites, provide information on the crystallization path followed by lavas parental to the rhyolite. The hornblende gabbros are magmatic cumulate residues and their mineral assemblages are preserved evidence of the phases that crystallized from an andesitic precursor lava to generate the rhyolite lavas. The andesitic inclusions represent samples of a parental andesite and record the early part of the differentiation history. Olivine, plagioclase and augite crystallization begins the differentiation history, followed by the disappearance of olivine and augite through reaction with the liquid to form orthopyroxene and amphibole. Further crystallization of the assemblage plagioclase, amphibole, orthopyroxene, magnetite, and apatite from a high-SiO2 andesite leads to rhyolite. This final crystallization process occurs on a cotectic that is nearly horizontal in temperature-composition space. Since a large amount of crystallization occurs over a limited temperature interval, a compositional gap develops between rhyolite and high SiO2 andesite. Liquidus surfaces with shallow slopes in temperature-composition space are characteristic of several late-stage crystallization assemblages in the andesite to rhyolite compositional range. Experimentally produced plagioclase+ amphibole+orthopyroxene+magnetite and plagioclase+ augite+low-Ca pyroxene+magnetite cotectics have liquidus slopes that are nearly flat. At other calc-alkaline volcanic centers crystallization processes involving large compositional changes over small temperature intervals may also be important in the development of bimodal volcanism (i.e. the existence of a composition gap). At Mt. Mazama and Mt. St. Helens, USA and Aso Caldera and Shikotsu, Japan the amphibole-bearing assemblage was important. At Krakatau, Indonesia and Katmai, USA, an augite+orthopyroxene-bearing assemblage was important. In addition to its role in the production of a compositional gap between intermediate and rhyolitic lavas, the crystallization process increases the H2O content of the residual liquid. This rapid increase in residual liquid volatile content which results from the precipitation of a large proportion of crystalline solids may be an important factor among several that lead to explosive silicic eruptions. ?? 1986 Springer-Verlag.

Contortionist bubbles in andesitic enclaves: implications for gas migration and phase segregation in crystal-rich magmas.

NASA Astrophysics Data System (ADS)

Oppenheimer, J. C.; Cashman, K. V.; Rust, A.; Dobson, K. J.; Bacon, C. R.; Dingwell, D. B.

2016-12-01

In order to constrain gas migration behaviors in crystal-rich magmas, we compare results of analogue experiments to frozen structures in andesitic enclaves. In the analogue experiments air was injected into mixtures of syrup and particles sandwiched between glass plates. We observed a significant increase in bubble deformation and coalescence when particle fractions increased beyond a critical value (the random loose packing). At high particle fractions, bubble growth re-organized (compacted) the particles adjacent to the bubble walls. This caused liquid segregation into patches within the particle suspension and into large void spaces near the outer edge of experiments. We compare these experiments to void morphologies in a 58 x 70 x 73 cm andesitic enclave from silicic-andesite lava flows of Mt Mazama, Oregon (Bacon, 1986). This enclave is zoned, with a vesicle-rich center and a glass-rich rim, suggesting gas-driven melt segregation from the center to the rim. We use both 2D (optical microscopy and SEM) and 3D (X-ray tomography) techniques to image crystal textures and bubble shapes. The center of the enclave bears scattered patches of groundmass in the main phenocryst framework. These patches are similar to those observed in experiments, and thus melt segregation in the enclave may have occurred both toward the rim and toward these patches. Bubble morphologies reveal two main types of bubbles. (1) Lobate and finger-like bubbles, similar to the deformed bubbles in experiments, are found exclusively in the groundmass patches. They are also often associated with compacted crystal structures at the bubble walls. (2) Diktytaxitic textures - angular bubbles flattened against phenocrysts - are abundant in the crystal networks. These voids are entirely connected in 3D and formed the gas-rich center of the enclave. They likely represent a gas migration regime where the expanding gas front cannot deform the crystal structure but instead invades the pore-space between crystals, pushing out residual melt (filter pressing). The switch between regimes appears to depend on crystal size and aspect ratio. The similar features between bubbles in the enclave and in experiments are encouraging, and suggest that crystal-induced bubble deformation, and gas-driven melt segregation, may be common in crystal-rich magmas.

The defective nature of ice Ic and its implications for atmospheric science

NASA Astrophysics Data System (ADS)

Kuhs, W. F.; Hansen, T. C.

2009-04-01

The possible atmospheric implication of ice Ic (cubic ice) has already been suggested some time ago in the context of snow crystal formation [1]. New findings from air-borne measurements in cirrus clouds and contrails have put ice Ic into the focus of interest to understand the so-called "supersaturation puzzle" [2,3,4,5]. Our recent microstructural work on ice Ic [6,7] appears to be highly relevant in this context. We have found that ice Ic is characterized by a complex stacking fault pattern, which changes as a function of temperature as well as time. Indeed, from our own [8] and other group's work [9] one knows that (in contrast to earlier believe) ice Ic can form up to temperatures at least as high as 240K - thus in the relevant range for cirrus clouds. We have good preliminary evidence that the "cubicity" (which can be related to stacking fault probabilities) as well as the particle size of ice Ic are the relevant parameters for this correlation. The "cubicity" of stacking faulty ice Ic (established by diffraction) correlates nicely with the increased supersaturation at decreasing temperatures observed in cirrus clouds and contrails, a fact, which may be considered as further evidence for the presence of ice Ic. Moreover, the stacking faults lead to kinks in the outer shapes of the minute ice Ic crystals as seen by cryo scanning electron microscopy (cryo-SEM); these defective sites are likely to play some role in heterogeneous reactions in the atmosphere. The cryo-SEM work suggests that stacking-faulty ice Ic has many more active centres for such reactions than the usually considered thermodynamically stable form, ice Ih. [1] T Kobayashi & T Kuroda (1987) Snow Crystals. In: Morphology of Crystals (ed. I Sunagawa), Terra Scientific Publishing, Tokyo, pp.649-743. [2] DM Murphy (2003) Dehydration in cold clouds is enhanced by a transition from from cubic to hexagonal ice. Geophys.Res.Lett.,30, 2230, doi:10.1029/2003GL018566. [3] RS Gao & 19 other authors (2004) Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds. Science 303, 516-520. [4] T Peter, C Marcolli, P Spaichinger, T Corti, MC Baker & T Koop (2006) When dry air is too humid. Science 314, 1399-1402. [5] JE Shilling, MA Tolbert, OB Toon, EJ Jensen, BJ Murray & AK Bertram (2006) Measurements of the vapor pressure of cubic ice and their implications for atmospheric ice clouds. Geophys.Res.Lett. 33, 026671. [6] TC Hansen, MM Koza & WF Kuhs (2008) Formation and annealing of cubic ice: I Modelling of stacking faults. J.Phys.Cond.Matt. 20, 285104. [7] TC Hansen, MM Koza, P Lindner & WF Kuhs (2008) Formation and annealing of cubic ice: II. Kinetic study. J.Phys.Cond.Matt. 20, 285105. [8] WF Kuhs, G Genov, DK Staykova & AN Salamatin (2004) Ice perfection and the onset of anomalous preservation of gas hydrates. Phys.Chem.Chem.Phys. 6, 4917-4920. [9] BJ Murray, DA Knopf & AK Bertram (2005) The formation of cubic ice under conditions relevant to Earth's atmosphere. Nature 434, 292-205.

Crystallization of the Nonameric Small Terminase Subunit of Bacteriophage P22

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

A Roy; A Bhardwaj; G Cingolani

2011-12-31

The packaging of viral genomes into preformed empty procapsids is powered by an ATP-dependent genome-translocating motor. This molecular machine is formed by a heterodimer consisting of large terminase (L-terminase) and small terminase (S-terminase) subunits, which is assembled into a complex of unknown stoichiometry, and a dodecameric portal protein. There is considerable confusion in the literature regarding the biologically relevant oligomeric state of terminases, which, like portal proteins, form ring-like structures. The number of subunits in a hollow oligomeric protein defines the internal diameter of the central channel and the ability to fit DNA inside. Thus, knowledge of the exact stoichiometrymore » of terminases is critical to decipher the mechanisms of terminase-dependent DNA translocation. Here, the gene encoding bacteriophage P22 S-terminase in Escherichia coli has been overexpressed and the protein purified under native conditions. In the absence of detergents and/or denaturants that may cause disassembly of the native oligomer and formation of aberrant rings, it was found that P22 S-terminase assembles into a concentration-independent nonamer of {approx}168 kDa. Nonameric S-terminase was crystallized in two different crystal forms at neutral pH. Crystal form I belonged to space group P2{sub 1}2{sub 1}2, with unit-cell parameters a = 144.2, b = 144.2, c = 145.3 {angstrom}, and diffracted to 3.0 {angstrom} resolution. Crystal form II belonged to space group P2{sub 1}, with unit-cell parameters a = 76.48, b = 100.9, c = 89.95 {angstrom}, {beta} = 93.73{sup o}, and diffracted to 1.75 {angstrom} resolution. Preliminary crystallographic analysis of crystal form II confirms that the S-terminase crystals contain a nonamer in the asymmetric unit and are suitable for high-resolution structure determination.« less

Crystallization of the Nonameric Small Terminase Subunit of bacteriophage P22

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

A Roy; A Bhardwaj; G Cingoloni

2011-12-31

The packaging of viral genomes into preformed empty procapsids is powered by an ATP-dependent genome-translocating motor. This molecular machine is formed by a heterodimer consisting of large terminase (L-terminase) and small terminase (S-terminase) subunits, which is assembled into a complex of unknown stoichiometry, and a dodecameric portal protein. There is considerable confusion in the literature regarding the biologically relevant oligomeric state of terminases, which, like portal proteins, form ring-like structures. The number of subunits in a hollow oligomeric protein defines the internal diameter of the central channel and the ability to fit DNA inside. Thus, knowledge of the exact stoichiometrymore » of terminases is critical to decipher the mechanisms of terminase-dependent DNA translocation. Here, the gene encoding bacteriophage P22 S-terminase in Escherichia coli has been overexpressed and the protein purified under native conditions. In the absence of detergents and/or denaturants that may cause disassembly of the native oligomer and formation of aberrant rings, it was found that P22 S-terminase assembles into a concentration-independent nonamer of {approx}168 kDa. Nonameric S-terminase was crystallized in two different crystal forms at neutral pH. Crystal form I belonged to space group P2{sub 1}2{sub 1}2, with unit-cell parameters a = 144.2, b = 144.2, c = 145.3 {angstrom}, and diffracted to 3.0 {angstrom} resolution. Crystal form II belonged to space group P2{sub 1}, with unit-cell parameters a = 76.48, b = 100.9, c = 89.95 {angstrom}, {beta} = 93.73{sup o}, and diffracted to 1.75 {angstrom} resolution. Preliminary crystallographic analysis of crystal form II confirms that the S-terminase crystals contain a nonamer in the asymmetric unit and are suitable for high-resolution structure determination.« less

Crystallization and preliminary X-ray diffraction studies of vitamin D3 hydroxylase, a novel cytochrome P450 isolated from Pseudonocardia autotrophica

PubMed Central

Yasutake, Yoshiaki; Fujii, Yoshikazu; Cheon, Woo-Kwang; Arisawa, Akira; Tamura, Tomohiro

2009-01-01

Vitamin D3 hydroxylase (Vdh) is a novel cytochrome P450 monooxygenase isolated from the actinomycete Pseudonocardia autotrophica and consisting of 403 amino-acid residues. Vdh catalyzes the activation of vitamin D3 via sequential hydroxylation reactions: these reactions involve the conversion of vitamin D3 (cholecalciferol or VD3) to 25-hydroxyvitamin D3 [25(OH)VD3] and the subsequent conversion of 25(OH)VD3 to 1α,25-dihydroxyvitamin D3 [calciferol or 1α,25(OH)2VD3]. Overexpression of recombinant Vdh was carried out using a Rhodococcus erythropolis expression system and the protein was subsequently purified and crystallized. Two different crystal forms were obtained by the hanging-drop vapour-diffusion method at 293 K using polyethylene glycol as a precipitant. The form I crystal belonged to the trigonal space group P31, with unit-cell parameters a = b = 61.7, c = 98.8 Å. There is one Vdh molecule in the asymmetric unit, with a solvent content of 47.6%. The form II crystal was grown in the presence of 25(OH)VD3 and belonged to the orthorhombic system P212121, with unit-cell parameters a = 63.4, b = 65.6 c = 102.2 Å. There is one Vdh molecule in the asymmetric unit, with a solvent content of 46.7%. Native data sets were collected to resolutions of 1.75 and 3.05 Å for form I and form II crystals, respectively, using synchrotron radiation. The structure solution was obtained by the molecular-replacement method and model refinement is in progress for the form I crystal. PMID:19342783

Preparation of interesterified plastic fats from fats and oils free of trans fatty acid.

PubMed

Lee, Jeung Hee; Akoh, Casimir C; Himmelsbach, David S; Lee, Ki-Teak

2008-06-11

Interesterified plastic fats were produced with trans-free substrates of fully hydrogenated soybean oil, extra virgin olive oil, and palm stearin in a weight ratio of 10:20:70, 10:40:50, and 10:50:40, respectively, by lipase catalysis. The major fatty acids of the products were palmitic (32.2-47.4%), stearic (12.0-12.4%), and oleic acid (33.6-49.5%). After storage at 5 degrees C (refrigerator temperature) or 24 degrees C (room temperature) for 16 h, the physical properties were evaluated for solid fat content, texture, melting, and crystallization behavior, viscoelastic properties, crystal polymorphism, and crystal microstructure. The interesterified fats contained desirable crystal polymorphs (beta' form) as determined by X-ray diffraction spectroscopy. They exhibited a wide plastic range of solid fat content of 52-58% at 10 degrees C and 15% at 40 degrees C. The physical properties were influenced by the ratio of palm stearin and olive oil. Harder and more brittle texture, crystallization and melting at higher temperature, higher solid fat contents, and more elastic (G') or viscous (G') characteristics were observed in the produced fats containing a higher content of palm stearin and lower content of olive oil. The produced fats stored at 5 degrees C consisted mostly of beta' form crystal together with a small content of beta form, while those at 24 degrees C had only beta' form. The produced fat with a higher amount of palm stearin appeared to have more beta' form crystal and small size crystal clusters. Thus, the physical properties of the produced plastic fats may be desirable for use in a bakery product.

Polarization-resolved second-harmonic generation microscopy as a method to visualize protein-crystal domains

PubMed Central

DeWalt, Emma L.; Begue, Victoria J.; Ronau, Judith A.; Sullivan, Shane Z.; Das, Chittaranjan; Simpson, Garth J.

2013-01-01

Polarization-resolved second-harmonic generation (PR-SHG) microscopy is described and applied to identify the presence of multiple crystallographic domains within protein-crystal conglomerates, which was confirmed by synchrotron X-ray diffraction. Principal component analysis (PCA) of PR-SHG images resulted in principal component 2 (PC2) images with areas of contrasting negative and positive values for conglomerated crystals and PC2 images exhibiting uniformly positive or uniformly negative values for single crystals. Qualitative assessment of PC2 images allowed the identification of domains of different internal ordering within protein-crystal samples as well as differentiation between multi-domain conglomerated crystals and single crystals. PR-SHG assessments of crystalline domains were in good agreement with spatially resolved synchrotron X-ray diffraction measurements. These results have implications for improving the productive throughput of protein structure determination through early identification of multi-domain crystals. PMID:23275165

Oriented attachment by enantioselective facet recognition in millimeter-sized gypsum crystals.

PubMed

Viedma, Cristóbal; Cuccia, Louis A; McTaggart, Alicia; Kahr, Bart; Martin, Alexander T; McBride, J Michael; Cintas, Pedro

2016-09-22

Crystal growth by oriented attachment involves the spontaneous self-assembly of adjoining crystals with common crystallographic orientations. Herein, we report the oriented attachment of gypsum crystals on agitation to form stereoselective mesoscale aggregates.

Crystal structure of minoxidil at low temperature and polymorph prediction.

PubMed

Martín-Islán, Africa P; Martín-Ramos, Daniel; Sainz-Díaz, C Ignacio

2008-02-01

An experimental and theoretical investigation on crystal forms of the popular and ubiquitous pharmaceutical Minoxidil is presented here. A new crystallization method is presented for Minoxidil (6-(1-piperidinyl)-2,4-pyrimidinediamide 3-oxide) in ethanol-poly(ethylene glycol), yielding crystals with good quality. The crystal structure is determined at low temperature, with a final R value of 0.035, corresponding to space group P2(1) (monoclinic) with cell dimensions a = 9.357(1) A, b = 8.231(1) A, c = 12.931(2) A, and beta = 90.353(4) degrees . Theoretical calculations of the molecular structure of Minoxidil are set forward using empirical force fields and quantum-mechanical methods. A theoretical prediction for Minoxidil crystal structure shows many possible polymorphs. The predicted crystal structures are compared with X-ray experimental data obtained in our laboratory, and the experimental crystal form is found to be one of the lowest energy polymorphs.

X-ray structural studies and physicochemical characterization of (E)-6-(3,4-dimethoxyphenyl)-1-ethyl-4-mesitylimino-3-methyl- 3,4-dihydro-2(1H)-pyrimidinone polymorphs.

PubMed

Miyamae, A; Kitamura, S; Tada, T; Koda, S; Yasuda, T

1991-10-01

The polymorphism of (E)-6-(3,4-dimethoxyphenyl)-1-ethyl-4-mesitylimino-3-methyl-3,4-di hydro- 2(1 H)-pyrimidinone (FK664; 1) was characterized by using X-ray powder diffractometry, differential scanning calorimetry (DSC), and IR spectroscopy. Structures of two polymorphs (Forms A and B) were determined by X-ray crystallographic analysis. Form A crystallized in the monoclinic space group P2(1)/c, with a = 13.504(2), b = 6.733(1), c = 24.910(8) A, beta = 96.55(4) degrees, z = 4, and dcal = 1.203 g/cm3, while Form B crystallized in the same space group, with a = 8.067(2), b = 15.128(4), c = 18.657(4) A, beta = 102.34(3) degrees, z = 4, and dcal = 1.216 g/cm3. The conformational features of 1 were very similar between the two polymorphs. Compound 1, in both crystal forms, took an energetically reasonable conformation in three rigid planes, such as 2-pyrimidone, trimethylphenyl, and dimethoxyphenyl rings, but the molecules were packed in different ways between the two polymorphs. In the Form B crystal, a short contact was possible, to form pi-pi interactions between two dimethoxyphenyl groups related with the inversion center in the crystal lattice; this interaction seems to contribute to stabilizing the crystal structure of Form B. Both Forms A and B showed only one endothermic peak due to fusion at 115 and 140 degrees C, respectively, on the DSC thermograms; therefore, it is suggested that there are no transition points between the two polymorphs. The heats of fusion obtained from the DSC thermograms were 33.2(2) kJ/mol for Form A and 36.8(1) kJ/mol for Form B.(ABSTRACT TRUNCATED AT 250 WORDS)

Two-dimensionally grown single-crystal silicon nanosheets with tunable visible-light emissions.

PubMed

Kim, Sung Wook; Lee, Jaejun; Sung, Ji Ho; Seo, Dong-jae; Kim, Ilsoo; Jo, Moon-Ho; Kwon, Byoung Wook; Choi, Won Kook; Choi, Heon-Jin

2014-07-22

Since the discovery of graphene, growth of two-dimensional (2D) nanomaterials has greatly attracted attention. However, spontaneous growth of atomic two-dimensional (2D) materials is limitedly permitted for several layered-structure crystals, such as graphene, MoS2, and h-BN, and otherwise it is notoriously difficult. Here we report the gas-phase 2D growth of silicon (Si), that is cubic in symmetry, via dendritic growth and an interdendritic filling mechanism and to form Si nanosheets (SiNSs) of 1 to 13 nm in thickness. Thin SiNSs show strong thickness-dependent photoluminescence in visible range including red, green, and blue (RGB) emissions with the associated band gap energies ranging from 1.6 to 3.2 eV; these emission energies were greater than those from Si quantum dots (SiQDs) of the similar sizes. We also demonstrated that electrically driven white, as well as blue, emission in a conventional organic light-emitting diode (OLED) geometry with the SiNS assembly as the active emitting layers. Tunable light emissions in visible range in our observations suggest practical implications for novel 2D Si nanophotonics.

Thermodynamic properties and crystallization kinetics at high liquid undercooling

NASA Technical Reports Server (NTRS)

Fecht, Hans J.

1990-01-01

The heat capacities of liquid and crystalline Au-Pb-Sb alloys in the glass-forming composition range were measured with droplet emulsion and bulk samples. Based on the measured C(sub p) data, the entropy, enthalpy, and Gibbs free energy functions of the eutectic, solid mixture, and undercooled liquid were determined as a function of undercooling and compared with theoretical predictions. The results indicate an isentropic temperature at 313 + or - 5 K, which agrees well with experimental data for the glass transition. A kinetics analysis of the nucleation undercooling response suggests that the proper choice for the Gibbs free energy change during crystallization is most important in analyzing the nucleation kinetics. By classical nucleation theory, the prefactors obtained, based on a variety of theoretical predictions for the driving force, can differ by six orders of magnitude. If the nucleation rates are extrapolated to high undercooling, the extrapolations based on measured heat capacity data show agreement, whereas the predicted nucleation rates are inconsistent with results from drop tower experiments. The implications for microg experiments are discussed.

Effect of Intrinsic Twist on Length of Crystalline and Disordered Regions in Cellulose Microfibrils

NASA Astrophysics Data System (ADS)

Nili, Abdolmadjid; Shklyaev, Oleg; Zhao, Zhen; Zhong, Linghao; Crespi, Vincent

2013-03-01

Cellulose is the most abundant biological material in the world. It provides mechanical reinforcement for plant cell wall, and could potentially serve as renewable energy source for biofuel. Native cellulose forms a non-centrosymmetric chiral crystal due to lack of roto-inversion symmetry of constituent glucose chains. Chirality of cellulose crystal could result in an overall twist. Competition between unwinding torsional/extensional and twisting energy terms leads to twist induced frustration along fibril's axis. The accumulated frustration could be the origin of periodic disordered regions observed in cellulose microfibrils. These regions could play significant role in properties of cellulose bundles and ribbons as well as biological implications on plant cell walls. We propose a mechanical model based on Frenkel-Kontorova mechanism to investigate effects of radius dependent twist on crystalline size in cellulose microfibrils. Parameters of the model are adjusted according to all-atom molecular simulations. This work is supported by the US Department of Energy, Office of Basic Energy Sciences as part of The Center for LignoCellulose Structure and Formation, an Energy Frontier Research Center

Identification of the first small-molecule ligand of the neuronal receptor sortilin and structure determination of the receptor–ligand complex

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

Andersen, Jacob Lauwring, E-mail: jla@mb.au.dk; Schrøder, Tenna Juul; Christensen, Søren

2014-02-01

The identification of the first small-molecule ligand of the neuronal receptor sortilin and structure determination of the receptor–ligand complex are reported. Sortilin is a type I membrane glycoprotein belonging to the vacuolar protein sorting 10 protein (Vps10p) family of sorting receptors and is most abundantly expressed in the central nervous system. Sortilin has emerged as a key player in the regulation of neuronal viability and has been implicated as a possible therapeutic target in a range of disorders. Here, the identification of AF40431, the first reported small-molecule ligand of sortilin, is reported. Crystals of the sortilin–AF40431 complex were obtained bymore » co-crystallization and the structure of the complex was solved to 2.7 Å resolution. AF40431 is bound in the neurotensin-binding site of sortilin, with the leucine moiety of AF40431 mimicking the binding mode of the C-terminal leucine of neurotensin and the 4-methylumbelliferone moiety of AF40431 forming π-stacking with a phenylalanine.« less

Process for Encapsulating Protein Crystals

NASA Technical Reports Server (NTRS)

Morrison, Dennis R.; Mosier, Benjamin

2003-01-01

A process for growing protein crystals encapsulated within membranes has been invented. This process begins with the encapsulation of a nearly saturated aqueous protein solution inside semipermeable membranes to form microcapsules. The encapsulation is effected by use of special formulations of a dissolved protein and a surfactant in an aqueous first liquid phase, which is placed into contact with a second, immiscible liquid phase that contains one or more polymers that are insoluble in the first phase. The second phase becomes formed into the semipermeable membranes that surround microglobules of the first phase, thereby forming the microcapsules. Once formed, the microcapsules are then dehydrated osmotically by exposure to a concentrated salt or polymer solution. The dehydration forms supersaturated solutions inside the microcapsules, thereby enabling nucleation and growth of protein crystals inside the microcapsules. By suitable formulation of the polymer or salt solution and of other physical and chemical parameters, one can control the rate of transport of water out of the microcapsules through the membranes and thereby create physicochemical conditions that favor the growth, within each microcapsule, of one or a few large crystals suitable for analysis by x-ray diffraction. The membrane polymer can be formulated to consist of low-molecular-weight molecules that do not interfere with the x-ray diffraction analysis of the encapsulated crystals. During dehydration, an electrostatic field can be applied to exert additional control over the rate of dehydration. This protein-crystal-encapsulation process is expected to constitute the basis of protein-growth experiments to be performed on the space shuttle and the International Space Station. As envisioned, the experiments would involve the exposure of immiscible liquids to each other in sequences of steps under microgravitational conditions. The experiments are expected to contribute to knowledge of the precise conditions under which protein crystals form. By enhancing the ability to grow crystals suitable for x-ray diffraction analysis, this knowledge can be expected to benefit not only the space program but also medicine and the pharmaceutical industry.

Microgravity

NASA Image and Video Library

2004-04-15

This is an image of a colloidal crystal from the CDOT-2 investigation flown on STS-95. There are so many colloidal particles in this sample that it behaves like a glass. In the laboratory on Earth, the sample remained in an amorphous state, showing no sign of crystal growth. In microgravity the sample crystallized in 3 days, as did the other glassy colloidal samples examined in the CDOT-2 experiment. During the investigation, crystallization occurred in samples that had a volume fraction (number of particles per total volume) larger than the formerly reported glass transition of 0.58. This has great implications for theories of the structural glass transition. These crystals were strong enough to survive space shuttle re-entry and landing.

Free-falling Crystals: Biological Macromolecular Crystal Growth Studies in Low Earth Orbit

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Snell, E. H.; Pusey, M. L.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Spacecraft orbiting the earth experience a reduced acceleration environment due to being in a state of continuous free-fall. This state colloquially termed microgravity, has produced improved X-ray diffraction quality crystals of biological macromolecules. Improvements in X-ray diffraction resolution (detail) or signal to noise, provide greater detail in the three-dimensional molecular structure providing information about the molecule, how it works, how to improve its function or how to impede it. Greater molecular detail obtained by crystallization in microgravity, has important implications for structural biology. In this article we examine the theories behind macromolecule crystal quality improvement in microgravity using results obtained from studies with the model protein, chicken egg white lysozyme.

Floating zone growth of α-Na 0.90MnO 2 single crystals

DOE PAGES

Dally, Rebecca; Clement, Raphaele J.; Chisnell, Robin; ...

2016-12-03

Here, single crystal growth of α-Na xMnO 2 (x=0.90) is reported via the floating zone technique. The conditions required for stable growth and intergrowth-free crystals are described along with the results of trials under alternate growth atmospheres. Chemical and structural characterizations of the resulting α-Na 0.90MnO 2 crystals are performed using ICP-AES NMR, XANES, XPS, and neutron diffraction measurements. As a layered transition metal oxide with large ionic mobility and strong correlation effects, α-Na xMnO 2 is of interest to many communities, and the implications of large volume, high purity, single crystal growth are discussed.

Influence of solvents on the habit modification of alpha lactose monohydrate single crystals

NASA Astrophysics Data System (ADS)

Parimaladevi, P.; Srinivasan, K.

2013-02-01

Restricted evaporation of solvent method was adopted for the growth of alpha lactose monohydrate single crystals from different solvents. The crystal habits of grown crystals were analysed. The form of crystallization was confirmed by powder x-ray diffraction analysis. Thermal behaviour of the grown crystals was studied by using differential scanning calorimetry.

Polycrystalline silicon thin-film transistors with location-controlled crystal grains fabricated by excimer laser crystallization

NASA Astrophysics Data System (ADS)

Tsai, Chun-Chien; Lee, Yao-Jen; Chiang, Ko-Yu; Wang, Jyh-Liang; Lee, I.-Che; Chen, Hsu-Hsin; Wei, Kai-Fang; Chang, Ting-Kuo; Chen, Bo-Ting; Cheng, Huang-Chung

2007-11-01

In this paper, location-controlled silicon crystal grains are fabricated by the excimer laser crystallization method which employs amorphous silicon spacer structure and prepatterned thin films. The amorphous silicon spacer in nanometer-sized width formed using spacer technology is served as seed crystal to artificially control superlateral growth phenomenon during excimer laser irradiation. An array of 1.8-μm-sized disklike silicon grains is formed, and the n-channel thin-film transistors whose channels located inside the artificially-controlled crystal grains exhibit higher performance of field-effect-mobility reaching 308cm2/Vs as compared with the conventional ones. This position-manipulated silicon grains are essential to high-performance and good uniformity devices.

Structure of initial crystals formed during human amelogenesis

NASA Astrophysics Data System (ADS)

Cuisinier, F. J. G.; Voegel, J. C.; Yacaman, J.; Frank, R. M.

1992-02-01

X-ray diffraction analysis revealed only the existence of carbonated hydroxyapatite (c.HA) during amelogenesis, whereas conventional transmission electron microscopy investigations showed that developing enamel crystals have a ribbon-like habit. The described compositional changes could be an indication for the presence of minerals different from c.HA. However, the absence of identification of such a mineral shows the need of studies by high resolution electron microscopy (HREM) of initial formed human enamel crystals. We demonstrate the existence of two crystal families involved in the early stages of biomineralization: (a) nanometer-size particles which appeared as a precursor phase; (b) ribbon-like crystals, with a structure closely related to c.HA, which by a progressive thickening process tend to attain the mature enamel crystal habit.

Studies on Aspirin Crystals Generated by a Modified Vapor Diffusion Method.

PubMed

Mittal, Amit; Malhotra, Deepak; Jain, Preeti; Kalia, Anupama; Shunmugaperumal, Tamilvanan

2016-08-01

The objectives of the current investigation were (1) to study the influence of selected two different non-solvents (diethylether and dichloromethane) on the drug crystal formation of a model drug, aspirin (ASP-I) by the modified vapor diffusion method and (2) to characterize and compare the generated crystals (ASP-II and ASP-III) using different analytical techniques with that of unprocessed ASP-I. When compared to the classical vapor diffusion method which consumes about 15 days to generate drug crystals, the modified method needs only 12 h to get the same. Fourier transform-infrared spectroscopy (FT-IR) reveals that the internal structures of ASP-II and ASP-III crystals were identical when compared with ASP-I. Although the drug crystals showed a close similarity in X-ray diffraction patterns, the difference in the relative intensities of some of the diffraction peaks (especially at 2θ values of around 7.7 and 15.5) could be attributed to the crystal habit or crystal size modification. Similarly, the differential scanning calorimetry (DSC) study speculates that only the crystal habit modifications might occur but without involving any change in internal structure of the generated drug polymorphic form I. This is further substantiated from the scanning electron microscopy (SEM) pictures that indicated the formation of platy shape for the ASP-II crystals and needle shape for the ASP-III crystals. In addition, the observed slow dissolution of ASP crystals should indicate polymorph form I formation. Thus, the modified vapor diffusion method could routinely be used to screen and legally secure all possible forms of other drug entities too.

Bulk single crystal ternary substrates for a thermophotovoltaic energy conversion system

DOEpatents

Charache, Greg W.; Baldasaro, Paul F.; Nichols, Greg J.

1998-01-01

A thermophotovoltaic energy conversion device and a method for making the device. The device includes a substrate formed from a bulk single crystal material having a bandgap (E.sub.g) of 0.4 eV

Cloning, preparation and preliminary crystallographic studies of penicillin V acylase autoproteolytic processing mutants

PubMed Central

Chandra, P. Manish; Brannigan, James A.; Prabhune, Asmita; Pundle, Archana; Turkenburg, Johan P.; Dodson, G. Guy; Suresh, C. G.

2005-01-01

The crystallization of three catalytically inactive mutants of penicillin V acylase (PVA) from Bacillus sphaericus in precursor and processed forms is reported. The mutant proteins crystallize in different primitive monoclinic space groups that are distinct from the crystal forms for the native enzyme. Directed mutants and clone constructs were designed to study the post-translational autoproteolytic processing of PVA. The catalytically inactive mutants will provide three-dimensional structures of precursor PVA forms, plus open a route to the study of enzyme–substrate complexes for this industrially important enzyme. PMID:16508111

Bulk single crystal ternary substrates for a thermophotovoltaic energy conversion system

DOEpatents

Charache, G.W.; Baldasaro, P.F.; Nichols, G.J.

1998-06-23

A thermophotovoltaic energy conversion device and a method for making the device are disclosed. The device includes a substrate formed from a bulk single crystal material having a bandgap (E{sub g}) of 0.4 eV < E{sub g} < 0.7 eV and an emitter fabricated on the substrate formed from one of a p-type or an n-type material. Another thermophotovoltaic energy conversion device includes a host substrate formed from a bulk single crystal material and lattice-matched ternary or quaternary III-V semiconductor active layers. 12 figs.

Hopper Growth of Salt Crystals.

PubMed

Desarnaud, Julie; Derluyn, Hannelore; Carmeliet, Jan; Bonn, Daniel; Shahidzadeh, Noushine

2018-06-07

The growth of hopper crystals is observed for many substances, but the mechanism of their formation remains ill understood. Here we investigate their growth by performing evaporation experiments on small volumes of salt solutions. We show that sodium chloride crystals that grow very fast from a highly supersaturated solution form a peculiar form of hopper crystal consisting of a series of connected miniature versions of the original cubic crystal. The transition between cubic and such hopper growth happens at a well-defined supersaturation where the growth rate of the cubic crystal reaches a maximum (∼6.5 ± 1.8 μm/s). Above this threshold, the growth rate varies as the third power of supersaturation, showing that a new mechanism, controlled by the maximum speed of surface integration of new molecules, induces the hopper growth of cubic crystals in cascade.

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

Kuz'mina, L. G., E-mail: kuzmina@igic.ras.ru; Kucherepa, N. S.; Syrbu, S. A.

The crystal and molecular structure of p-(decaoxybenzylidene)-p'-toluidine C{sub 10}H{sub 21}O-C{sub 6}H{sub 4}-CH=N-C{sub 6}H{sub 4}-CH{sub 3} is studied. The molecule is nearly planar. In the crystal packing, loose regions formed by aliphatic fragments of molecules alternate with pseudostacks of aromatic fragments of molecules that are related by the centers of symmetry. The stacks are built of dimers, in which molecules are linked by {pi}-stacking interactions between benzene rings. There are no weak directional interactions between dimers in a stack. The presence of a single structure-forming element in the crystal, namely, the {pi}-stacking interactions in the dimers, along with the similarity ofmore » the crystal packing to that of the C{sub 8}H{sub 17}O-homologue, which forms a nematic mesophase on melting, indicate that the crystals under study should exhibit nematic properties.« less

Structural analysis of β-glucosidase mutants derived from a hyperthermophilic tetrameric structure

PubMed Central

Nakabayashi, Makoto; Kataoka, Misumi; Mishima, Yumiko; Maeno, Yuka; Ishikawa, Kazuhiko

2014-01-01

β-Glucosidase from Pyrococcus furiosus (BGLPf) is a hyperthermophilic tetrameric enzyme which can degrade cellooligosaccharides to glucose under hyperthermophilic conditions and thus holds promise for the saccharification of lignocellulosic biomass at high temperature. Prior to the production of large amounts of this enzyme, detailed information regarding the oligomeric structure of the enzyme is required. Several crystals of BGLPf have been prepared over the past ten years, but its crystal structure had not been solved until recently. In 2011, the first crystal structure of BGLPf was solved and a model was constructed at somewhat low resolution (2.35 Å). In order to obtain more detailed structural data on BGLPf, the relationship between its tetrameric structure and the quality of the crystal was re-examined. A dimeric form of BGLPf was constructed and its crystal structure was solved at a resolution of 1.70 Å using protein-engineering methods. Furthermore, using the high-resolution crystal structural data for the dimeric form, a monomeric form of BGLPf was constructed which retained the intrinsic activity of the tetrameric form. The thermostability of BGLPf is affected by its oligomeric structure. Here, the biophysical and biochemical properties of engineered dimeric and monomeric BGLPfs are reported, which are promising prototype models to apply to the saccharification reaction. Furthermore, details regarding the oligomeric structures of BGLPf and the reasons why the mutations yielded improved crystal structures are discussed. PMID:24598756

Isothermal Crystallization Behavior of Cocoa Butter at 17 and 20 °C with and without Limonene.

PubMed

Rigolle, Annelien; Goderis, Bart; Van Den Abeele, Koen; Foubert, Imogen

2016-05-04

Differential scanning calorimetry and real-time X-ray diffraction using synchrotron radiation were used to elucidate isothermal cocoa butter crystallization at 17 and 20 °C in the absence and presence of different limonene concentrations. At 17 °C, a three-step crystallization process was visible for pure cocoa butter, whereby first an unknown structure with long spacings between a 2L and 3L structure was formed that rapidly transformed into the more stable α structure, which in turn was converted into more stable β' crystals. At 20 °C, an α-mediated β' crystallization was observed. The addition of limonene resulted in a reduction of the amount of unstable crystals and an acceleration of polymorphic transitions. At 17 °C, the crystallization process was accelerated due to the acceleration of the formation of more stable polymorphic forms, whereas there were insufficient α crystals for an α-mediated β' nucleation at 20 °C, resulting in a slower crystallization process.

Impact of Supramolecular Aggregation on the Crystallization Kinetics of Organic Compounds from the Supercooled Liquid State.

PubMed

Kalra, Arjun; Tishmack, Patrick; Lubach, Joseph W; Munson, Eric J; Taylor, Lynne S; Byrn, Stephen R; Li, Tonglei

2017-06-05

Despite numerous challenges in their theoretical description and practical implementation, amorphous drugs are of growing importance to the pharmaceutical industry. One such challenge is to gain molecular level understanding of the propensity of a molecule to form and remain as a glassy solid. In this study, a series of structurally similar diarylamine compounds was examined to elucidate the role of supramolecular aggregation on crystallization kinetics from supercooled liquid state. The structural similarity of the compounds makes it easier to isolate the molecular features that affect crystallization kinetics and glass forming ability of these compounds. To examine the role of hydrogen-bonded aggregation and motifs on crystallization kinetics, a combination of thermal and spectroscopic techniques was employed. Using variable temperature FTIR, Raman, and solid-state NMR spectroscopies, the presence of hydrogen bonding in the melt and glassy state was examined and correlated with observed phase transition behaviors. Spectroscopic results revealed that the formation of hydrogen-bonded aggregates involving carboxylic acid and pyridine nitrogen (acid-pyridine aggregates) between neighboring molecules in the melt state impedes crystallization, while the presence of carboxylic acid dimers (acid-acid dimers) in the melt favors crystallization. This study suggests that glass formation of small molecules is influenced by the type of intermolecular interactions present in the melt state and the kinetics associated with the molecules to assemble into a crystalline lattice. For the compounds that form acid-pyridine aggregates, the formation of energy degenerate chains, produced due to conformational flexibility of the molecules, presents a kinetic barrier to crystallization. The poor crystallization tendency of these aggregates stems from the highly directional hydrogen-bonding interactions needed to form the acid-pyridine chains. Conversely, for the compounds that form acid-acid dimers, the nondirectional van der Waals forces needed to construct a nucleus promote rapid assembly and crystallization.

The effect of temperature and moisture on the amorphous-to-crystalline transformation of stavudine.

PubMed

Strydom, Schalk; Liebenberg, Wilna; Yu, Lian; de Villiers, Melgardt

2009-09-08

Stavudine is a nucleoside reverse transcriptase inhibitor active against HIV, and is known to exist in two polymorphic forms designated as forms I and II, and a hydrate form III. An amorphous solid of stavudine was successfully prepared and characterized during this investigation. A comprehensive evaluation of the stability of this amorphous solid showed that the amorphous solid transforms to either form II (anhydrous) or form III (hydrate) when exposed to temperature, in the absence or presence of moisture, respectively. The amorphous-to-hydrate transformation occurred at relatively low RH (>32%) and led to the formation of crystal aggregates of the hydrated form. Steady state growth rate analyses also showed that the amorphous-to-crystalline transformation occurs at a greater rate in the presence of moisture, compared to the transformation at the same temperature in a dry environment. Crystal growth studies showed that it is possible to stabilize the amorphous solid of stavudine against crystal transformations in the absence of moisture by coating it with poly(methyl methacrylate). However, this polymer coating could not prevent crystal growth from the amorphous solid during exposure to moisture.

Highly Non-Linear Optical (NLO) organic crystals

NASA Technical Reports Server (NTRS)

Harris, J. Milton

1987-01-01

This research project involves the synthesis and characterization of organic materials having powerful nonlinear optical (NLO) properties and the growth of highly ordered crystals and monomolecular films of these materials. Research in four areas is discussed: theoretical design of new materials, characterization of NLO materials, synthesis of new materials and development of coupling procedures for forming layered films, and improvement of the techniques for vapor phase and solution phase growth of high quality organic crystals. Knowledge gained from these experiments will form the basis for experiments in the growth of these crystals.

Methods of making composite optical devices employing polymer liquid crystal

DOEpatents

Jacobs, Stephen D.; Marshall, Kenneth L.; Cerqua, Kathleen A.

1991-01-01

Composite optical devices using polymer liquid crystal materials both as optical and adhesive elements. The devices are made by assembling a heated polymer liquid crystal compound, while in a low viscosity form between optically transparent substrates. The molecules of the polymer are oriented, while in the liquid crystalline state and while above the glass transition temperature (T.sub.g) of the polymer, to provide the desired optical effects, such as polarization, and selective reflection. The liquid crystal polymer cements the substrates together to form an assembly providing the composite optical device.

Synthesis of macroporous structures

DOEpatents

Stein, Andreas; Holland, Brian T.; Blanford, Christopher F.; Yan, Hongwei

2004-01-20

The present application discloses a method of forming an inorganic macroporous material. In some embodiments, the method includes: providing a sample of organic polymer particles having a particle size distribution of no greater than about 10%; forming a colloidal crystal template of the sample of organic polymer particles, the colloidal crystal template including a plurality of organic polymer particles and interstitial spaces therebetween; adding an inorganic precursor composition including a noncolloidal inorganic precursor to the colloidal crystal template such that the precursor composition permeates the interstitial spaces between the organic polymer particles; converting the noncolloidal inorganic precursor to a hardened inorganic framework; and removing the colloidal crystal template from the hardened inorganic framework to form a macroporous material. Inorganic macroporous materials are also disclosed.

Common path point diffraction interferometer using liquid crystal phase shifting

NASA Technical Reports Server (NTRS)

Mercer, Carolyn R. (Inventor)

1997-01-01

A common path point diffraction interferometer uses dyed, parallel nematic liquid crystals which surround an optically transparent microsphere. Coherent, collimated and polarized light is focused on the microsphere at a diameter larger than that of the microsphere. A portion of the focused light passes through the microsphere to form a spherical wavefront reference beam and the rest of the light is attenuated by the dyed liquid crystals to form an object beam. The two beams form an interferogram which is imaged by a lens onto an electronic array sensor and into a computer which determines the wavefront of the object beam. The computer phase shifts the interferogram by stepping up an AC voltage applied across the liquid crystals without affecting the reference beam.

Glass Forming Ability in Systems with Competing Orderings

NASA Astrophysics Data System (ADS)

Russo, John; Romano, Flavio; Tanaka, Hajime

2018-04-01

Some liquids, if cooled rapidly enough to avoid crystallization, can be frozen into a nonergodic glassy state. The tendency for a material to form a glass when quenched is called "glass-forming ability," and it is of key significance both fundamentally and for materials science applications. Here, we consider liquids with competing orderings, where an increase in the glass-forming ability is signaled by a depression of the melting temperature towards its minimum at triple or eutectic points. With simulations of two model systems where glass-forming ability can be tuned by an external parameter, we are able to interpolate between crystal-forming and glass-forming behavior. We find that the enhancement of the glass-forming ability is caused by an increase in the structural difference between liquid and crystal: stronger competition in orderings towards the melting point minimum makes a liquid structure more disordered (more complex). This increase in the liquid-crystal structure difference can be described by a single adimensional parameter, i.e., the interface energy cost scaled by the thermal energy, which we call the "thermodynamic interface penalty." Our finding may provide a general physical principle for not only controlling the glass-forming ability but also the emergence of glassy behavior of various systems with competing orderings, including orderings of structural, magnetic, electronic, charge, and dipolar origin.

Refined structures of three crystal forms of toxic shock syndrome toxin-1 and of a tetramutant with reduced activity.

PubMed Central

Prasad, G. S.; Radhakrishnan, R.; Mitchell, D. T.; Earhart, C. A.; Dinges, M. M.; Cook, W. J.; Schlievert, P. M.; Ohlendorf, D. H.

1997-01-01

The structure of toxic shock syndrome toxin-1 (TSST-1), the causative agent in toxic shock syndrome, has been determined in three crystal forms. The three structural models have been refined to R-factors of 0.154, 0.150, and 0.198 at resolutions of 2.05 A, 2.90 A, and 2.75 A, respectively. One crystal form of TSST-1 contains a zinc ion bound between two symmetry-related molecules. Although not required for biological activity, zinc dramatically potentiates the mitogenicity of TSST-1 at very low concentrations. In addition, the structure of the tetramutant TSST-1H [T69I, Y80W, E132K, I140T], which is nonmitogenic and does not amplify endotoxin shock, has been determined and refined in a fourth crystal form (R-factor = 0.173 to 1.9 A resolution). PMID:9194182

Solitons in a one-dimensional Wigner crystal

DOE PAGES

Pustilnik, M.; Matveev, K. A.

2015-04-16

In one-dimensional quantum systems with strong long-range repulsion particles arrange in a quasi-periodic chain, the Wigner crystal. Here, we demonstrate that besides the familiar phonons, such one-dimensional Wigner crystal supports an additional mode of elementary excitations, which can be identified with solitons in the classical limit. Furthermore, we compute the corresponding excitation spectrum and argue that the solitons have a parametrically small decay rate at low energies. Finally, we discuss implications of our results for the behavior of the dynamic structure factor.

Parallel computational and experimental studies of the morphological modification of calcium carbonate by cobalt

NASA Astrophysics Data System (ADS)

Braybrook, A. L.; Heywood, B. R.; Jackson, R. A.; Pitt, K.

2002-08-01

Crystal growth can be controlled by the incorporation of dopant ions into the lattice and yet the question of how such substituents affect the morphology has not been addressed. This paper describes the forms of calcite (CaCO 3) which arise when the growth assay is doped with cobalt. Distinct and specific morphological changes are observed; the calcite crystals adopt a morphology which is dominated by the {01.1} family of faces. These experimental studies paralleled the development of computational methods for the analysis of crystal habit as a function of dopant concentration. In this case, the predicted defect morphology also argued for the dominance of the (01.1) face in the growth form. The appearance of this face was related to the preferential segregation of the dopant ions to the crystal surface. This study confirms the evolution of a robust computational model for the analysis of calcite growth forms under a range of environmental conditions and presages the use of such tools for the predictive development of crystal morphologies in those applications where chemico-physical functionality is linked closely to a specific crystallographic form.

Structure of Bacillus halmapalus α-amylase crystallized with and without the substrate analogue acarbose and maltose

PubMed Central

Lyhne-Iversen, Louise; Hobley, Timothy J.; Kaasgaard, Svend G.; Harris, Pernille

2006-01-01

Recombinant Bacillus halmapalus α-amylase (BHA) was studied in two different crystal forms. The first crystal form was obtained by crystallization of BHA at room temperature in the presence of acarbose and maltose; data were collected at cryogenic temperature to a resolution of 1.9 Å. It was found that the crystal belonged to space group P212121, with unit-cell parameters a = 47.0, b = 73.5, c = 151.1 Å. A maltose molecule was observed and found to bind to BHA and previous reports of the binding of a nonasaccharide were confirmed. The second crystal form was obtained by pH-induced crystallization of BHA in a MES–HEPES–boric acid buffer (MHB buffer) at 303 K; the solubility of BHA in MHB has a retrograde temperature dependency and crystallization of BHA was only possible by raising the temperature to at least 298 K. Data were collected at cryogenic temperature to a resolution of 2.0 Å. The crystal belonged to space group P212121, with unit-cell parameters a = 38.6, b = 59.0, c = 209.8 Å. The structure was solved using molecular replacement. The maltose-binding site is described and the two structures are compared. No significant changes were seen in the structure upon binding of the substrates. PMID:16946462

Crystallization of a 2:2 complex of granulocyte-colony stimulating factor (GCSF) with the ligand-binding region of the GCSF receptor

PubMed Central

Honjo, Eijiro; Tamada, Taro; Maeda, Yoshitake; Koshiba, Takumi; Matsukura, Yasuko; Okamoto, Tomoyuki; Ishibashi, Matsujiro; Tokunaga, Masao; Kuroki, Ryota

2005-01-01

The granulocyte-colony stimulating factor (GCSF) receptor receives signals for regulating the maturation, proliferation and differentiation of the precursor cells of neutrophilic granulocytes. The signalling complex composed of two GCSFs (GCSF, 19 kDa) and two GCSF receptors (GCSFR, 34 kDa) consisting of an Ig-like domain and a cytokine-receptor homologous (CRH) domain was crystallized. A crystal of the complex was grown in 1.0 M sodium formate and 0.1 M sodium acetate pH 4.6 and belongs to space group P41212 (or its enantiomorph P43212), with unit-cell parameters a = b = 110.1, c = 331.8 Å. Unfortunately, this crystal form did not diffract beyond 5 Å resolution. Since the heterogeneity of GCSF receptor appeared to prevent the growth of good-quality crystals, the GCSF receptor was fractionated by anion-exchange chromatography. Crystals of the GCSF–fractionated GCSF receptor complex were grown as a new crystal form in 0.2 M ammonium phosphate. This new crystal form diffracted to beyond 3.0 Å resolution and belonged to space group P3121 (or its enantiomorph P3221), with unit-cell parameters a = b = 134.8, c = 105.7 Å. PMID:16511159

Characterization of crystal forms of β-estradiol thermal analysis, Raman microscopy, X-ray analysis and solid-state NMR

NASA Astrophysics Data System (ADS)

Variankaval, N. E.; Jacob, K. I.; Dinh, S. M.

2000-08-01

The structure and select crystalline properties of a common drug (estradiol) used in a transdermal drug delivery system are investigated. Four different crystal forms of estradiol (EA, EC, ED and EM) were prepared in the laboratory and characterized by thermal analysis, optical microscopy, Raman microspectroscopy, and solid-state NMR. Variable temperature X-ray studies were carried out on form A (EA) to determine whether the crystal structure changed as a function of temperature. These four forms exhibited different thermal behavior. EA and EC had similar melting points. This study clearly shows that water cannot be released from the crystal lattice of EA unless melting is achieved, and exposing EA to temperatures below the melting point only results in a partial release of hydrogen bonded water. EC was prepared by melting EA and subsequently cooling it to room temperature. Form EC was anhydrous, as it did not exhibit water loss, as opposed to EA, which had about 3.5% water in its crystal structure. ED was very difficult to prepare and manifested itself only as a mixture with EC. Its melting point was about 10°C lower than that of EC. It is thought to be an unstable form due to its simultaneous occurrence with EC and the inability to isolate it. EM is a solvate of methanol, not a polymorph. Its melting point was similar to EA and EC. From thermogravimetry/differential thermal analysis and differential scanning calorimetry data, it was apparent that estradiol formed a hemisolvate with methanol. All four forms had different morphologies. Raman microscopy was carried out on the different crystal forms. The spectra of EC and ED were almost identical. Thermal analysis revealed that this is due to the highly unstable nature of ED and its tendency to either convert spontaneously to EC or occur in mixtures with it.

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

Jones, B.; Renaut, R.W.

Complex calcite crystals are an integral component of precipitates that form around the orifices of the Loburu and Mawe Moto hot springs on the shores of Lake bogoria, Kenya. Two types of large (up to 4 cm long) noncrystallographic dendrites are important components of these deposits. Feather dendrites are characterized by multiple levels of branching with individual branches developed through crystal splitting and spherulitic growth. Scandulitic (from Latin meaning shingle) dendrites are formed of stacked calcite crystals and are generally more compact than feather dendrites. These developed through the incremental stacking of rectangular-shaped calcite crystals that initially grew as skeletalmore » crystals. Feather and scandulitic dendrites precipitated from the same waters in the same springs. The difference in morphology is therefore related to microenvironments in which they grew. Feather dendrites grew in any direction in pools of free-standing water provided that they were in constant contact with the solute. Conversely, scandulitic dendrites grew on rims of dams where water flowed over the surface in concert with the pulses of spring water. Thus, each calcite crystal in these dendrites represents one episode of crystal growth. The orientation of the component crystals in scandulitic dendrites is controlled by the topography of the dam or surface, not crystallographic criteria. The noncrystallographic dendrites formed from spring waters with initial temperatures of 90--99 C. Surficial water cooling, loss of CO{sub 2}, and presence of other elements that can interfere with crystal growth contributed to the formation of these unusual crystals.« less

Crystallization and dynamical arrest of attractive hard spheres.

PubMed

Babu, Sujin; Gimel, Jean-Christophe; Nicolai, Taco

2009-02-14

Crystallization of hard spheres interacting with a square well potential was investigated by numerical simulations using so-called Brownian cluster dynamics. The phase diagram was determined over a broad range of volume fractions. The crystallization rate was studied as a function of the interaction strength expressed in terms of the second virial coefficient. For volume fractions below about 0.3 the rate was found to increase abruptly with increasing attraction at the binodal of the metastable liquid-liquid phase separation. The rate increased until a maximum was reached after which it decreased with a power law dependence on the second virial coefficient. Above a critical percolation concentration, a transient system spanning network of connected particles was formed. Crystals were formed initially as part of the network, but eventually crystallization led to the breakup of the network. The lifetime of the transient gels increased very rapidly over a small range of interaction energies. Weak attraction destabilized the so-called repulsive crystals formed in pure hard sphere systems and shifted the coexistence line to higher volume fractions. Stronger attraction led to the formation of a denser, so-called attractive, crystalline phase. Nucleation of attractive crystals in the repulsive crystalline phase was observed close to the transition.

Crystallization and preliminary X-ray crystallographic study of a 3.8-MDa respiratory supermolecule hemocyanin.

PubMed

Matsuno, Asuka; Gai, Zuoqi; Tanaka, Miyuki; Kato, Koji; Kato, Sanae; Katoh, Tsuyoshi; Shimizu, Takeshi; Yoshioka, Takeya; Kishimura, Hideki; Tanaka, Yoshikazu; Yao, Min

2015-06-01

Many molluscs transport oxygen using a very large cylindrical multimeric copper-containing protein named hemocyanin. The molluscan hemocyanin forms a decamer (cephalopods) or multidecamer (gastropods) of approximately 330-450kDa subunits, resulting in a molecular mass >3.3MDa. Therefore, molluscan hemocyanin is one of the largest proteins. The reason why these organisms use such a large supermolecule for oxygen transport remains unclear. Atomic-resolution X-ray crystallographic analysis is necessary to unveil the detailed molecular structure of this mysterious large molecule. However, its propensity to dissociate in solution has hampered the crystallization of its intact form. In the present study, we successfully obtained the first crystals of an intact decameric molluscan hemocyanin. The diffraction dataset at 3.0-Å resolution was collected by merging the datasets of two isomorphic crystals. Electron microscopy analysis of the dissolved crystals revealed cylindrical particles. Furthermore, self-rotation function analysis clearly showed the presence of a fivefold symmetry with several twofold symmetries perpendicular to the fivefold axis. The absorption spectrum of the crystals showed an absorption peak around 345nm. These results indicated that the crystals contain intact hemocyanin decamers in the oxygen-bound form. Copyright © 2015 Elsevier Inc. All rights reserved.

Effects of Purification on the Crystallization of Lysozyme

NASA Technical Reports Server (NTRS)

Ewing, Felecia L.; Forsythe, Elizabeth L.; Van Der Woerd, Mark; Pusey, Marc L.

1996-01-01

We have additionally purified a commercial lysozyme preparation by cation exchange chromatography, followed by recrystallization. This material is 99.96% pure with respect to macromolecular impurities. At basic pH, the purified lysozyme gave only tetragonal crystals at 20 C. Protein used directly from the bottle, prepared by dialysis against distilled water, or which did not bind to the cation exchange column had considerably altered crystallization behavior. Lysozyme which did not bind to the cation exchange column was subsequently purified by size exclusion chromatography. This material gave predominately bundles of rod-shaped crystals with some small tetragonal crystals at lower pHs. The origin of the bundled rod habit was postulated to be a thermally dependent tetragonal- orthorhombic change in the protein structure. This was subsequently ruled out on the basis of crystallization behavior and growth rate experiments. This suggests that heterogeneous forms of lysozyme may be responsible. These results demonstrate three classes of impurities: (1) small molecules, which may be removed by dialysis; (2) macromolecules, which are removable by chromatographic techniques; and (3) heterogeneous forms of the protein, which can be removed in this case by cation exchange chromatography. Of these, heterogeneous forms of the lysozyme apparently have the greatest affect on its crystallization behavior.

Crystallization of Chicken Egg White Lysozyme from Assorted Sulfate Salts

NASA Technical Reports Server (NTRS)

Forsythe, Elizabeth L.; Snell, Edward H.; Malone, Christine C.; Pusey, Marc L.

1998-01-01

Chicken egg white lysozyme has been found to crystallize from ammonium, sodium, potassium, rubidium, magnesium, and manganese sulfates at acidic and basic pH, with protein concentrations from 60 to 190 mg/ml. Four different crystal morphologies have been obtained, depending upon the temperature, protein concentration, and precipitating salt employed, Crystals grown at 15 C were generally tetragonal, with space group P43212. Crystallization at 20 C typically resulted in the formation of orthorhombic crystals, space group P21212 1. The tetragonal much less than orthorhombic morphology transition appeared to be a function of both the temperature and protein concentration, occurring between 15 and 20 C and between 100 and 125 mg/ml protein concentration. Crystallization from 0.8 -1.2M magnesium sulfate at pH 7.6 - 8.0 gave a hexagonal (trigonal) crystal form, space group P3121, which diffracted to 2.8 A. Ammonium sulfate was also found to result in a monoclinic form, space group C2. Small twinned monoclinic crystals of approx. 0.2 mm on edge were grown by dialysis followed by seeded sitting drop crystallization.

Solid-state supramolecular architectures formed by co-crystallization of melamine and 2-, 3- and 4-fluorophenylacetic acids

NASA Astrophysics Data System (ADS)

Perpétuo, Genivaldo Julio; Janczak, Jan

2018-01-01

A family of supramolecular complexes of melamine with fluorophenylacetic acid isomers using solvent-assisted and evaporation-based techniques has been prepared. Crystallization of melamine with 2-fluorophenylacetic acid yield hydrated ionic supramolecular complex (1), whereas crystallization of melamine with 3- and 4-fluorophenylacetic acids leads to formation of neutral supramolecular complexes (2, 3), all with base to acid ratio of 1:2. The supramolecular assembly is driven by the noncovalent interactions, most commonly by the hydrogen bonds. The components of the crystal 1 interact via Nsbnd H⋯O and Osbnd H⋯N hydrogen bonds with R22(8) and R32(10) graphs forming ionic supramolecular complex, whereas the components in the crystals 2 and 3 interact with a graph of R22(8) forming neutral supramolecular complexes. The singly protonated melamin-1-ium residues in 1 interact each other via a pair of Nsbnd H⋯N hydrogen bonds forming one dimensional chains along [-110] that interact via Nsbnd H⋯O with deprotonated and neutral 2-fluorophenylacetic acid units and water molecules forming ribbon. In 2 and 3 co-crystals the melamine interacts with 3- and 4-fluorophenylacetic acids via a pair of Nsbnd H⋯O hydrogen bonds forming pseudo one-dimensional supramolecular chains along [010] direction. Hirshfeld surface and analysis of 2D fingerprint plots have been analysed both quantitatively and qualitatively interactions that governing the supramolecular organisation. The IR and Raman vibrational characterization of the supramolecular complexes 1-3 was supported by the spectra of their deuterated analogues.

New solid state forms of antineoplastic 5-fluorouracil with anthelmintic piperazine

NASA Astrophysics Data System (ADS)

Moisescu-Goia, C.; Muresan-Pop, M.; Simon, V.

2017-12-01

The aim of the present study was to asses the formation of solid forms between the 5-fluorouracil chemotherapy drug and the anthelmintic piperazine. Two new solid forms of antineoplastic agent 5-fluorouracil with anthelmintic piperazine were obtained by liquid assisted ball milling and slurry crystallization methods. The Nsbnd H hydrogen bonding donors and C = O hydrogen bonding acceptors of 5-fluorouracil allow to form co-crystals with other drugs delivering improved properties for medical applications, as proved for other compounds of pharmaceutical interest. Both new solid forms were investigated using X-ray powder diffraction (XRD), differential thermal analysis (DTA) and Fourier transform infrared (FTIR) spectroscopy. The XRD results show that by both methods were successfully synthesized new solid forms of 5-fluorouracil with piperazine. According to FTIR results the form prepared by lichid assisted grinding process was obtained as co-crystal and the other one, prepared by slurry method, resulted as a salt.

Spray Drying as a Reliable Route to Produce Metastable Carbamazepine Form IV.

PubMed

Halliwell, Rebecca A; Bhardwaj, Rajni M; Brown, Cameron J; Briggs, Naomi E B; Dunn, Jaclyn; Robertson, John; Nordon, Alison; Florence, Alastair J

2017-07-01

Carbamazepine (CBZ) is an active pharmaceutical ingredient used in the treatment of epilepsy that can form at least 5 polymorphic forms. Metastable form IV was originally discovered from crystallization with polymer additives; however, it has not been observed from subsequent solvent-only crystallization efforts. This work reports the reproducible formation of phase pure crystalline form IV by spray drying of methanolic CBZ solution. Characterization of the material was carried out using diffraction, scanning electron microscopy, and differential scanning calorimetry. In situ Raman spectroscopy was used to monitor the spray-dried product during the spray drying process. This work demonstrates that spray drying provides a robust method for the production of form IV CBZ, and the combination of high supersaturation and rapid solid isolation from solution overcomes the apparent limitation of more traditional solution crystallization approaches to produce metastable crystalline forms. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Niclosamide methanol solvate and niclosamide hydrate: structure, solvent inclusion mode and implications for properties.

PubMed

Harriss, Bethany I; Wilson, Claire; Radosavljevic Evans, Ivana

2014-08-01

Structural studies have been carried out of two solid forms of niclosamide [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide, NCL], a widely used anthelmintic drug, namely niclosamide methanol monosolvate, C13H8Cl2N2O4·CH3OH or NCL·MeOH, and niclosamide monohydrate, denoted HA. The structure of the methanol solvate obtained from single-crystal X-ray diffraction is reported for the first time, elucidating the key host-guest hydrogen-bonding interactions which lead to solvate formation. The essentially planar NCL host molecules interact via π-stacking and pack in a herringbone-type arrangement, giving rise to channels along the crystallographic a axis in which the methanol guest molecules are located. The methanol and NCL molecules interact via short O-H...O hydrogen bonds. Laboratory powder X-ray diffraction (PXRD) measurements reveal that the initially phase-pure NCL·MeOH solvate readily transforms into NCL monohydrate within hours under ambient conditions. PXRD further suggests that the NCL monohydrate, HA, is isostructural with the NCL·MeOH solvate. This is consistent with the facile transformation of the methanol solvate into the hydrate when stored in air. The crystal packing and the topology of guest-molecule inclusion are compared with those of other NCL solvates for which the crystal structures are known, giving a consistent picture which correlates well with known experimentally observed desolvation properties.

Examining the role of canister cooling conditions on the formation of nepheline from nuclear waste glasses

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

Christian, J. H.

2015-09-01

Nepheline (NaAlSiO₄) crystals can form during slow cooling of high-level waste (HLW) glass after it has been poured into a waste canister. Formation of these crystals can adversely affect the chemical durability of the glass. The tendency for nepheline crystallization to form in a HLW glass increases with increasing concentrations of Al₂O₃ and Na₂O.

System and method for forming synthetic protein crystals to determine the conformational structure by crystallography

DOEpatents

Craig, George D.; Glass, Robert; Rupp, Bernhard

1997-01-01

A method for forming synthetic crystals of proteins in a carrier fluid by use of the dipole moments of protein macromolecules that self-align in the Helmholtz layer adjacent to an electrode. The voltage gradients of such layers easily exceed 10.sup.6 V/m. The synthetic protein crystals are subjected to x-ray crystallography to determine the conformational structure of the protein involved.

Protein Crystal Based Nanomaterials

NASA Technical Reports Server (NTRS)

Bell, Jeffrey A.; VanRoey, Patrick

2001-01-01

This is the final report on a NASA Grant. It concerns a description of work done, which includes: (1) Protein crystals cross-linked to form fibers; (2) Engineering of protein to favor crystallization; (3) Better knowledge-based potentials for protein-protein contacts; (4) Simulation of protein crystallization.

Did an Impact Make the Mysterious Microscopic Magnetite Crystals in ALH 84001?

NASA Astrophysics Data System (ADS)

Taylor, G. J.

2007-10-01

Fervent debate swirls around microscopic crystals of magnetite (Fe3O4) in Martian meteorite ALH 84001. Some investigators suggest that the crystals are evidence of past life on Mars, citing magnetite crystals of similar chemical compositions and sizes made by magnetotactic bacteria on Earth. Others cite assorted experiments and observations to argue that the important little crystals formed entirely by non-biological processes, hence say nothing about life on Mars. One of those processes is the decomposition of iron carbonate (the mineral siderite), which occurs in ALH 84001. Researchers argue that heating this mineral causes it to decompose into magnetite and CO2 gas. Experiments showing this were done by heating siderite and observing that it decomposed and formed magnetite, but nobody had shock-heated siderite to see if magnetite crystals formed. (Shock is a rapid, strong rise and fall in pressure. It happens under many circumstances, including meteorite impacts.) The lack of shock experiments has been solved by Mary Sue Bell (University of Houston and Jacobs Engineering). She experimentally shocked samples of siderite at the Experimental Impact Laboratory at the Johnson Space Center. She shows that magnetite crystals of the right size and composition formed when samples were shocked to 49 GPa (about 500,000 times the pressure at the Earth's surface). This is more evidence for a non-biological origin for the magnetite crystals in ALH 84001 and is consistent with what we know about the impact history of the rock. There seems to be growing evidence against a biological origin, but don't expect these results to completely settle the debate!

Absolute configuration and crystal packing chirality for three conglomerate-forming ortho-halogen substituted phenyl glycerol ethers

NASA Astrophysics Data System (ADS)

Bredikhin, Alexander A.; Gubaidullin, Aidar T.; Bredikhina, Zemfira A.

2010-06-01

Three conglomerate-forming ortho-Hal (Hal = Cl, Br, I) substituted phenyl glycerol ethers 1- 3 were investigated by single-crystal X-ray analysis, and the absolute configuration for all substances was established. The molecular structures and crystal packing details for halogen derivatives were compared with the same characteristics for ortho-OCH 3 and ortho-CH 3 analogues. Two different types of crystal packing were evaluated for these very much alike compounds. The interplay of the supramolecular crystal organization chirality sense and the single molecule absolute configuration was demonstrated. Some stabilizing and destabilizing interactions involving the ortho-substituents were revealed. The resolution of rac-2 by entrainment procedure was successfully realized.

Structure of α, ω-bis-(pentane-2,4-dione-3-ylmethylsulfanyl)alkanes and even/odd crystallization effects

NASA Astrophysics Data System (ADS)

Khalilov, Leonard M.; Tulyabaev, Arthur R.; Mescheryakova, Ekaterina S.; Akhmadiev, Nail S.; Timirov, Yulai I.; Skaldin, Oleg A.; Akhmetova, Vnira R.

2015-09-01

The relationships between structural features and crystallization of the С1-С6 α,ω-bis-(pentane-2,4-dione-3-ylmethylsulfanyl)alkanes are considered. It was shown that the conjugated enol bis-pentadiones which form pseudo six-membered rings and stabilized by intramolecular hydrogen bonds favor the crystallization. Using a polarized optical technique, it has been found that crystallization rate of the melts of crystalline compounds decreases with elongation of the aliphatic chain between sulfur atoms. It is assumed that one of the main factors that contributes to probability to form single crystals is a small twist angle between two pseudo six-membered rings.

Verb Selection and Past-Tense Morphology: Crystal's Criteria Revisited

ERIC Educational Resources Information Center

Weiler, Brian

2013-01-01

Research findings concerning verb-level influences on past-tense morphology carry implications for the careful selection of treatment targets. Using 6 of the broad criteria for "good verbs to choose" proposed by D. Crystal (1985) more than 25 years ago as a framework, this article summarizes some of the more recent research with a nod…

Interdiffusion behavior between NiAlHf coating and Ni-based single crystal superalloy with different crystal orientations

NASA Astrophysics Data System (ADS)

Wang, Ruili; Gong, Xueyuan; Peng, Hui; Ma, Yue; Guo, Hongbo

2015-01-01

NiAlHf coatings were deposited onto Ni-based single crystal (SC) superalloy with different crystal orientations by electron beam physical vapor deposition (EB-PVD). The effects of the crystal orientations of the superalloy substrate on inter-diffusion behavior between the substrate and the NiAlHf coating were investigated. Substrate diffusion zone (SDZ) containing needle-like μ phases and interdiffusion zone (IDZ) mainly consisting of the ellipsoidal and rod-like μ phases were formed in the SC alloy after heat-treatment 10 h at 1100 °C. The thickness of secondary reaction zone (SRZ) formed in the SC alloy with (0 1 1) crystal orientation is about 14 μm after 50 h heat-treatment at 1100 °C, which is relatively thicker than that in the SC alloy with (0 0 1) crystal orientation, whereas the IDZ revealed similar thickness.

Two conformations of the integrin A-domain (I-domain): a pathway for activation?

PubMed

Lee, J O; Bankston, L A; Arnaout, M A; Liddington, R C

1995-12-15

Integrins are plasma membrane proteins that mediate adhesion to other cells and to components of the extracellular matrix. Most integrins are constitutively inactive in resting cells, but are rapidly and reversibly activated in response to agonists, leading to highly regulated cell adhesion. This activation is associated with conformational changes in their extracellular portions, but the nature of the structural changes that lead to a change in adhesiveness is not understood. The interactions of several integrins with their extracellular ligands are mediated by an A-type domain (generally called the I-domain in integrins). Binding of the I-domain to protein ligands is dependent on divalent cations. We have described previously the structure of the I-domain from complement receptor 3 with bound Mg2+, in which the glutamate side chain from a second I-domain completes the octahedral coordination sphere of the metal, acting as a ligand mimetic. We now describe a new crystal form of the I-domain with bound Mn2+, in which water completes the metal coordination sphere and there is no equivalent of the glutamate ligand. Comparison of the two crystal forms reveals a change in metal coordination which is linked to a large (10 A) shift of the C-terminal helix and the burial of two phenylalanine residues into the hydrophobic core of the Mn2+ form. These structural changes, analogous to those seen in the signal-transducing G-proteins, alter the electrophilicity of the metal, reducing its ability to bind ligand-associated acidic residues, and dramatically alter the surface of the protein implicated in binding ligand. Our observations provide the first atomic resolution view of conformational changes in an integrin domain, and suggest how these changes are linked to a change in integrin adhesiveness. We propose that the Mg2+ form represents the conformation of the domain in the active state and the Mn2+ form the conformation in the inactive state of the integrin.

Spectral properties of ice-particulate mixtures and implications for remote sensing. 1. Intimate mixtures.

USGS Publications Warehouse

Clark, R.N.; Lucey, P.G.

1984-01-01

The spectral properties of water ice-partitioning mixtures are studied for the purpose of deriving the ice and particulate abundances from remotely obtained spectra (particulates referring to non-icy materials in the form of grains). Reflectance levels and ice absorption band depths are a complex function of the single scattering albedo of the particulates embedded in the ice. The ice absorption band depths are related to the mean optical path length of photons in ice through Beers law, Fresnel reflection from the ice-crystal faces on the surface, and ice absorption coefficient as a function of wavelength. Laboratory spectra of many ice- particulate mixtures are studied with high-, medium-, and low-albedo particulates.-from Authors

Crystal fractionation in the SNC meteorites: Implications for sample selection

NASA Technical Reports Server (NTRS)

Treiman, Allan H.

1988-01-01

Almost all rock types in the SNC meteorites are cumulates, products of magma differentiation by crystal fractionation (addition or removal of crystals). If the SNC meteorites are from the surface of Mars or near subsurface, then most of the igneous units on Mars are differentiated. Basaltic units probably experienced minor to moderate differientation, but ultrabasic units probably experienced extreme differentiation. Products of this differentiation may include Fe-rich gabbro, pyroxenite, periodotite (and thus serpentine), and possibly massive sulfides. The SNC meteorites include ten lithologies (three in EETA79001), eight of which are crystal cumulates. The other lithologies, EETA79001 A and B are subophitic basalts.

Chemo-mechanics of salt damage in stone.

PubMed

Flatt, Robert J; Caruso, Francesco; Sanchez, Asel Maria Aguilar; Scherer, George W

2014-09-11

Many porous materials are damaged by pressure exerted by salt crystals growing in their pores. This is a serious issue in conservation science, geomorphology, geotechnical engineering and concrete materials science. In all cases, a central question is whether crystallization pressure will cause damage. Here we present an experiment in which the crystallization pressure and the pore saturation are varied in a controlled way. We demonstrate that a strain energy failure criterion can be used to predict when damage will occur. The experiment considered is the most widely used means to study the susceptibility to salt crystallization, so quantification of this test has far-reaching implications.

Lysozyme Crystal

NASA Technical Reports Server (NTRS)

2004-01-01

To the crystallographer, this may not be a diamond but it is just as priceless. A Lysozyme crystal grown in orbit looks great under a microscope, but the real test is X-ray crystallography. The colors are caused by polarizing filters. Proteins can form crystals generated by rows and columns of molecules that form up like soldiers on a parade ground. Shining X-rays through a crystal will produce a pattern of dots that can be decoded to reveal the arrangement of the atoms in the molecules making up the crystal. Like the troops in formation, uniformity and order are everything in X-ray crystallography. X-rays have much shorter wavelengths than visible light, so the best looking crystals under the microscope won't necessarily pass muster under the X-rays. In order to have crystals to use for X-ray diffraction studies, crystals need to be fairly large and well ordered. Scientists also need lots of crystals since exposure to air, the process of X-raying them, and other factors destroy them. Growing protein crystals in space has yielded striking results. Lysozyme's structure is well known and it has become a standard in many crystallization studies on Earth and in space.

A synergistic approach to protein crystallization: Combination of a fixed-arm carrier with surface entropy reduction

PubMed Central

Moon, Andrea F; Mueller, Geoffrey A; Zhong, Xuejun; Pedersen, Lars C

2010-01-01

Protein crystallographers are often confronted with recalcitrant proteins not readily crystallizable, or which crystallize in problematic forms. A variety of techniques have been used to surmount such obstacles: crystallization using carrier proteins or antibody complexes, chemical modification, surface entropy reduction, proteolytic digestion, and additive screening. Here we present a synergistic approach for successful crystallization of proteins that do not form diffraction quality crystals using conventional methods. This approach combines favorable aspects of carrier-driven crystallization with surface entropy reduction. We have generated a series of maltose binding protein (MBP) fusion constructs containing different surface mutations designed to reduce surface entropy and encourage crystal lattice formation. The MBP advantageously increases protein expression and solubility, and provides a streamlined purification protocol. Using this technique, we have successfully solved the structures of three unrelated proteins that were previously unattainable. This crystallization technique represents a valuable rescue strategy for protein structure solution when conventional methods fail. PMID:20196072

Crystallization and preliminary crystallographic analysis of maganese(II)-dependent 2,3-dihydroxybiphenyl 1,2-dioxygenase from Bacillus sp. JF8

PubMed Central

Senda, Miki; Hatta, Takashi; Kimbara, Kazuhide; Senda, Toshiya

2010-01-01

A thermostable manganese(II)-dependent 2,3-dihydroxybiphenyl-1,2-dioxygenase derived from Bacillus sp. JF8 was crystallized. The initial screening for crystallization was performed by the sitting-drop vapour-diffusion method using a crystallization robot, resulting in the growth of two crystal forms. The first crystal belonged to space group P1, with unit-cell parameters a = 62.7, b = 71.4, c = 93.6 Å, α = 71.2, β = 81.0, γ = 64.0°, and diffracted to 1.3 Å resolution. The second crystal belonged to space group I222, with unit-cell parameters a = 74.2, b = 90.8, c = 104.3 Å, and diffracted to 1.3 Å resolution. Molecular-replacement trials using homoprotocatechuate 2,3-dioxygenase from Arthrobacter globiformis (28% amino-acid sequence identity) as a search model provided a satisfactory solution for both crystal forms. PMID:20208161

Observing the overall rocking motion of a protein in a crystal

NASA Astrophysics Data System (ADS)

Ma, Peixiang; Xue, Yi; Coquelle, Nicolas; Haller, Jens D.; Yuwen, Tairan; Ayala, Isabel; Mikhailovskii, Oleg; Willbold, Dieter; Colletier, Jacques-Philippe; Skrynnikov, Nikolai R.; Schanda, Paul

2015-10-01

The large majority of three-dimensional structures of biological macromolecules have been determined by X-ray diffraction of crystalline samples. High-resolution structure determination crucially depends on the homogeneity of the protein crystal. Overall `rocking' motion of molecules in the crystal is expected to influence diffraction quality, and such motion may therefore affect the process of solving crystal structures. Yet, so far overall molecular motion has not directly been observed in protein crystals, and the timescale of such dynamics remains unclear. Here we use solid-state NMR, X-ray diffraction methods and μs-long molecular dynamics simulations to directly characterize the rigid-body motion of a protein in different crystal forms. For ubiquitin crystals investigated in this study we determine the range of possible correlation times of rocking motion, 0.1-100 μs. The amplitude of rocking varies from one crystal form to another and is correlated with the resolution obtainable in X-ray diffraction experiments.

Bidomain structures formed in lithium niobate and lithium tantalate single crystals by light annealing

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

Kubasov, I. V., E-mail: kubasov.ilya@gmail.com; Kislyuk, A. M.; Bykov, A. S.

The bidomain structures produced by light external heating in z-cut lithium niobate and lithium tantalate single crystals are formed and studied. Interdomain regions about 200 and 40 μm wide in, respectively, LiNbO{sub 3} and LiTaO{sub 3} bidomain crystals are visualized and studied by optical microscopy and piezoresponse force microscopy. Extended chains and lines of domains in the form of thin layers with a width less than 10 μm in volume, which penetrate the interdomain region and spread over distances of up to 1 mm, are found.

The topological pressure-temperature phase diagram and crystal structures of the dimorphic system spiperone.

PubMed

Robert, B; Perrin, M-A; Coquerel, G; Céolin, R; Rietveld, I B

2016-03-01

The topological pressure-temperature phase diagram for the dimorphism of spiperone, a potent neuroleptic drug, has been constructed using literature data and improved crystal structures obtained with new crystallographic data from single-crystal X-ray diffraction at various temperatures. It is inferred that form II, which is the more dense form and exhibits the lower melting temperature, becomes the more stable phase under pressure. Under ambient conditions, form I is more stable. Copyright © 2015 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.

Solution-Phase Processes of Macromolecular Crystallization

NASA Technical Reports Server (NTRS)

Pusey, Marc L.; Minamitani, Elizabeth Forsythe

2004-01-01

We have proposed, for the tetragonal form of chicken egg lysozyme, that solution phase assembly processes are needed to form the growth units for crystal nucleation and growth. The starting point for the self-association process is the monomeric protein, and the final crystallographic symmetry is defined by the initial dimerization interactions of the monomers and subsequent n-mers formed, which in turn are a function of the crystallization conditions. It has been suggested that multimeric proteins generally incorporate the underlying multimers symmetry into the final crystallographic symmetry. We posed the question of what happens to a protein that is known to grow as an n-mer when it is placed in solution conditions where it is monomeric. The trypsin-treated, or cut, form of the protein canavalin (CCAN) has been shown to nucleate and grow crystals as a trimer from neutral to slightly acidic solutions. Under these conditions the solution is composed almost wholly of trimers. The insoluble protein can be readily dissolved by weakly basic solution, which results in a solution that is monomeric. There are three possible outcomes to an attempt at crystallization of the protein under monomeric (high pH) conditions: 1) we will obtain the same crystals as under trimer conditions, but at different protein concentrations governed by the self association equilibria; 2) we will obtain crystals having a different symmetry, based upon a monomeric growth unit; 3) we will not obtain crystals. Obtaining the first result would be indicative that the solution-phase self-association process is critical to the crystal nucleation and growth process. The second result would be less clear, as it may also reflect a pH-dependent shift in the trimer-trimer molecular interactions. The third result, particularly for experiments in the transition pH's between trimeric and monomeric CCAN, would indicate that the monomer does not crystallize, and that solution phase self association is not part of the crystal nucleation and growth path. Results are presented for crystallization experiments of CCAN over the pH 6.8 to 9.6 range.

Recalescence during crystallization of stardust: Resolution of the amorphous interstellar medium paradox

NASA Astrophysics Data System (ADS)

Whittington, A. G.; Sehlke, A.; Speck, A. K.

2017-12-01

Dust that coalesces to form planetary systems originates around dying stars, before passing into the interstellar medium (ISM). Historically, observations of broad smooth features in the 10-µm region suggested that dust in circumstellar regions, and in the ISM, was mostly amorphous rather than crystalline. With improved space telescope capabilities, crystalline silicates were discovered in the circumstellar regions around both young and old stars, although they remain undetected in the ISM. Despite intensive study the precise conditions that lead to the formation of crystalline silicates are still unknown, and their absence in the ISM remains problematic. Here we show that recalescence (spontaneous reheating) of rapidly crystallizing dust can explain the formation and apparent disappearance of crystalline silicates in space. We have documented recalescence in rapidly crystallizing Mg-rich silicate melts, with local heating at the crystallization front exceeding 160˚C in some cases. In circumstellar dust shells, amorphous grains with similar compositions condense at temperatures near their glass transition, and if they crystallize, they will recalesce. The higher temperature (T) of newly crystallized dust allows crystalline spectral features to be seen, because flux emitted depends on T4. After cooling to ambient temperature, crystalline spectral features in the ISM are concealed by volumetrically dominant amorphous dust. Our results explain the existence of crystalline silicate pre-solar grains, which are older than the solar system, and have implications for radiative transfer modeling and hydrodynamics of dusty environments, which are sensitive to small variations in optical properties. Our observations of mm-scale temperature differences up to 100˚C in cooling lava suggest that thermal imaging of basaltic lava flows needs to be conducted with mm-scale spatial resolution (see figure; crucible is 5mm diameter). Temperatures recorded with low spatial resolution, which average cooler melt and hotter crystals in a single pixel, will systematically overestimate the temperature of the liquid phase. Only the surface of a lava flow is likely to cool quickly enough for recalescence to occur, but this is precisely the part of the lava that is monitored by thermal imaging.

Semiconductor liquid crystal composition and methods for making the same

DOEpatents

Alivisatos, A. Paul; Li, Liang-shi

2005-04-26

Semiconductor liquid crystal compositions and methods for making such compositions are disclosed. One embodiment of the invention is directed to a liquid crystal composition including a solvent and semiconductor particles in the solvent. The solvent and the semiconductor particles are in an effective amount in the liquid crystal composition to form a liquid crystal phase.

Glass-ceramic nuclear waste forms obtained by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th): Study of the crystallization from the surface

NASA Astrophysics Data System (ADS)

Loiseau, P.; Caurant, D.

2010-07-01

Glass-ceramic materials containing zirconolite (nominally CaZrTi 2O 7) crystals in their bulk can be envisaged as potential waste forms for minor actinides (Np, Am, Cm) and Pu immobilization. In this study such matrices are synthesized by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th) as surrogates. A thin partially crystallized layer containing titanite and anorthite (nominally CaTiSiO 5 and CaAl 2Si 2O 8, respectively) growing from glass surface is also observed. The effect of the nature and concentration of surrogates on the structure, the microstructure and the composition of the crystals formed in the surface layer is presented in this paper. Titanite is the only crystalline phase able to significantly incorporate trivalent lanthanides whereas ThO 2 precipitates in the layer. The crystal growth thermal treatment duration (2-300 h) at high temperature (1050-1200 °C) is shown to strongly affect glass-ceramics microstructure. For the system studied in this paper, it appears that zirconolite is not thermodynamically stable in comparison with titanite growing form glass surface. Nevertheless, for kinetic reasons, such transformation (i.e. zirconolite disappearance to the benefit of titanite) is not expected to occur during interim storage and disposal of the glass-ceramic waste forms because their temperature will never exceed a few hundred degrees.

Computed crystal energy landscapes for understanding and predicting organic crystal structures and polymorphism.

PubMed

Price, Sarah Sally L

2009-01-20

The phenomenon of polymorphism, the ability of a molecule to adopt more than one crystal structure, is a well-established property of crystalline solids. The possible variations in physical properties between polymorphs make the reliable reproduction of a crystalline form essential for all research using organic materials, as well as quality control in manufacture. Thus, the last two decades have seen both an increase in interest in polymorphism and the availability of the computer power needed to make the computational prediction of organic crystal structures a practical possibility. In the past decade, researchers have made considerable improvements in the theoretical basis for calculating the sets of structures that are within the energy range of possible polymorphism, called crystal energy landscapes. It is common to find that a molecule has a wide variety of ways of packing with lattice energy within a few kilojoules per mole of the most stable structure. However, as we develop methods to search for and characterize "all" solid forms, it is also now usual for polymorphs and solvates to be found. Thus, the computed crystal energy landscape reflects and to an increasing extent "predicts" the emerging complexity of the solid state observed for many organic molecules. This Account will discuss the ways in which the calculation of the crystal energy landscape of a molecule can be used as a complementary technique to solid form screening for polymorphs. Current methods can predict the known crystal structure, even under "blind test" conditions, but such successes are generally restricted to those structures that are the most stable over a wide range of thermodynamic conditions. The other low-energy structures can be alternative polymorphs, which have sometimes been found in later experimental studies. Examining the computed structures reveals the various compromises between close packing, hydrogen bonding, and pi-pi stacking that can result in energetically feasible structures. Indeed, we have observed that systems with many almost equi-energetic structures that contain a common interchangeable motif correlate with a tendency to disorder and problems with control of the crystallization product. Thus, contrasting the computed crystal energy landscape with the known crystal structures of a given molecule provides a valuable complement to solid form screening, and the examination of the low-energy structures often leads to a rationalization of the forms found.

Reverse Micelle Based Synthesis of Microporous Materials in Microgravity

NASA Technical Reports Server (NTRS)

Dutta, Prabir K.

1995-01-01

Formation of zincophosphates from zinc and phosphate containing reverse micelles (water droplets in hexane) has been examined. The frameworks formed resemble that made by conventional hydrothermal synthesis. Dynamics of crystal growth are however quite different, and form the main focus of this study. In particular, the formation of zincophosphate with the sodalite framework was examined in detail. The intramicellar pH was found to have a strong influence on crystal growth. Crystals with a cubic morphology were formed directly from the micelles, without an apparent intermediate amorphous phase over a period of four days by a layer-bylayer growth at the intramicellar pH of 7.6. At a pH of 6.8, an amorphous precipitate rapidly sediments in hours. Sodalite was eventually formed from this settled phase via surface diffusion and reconstruction within four days. With a rotating cell, it was possible to minimize sedimentation and crystals were found to grow epitaxially from the spherical, amorphous particles. Intermediate pH's of 7.2 led to formation of aggregated sodalite crystals prior to settling, again without any indication of an intermediate amorphous phase. These diverse pathways were possible due to changes in intramicellar supersaturation conditions by minor changes in pH. In contrast, conventional syntheses in this pH range all proceeded by similar crystallization pathways through an amorphous gel. This study establishes that synthesis of microporous frameworks is not only possible in reverse micellar systems, but they also allow examination of possible crystallization pathways.

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

Flow induced/ refined solution crystallization of a semiconducting polymer

NASA Astrophysics Data System (ADS)

Nguyen, Ngoc A.

Organic photovoltaics, a new generation of solar cells, has gained scientific and economic interests due to the ability of solution-processing and potentially low-cost power production. Though, the low power conversion efficiency of organic/ plastic solar cells is one of the most pertinent challenges that has appealed to research communities from many different fields including materials science and engineering, electrical engineering, chemical engineering, physics and chemistry. This thesis focuses on investigating and controlling the morphology of a semi-conducting, semi-crystalline polymer formed under shear-flow. Molecular structures and processing techniques are critical factors that significantly affect the morphology formation in the plastic solar cells, thus influencing device performance. In this study, flow-induced solution crystallization of poly (3-hexylthiophene) (P3HT) in a poor solvent, 2-ethylnapthalene (2-EN) was utilized to make a paint-like, structural liquid. The polymer crystals observed in this structured paint are micrometers long, nanometers in cross section and have a structure similar to that formed under quiescent conditions. There is pi-pi stacking order along the fibril axis, while polymer chain folding occurs along the fibril width and the order of the side-chain stacking is along fibril height. It was revealed that shear-flow not only induces P3HT crystallization from solution, but also refines and perfects the P3HT crystals. Thus, a general strategy to refine the semiconducting polymer crystals from solution under shear-flow has been developed and employed by simply tuning the processing (shearing) conditions with respect to the dissolution temperature of P3HT in 2-EN. The experimental results demonstrated that shear removes defects and allows more perfect crystals to be formed. There is no glass transition temperature observed in the crystals formed using the flow-induced crystallization indicating a significantly different morphology formation in comparison to that of the pristine (as-received) P3HT. As a result, single P3HT crystals with high surface energy chain folds were analyzed and determined. Previous reported results of infinite melting enthalpy of extended chain P3HT crystals are much higher than the result discovered in this study. The findings in this study revealed that the infinite melting enthalpy of chain-folded P3HT crystals is considerably decreased due to the presence of this P3HT chain-folded surface energy. In this study, the kinetics and mechanism of P3HT crystallization under shear-flow was thoroughly investigated as well. A homogeneous nucleation of P3HT was observed that allows one dimensional fibril crystal growth. The micrometer long P3HT crystals are formed and limited by the contact time between the P3HT molecules. Furthermore, it was found that phenyl-C61-butyric acid methyl ester (PCBM) nanoparticles inhibit the crystallization of P3HT under shear. However, the shear-flow leads to nanophase agglomeration of PCBM and creates percolation of P3HT fibril crystal networks and the PCBM phase separated domains that apparently present better pathways for transporting electrons and holes. Interestingly, the structured liquid was simply applied onto substrates with a paintbrush resulting in similar device performance to those made with current techniques in which the morphology is commonly formed during application or post-processing steps. These detailed findings are given and discussed in the thesis.

Methods of making composite optical devices employing polymer liquid crystal

DOEpatents

Jacobs, S.D.; Marshall, K.L.; Cerqua, K.A.

1991-10-08

Composite optical devices are disclosed using polymer liquid crystal materials both as optical and adhesive elements. The devices are made by assembling a heated polymer liquid crystal compound, while in a low viscosity form between optically transparent substrates. The molecules of the polymer are oriented, while in the liquid crystalline state and while above the glass transition temperature (T[sub g]) of the polymer, to provide the desired optical effects, such as polarization, and selective reflection. The liquid crystal polymer cements the substrates together to form an assembly providing the composite optical device. 7 figures.

The solubility of hen egg-white lysozyme

NASA Technical Reports Server (NTRS)

Howard, Sandra B.; Twigg, Pamela J.; Baird, James K.; Meehan, Edward J.

1988-01-01

The equilibrium solubility of chicken egg-white lysozyme in the presence of crystalline solid state was determined as a function of NaCl concentration, pH, and temperature. The solubility curves obtained represent a region of the lysozyme phase diagram. This diagram makes it possible to determine the supersaturation of a given set of conditions or to achieve identical supersaturations by different combinations of parameters. The temperature dependence of the solubility permits the evaluation of Delta-H of crystallization. The data indicate a negative heat of crystallization for the tetragonal crystal form but a positive heat of crystallization for the high-temperature orthorhombic form.

Crystallization and diffraction analysis of [beta]-N-acetylhexosaminidase from Aspergillus oryzae

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

Vanek, Ondrej; Brynd, Jirí; Hofbauerová, Katerina

2012-05-08

Fungal {beta}-N-acetylhexosaminidases are enzymes that are used in the chemoenzymatic synthesis of biologically interesting oligosaccharides. The enzyme from Aspergillus oryzae was produced and purified from its natural source and crystallized using the hanging-drop vapor-diffusion method. Diffraction data from two crystal forms (primitive monoclinic and primitive tetragonal) were collected to resolutions of 3.2 and 2.4 {angstrom}, respectively. Electrophoretic and quantitative N-terminal protein-sequencing analyses confirmed that the crystals are formed by a complete biologically active enzyme consisting of a glycosylated catalytic unit and a noncovalently attached propeptide.

System and method for forming synthetic protein crystals to determine the conformational structure by crystallography

DOEpatents

Craig, G.D.; Glass, R.; Rupp, B.

1997-01-28

A method is disclosed for forming synthetic crystals of proteins in a carrier fluid by use of the dipole moments of protein macromolecules that self-align in the Helmholtz layer adjacent to an electrode. The voltage gradients of such layers easily exceed 10{sup 6}V/m. The synthetic protein crystals are subjected to x-ray crystallography to determine the conformational structure of the protein involved. 2 figs.

Crystal forms of the hydrogen oxalate salt of o-desmethylvenlafaxine.

PubMed

Dichiarante, Elena; Curzi, Marco; Giaffreda, Stefano L; Grepioni, Fabrizia; Maini, Lucia; Braga, Dario

2015-06-01

To prepare new crystalline forms of the antidepressant o-desmethylvenlafaxine salt as potential new commercial forms and evaluate their physicochemical properties, in particular the dissolution rate. A new hydrogen oxalate salt of o-desmethylvenlafaxine hydrogen oxalate (ODV-OX) was synthesized, and a polymorph screening was performed using different solvents and crystallization conditions. Crystalline forms were characterized by a combination of solid-state techniques: X-ray powder diffraction, differential scanning calorimetry, thermogravimetric analysis, FT-IR spectroscopy and single crystal X-ray diffraction. The stability of all crystalline phases was tested under International Conference on Harmonisation (ICH) conditions (40°C and 75% Relative Humidity (RH)) for 1 week. Dissolution tests were performed on the hydrogen oxalate salt ODV-OX Form 1 and compared with dissolution test on the commercial form of the succinate salt of o-desmethylvenlafaxine. Five crystalline forms of ODV-OX were isolated, namely three hydrated forms (Form 1, Form 2, Form 3) and two anhydrous forms (Form 4 and Form 5). Comparative solubility tests on ODV-OX Form 1 and o-desmethylvenlafaxine succinate evidenced a significant increase in solubility for the hydrogen oxalate salt (142 g/l) with respect to the succinate salt (70 g/l). © 2015 Royal Pharmaceutical Society.

Thermally-prepared polymorphic forms of cilostazol.

PubMed

Stowell, Grayson W; Behme, Robert J; Denton, Stacy M; Pfeiffer, Inigo; Sancilio, Frederick D; Whittall, Linda B; Whittle, Robert R

2002-12-01

Prior to this study, cilostazol, an antithrombotic drug, was thought to exist as a single crystalline phase with a melting point of approximately 159 degrees C (Form A). On cooling, melts often form a glass that, when heated, may crystallize as additional crystalline polymorphic forms. Cilostazol, when reheated, subsequently forms polymorphs that melt at approximately 136 degrees C (Form B) and 146 degrees C (Form C). Free-energy temperature diagrams estimated from calorimetry data reveal that each pair of the cilostazol polymorphs (A-B, B-C, and A-C) is monotropic. Essentially pure samples of suitable crystalline shape and size permitted single crystal structural analysis of Forms A and C. Theoretical solubility ratios calculated using calorimetry data indicate that at 37 degrees C, Form B should be more than four times more soluble and Form C should be more than two times more soluble than Form A. Forms B and C could not be crystallized from solvents. Metastable forms from super cooled melts analyzed by intrinsic dissolution and Fourier transform-Raman experiments demonstrated that Forms B and C undergo a rapid, solvent-mediated recrystallization to Form A, making dissolution rate measurements difficult. Copyright 2002 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 91:2481-2488, 2002

Characterization of Medicago truncatula reduced calcium oxalate crystal mutant alleles

USDA-ARS?s Scientific Manuscript database

Calcium oxalate crystal formation is common in plants. Formation of these crystals has been shown to function in plant defense, calcium regulation, and aluminum tolerance. Although calcium oxalate is common and plays important roles in plant development, our understanding of how these crystals form ...

Defect studies of ZnO single crystals electrochemically doped with hydrogen

NASA Astrophysics Data System (ADS)

Čížek, J.; Žaludová, N.; Vlach, M.; Daniš, S.; Kuriplach, J.; Procházka, I.; Brauer, G.; Anwand, W.; Grambole, D.; Skorupa, W.; Gemma, R.; Kirchheim, R.; Pundt, A.

2008-03-01

Various defect studies of hydrothermally grown (0001) oriented ZnO crystals electrochemically doped with hydrogen are presented. The hydrogen content in the crystals is determined by nuclear reaction analysis and it is found that already 0.3at.% H exists in chemically bound form in the virgin ZnO crystals. A single positron lifetime of 182ps is detected in the virgin crystals and attributed to saturated positron trapping at Zn vacancies surrounded by hydrogen atoms. It is demonstrated that a very high amount of hydrogen (up to ˜30at.%) can be introduced into the crystals by electrochemical doping. More than half of this amount is chemically bound, i.e., incorporated into the ZnO crystal lattice. This drastic increase of the hydrogen concentration is of marginal impact on the measured positron lifetime, whereas a contribution of positrons annihilated by electrons belonging to O-H bonds formed in the hydrogen doped crystal is found in coincidence Doppler broadening spectra. The formation of hexagonal shape pyramids on the surface of the hydrogen doped crystals by optical microscopy is observed and discussed.

Effects of protein engineering and rational mutagenesis on crystal lattice of single chain antibody fragments

PubMed Central

Kalyoncu, Sibel; Hyun, Jeongmin; Pai, Jennifer C.; Johnson, Jennifer L.; Entzminger, Kevin; Jain, Avni; Heaner, David P.; Morales, Ivan A.; Truskett, Thomas M.; Maynard, Jennifer A.; Lieberman, Raquel L.

2014-01-01

Protein crystallization is dependent upon, and sensitive to, the intermolecular contacts that assist in ordering proteins into a three dimensional lattice. Here we used protein engineering and mutagenesis to affect the crystallization of single chain antibody fragments (scFvs) that recognize the EE epitope (EYMPME) with high affinity. These hypercrystallizable scFvs are under development to assist difficult proteins, such as membrane proteins, in forming crystals, by acting as crystallization chaperones. Guided by analyses of intermolecular crystal lattice contacts, two second-generation anti-EE scFvs were produced, which bind to proteins with installed EE tags. Surprisingly, although non-complementarity determining region (CDR) lattice residues from the parent scFv framework remained unchanged through the processes of protein engineering and rational design, crystal lattices of the derivative scFvs differ. Comparison of energy calculations and the experimentally-determined lattice interactions for this basis set provides insight into the complexity of the forces driving crystal lattice choice and demonstrates the availability of multiple well-ordered surface features in our scFvs capable of forming versatile crystal contacts. PMID:24615866

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.

A potentiometric titration method for the crystallization of drug-like organic molecules.

PubMed

Du-Cuny, Lei; Huwyler, Jörg; Fischer, Holger; Kansy, Manfred

2007-09-05

It is generally accepted, that crystalline solids representing a low energy polymorph should be selected for development of oral dosage forms. As a consequence, efficient and robust procedures are needed at an early stage during drug discovery to prepare crystals from drug-like organic molecules. In contrast to the use of supersaturated solutions, we present a potentiometric crystallization procedure where saturated solutions are prepared in a controlled manner by pH-titration. Crystallization is carried out under defined conditions using the sample concentration and experimental pK(a) values as input parameters. Crystals of high quality were obtained for 11 drugs selected to demonstrate the efficiency and applicability of the new method. Technical improvements are suggested to overcome practical limitations and to enhance the possibility of obtaining crystals from molecules in their uncharged form.

Crystallization and preliminary X-ray diffraction analysis of ω-amino acid:pyruvate transaminase from Chromobacterium violaceum

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

Sayer, Christopher; Isupov, Michail N.; Littlechild, Jennifer A., E-mail: j.a.littlechild@exeter.ac.uk

2007-02-01

An ω-amino acid:pyruvate transaminase from C. violaceum has been purified and crystallized in two crystal forms. The structure has been solved using molecular replacement. The enzyme ω-transaminase catalyses the conversion of chiral ω-amines to ketones. The recombinant enzyme from Chromobacterium violaceum has been purified to homogeneity. The enzyme was crystallized from PEG 4000 using the microbatch method. Data were collected to 1.7 Å resolution from a crystal belonging to the triclinic space group P1, with unit-cell parameters a = 58.9, b = 61.9, c = 63.9 Å, α = 71.9, β = 87.0, γ = 74.6°. Data were also collectedmore » to 1.95 Å from a second triclinic crystal form. The structure has been solved using the molecular-replacement method.« less

Conglomerate formative precursor of chiral drug timolol: 3-(4-Morpholino-1,2,5-thiadiazol-3-yloxy)-propane-1,2-diol

NASA Astrophysics Data System (ADS)

Bredikhin, Alexander A.; Zakharychev, Dmitry V.; Fayzullin, Robert R.; Bredikhina, Zemfira A.; Gubaidullin, Aidar T.

2015-05-01

Solid state properties of 3-(4-N-morpholino-1,2,5-thiadiazol-3-yloxy)-propane-1,2-diol 3, the synthetic precursor of popular drug timolol, have been investigated. The original solubility test, the data of X-ray diffraction and DSC methods indicate that the compound is prone to spontaneous resolution. Diol 3 crystallizing from both enantiopure or racemic feed material forms "guaifenesin-like" crystal packing in which the classic H-bonded bilayers, framed in both sides by hydrophobic molecular fragments, act as the basic supramolecular motif. The main chain conformation of the molecules in the crystals of diol 3 differs from that in the guaifenesin crystals, and this fact changes the absolute configuration of spiral columns formed by intermolecular hydrogen bonds in crystals of 3 as compared with guaifenesin crystals.

CRYSTAL GROWTH. Crystallization by particle attachment in synthetic, biogenic, and geologic environments.

PubMed

De Yoreo, James J; Gilbert, Pupa U P A; Sommerdijk, Nico A J M; Penn, R Lee; Whitelam, Stephen; Joester, Derk; Zhang, Hengzhong; Rimer, Jeffrey D; Navrotsky, Alexandra; Banfield, Jillian F; Wallace, Adam F; Michel, F Marc; Meldrum, Fiona C; Cölfen, Helmut; Dove, Patricia M

2015-07-31

Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments. Copyright © 2015, American Association for the Advancement of Science.

Matrix metalloproteinase-20 mediates dental enamel biomineralization by preventing protein occlusion inside apatite crystals

PubMed Central

Prajapati, Saumya; Tao, Jinhui; Ruan, Qichao; De Yoreo, James J.; Moradian-Oldak, Janet

2015-01-01

Reconstruction of enamel-like materials is a central topic of research in dentistry and material sciences. The importance of precise proteolytic mechanisms in amelogenesis to form a hard tissue with more than 95% mineral content has already been reported. A mutation in the Matrix Metalloproteinase-20 (MMP-20) gene results in hypomineralized enamel that is thin, disorganized and breaks from the underlying dentin. We hypothesized that the absence of MMP-20 during amelogenesis results in the occlusion of amelogenin in the enamel hydroxyapatite crystals. We used spectroscopy and electron microscopy techniques to qualitatively and quantitatively analyze occluded proteins within the isolated enamel crystals from MMP-20 null and Wild type (WT) mice. Our results showed that the isolated enamel crystals of MMP-20 null mice had more organic macromolecules occluded inside them than enamel crystals from the WT. The crystal lattice arrangements of MMP-20 null enamel crystals analyzed by High Resolution Transmission Electron Microscopy (HRTEM) were found to be significantly different from those of the WT. Raman studies indicated that the crystallinity of the MMP-20 null enamel crystals was lower than that of the WT. In conclusion, we present a novel functional mechanism of MMP-20, specifically prevention of unwanted organic material entrapped in the forming enamel crystals, which occurs as the result of precise amelogenin cleavage. MMP-20 action guides the growth morphology of the forming hydroxyapatite crystals and enhances their crystallinity. Elucidating such molecular mechanisms can be applied in the design of novel biomaterials for future clinical applications in dental restoration or repair. PMID:26513418

Matrix metalloproteinase-20 mediates dental enamel biomineralization by preventing protein occlusion inside apatite crystals.

PubMed

Prajapati, Saumya; Tao, Jinhui; Ruan, Qichao; De Yoreo, James J; Moradian-Oldak, Janet

2016-01-01

Reconstruction of enamel-like materials is a central topic of research in dentistry and material sciences. The importance of precise proteolytic mechanisms in amelogenesis to form a hard tissue with more than 95% mineral content has already been reported. A mutation in the Matrix Metalloproteinase-20 (MMP-20) gene results in hypomineralized enamel that is thin, disorganized and breaks from the underlying dentin. We hypothesized that the absence of MMP-20 during amelogenesis results in the occlusion of amelogenin in the enamel hydroxyapatite crystals. We used spectroscopy and electron microscopy techniques to qualitatively and quantitatively analyze occluded proteins within the isolated enamel crystals from MMP-20 null and Wild type (WT) mice. Our results showed that the isolated enamel crystals of MMP-20 null mice had more organic macromolecules occluded inside them than enamel crystals from the WT. The crystal lattice arrangements of MMP-20 null enamel crystals analyzed by High Resolution Transmission Electron Microscopy (HRTEM) were found to be significantly different from those of the WT. Raman studies indicated that the crystallinity of the MMP-20 null enamel crystals was lower than that of the WT. In conclusion, we present a novel functional mechanism of MMP-20, specifically prevention of unwanted organic material entrapped in the forming enamel crystals, which occurs as the result of precise amelogenin cleavage. MMP-20 action guides the growth morphology of the forming hydroxyapatite crystals and enhances their crystallinity. Elucidating such molecular mechanisms can be applied in the design of novel biomaterials for future clinical applications in dental restoration or repair. Copyright © 2015 Elsevier Ltd. All rights reserved.

The Crystal Hotel: A Microfluidic Approach to Biomimetic Crystallization.

PubMed

Gong, Xiuqing; Wang, Yun-Wei; Ihli, Johannes; Kim, Yi-Yeoun; Li, Shunbo; Walshaw, Richard; Chen, Li; Meldrum, Fiona C

2015-12-02

A "crystal hotel" microfluidic device that allows crystal growth in confined volumes to be studied in situ is used to produce large calcite single crystals with predefined crystallographic orientation, microstructure, and shape by control of the detailed physical environment, flow, and surface chemistry. This general approach can be extended to form technologically important, nanopatterned single crystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The crystal structures of two chalcones: (2E)-1-(5-chloro-thio-phen-2-yl)-3-(2-methyl-phen-yl)prop-2-en-1-one and (2E)-1-(anthracen-9-yl)-3-[4-(propan-2-yl)phen-yl]prop-2-en-1-one.

PubMed

Girisha, Marisiddaiah; Yathirajan, Hemmige S; Jasinski, Jerry P; Glidewell, Christopher

2016-08-01

In the crystal of compound (I), C14H11ClOS, mol-ecules are linked by C-H⋯O hydrogen bonds to form simple C(5) chains. Compound (II), C26H22O, crystallizes with Z' = 2 in space group P-1; one of the mol-ecules is fully ordered but the other is disordered over two sets of atomic sites having occupancies 0.644 (3) and 0.356 (3). The two disordered components differ from one another in the orientation of the isopropyl substituents, and both differ from the ordered mol-ecules in the arrangement of the central propenone spacer unit, so that the crystal of (II) contains three distinct conformers. The ordered and disordered conformers each form a C(8) chain built from a single type of C-H⋯O hydrogen bond but those formed by the disordered conformers differ from that formed by the ordered form.

Formation of a new crystalline form of anhydrous β-maltose by ethanol-mediated crystal transformation.

PubMed

Verhoeven, Nicolas; Neoh, Tze Loon; Ohashi, Tetsuya; Furuta, Takeshi; Kurozumi, Sayaka; Yoshii, Hidefumi

2012-04-01

β-Maltose monohydrate was transformed into an anhydrous form by ethanol-mediated method under several temperatures with agitation. A new stable anhydrous form of β-maltose (Mβ(s)) was obtained, as substantiated by the X-ray diffraction patterns. Mβ(s) obtained by this method presented a fine porous structure, resulting in greater specific surface area compared to those of β-maltose monohydrate and anhydrous β-maltose obtained by vacuum drying (Mβ(h)). The crystal transformation presumably consisted of two steps: dehydration reaction from the hydrous to amorphous forms and crystal formation from the amorphous forms to the noble anhydrous form. The kinetics of these reactions were determined by thermal analysis using Jander's equation and Arrhenius plots. The overall activation energies of the dehydration reaction and the formation of anhydrous maltose were evaluated to be 100 and 90 kJ/mol, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Conformational change of adenosine deaminase during ligand-exchange in a crystal.

PubMed

Kinoshita, Takayoshi; Tada, Toshiji; Nakanishi, Isao

2008-08-15

Adenosine deaminase (ADA) perpetuates chronic inflammation by degrading extracellular adenosine which is toxic for lymphocytes. ADA has two distinct conformations: open form and closed form. From the crystal structures with various ligands, the non-nucleoside type inhibitors bind to the active site occupying the critical water-binding-position and sustain the open form of apo-ADA. In contrast, substrate mimics do not occupy the critical position, and induce the large conformational change to the closed form. However, it is difficult to predict the binding of (+)-erythro-9-(2-hydroxy-3-nonyl)adenine (EHNA), as it possesses characteristic parts of both the substrate and the non-nucleoside inhibitors. The crystal structure shows that EHNA binds to the open form through a novel recognition of the adenine base accompanying conformational change from the closed form of the PR-ADA complex in crystalline state.

Polymorphism in phenobarbital: discovery of a new polymorph and crystal structure of elusive form V.

PubMed

Roy, Saikat; Goud, N Rajesh; Matzger, Adam J

2016-03-21

This report highlights the discovery of a new polymorph of the anticonvulsant drug phenobarbital (PB) using polymer-induced heteronucleation (PIHn) and unravelling the crystal structure of the elusive form V. Both forms are characterized by structural, thermal and VT-Raman spectroscopy methods to elucidate phase transformation behavior and shed light on stability relationships.

Unusual Features of Crystal Structures of Some Simple Copper Compounds

ERIC Educational Resources Information Center

Douglas, Bodie

2009-01-01

Some simple copper compounds have unusual crystal structures. Cu[subscript 3]N is cubic with N atoms at centers of octahedra formed by 6 Cu atoms. Cu[subscript 2]O (cuprite) is also cubic; O atoms are in tetrahedra formed by 4 Cu atoms. These tetrahedra are linked by sharing vertices forming two independent networks without linkages between them.…

Crystal structure of rivastigmine hydrogen tartrate Form I (Exelon®), C 14H 23N 2O 2(C 4H 5O 6)

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

Kaduk, James A.; Zhong, Kai; Gindhart, Amy M.

2016-03-08

The crystal structure of rivastigmine hydrogen tartrate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Rivastigmine hydrogen tartrate crystallizes in space groupP2 1(#4) witha= 17.538 34(5),b= 8.326 89(2),c= 7.261 11(2) Å,β= 98.7999(2)°,V= 1047.929(4) Å 3, andZ= 2. The un-ionized end of the hydrogen tartrate anions forms a very strong hydrogen bond with the ionized end of another anion to form a chain. The ammonium group of the rivastigmine cation forms a strong discrete hydrogen bond with the carbonyl oxygen atom of the un-ionized end of the tartrate anion. These hydrogen bondsmore » form a corrugated network in thebc-plane. Both hydroxyl groups of the tartrate anion form intramolecular O–H···O hydrogen bonds. Several C–H···O hydrogen bonds appear to contribute to the crystal energy. The powder pattern is included in the Powder Diffraction File ™as entry 00-064-1501.« less

Causes of fragmented crystals in ignimbrites: a case study of the Cardones ignimbrite, Northern Chile

NASA Astrophysics Data System (ADS)

van Zalinge, M. E.; Cashman, K. V.; Sparks, R. S. J.

2018-03-01

Broken crystals have been documented in many large-volume caldera-forming ignimbrites and can help to understand the role of crystal fragmentation in both eruption and compaction processes, the latter generally overlooked in the literature. This study investigates the origin of fragmented crystals in the > 1260 km3, crystal-rich Cardones ignimbrites located in the Central Andes. Observations of fragmented crystals in non-welded pumice clasts indicate that primary fragmentation includes extensive crystal breakage and an associated ca. 5 vol% expansion of individual crystals while preserving their original shapes. These observations are consistent with the hypothesis that crystals fragment in a brittle response to rapid decompression associated with the eruption. Additionally, we observe that the extent of crystal fragmentation increases with increasing stratigraphic depth in the ignimbrite, recording secondary crystal fragmentation during welding and compaction. Secondary crystal fragmentation aids welding and compaction in two ways. First, enhanced crystal fragmentation at crystal-crystal contacts accommodates compaction along the principal axis of stress. Second, rotation and displacement of individual crystal fragments enhances lateral flow in the direction(s) of least principal stress. This process increases crystal aspect ratios and forms textures that resemble mantled porphyroclasts in shear zones, indicating lateral flow adds to processes of compaction and welding alongside bubble collapse. In the Cardones ignimbrite, secondary fragmentation commences at depths of 175-250 m (lithostatic pressures 4-6 MPa), and is modulated by both the overlying crystal load and the time spent above the glass transition temperature. Under these conditions, the existence of force-chains can produce stresses at crystal-crystal contacts of a few times the lithostatic pressure. We suggest that documenting crystal textures, in addition to conventional welding parameters, can provide useful information about welding processes in thick crystal-rich ignimbrites.

Hyaluronan and Stone Disease

NASA Astrophysics Data System (ADS)

Asselman, Marino

2008-09-01

Kidney stones cannot be formed as long as crystals are passed in the urine. However, when crystals are retained it becomes possible for them to aggregate and form a stone. Crystals are expected to be formed not earlier than the distal tubules and collecting ducts. Studies both in vitro and in vivo demonstrate that calcium oxalate monohydrate crystals do not adhere to intact distal epithelium, but only when the epithelium is proliferating or regenerating, so that it possesses dedifferentiated cells expressing hyaluronan, osteopontin (OPN) and their mutual receptor CD44 at the apical cell membrane. The polysaccharide hyaluronan is an excellent crystal binding molecule because of its negative ionic charge. We hypothesized that the risk for crystal retention in the human kidney would be increased when tubular cells express hyaluronan at their apical cell membrane. Two different patient categories in which nephrocalcinosis frequently occurs were studied to test this hypothesis (preterm neonates and kidney transplant patients). Hyaluronan (and OPN) expression at the luminal membrane of tubular cells indeed was observed, which preceded subsequent retention of crystals in the distal tubules. Tubular nephrocalcinosis has been reported to be associated with decline of renal function and thus further studies to extend our knowledge of the mechanisms of retention and accumulation of crystals in the kidney are warranted. Ultimately, this may allow the design of new strategies for the prevention and treatment of both nephrocalcinosis and nephrolithiasis in patients.

Medical ice slurry production device

DOEpatents

Kasza, Kenneth E [Palos Park, IL; Oras, John [Des Plaines, IL; Son, HyunJin [Naperville, IL

2008-06-24

The present invention relates to an apparatus for producing sterile ice slurries for medical cooling applications. The apparatus is capable of producing highly loaded slurries suitable for delivery to targeted internal organs of a patient, such as the brain, heart, lungs, stomach, kidneys, pancreas, and others, through medical size diameter tubing. The ice slurry production apparatus includes a slurry production reservoir adapted to contain a volume of a saline solution. A flexible membrane crystallization surface is provided within the slurry production reservoir. The crystallization surface is chilled to a temperature below a freezing point of the saline solution within the reservoir such that ice particles form on the crystallization surface. A deflector in the form of a reciprocating member is provided for periodically distorting the crystallization surface and dislodging the ice particles which form on the crystallization surface. Using reservoir mixing the slurry is conditioned for easy pumping directly out of the production reservoir via medical tubing or delivery through other means such as squeeze bottles, squeeze bags, hypodermic syringes, manual hand delivery, and the like.

Manufacturing Amorphous Solid Dispersions with a Tailored Amount of Crystallized API for Biopharmaceutical Testing.

PubMed

Theil, Frank; Milsmann, Johanna; Anantharaman, Sankaran; van Lishaut, Holger

2018-05-07

The preparation of an amorphous solid dispersion (ASD) by dissolving a poorly water-soluble active pharmaceutical ingredient (API) in a polymer matrix can improve the bioavailability by orders of magnitude. Crystallization of the API in the ASD, though, is an inherent threat for bioavailability. Commonly, the impact of crystalline API on the drug release of the dosage form is studied with samples containing spiked crystallinity. These spiked samples possess implicit differences compared to native crystalline samples, regarding size and spatial distribution of the crystals as well as their molecular environment. In this study, we demonstrate that it is possible to grow defined amounts of crystalline API in solid dosage forms, which enables us to study the biopharmaceutical impact of actual crystallization. For this purpose, we studied the crystal growth in fenofibrate tablets over time under an elevated moisture using transmission Raman spectroscopy (TRS). As a nondestructive method to assess API crystallinity in ASD formulations, TRS enables the monitoring of crystal growth in individual dosage forms. Once the kinetic trace of the crystal growth for a certain environmental condition is determined, this method can be used to produce samples with defined amounts of crystallized API. To investigate the biopharmaceutical impact of crystallized API, non-QC dissolution methods were used, designed to identify differences between the various amounts of crystalline materials present. The drug release in the samples manufactured in this fashion was compared to that of samples with spiked crystallinity. In this study, we present for the first time a method for targeted crystallization of amorphous tablets to simulate crystallized ASDs. This methodology is a valuable tool to generate model systems for biopharmaceutical studies on the impact of crystallinity on the bioavailability.

Screening of detergents for solubilization, purification and crystallization of membrane proteins: a case study on succinate:ubiquinone oxidoreductase from Escherichia coli

PubMed Central

Shimizu, Hironari; Nihei, Coh-ichi; Inaoka, Daniel Ken; Mogi, Tatushi; Kita, Kiyoshi; Harada, Shigeharu

2008-01-01

Succinate:ubiquinone oxidoreductase (SQR) was solubilized and purified from Escherichia coli inner membranes using several different detergents. The number of phospholipid molecules bound to the SQR molecule varied greatly depending on the detergent combination that was used for the solubilization and purification. Crystallization conditions were screened for SQR that had been solubilized and purified using 2.5%(w/v) sucrose monolaurate and 0.5%(w/v) Lubrol PX, respectively, and two different crystal forms were obtained in the presence of detergent mixtures composed of n-alkyl-oligoethylene glycol monoether and n-alkyl-maltoside. Crystallization took place before detergent phase separation occurred and the type of detergent mixture affected the crystal form. PMID:18765923

Screening of detergents for solubilization, purification and crystallization of membrane proteins: a case study on succinate:ubiquinone oxidoreductase from Escherichia coli.

PubMed

Shimizu, Hironari; Nihei, Coh-ichi; Inaoka, Daniel Ken; Mogi, Tatushi; Kita, Kiyoshi; Harada, Shigeharu

2008-09-01

Succinate:ubiquinone oxidoreductase (SQR) was solubilized and purified from Escherichia coli inner membranes using several different detergents. The number of phospholipid molecules bound to the SQR molecule varied greatly depending on the detergent combination that was used for the solubilization and purification. Crystallization conditions were screened for SQR that had been solubilized and purified using 2.5%(w/v) sucrose monolaurate and 0.5%(w/v) Lubrol PX, respectively, and two different crystal forms were obtained in the presence of detergent mixtures composed of n-alkyl-oligoethylene glycol monoether and n-alkyl-maltoside. Crystallization took place before detergent phase separation occurred and the type of detergent mixture affected the crystal form.

Growth of a New Ternary BON Crystal on Si(100) by Plasma-Assisted MOCVD and Study on the Effects of Fed Gas and Growth Temperature

NASA Astrophysics Data System (ADS)

Chen, G. C.; Lee, S.-B.; Boo, J.-H.

A new ternary BOxNy crystal was grown on Si(100) substrate at 500°C by low-frequency (100 kHz) radio-frequency (rf) derived plasma-assisted MOCVD with an organoborate precursor. The as-grown deposits were characterized by SEM, TED, XPS, XRD, AFM and FT-IR. The experimental results showed that BOxNy crystal was apt to be formed at N-rich atmosphere and high temperature. The decrease of hydrogen flux in fed gases was of benefit to form BON crystal structure. The crystal structure of BOxNy was as similar to that of H3BO3 in this study.

Crystal structure of carnidazole form II from synchrotron X-ray powder diffraction: structural comparison with form I, the hydrated form and the low energy conformations in vacuo.

PubMed

de Armas, Héctor Novoa; Peeters, Oswald M; Blaton, Norbert; Van den Mooter, Guy; De Ridder, Dirk J A; Schenk, Henk

2006-10-01

The crystal structure of carnidazole form II, O-methyl [2-(2-methyl-5-nitro-1H-imidazole-1-yl)ethyl]thiocarbamate, has been determined using synchrotron X-ray powder diffraction in combination with simulated annealing and whole profile pattern matching, and refined by the Rietveld method. For structure solution, 12 degrees of freedom were defined: one motion group and six torsions. Form II crystallizes in space group P2(1)/n, Z=4, with unit cell parameters after Rietveld refinement: a=13.915(4), b=8.095(2), c=10.649(3) A, beta=110.83(1) degrees, and V=1121.1(5) A3. The two polymorphic forms, as well as the hydrate, crystallize in the monoclinic space group P2(1)/n having four molecules in the cell. In form II, the molecules are held together by forming two infinite zig-zag chains via hydrogen bonds of the type N--H...N, the same pattern as in form I. A conformational study of carnidazole, at semiempirical PM3 level, was performed using stochastic approaches based on modification of the flexible torsion angles. The values of the torsion angles for the molecules of the two polymorphic forms and the hydrate of carnidazole are compared to those obtained from the conformational search. Form I and form II are enantiotropic polymorphic pairs this agrees with the fact that the two forms are conformational polymorphs. Copyright (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association

Myelin structures formed by thermotropic smectic liquid crystals

NASA Astrophysics Data System (ADS)

Peddireddy, Karthik Reddy; Kumar, Pramoda; Thutupalli, Shashi; Herminghaus, Stephan; Bahr, Christian

2014-03-01

We report on transient structures, formed by thermotropic smectic-A liquid crystals, resembling the myelin figures of lyotropic lamellar liquid crystals. The thermotropic myelin structures form during the solubilization of a smectic-A droplet in an aqueous phase containing a cationic surfactant at concentrations above the critical micelle concentration. Similar to the lyotropic myelin figures, the thermotropic myelins appear in an optical microscope as flexible tube-like structures growing at the smectic/aqueous interface. Polarizing microscopy and confocal fluorescence microscopy show that the smectic layers are parallel to the tube surface and form a cylindrically bent arrangement around a central line defect in the tube. We study the growth behavior of this new type of myelins and discuss similarities and differences to the classical lyotropic myelin figures.

Exploring Solid-State Structure and Physical Properties: A Molecular and Crystal Model Exercise

ERIC Educational Resources Information Center

Bindel, Thomas H.

2008-01-01

A crystal model laboratory exercise is presented that allows students to examine relations among the microscopic-macroscopic-symbolic levels, using crystalline mineral samples and corresponding crystal models. Students explore the relationship between solid-state structure and crystal form. Other structure-property relationships are explored. The…

Gravity driven and in situ fractional crystallization processes in the Centre Hill complex, Abitibi Subprovince, Canada: Evidence from bilaterally-paired cyclic units

NASA Astrophysics Data System (ADS)

Thériault, R. D.; Fowler, A. D.

1996-12-01

The formation of layers in mafic intrusions has been explained by various processes, making it the subject of much controversy. The concept that layering originates from gravitational settling of crystals has been superseded in recent years by models involving in situ fractional crystallization. Here we present evidence from the Centre Hill complex that both processes may be operative simultaneously within the same intrusion. The Centre Hill complex is part of the Munro Lake sill, an Archean layered mafic intrusion emplaced in volcanic rocks of the Abitibi Subprovince. The Centre Hill complex comprises the following lithostratigraphic units: six lower cyclic units of peridotite and clinopyroxenite; a middle unit of leucogabbro; six upper cyclic units of branching-textured gabbro (BTG) and clotted-textured gabbro (CTG), the uppermost of these units being overlain by a marginal zone of fine-grained gabbro. The cyclic units of peridotite/clinopyroxenite and BTG/CTG are interpreted to have formed concurrently through fractional crystallization, associated with periodic replenishment of magma to the chamber. The units of peridotite and clinopyroxenite formed by gravitational accumulation of crystals that grew under the roof. The cyclic units of BTG and CTG formed along the upper margin of the sill by two different mechanisms: (1) layers of BTG crystallized in situ along an inward-growing roof and (2) layers of CTG formed by accumulation of buoyant plagioclase crystals. The layers of BTG are characterized by branching pseudomorphs after fayalite up to 50 cm in length that extend away from the upper margin. The original branching crystals are interpreted to have grown from stagnant intercumulus melt in a high thermal gradient resulting from the injection of new magma to the chamber.

Epidote from the Zard Mountains, Kharan, Balochistan, Pakistan

USGS Publications Warehouse

Brownfield, Michael E.; Lowers, Heather; Betterton, William K.

2013-01-01

The authors received two unusual crystals of epidote from Rock Currier, Jewel Tunnel Imports, in 2012. The mineral specimens were collected at Zard Mountain (Zard Koh), in the central part of the Ruskoh Mountains (Rusk Koh), west of Kharan, Balochistan, Pakistan (written communication, Rock Currier, 2013). The epidote locality was most likely discovered in 2010. These epidote crystals were unusual in both form and composition. The large crystals were flat tabular and pseudohexagonal in shape which is an uncommon crystal form for a monoclinic mineral (fig. 1). Other specimens from the same locality have been described as pseudo-octahedral in shape. The two crystals range in size from 5.5 to 6.5 centimeters (2.2 to 2.6 inches) and are slightly magnetic. The epidote crystals have a core matrix that resembles a weathered igneous rock. Some micro brown- to reddish-titanite crystals were observed under a binocular microscope on the surface and core areas of the crystals (figs. 2 and 3). Other minerals observed in the core areas include feldspar, biotite, and quartz. The crystals display evidence of cluster-growth with points of attachment to other crystals. The epidotes were most likely collected in pockets of a weathered igneous-skarn deposit.

Microgravity

NASA Image and Video Library

2004-04-15

To the crystallographer, this may not be a diamond but it is just as priceless. A Lysozyme crystal grown in orbit looks great under a microscope, but the real test is X-ray crystallography. The colors are caused by polarizing filters. Proteins can form crystals generated by rows and columns of molecules that form up like soldiers on a parade ground. Shining X-rays through a crystal will produce a pattern of dots that can be decoded to reveal the arrangement of the atoms in the molecules making up the crystal. Like the troops in formation, uniformity and order are everything in X-ray crystallography. X-rays have much shorter wavelengths than visible light, so the best looking crystals under the microscope won't necessarily pass muster under the X-rays. In order to have crystals to use for X-ray diffraction studies, crystals need to be fairly large and well ordered. Scientists also need lots of crystals since exposure to air, the process of X-raying them, and other factors destroy them. Growing protein crystals in space has yielded striking results. Lysozyme's structure is well known and it has become a standard in many crystallization studies on Earth and in space.

Alternative dimerization interfaces in the glucocorticoid receptor-α ligand binding domain.

PubMed

Bianchetti, Laurent; Wassmer, Bianca; Defosset, Audrey; Smertina, Anna; Tiberti, Marion L; Stote, Roland H; Dejaegere, Annick

2018-04-30

Nuclear hormone receptors (NRs) constitute a large family of multi-domain ligand-activated transcription factors. Dimerization is essential for their regulation, and both DNA binding domain (DBD) and ligand binding domain (LBD) are implicated in dimerization. Intriguingly, the glucocorticoid receptor-α (GRα) presents a DBD dimeric architecture similar to that of the homologous estrogen receptor-α (ERα), but an atypical dimeric architecture for the LBD. The physiological relevance of the proposed GRα LBD dimer is a subject of debate. We analyzed all GRα LBD homodimers observed in crystals using an energetic analysis based on the PISA and on the MM/PBSA methods and a sequence conservation analysis, using the ERα LBD dimer as a reference point. Several dimeric assemblies were observed for GRα LBD. The assembly generally taken to be physiologically relevant showed weak binding free energy and no significant residue conservation at the contact interface, while an alternative homodimer mediated by both helix 9 and C-terminal residues showed significant binding free energy and residue conservation. However, none of the GRα LBD assemblies found in crystals are as stable or conserved as the canonical ERα LBD dimer. GRα C-terminal sequence (F-domain) forms a steric obstacle to the canonical dimer assembly in all available structures. Our analysis calls for a re-examination of the currently accepted GRα homodimer structure and experimental investigations of the alternative architectures. This work questions the validity of the currently accepted architecture. This has implications for interpreting physiological data and for therapeutic design pertaining to glucocorticoid research. Copyright © 2018. Published by Elsevier B.V.

Liquid Crystalline Thermosets from Ester, Ester-Imide, and Ester-Amide Oligomers

NASA Technical Reports Server (NTRS)

Dingemans, Theodornus J. (Inventor); Weiser, Erik S. (Inventor); SaintClair, Terry L. (Inventor)

2005-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,OOO grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end- capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers

NASA Technical Reports Server (NTRS)

Dingemans, Theodorous J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

2005-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and were end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The resulting reactive end-capped liquid crystal oligomers exhibit a variety of improved and preferred physical properties. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystal oligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oligomers are stable for up to an hour in the melt phase. These properties make the end-capped liquid crystal oligomers highly processable by a variety of melt process shape forming and blending techniques including film extrusion, fiber spinning, reactive injection molding (RIM), resin transfer molding (RTM), resin film injection (RFI), powder molding, pultrusion, injection molding, blow molding, plasma spraying and thermo-forming. Once processed and shaped, the end-capped liquid crystal oligomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures. The resulting thermosets display many properties that are superior to their non-end-capped high molecular weight analogs.

Structures of human thymidylate synthase R163K with dUMP, FdUMP and glutathione show asymmetric ligand binding

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

Gibson, Lydia M.; Celeste, Lesa R.; Lovelace, Leslie L.

Thymidylate synthase (TS) is a well validated target in cancer chemotherapy. Here, a new crystal form of the R163K variant of human TS (hTS) with five subunits per asymmetric part of the unit cell, all with loop 181-197 in the active conformation, is reported. This form allows binding studies by soaking crystals in artificial mother liquors containing ligands that bind in the active site. Using this approach, crystal structures of hTS complexes with FdUMP and dUMP were obtained, indicating that this form should facilitate high-throughput analysis of hTS complexes with drug candidates. Crystal soaking experiments using oxidized glutathione revealed thatmore » hTS binds this ligand. Interestingly, the two types of binding observed are both asymmetric. In one subunit of the physiological dimer covalent modification of the catalytic nucleophile Cys195 takes place, while in another dimer a noncovalent adduct with reduced glutathione is formed in one of the active sites.« less

Apparatus for growing crystals

NASA Technical Reports Server (NTRS)

Jasinski, Thomas J. (Inventor); Witt, August F. (Inventor)

1986-01-01

An improved apparatus and method for growing crystals from a melt employing a heat pipe, consisting of one or more sections, each section serving to control temperature and thermal gradients in the crystal as it forms inside the pipe.

Conformational flexibility and packing plausibility of repaglinide polymorphs

NASA Astrophysics Data System (ADS)

Rani, Dimpy; Goyal, Parnika; Chadha, Renu

2018-04-01

The present manuscript highlights the structural insight into the repaglinide polymorphs. The experimental screening for the possible crystal forms were carried out using various solvents, which generated three forms. The crystal structure of Form II and III was determined using PXRD pattern whereas structural analysis of Form I has already been reported. Form I, II and II was found to exist in P212121, PNA21 and P21/c space groups respectively. Conformational analysis was performed to account the conformational flexibility of RPG. The obtained conformers were further utilized to obtain the information about the crystal packing pattern of RPG polymorphs by polymorph prediction module. The lattice energy landscape, depicting the relationship between lattice energy and density of the polymorphs has been obtained for various possible polymorphs. The experimentally isolated polymorphs were successfully fitted into lattice energy landscape.

Optimum Concentration Ratio Analysis Using Dynamic Thermal Model for Concentrated Photovoltaic System

DTIC Science & Technology

2012-03-22

covalent bond with four adjacent atoms. Compound semiconductors such as GaAs have a crystal lattice similar to the diamond lattice, but since the...are found in both elemental (e.g. Si) and compound form (e.g. GaAs), but every semiconductor material is characterized by the properties of its crystal...lattice. The covalent bonds formed within a semiconducting material determine the shape of the crystal lattice [8]. For an in depth explanation

Crystal structure of 4,5-dinitro-1 H-imidazole

DOE PAGES

Windler, G. Kenneth; Scott, Brian L.; Tomson, Neil C.; ...

2015-01-01

Here, the title compound, C 3H 2N 4O 4, forms crystals with two molecules in the asymmetric unit which are conformationally similar. With the exception of the O atoms of the nitro groups, the molecules are essentially planar. In the crystal, adjacent molecules are associated by N—H...N hydrogen bonds involving the imidazole N—H donors and N-atom acceptors of the unsaturated nitrogen of neighboring rings, forming layers parallel to (010).

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

Investigation of the L-Glutamic acid polymorphism: Comparison between stirred and stagnant conditions

NASA Astrophysics Data System (ADS)

Tahri, Yousra; Gagnière, Emilie; Chabanon, Elodie; Bounahmidi, Tijani; Mangin, Denis

2016-02-01

This work highlights the effect of the stirring, the temperature and the supersaturation on the cooling crystallization of L-Glutamic acid (LGlu) polymorphs. First, solubility measurements of the metastable polymorph α and the stable polymorph β were performed. Then, crystallization experiments were carried out in stirred vessel and in stagnant cell. All these experiments were monitored by in situ devices. The effect of the temperature on the LGlu polymorphs was found to be more relevant than the supersaturation in the stirred crystallizer. In the stagnant cell, only the stable form β crystallized regardless of the operating conditions. Moreover, an unexpected and new habit of the β form was discovered and confirmed. These results suggest that the temperature and the stirring can strongly affect the nucleation and the growth kinetics of polymorphic forms.

Crystallization and characterization of human chorionic gonadotropin in chemically deglycosylated and enzymatically desialylated states

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

Lustbader, J.W.; Birken, S.; Pileggi, N.F.

1989-11-28

Crystals suitable for X-ray diffraction studies at moderate resolution have been grown from two forms of human chorionic gonadotropin (hCG): HF-treated hCG and neuraminidase-treated hCG. The enzymatically desialylated form of hCG produced crystals that diffract to 2.8 {angstrom} as compared to the HF-treated hCG crystals that diffract to 3.0 {angstrom}. Although it was assumed that the high and heterogeneous carbohydrate content of the glycoprotein hormones inhibited their crystallization, this report suggests that it is the negatively charged surface sugars and neither the total carbohydrate content nor its heterogeneity which interferes with crystal formation. Chemical deglycosylation resulted in significantly increased proteinmore » degradation during crystal growth. Such peptide bond cleavages were observed to a much lesser extent in the crystals grown from neuraminidase-digested hCG. Sequence analysis of the HF-treated hCG crystals suggested that up to 45% of the molecules within the crystal had an acid-labile peptide bond cleaved. In contrast, the neuraminidase-treated hCG exhibited less than 9% of this type of cleavage. The manner in which hCG was treated prior to crystallization was found to be a very important factor in the extent of peptide bound cleavages occurring during crystal growth. HF treatment of glycoproteins may render glycoproteins more susceptible to peptide bond cleavage during crystal growth.« less

A preliminary study of the fabrics in the Skaergaard Layered Series and implications for the significance of compaction

NASA Astrophysics Data System (ADS)

Vukmanovic, Z.; Holness, M. B.; Mariani, E.

2016-12-01

Gabbroic cumulates often have foliations and/or lineations defined by shape-preferred orientations of cumulus grains (SPO). These fabrics are commonly interpreted as a product of crystal alignment by flowing magma or by slumping of a non-cohesive mush. Conversely it has also been argued that cumulate fabrics are secondary and formed during compaction via dislocation creep and/or solution-reprecipitation creep. The dominant plagioclase slip system, (010)[001], creates a crystallographic preferred orientation (CPO) defined by the alignment of (010) planes, with [001] parallel to lineation. Solution-reprecipitation results in a CPO with (010) planes aligned parallel to the principal compressive stress, and preferential mineral growth on (010) planes to form an SPO defined by grains elongated perpendicular to (010). In the Skaergaard Layered Series, the shape of cumulus plagioclase grains changes systematically from highly tabular to equant up the stratigraphy. Foliations, defined both by a plagioclase SPO (with tabular grains aligned horizontally) and an associated CPO ((010) parallel to foliation), are strongest lower in the stratigraphy and reduce in strength upwards. Lineations are generally absent or weak. Evidence for crystal plasticity is limited to bending of some plagioclase crystals and small numbers of low angle boundaries in all phases. Compositional zoning is present on all plagioclase growth faces in the lower part of the stratigraphy, inconsistent with preferential solution - reprecipitation during compression. There are no fabrics or microstructures that can be attributed to solution-reprecipitation, and evidence for only minor microstructural modification by dislocation creep. Plagioclase grain shape and strength of foliations are approximately anti-correlated with incompatible element concentration. It has been argued that the upwards decrease in incompatible element concentration in the Skaergaard Layered Series is due to an upwards increasing significance of compaction driven by gravitational loading. Our observations suggest that the Skaergaard fabrics are primary and formed at or close to the magma-mush interface, with only minor deformation-related modification deeper in the mush. The Skaergaard adcumulates cannot therefore be attributed to compaction.

Method of forming calthrate ice

DOEpatents

Hino, T.; Gorski, A.J.

1985-09-30

A method of forming clathrate ice in a supercooled water-based liquid contained in a vessel is disclosed. Initially, an oscillator device is located in the liquid in the vessel. The oscillator device is then oscillated ultransonically so that small crystals are formed in the liquid. Thes small crystals serve as seed crystals for ice formation in the liquid and thereby prevent supercooling of the liquid. Preferably, the oscillating device is controlled by a thermostat which initiates operation of the oscillator device when the temperature of the liquid is lowered to the freezing point. Thereafter, the operation of the oscillator device is terminated when ice is sensed in the liquid by an ice sensor.

Method of forming clathrate ice

DOEpatents

Hino, Toshiyuki; Gorski, Anthony J.

1987-01-01

A method of forming clathrate ice in a supercooled water-based liquid contained in a vessel is disclosed. Initially, an oscillator device is located in the liquid in the vessel. The oscillator device is then oscillated ultrasonically so that small crystals are formed in the liquid. These small crystals serve as seed crystals for ice formation in the liquid and thereby prevent supercooling of the liquid. Preferably, the oscillating device is controlled by a thermostat which initiates operation of the oscillator device when the temperature of the liquid is lowered to the freezing point. Thereafter, the operation of the oscillator device is terminated when ice is sensed in the liquid by an ice sensor.

Antisolvent membrane crystallization of pharmaceutical compounds.

PubMed

Di Profio, Gianluca; Stabile, Carmen; Caridi, Antonella; Curcio, Efrem; Drioli, Enrico

2009-12-01

This article describes a modification of the conventional membrane crystallization technique in which a membrane is used to dose the solvent/antisolvent composition to generate supersaturation and induce crystallization in a drug solution. Two operative configurations are proposed: (a) solvent/antisolvent demixing crystallization, where the solvent is removed in at higher flow rate than the antisolvent so that phase inversion promotes supersaturation and (b) antisolvent addition, in which the antisolvent is dosed into the crystallizing drug solution. In both cases, solvent/antisolvent migration occurs in vapor phase and it is controlled by the porous membrane structure, acting on the operative process parameters. This mechanism is different than that observed when forcing the liquid phases through the pores and the more finely controllable supersaturated environment would generate crystals with the desired characteristics. Two organic molecules of relevant industrial implication, like paracetamol and glycine, were used to test the new systems. Experiments demonstrated that, by using antisolvent membrane crystallization in both configurations, accurate control of solution composition at the crystallization point has been achieved with effects on crystals morphology. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Heterogeneous pumice populations in the 2.08-Ma Cerro Galán Ignimbrite: Implications for magma recharge and ascent preceding a large-volume silicic eruption

USGS Publications Warehouse

Wright, Heather M.; Folkes, Christopher B.; Cas, Ray A.F.; Cashman, Katharine V.

2011-01-01

Triggering mechanisms of large silicic eruptions remain a critical unsolved problem. We address this question for the ~2.08-Ma caldera-forming eruption of Cerro Galán volcano, Argentina, which produced distinct pumice populations of two colors: grey (5%) and white (95%) that we believe may hold clues to the onset of eruptive activity. We demonstrate that the color variations correspond to both textural and compositional variations between the clast types. Both pumice types have bulk compositions of high-K, high-silica dacite to low-silica rhyolite, but there are sufficient compositional differences (e.g., ~150 ppm lower Ba at equivalent SiO2 content and 0.03 wt.% higher TiO2 in white pumice than grey) to suggest that the two pumice populations are not related by simple fractionation. Trace element concentrations in crystals mimic bulk variations between clast types, with grey pumice containing elevated Ba, Cu, Pb, and Zn concentrations in both bulk samples (average Cu, Pb, and Zn concentrations are 27, 35, and 82 in grey pumice vs. 11, 19, and 60 in white pumice) and biotite phenocrysts and white pumice showing elevated Li concentrations in biotite and plagioclase phenocrysts. White and grey clasts are also texturally distinct: White pumice clasts contain abundant phenocrysts (44–57%), lack microlites, and have highly evolved groundmass glass compositions (76.4–79.6 wt.% SiO2), whereas grey pumice clasts contain a lower percentage of phenocrysts/microphenocrysts (35–49%), have abundant microlites, and have less evolved groundmass glass compositions (69.4–73.8 wt.% SiO2). There is also evidence for crystal transfer between magma producing white and grey pumice. Thin highly evolved melt rims surround some fragmental crystals in grey pumice clasts and appear to have come from magma that produced white pumice. Furthermore, based on crystal compositions, white bands within banded pumice contain crystals originating in grey magma. Finally, only grey pumice clasts form breadcrusted surface textures. We interpret these compositional and textural variations to indicate distinct magma batches, where grey pumice originated from an originally deeper, more volatile-rich dacite recharge magma that ascended through and mingled with the volumetrically dominant, more highly crystalline chamber that produced white pumice. Shortly before eruption, the grey pumice magma stalled within shallow fractures, forming a vanguard magma phase whose ascent may have provided a trigger for eruption of the highly crystalline rhyodacite magma. We suggest that in the case of the Cerro Galán eruption, grey pumice provides evidence not only for cryptic silicic recharge in a large caldera system but also a probable trigger for the eruption.

Heterogeneous pumice populations in the 2.08-Ma Cerro Galán Ignimbrite: implications for magma recharge and ascent preceding a large-volume silicic eruption

NASA Astrophysics Data System (ADS)

Wright, Heather M. N.; Folkes, Chris B.; Cas, Raymond A. F.; Cashman, Katharine V.

2011-12-01

Triggering mechanisms of large silicic eruptions remain a critical unsolved problem. We address this question for the ~2.08-Ma caldera-forming eruption of Cerro Galán volcano, Argentina, which produced distinct pumice populations of two colors: grey (5%) and white (95%) that we believe may hold clues to the onset of eruptive activity. We demonstrate that the color variations correspond to both textural and compositional variations between the clast types. Both pumice types have bulk compositions of high-K, high-silica dacite to low-silica rhyolite, but there are sufficient compositional differences (e.g., ~150 ppm lower Ba at equivalent SiO2 content and 0.03 wt.% higher TiO2 in white pumice than grey) to suggest that the two pumice populations are not related by simple fractionation. Trace element concentrations in crystals mimic bulk variations between clast types, with grey pumice containing elevated Ba, Cu, Pb, and Zn concentrations in both bulk samples (average Cu, Pb, and Zn concentrations are 27, 35, and 82 in grey pumice vs. 11, 19, and 60 in white pumice) and biotite phenocrysts and white pumice showing elevated Li concentrations in biotite and plagioclase phenocrysts. White and grey clasts are also texturally distinct: White pumice clasts contain abundant phenocrysts (44-57%), lack microlites, and have highly evolved groundmass glass compositions (76.4-79.6 wt.% SiO2), whereas grey pumice clasts contain a lower percentage of phenocrysts/microphenocrysts (35-49%), have abundant microlites, and have less evolved groundmass glass compositions (69.4-73.8 wt.% SiO2). There is also evidence for crystal transfer between magma producing white and grey pumice. Thin highly evolved melt rims surround some fragmental crystals in grey pumice clasts and appear to have come from magma that produced white pumice. Furthermore, based on crystal compositions, white bands within banded pumice contain crystals originating in grey magma. Finally, only grey pumice clasts form breadcrusted surface textures. We interpret these compositional and textural variations to indicate distinct magma batches, where grey pumice originated from an originally deeper, more volatile-rich dacite recharge magma that ascended through and mingled with the volumetrically dominant, more highly crystalline chamber that produced white pumice. Shortly before eruption, the grey pumice magma stalled within shallow fractures, forming a vanguard magma phase whose ascent may have provided a trigger for eruption of the highly crystalline rhyodacite magma. We suggest that in the case of the Cerro Galán eruption, grey pumice provides evidence not only for cryptic silicic recharge in a large caldera system but also a probable trigger for the eruption.

Crystallographic and Molecular Dynamics Analysis of Loop Motions Unmasking the Peptidoglycan-Binding Site in Stator Protein MotB of Flagellar Motor

PubMed Central

Nahar, Musammat F.; Buckle, Ashley M.; Roujeinikova, Anna

2011-01-01

Background The C-terminal domain of MotB (MotB-C) shows high sequence similarity to outer membrane protein A and related peptidoglycan (PG)-binding proteins. It is believed to anchor the power-generating MotA/MotB stator unit of the bacterial flagellar motor to the peptidoglycan layer of the cell wall. We previously reported the first crystal structure of this domain and made a puzzling observation that all conserved residues that are thought to be essential for PG recognition are buried and inaccessible in the crystal structure. In this study, we tested a hypothesis that peptidoglycan binding is preceded by, or accompanied by, some structural reorganization that exposes the key conserved residues. Methodology/Principal Findings We determined the structure of a new crystalline form (Form B) of Helicobacter pylori MotB-C. Comparisons with the existing Form A revealed conformational variations in the petal-like loops around the carbohydrate binding site near one end of the β-sheet. These variations are thought to reflect natural flexibility at this site required for insertion into the peptidoglycan mesh. In order to understand the nature of this flexibility we have performed molecular dynamics simulations of the MotB-C dimer. The results are consistent with the crystallographic data and provide evidence that the three loops move in a concerted fashion, exposing conserved MotB residues that have previously been implicated in binding of the peptide moiety of peptidoglycan. Conclusion/Significance Our structural analysis provides a new insight into the mechanism by which MotB inserts into the peptidoglycan mesh, thus anchoring the power-generating complex to the cell wall. PMID:21533052

Studies of Toxoplasma gondii and Plasmodium falciparum enoyl acyl carrier protein reductase and implications for the development of antiparasitic agents

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

Muench, Stephen P.; Prigge, Sean T.; McLeod, Rima

2007-03-01

The crystal structures of T. gondii and P. falciparum ENR in complex with NAD{sup +} and triclosan and of T. gondii ENR in an apo form have been solved to 2.6, 2.2 and 2.8 Å, respectively. Recent studies have demonstrated that submicromolar concentrations of the biocide triclosan arrest the growth of the apicomplexan parasites Plasmodium falciparum and Toxoplasma gondii and inhibit the activity of the apicomplexan enoyl acyl carrier protein reductase (ENR). The crystal structures of T. gondii and P. falciparum ENR in complex with NAD{sup +} and triclosan and of T. gondii ENR in an apo form have beenmore » solved to 2.6, 2.2 and 2.8 Å, respectively. The structures of T. gondii ENR have revealed that, as in its bacterial and plant homologues, a loop region which flanks the active site becomes ordered upon inhibitor binding, resulting in the slow tight binding of triclosan. In addition, the T. gondii ENR–triclosan complex reveals the folding of a hydrophilic insert common to the apicomplexan family that flanks the substrate-binding domain and is disordered in all other reported apicomplexan ENR structures. Structural comparison of the apicomplexan ENR structures with their bacterial and plant counterparts has revealed that although the active sites of the parasite enzymes are broadly similar to those of their bacterial counterparts, there are a number of important differences within the drug-binding pocket that reduce the packing interactions formed with several inhibitors in the apicomplexan ENR enzymes. Together with other significant structural differences, this provides a possible explanation of the lower affinity of the parasite ENR enzyme family for aminopyridine-based inhibitors, suggesting that an effective antiparasitic agent may well be distinct from equivalent antimicrobials.« less

Plagioclase zonation styles in hornblende gabbro inclusions from Little Glass Mountain, Medicine Lake volcano, California: Implications for fractionation mechanisms and the formation of composition gaps

USGS Publications Warehouse

Brophy, J.G.; Dorais, M.J.; Donnelly-Nolan, J.; Singer, B.S.

1997-01-01

The rhyolite of Little Glass Mountain (73-74% SiO2) is a single eruptive unit that contains inclusions of quenched andesite liquid (54-61% SiO2) and partially crystalline cumulate hornblende gabbro (53-55% SiO2). Based on previous studies, the quenched andesite inclusions and host rhyolite lava are related to one another through fractional crystallization and represent an example of a fractionation-generated composition gap. The hornblende gabbros represent the cumulate residue associated with the rhyolite-producing and composition gap-forming fractionation event. This study combines textural (Nomarski Differential Interference Contrast, NDIC, imaging), major element (An content) and trace element (Mg, Fe, Sr, K, Ti, Ba) data on the style of zonation of plagioclase crystals from representative andesite and gabbro inclusions, to assess the physical environment in which the fractionation event and composition gap formation took place. The andesite inclusions (54-61% SiO2) are sparsely phyric with phenocrysts of plagioclase, augite and Fe-oxide??olivine, +/-orthopyroxene, +/-hornblende set within a glassy to crystalline matrix. The gabbro cumulates (53-55% SiO2) consist of an interconnected framework of plagioclase, augite, olivine, orthopyroxene, hornblende and Fe-oxide along with highly vesicular interstitial glass (70-74% SiO2). The gabbros record a two-stage crystallization history of plagioclase + olivine + augite (Stage I) followed by plagioclase+orthopyroxene + hornblende + Fe-oxide (Stage II). Texturally, the plagioclase crystals in the andesite inclusions are characterized by complex, fine-scale oscillatory zonation and abundant dissolution surfaces. Compositionally (An content) the crystals are essentially unzoned from core-to-rim. These features indicate growth within a dynamic (convecting?), reservoir of andesite magma. In contrast, the plagioclase crystals in the gabbros are texturally smooth and featureless with strong normal zonation from An74 at the core to around An30, K, and Ba abundances increase and Mg abundances decrease steadily towards the rim. Ti, Fe, and Sr abundances increase and then decrease towards the rim. The trace element variations are fully consistent with the two-stage crystallization sequence inferred from the gabbro mineralogy. These results indicate progressive closed-system in situ crystallization in a quiescent magmatic boundary layer environment located along the margins of the andesite magma body. The fractional crystallization that generated the host rhyolite lava is one of inward solidification of a crystallizing boundary layer followed by melt extraction and accumulation of highly evolved interstitial liquid. This mechanism explains the formation of the composition gap between parental andesite and rhyolite magma compositions.

Post-column reaction for simultaneous analysis of chromatic and leuco forms of malachite green and crystal violet by high-performance liquid chromatography with photometric detection

USGS Publications Warehouse

Allen, J.L.; Meinertz, J.R.

1991-01-01

The chromatic and leuco forms of malachite green and crystal violet were readily separated and detected by a sensitive and selective high-performance liquid chromatographic procedure. The chromatic and leuco forms of the dyes were separated within 11 min on a C18 column with a mobile phase of 0.05 M sodium acetate and 0.05 M acetic acid in water (19%) and methanol (81%). A reaction chamber, containing 10% PbO2 in Celite 545, was placed between the column and the spectrophotometric detector to oxidize the leuco forms of the dyes to their chromatic forms. Chromatic and leuco malachite green were quantified by their absorbance at 618 nm; and chromatic and leuco Crystal Violet by their absorbance at 588 nm. Detection limits for chromatic and leuco forms of both dyes ranged from 0.12 to 0.28 ng. A linear range of 1 to 100 ng was established for both forms of the dyes.

The time-dependence of the defective nature of ice Ic (cubic ice) and its implications for atmospheric science

NASA Astrophysics Data System (ADS)

Sippel, Christian; Koza, Michael M.; Hansen, Thomas C.; Kuhs, Werner F.

2010-05-01

The possible atmospheric implication of ice Ic (cubic ice) has already been suggested some time ago in the context of snow crystal formation [1]. New findings from air-borne measurements in cirrus clouds and contrails have put ice Ic into the focus of interest to understand the so-called "supersaturation puzzle" [2,3,4]. Our recent microstructural work on ice Ic [5,6] appears to be highly relevant in this context. We have found that ice Ic is characterized by a complex stacking fault pattern, which changes as a function of temperature as well as time. Indeed, from our own [7] and other group's work [8] one knows that (in contrast to earlier believe) ice Ic can form up to temperatures at least as high as 240K - thus in the relevant range for cirrus clouds. We have good preliminary evidence that the "cubicity" (which can be related to stacking fault probabilities) as well as the particle size of ice Ic are the relevant parameters for this correlation. The "cubicity" of stacking faulty ice Ic (established by diffraction) correlates nicely with the increased supersaturation at decreasing temperatures observed in cirrus clouds and contrails, a fact, which may be considered as further evidence for the presence of ice Ic. Recently, we have studied the time-dependency of the changes in both "cubicity" and particle size at various temperatures of relevance for cirrus clouds and contrails by in-situ neutron powder diffraction. The timescales over which changes occur (several to many hours) are similar to the life-time of cirrus clouds and contrails and suggest that the supersaturation situation may change within this time span in the natural environment too. Some accompanying results obtained by cryo-SEM (scanning electron microscopy) work will also be presented and suggest that stacking-faulty ice Ic has kinky surfaces providing many more active centres for heterogeneous reactions on the surface than in the usually assumed stable hexagonal form of ice Ih with its rather flat low-indexed crystal faces. [1] T Kobayashi & T Kuroda (1987) Snow Crystals. In: Morphology of Crystals (ed. I Sunagawa), Terra Scientific Publishing, Tokyo, pp.649-743. [2] RS Gao & 19 other authors (2004) Evidence that nitric acid increases relative humidity in low-temperature cirrus clouds. Science 303, 516-520. [3] T Peter, C Marcolli, P Spichtinger, T Corti, MC Baker & T Koop (2006) When dry air is too humid. Science 314, 1399-1402. [4] JE Shilling, MA Tolbert, OB Toon, EJ Jensen, BJ Murray & AK Bertram (2006) Measurements of the vapor pressure of cubic ice and their implications for atmospheric ice clouds. Geophys.Res.Lett. 33, 026671. [5] TC Hansen, MM Koza & WF Kuhs (2008) Formation and annealing of cubic ice: I Modelling of stacking faults. J.Phys.Cond.Matt. 20, 285104. [6] TC Hansen, MM Koza, P Lindner & WF Kuhs (2008) Formation and annealing of cubic ice: II. Kinetic study. J.Phys.Cond.Matt. 20, 285105. [7] WF Kuhs, G Genov, DK Staykova & AN Salamatin, T Hansen (2004) Ice perfection and the onset of anomalous preservation of gas hydrates. Phys.Chem.Chem.Phys. 6, 4917-4920. [8] BJ Murray, DA Knopf & AK Bertram (2005) The formation of cubic ice under conditions relevant to Earth's atmosphere. Nature 434, 292-205.

Liquid Crystalline Behavior and Related Properties of Colloidal Systems of Inorganic Oxide Nanosheets

PubMed Central

Nakato, Teruyuki; Miyamoto, Nobuyoshi

2009-01-01

Inorganic layered crystals exemplified by clay minerals can be exfoliated in solvents to form colloidal dispersions of extremely thin inorganic layers that are called nanosheets. The obtained “nanosheet colloids” form lyotropic liquid crystals because of the highly anisotropic shape of the nanosheets. This system is a rare example of liquid crystals consisting of inorganic crystalline mesogens. Nanosheet colloids of photocatalytically active semiconducting oxides can exhibit unusual photoresponses that are not observed for organic liquid crystals. This review summarizes experimental work on the phase behavior of the nanosheet colloids as well as photochemical reactions observed in the clay and semiconducting nanosheets system.

Crystallization and preliminary X-ray analysis of a complex formed between the antibiotic simocyclinone D8 and the DNA breakage–reunion domain of Escherichia coli DNA gyrase

PubMed Central

Edwards, Marcus J.; Flatman, Ruth H.; Mitchenall, Lesley A.; Stevenson, Clare E. M.; Maxwell, Anthony; Lawson, David M.

2009-01-01

Crystals of a complex formed between the 59 kDa N-terminal fragment of the Escherichia coli DNA gyrase A subunit (also known as the breakage–reunion domain) and the antibiotic simocyclinone D8 were grown by vapour diffusion. The complex crystallized with I-centred orthorhombic symmetry and X-ray data were recorded to a resolution of 2.75 Å from a single crystal at the synchrotron. DNA gyrase is an essential bacterial enzyme and thus represents an attractive target for drug development. PMID:19652356

Crystallization processes in pharmaceutical technology and drug delivery design

NASA Astrophysics Data System (ADS)

Shekunov, B. Yu; York, P.

2000-04-01

Crystallization is a major technological process for particle formation in pharmaceutical industry and, in addition, plays an important role in defining the stability and drug release properties of the final dosage forms. Industrial and regulatory aspects of crystallization are briefly reviewed with reference to solid-state properties of pharmaceuticals. Crystallization, incorporating wider definition to include precipitation and solid-state transitions, is considered in terms of preparation of materials for direct compression, formation of amorphous, solvated and polymorphic forms, chiral separation of drugs, production of materials for inhalation drug delivery and injections. Finally, recent developments in supercritical fluid particle technology is considered in relationship to the areas discussed.

In cellulo serial crystallography of alcohol oxidase crystals inside yeast cells

DOE PAGES

Jakobi, Arjen J.; Passon, Daniel M.; Knoops, Kevin; ...

2016-03-01

The possibility of using femtosecond pulses from an X-ray free-electron laser to collect diffraction data from protein crystals formed in their native cellular organelle has been explored. X-ray diffraction of submicrometre-sized alcohol oxidase crystals formed in peroxisomes within cells of genetically modified variants of the methylotrophic yeast Hansenula polymorpha is reported and characterized. Furthermore, the observations are supported by synchrotron radiation-based powder diffraction data and electron microscopy. Based on these findings, the concept of in cellulo serial crystallography on protein targets imported into yeast peroxisomes without the need for protein purification as a requirement for subsequent crystallization is outlined.

In cellulo serial crystallography of alcohol oxidase crystals inside yeast cells

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

Jakobi, Arjen J.; Passon, Daniel M.; Knoops, Kevin

The possibility of using femtosecond pulses from an X-ray free-electron laser to collect diffraction data from protein crystals formed in their native cellular organelle has been explored. X-ray diffraction of submicrometre-sized alcohol oxidase crystals formed in peroxisomes within cells of genetically modified variants of the methylotrophic yeast Hansenula polymorpha is reported and characterized. Furthermore, the observations are supported by synchrotron radiation-based powder diffraction data and electron microscopy. Based on these findings, the concept of in cellulo serial crystallography on protein targets imported into yeast peroxisomes without the need for protein purification as a requirement for subsequent crystallization is outlined.

Imaging and engineering the nanoscale-domain structure of a Sr0.61Ba0.39Nb2O6 crystal using a scanning force microscope

NASA Astrophysics Data System (ADS)

Terabe, K.; Takekawa, S.; Nakamura, M.; Kitamura, K.; Higuchi, S.; Gotoh, Y.; Gruverman, A.

2002-09-01

We have investigated the ferroelectric domain structure formed in a Sr0.61Ba0.39Nb2O6 single crystal by cooling the crystal through the Curie point. Imaging the etched surface structure using a scanning force microscope (SFM) in both the topographic mode and the piezoresponse mode revealed that a multidomain structure of nanoscale islandlike domains was formed. The islandlike domains could be inverted by applying an appropriate voltage using a conductive SFM tip. Furthermore, a nanoscale periodically inverted-domain structure was artificially fabricated using the crystal which underwent poling treatment.

In cellulo serial crystallography of alcohol oxidase crystals inside yeast cells

PubMed Central

Jakobi, Arjen J.; Passon, Daniel M.; Knoops, Kèvin; Stellato, Francesco; Liang, Mengning; White, Thomas A.; Seine, Thomas; Messerschmidt, Marc; Chapman, Henry N.; Wilmanns, Matthias

2016-01-01

The possibility of using femtosecond pulses from an X-ray free-electron laser to collect diffraction data from protein crystals formed in their native cellular organelle has been explored. X-ray diffraction of submicrometre-sized alcohol oxidase crystals formed in peroxisomes within cells of genetically modified variants of the methylotrophic yeast Hansenula polymorpha is reported and characterized. The observations are supported by synchrotron radiation-based powder diffraction data and electron microscopy. Based on these findings, the concept of in cellulo serial crystallography on protein targets imported into yeast peroxisomes without the need for protein purification as a requirement for subsequent crystallization is outlined. PMID:27006771

Crystal Nucleation and Growth in Undercooled Melts of Pure Zr, Binary Zr-Based and Ternary Zr-Ni-Cu Glass-Forming Alloys

NASA Astrophysics Data System (ADS)

Herlach, Dieter M.; Kobold, Raphael; Klein, Stefan

2018-03-01

Glass formation of a liquid undercooled below its melting temperature requires the complete avoidance of crystal nucleation and subsequent crystal growth. Even though they are not part of the glass formation process, a detailed knowledge of both processes involved in crystallization is mandatory to determine the glass-forming ability of metals and metallic alloys. In the present work, methods of containerless processing of drops by electrostatic and electromagnetic levitation are applied to undercool metallic melts prior to solidification. Heterogeneous nucleation on crucible walls is completely avoided giving access to large undercoolings. A freely suspended drop offers the additional benefit of showing the rapid crystallization process of an undercooled melt in situ by proper diagnostic means. As a reference, crystal nucleation and dendrite growth in the undercooled melt of pure Zr are experimentally investigated. Equivalently, binary Zr-Cu, Zr-Ni and Zr-Pd and ternary Zr-Ni-Cu alloys are studied, whose glass-forming abilities differ. The experimental results are analyzed within classical nucleation theory and models of dendrite growth. The findings give detailed knowledge about the nucleation-undercooling statistics and the growth kinetics over a large range of undercooling.

Inclusion property of Cs, Sr, and Ba impurities in LiCl crystal formed by layer-melt crystallization

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

Choi, Jung-Hoon; Cho, Yung-Zun; Lee, Tae-Kyo

Pyroprocessing is one of the promising technologies enabling the recycling of spent nuclear fuels from a commercial light water reactor (LWR). In general, pyroprocessing uses dry molten salts as electrolytes. In particular, LiCl waste salt after pyroprocessing contains highly radioactive I/II group fission products mainly composed of Cs, Sr, and Ba impurities. Therefore, it is beneficial to reuse LiCl salt in the pyroprocessing as an electrolyte for economic and environmental issues. Herein, to understand the inclusion property of impurities within LiCl crystal, the physical properties such as lattice parameter change, bulk modulus, and substitution enthalpy of a LiCl crystal havingmore » 0-6 at% Cs{sup +} or Ba{sup 2+} impurities under existence of 1 at% Sr{sup 2+} impurity were calculated via the first-principles density functional theory. The substitution enthalpy of LiCl crystals having 1 at% Sr{sup 2+} showed slightly decreased value than those without Sr{sup 2+} impurity. Therefore, through the substitution enthalpy calculation, it is expected that impurities will be incorporated within LiCl crystal as co-existed form rather than as a single component form. (authors)« less

Crystallization of the C-terminal globular domain of avian reovirus fibre

PubMed Central

van Raaij, Mark J.; Hermo Parrado, X. Lois; Guardado Calvo, Pablo; Fox, Gavin C.; Llamas-Saiz, Antonio L.; Costas, Celina; Martínez-Costas, José; Benavente, Javier

2005-01-01

Avian reovirus fibre, a homotrimer of the σC protein, is responsible for primary host-cell attachment. Using the protease trypsin, a C-terminal σC fragment containing amino acids 156–326 has been generated which was subsequently purified and crystallized. Two different crystal forms were obtained, one grown in the absence of divalent cations and belonging to space group P6322 (unit-cell parameters a = 75.6, c = 243.1 Å) and one grown in the presence of either zinc or cadmium sulfate and belonging to space group P321 (unit-cell parameters a = 74.7, c = 74.5 Å and a = 73.1, c = 69.9 Å for the ZnII- and CdII-grown crystals, respectively). The first crystal form diffracted synchrotron radiation to 3.0 Å resolution and the second form to 2.2–2.3 Å. Its closest related structure, the C-­terminal fragment of mammalian reovirus fibre, has only 18% sequence identity and molecular-replacement attempts were unsuccessful. Therefore, a search is under way for suitable heavy-atom derivatives and attempts are being made to grow protein crystals containing selenomethionine instead of methionine. PMID:16511119

Growth Stresses in Thermally Grown Oxides on Nickel-Based Single-Crystal Alloys

NASA Astrophysics Data System (ADS)

Rettberg, Luke H.; Laux, Britta; He, Ming Y.; Hovis, David; Heuer, Arthur H.; Pollock, Tresa M.

2016-03-01

Growth stresses that develop in α-Al2O3 scale that form during isothermal oxidation of three Ni-based single crystal alloys have been studied to elucidate their role in coating and substrate degradation at elevated temperatures. Piezospectroscopy measurements at room temperature indicate large room temperature compressive stresses in the oxides formed at 1255 K or 1366 K (982 °C or 1093 °C) on the alloys, ranging from a high of 4.8 GPa for René N4 at 1366 K (1093 °C) to a low of 3.8 GPa for René N5 at 1255 K (982 °C). Finite element modeling of each of these systems to account for differences in coefficients of thermal expansion of the oxide and substrate indicates growth strains in the range from 0.21 to 0.44 pct at the oxidation temperature, which is an order of magnitude higher than the growth strains measured in the oxides on intermetallic coatings that are typically applied to these superalloys. The magnitudes of the growth strains do not scale with the parabolic oxidation rate constants measured for the alloys. Significant spatial inhomogeneities in the growth stresses were observed, due to (i) the presence of dendritic segregation and (ii) large carbides in the material that locally disrupts the structure of the oxide scale. The implications of these observations for failure during cyclic oxidation, fatigue cycling, and alloy design are considered.

The crystallization water of gypsum rocks is a relevant water source for plants.

PubMed

Palacio, Sara; Azorín, José; Montserrat-Martí, Gabriel; Ferrio, Juan Pedro

2014-08-18

Some minerals, like gypsum, hold water in their crystalline structure. Although still unexplored, the use of such crystallization water by organisms would point to a completely new water source for life, critical under dry conditions. Here we use the fact that the isotopic composition of free water differs from gypsum crystallization water to show that plants can use crystallization water from the gypsum structure. The composition of the xylem sap of gypsum plants during summer shows closer values to gypsum crystallization water than to free soil water. Crystallization water represents a significant water source for organisms growing on gypsum, especially during summer, when it accounts for 70-90% of the water used by shallow-rooted plants. Given the widespread occurrence of gypsum in dry lands throughout the Earth and in Mars, these results may have important implications for arid land reclamation and exobiology.

Segregation effects during solidification in weightless melts. [effects of evaporation and solidification on crystalization

NASA Technical Reports Server (NTRS)

Li, C.

1975-01-01

Computer programs are developed and used in the study of the combined effects of evaporation and solidification in space processing. The temperature and solute concentration profiles during directional solidification of binary alloys with surface evaporation were mathematically formulated. Computer results are included along with an econotechnical model of crystal growth. This model allows: prediction of crystal size, quality, and cost; systematic selection of the best growth equipment or alloy system; optimization of growth or material parameters; and a maximization of zero-gravity effects. Segregation in GaAs crystals was examined along with vibration effects on GaAs crystal growth. It was found that a unique segregation pattern and strong convention currents exist in GaAs crystal growth. Some beneficial effects from vibration during GaAs growth were discovered. The implications of the results in space processing are indicated.

Method of making single crystal fibers

NASA Technical Reports Server (NTRS)

Westfall, Leonard J. (Inventor)

1990-01-01

Single crystal fibers are made from miniature extruded ceramic feed rods. A decomposable binder is mixed with powders to inform a slurry which is extruded into a small rod which may be sintered, either in air or in vacuum, or it may be used in the extruded and dried condition. A pair of laser beams focuses onto the tip of the rod to melt it thereby forming a liquid portion. A single crystal seed fiber of the same material as the feed rod contacts this liquid portion to establish a zone of liquid material between the feed rod and the single crystal seed fiber. The feed rod and the single crystal feed fiber are moved at a predetermined speed to solidify the molten zone onto the seed fiber while simultaneously melting additional feed rod. In this manner a single crystal fiber is formed from the liquid portion.

Four highly pseudosymmetric and/or twinned structures of d(CGCGCG) 2 extend the repertoire of crystal structures of Z-DNA

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

Luo, Zhipu; Dauter, Zbigniew; Gilski, Miroslaw

DNA oligomer duplexes containing alternating cytosines and guanines in their sequences tend to form left-handed helices of the Z-DNA type, with the sugar and phosphate backbone in a zigzag conformation and a helical repeat of two successive nucleotides. Z-DNA duplexes usually crystallize as hexagonally arranged parallel helical tubes, with various relative orientations and translation of neighboring duplexes. Four novel high-resolution crystal structures of d(CGCGCG) 2duplexes are described here. They are characterized by a high degree of pseudosymmetry and/or twinning, with three or four independent duplexes differently oriented in a monoclinicP2 1lattice of hexagonal metric. The various twinning criteria give somewhatmore » conflicting indications in these complicated cases of crystal pathology. The details of molecular packing in these crystal structures are compared with other known crystal forms of Z-DNA.« less

Structural properties and defects of GaN crystals grown at ultra-high pressures: A molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Gao, Tinghong; Li, Yidan; Xie, Quan; Tian, Zean; Chen, Qian; Liang, Yongchao; Ren, Lei; Hu, Xuechen

2018-01-01

The growth of GaN crystals at different pressures was studied by molecular dynamics simulation employing the Stillinger-Weber potential, and their structural properties and defects were characterized using the radial distribution function, the Voronoi polyhedron index method, and a suitable visualization technology. Crystal structures formed at 0, 1, 5, 10, and 20 GPa featured an overwhelming number of <4 0 0 0> Voronoi polyhedra, whereas amorphous structures comprising numerous disordered polyhedra were produced at 50 GPa. During quenching, coherent twin boundaries were easily formed between zinc-blende and wurtzite crystal structures in GaN. Notably, point defects usually appeared at low pressure, whereas dislocations were observed at high pressure, since the simultaneous growth of two crystal grains with different crystal orientations and their boundary expansion was hindered in the latter case, resulting in the formation of a dislocation between these grains.

Chiral Asymmetric Structures in Aspartic Acid and Valine Crystals Assessed by Atomic Force Microscopy.

PubMed

Teschke, Omar; Soares, David Mendez

2016-03-29

Structures of crystallized deposits formed by the molecular self-assembly of aspartic acid and valine on silicon substrates were imaged by atomic force microscopy. Images of d- and l-aspartic acid crystal surfaces showing extended molecularly flat sheets or regions separated by single molecule thick steps are presented. Distinct orientation surfaces were imaged, which, combined with the single molecule step size, defines the geometry of the crystal. However, single molecule step growth also reveals the crystal chirality, i.e., growth orientations. The imaged ordered lattice of aspartic acid (asp) and valine (val) mostly revealed periodicities corresponding to bulk terminations, but a previously unreported molecular hexagonal lattice configuration was observed for both l-asp and l-val but not for d-asp or d-val. Atomic force microscopy can then be used to identify the different chiral forms of aspartic acid and valine crystals.

Experimental evidence for a chiral symmetry-breaking mechanism in aspartic acid: Lattice and sub-lattice matching

NASA Astrophysics Data System (ADS)

Teschke, Omar; Soares, David Mendez

2017-10-01

A mother crystal formed from a transient molecular structure of (D+L) aspartic acid in solution is reported. Hexagonal structures with a lattice constant of 1.04 nm were crystallized from a solution in which three aspartic acid species coexist: right- and left-handed enantiomorphs, denoted D-aspartic and L-aspartic, respectively, and transitory (D+L) aspartic acid specie. Atomic force microscopy images of the crystalline deposits reveal domains of the transitory (D+L) aspartic acid crystal forming the substrate deposit on silicon wafers, and on top of this hexagonal lattice only L-aspartic acid is observed to conform and crystallize. A preferential crystallization mechanism is then observed for (D+L) aspartic acid crystals that seed only L-aspartic deposits by the geometrical matching of their multiple hexagonal lattice structures with periodicities of 1.04 nm and 0.52 nm, respectively.

Disappearing Enantiomorphs: Single Handedness in Racemate Crystals.

PubMed

Parschau, Manfred; Ernst, Karl-Heinz

2015-11-23

Although crystallization is the most important method for the separation of enantiomers of chiral molecules in the chemical industry, the chiral recognition involved in this process is poorly understood at the molecular level. We report on the initial steps in the formation of layered racemate crystals from a racemic mixture, as observed by STM at submolecular resolution. Grown on a copper single-crystal surface, the chiral hydrocarbon heptahelicene formed chiral racemic lattice structures within the first layer. In the second layer, enantiomerically pure domains were observed, underneath which the first layer contained exclusively the other enantiomer. Hence, the system changed from a 2D racemate into a 3D racemate with enantiomerically pure layers after exceeding monolayer-saturation coverage. A chiral bias in form of a small enantiomeric excess suppressed the crystallization of one double-layer enantiomorph so that the pure minor enantiomer crystallized only in the second layer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An automated parallel crystallisation search for predicted crystal structures and packing motifs of carbamazepine.

PubMed

Florence, Alastair J; Johnston, Andrea; Price, Sarah L; Nowell, Harriott; Kennedy, Alan R; Shankland, Norman

2006-09-01

An automated parallel crystallisation search for physical forms of carbamazepine, covering 66 solvents and five crystallisation protocols, identified three anhydrous polymorphs (forms I-III), one hydrate and eight organic solvates, including the single-crystal structures of three previously unreported solvates (N,N-dimethylformamide (1:1); hemi-furfural; hemi-1,4-dioxane). Correlation of physical form outcome with the crystallisation conditions demonstrated that the solvent adopts a relatively nonspecific role in determining which polymorph is obtained, and that the previously reported effect of a polymer template facilitating the formation of form IV could not be reproduced by solvent crystallisation alone. In the accompanying computational search, approximately half of the energetically feasible predicted crystal structures exhibit the C=O...H--N R2(2)(8)dimer motif that is observed in the known polymorphs, with the most stable correctly corresponding to form III. Most of the other energetically feasible structures, including the global minimum, have a C=O...H--N C(4) chain hydrogen bond motif. No such chain structures were observed in this or any other previously published work, suggesting that kinetic, rather than thermodynamic, factors determine which of the energetically feasible crystal structures are observed experimentally, with the kinetics apparently favouring nucleation of crystal structures based on the CBZ-CBZ R2(2)(8) motif. (c) 2006 Wiley-Liss, Inc. and the American Pharmacists Association.

Architecture of TAF11/TAF13/TBP complex suggests novel regulation properties of general transcription factor TFIID

PubMed Central

Gupta, Kapil; Watson, Aleksandra A; Baptista, Tiago; Scheer, Elisabeth; Chambers, Anna L; Koehler, Christine; Zou, Juan; Obong-Ebong, Ima; Kandiah, Eaazhisai; Temblador, Arturo; Round, Adam; Forest, Eric; Man, Petr; Bieniossek, Christoph; Laue, Ernest D; Lemke, Edward A; Rappsilber, Juri; Robinson, Carol V; Devys, Didier

2017-01-01

General transcription factor TFIID is a key component of RNA polymerase II transcription initiation. Human TFIID is a megadalton-sized complex comprising TATA-binding protein (TBP) and 13 TBP-associated factors (TAFs). TBP binds to core promoter DNA, recognizing the TATA-box. We identified a ternary complex formed by TBP and the histone fold (HF) domain-containing TFIID subunits TAF11 and TAF13. We demonstrate that TAF11/TAF13 competes for TBP binding with TATA-box DNA, and also with the N-terminal domain of TAF1 previously implicated in TATA-box mimicry. In an integrative approach combining crystal coordinates, biochemical analyses and data from cross-linking mass-spectrometry (CLMS), we determine the architecture of the TAF11/TAF13/TBP complex, revealing TAF11/TAF13 interaction with the DNA binding surface of TBP. We identify a highly conserved C-terminal TBP-interaction domain (CTID) in TAF13, which is essential for supporting cell growth. Our results thus have implications for cellular TFIID assembly and suggest a novel regulatory state for TFIID function. PMID:29111974

Early stages of carbonate mineralization revealed from molecular simulations: Implications for biomineral formation

NASA Astrophysics Data System (ADS)

Wallace, A. F.; DeYoreo, J.; Banfield, J. F.

2011-12-01

The carbonate mineral constituents of many biomineralized products, formed both in and ex vivo, grow by a multi-stage crystallization process that involves the nucleation and structural reorganization of transient amorphous phases. The existence of transient phases and cluster species has significant implications for carbonate nucleation and growth in natural and engineered environments, both modern and ancient. The structure of these intermediate phases remains elusive, as does the nature of the disorder to order transition, however, these process details may strongly influence the interpretation of elemental and isotopic climate proxy data obtained from authigenic and biogenic carbonates. While molecular simulations have been applied to certain aspects of crystal growth, studies of metal carbonate nucleation are strongly inhibited by the presence of kinetic traps that prevent adequate sampling of the potential landscape upon which the growing clusters reside within timescales accessible by simulation. This research addresses this challenge by marrying the recent Kawska-Zahn (KZ) approach to simulation of crystal nucleation and growth from solution with replica-exchange molecular dynamics (REMD) techniques. REMD has been used previously to enhance sampling of protein conformations that occupy energy wells that are separated by sizable thermodynamic and kinetic barriers, and is used here to probe the initial formation and onset of order within hydrated calcium and iron carbonate cluster species during nucleation. Results to date suggest that growing clusters initiate as short linear ion chains that evolve into two- and three-dimensional structures with continued growth. The planar structures exhibit an obvious 2d lattice, while establishment of a 3d lattice is hindered by incomplete ion desolvation. The formation of a dehydrated core consisting of a single carbonate ion is observed when the clusters are ~0.75 nm. At the same size a distorted, but discernible calcite-type lattice is also apparent. Continued growth results in expansion of the dehydrated core, however, complete desolvation and incorporation of cations into the growing carbonate phase is not achieved until the cluster grows to ~1.2 nm. Exploration of the system free energy along the crystallization path reveals "special" cluster sizes that correlate with ion desolvation milestones. The formation of these species comprise critical bottlenecks on the energy landscape and for the establishment of order within the growing clusters.

Optimized Wavelength-Tuned Nonlinear Frequency Conversion Using a Liquid Crystal Clad Waveguide

NASA Technical Reports Server (NTRS)

Stephen, Mark A. (Inventor)

2018-01-01

An optimized wavelength-tuned nonlinear frequency conversion process using a liquid crystal clad waveguide. The process includes implanting ions on a top surface of a lithium niobate crystal to form an ion implanted lithium niobate layer. The process also includes utilizing a tunable refractive index of a liquid crystal to rapidly change an effective index of the lithium niobate crystal.

Linking Crystal Populations to Dynamic States: Crystal Dissolution and Growth During an Open-System Event

NASA Astrophysics Data System (ADS)

Bergantz, G. W.; Schleicher, J.; Burgisser, A.

2016-12-01

The identification of shared characteristics in zoned crystals has motivated the definition of crystal populations. These populations reflect the simultaneous transport of crystals, heat and composition during open-system events. An obstacle to interpreting the emergence of a population is the absence of a way to correlate specific dynamic conditions with the characteristic attributes of a population. By combining a boundary-layer diffusion controlled model for crystal growth/dissolution with discrete-element magma dynamics simulations of crystal-bearing magmas, the creation of populations can be simulated. We have implemented a method that decomposes the chemical potential into the thermal and compositional contributions to crystal dissolution/growth. This allows for the explicit treatment of thermal inertia and thermal-compositional decoupling as fluid circulation stirs the system during an open-system event. We have identified three distinct dynamic states producing crystal populations. They are based on the volume fraction of crystals. In a mushy system, thermal and compositional states are tightly linked as the volume involved in the mixing is constrained by the so-called mixing bowl (Bergantz et al., 2015). The mixing bowl volume is a function of the visco-plastic response of the mush and the intrusion width, not by the progressive entrainment of the new intrusion as commonly assumed. Crystal dissolution is the dominate response to input of more primitive magma. At the other endmember, under very dilute conditions, thermal and compositional conditions can become decoupled, and the in-coming magma forms a double-diffusive low-Re jet. This can allow for both dissolution and growth as crystals circulate widely into an increasingly stratified system. A middle range of crystal concentration produces a very complex feedback, as sedimenting crystals form fingers and chains that interact with the incoming magma, break-up the entrainment with chaotic stirring and add a second length scale to the mixing. It simultaneously forms a small mixing bowl in the pile of crystals sedimenting at the base. This can produce very complex populations even in a simple open-system event. Bergantz et al., 2015, Open-system dynamics and mixing in magma mushes, Nature Geosci., DOI: 10.1038/NGEO2534

LiCoO2 Concaved Cuboctahedrons from Symmetry-Controlled Topological Reactions

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

Chen, H.; Wu, L.; Zhang, L.

2011-01-19

Morphology control of functional materials is generally performed by controlling the growth rates on selected orientations or faces. Here, we control particle morphology by 'crystal templating': by choosing appropriate precursor crystals and reaction conditions, we demonstrate that a material with rhombohedral symmetry - namely the layered, positive electrode material, LiCoO{sub 2} - can grow to form a quadruple-twinned crystal with overall cubic symmetry. The twinned crystals show an unusual, concaved-cuboctahedron morphology, with uniform particle sizes of 0.5-2 {micro}m. On the basis of a range of synthetic and analytical experiments, including solid-state NMR, X-ray powder diffraction analysis and HRTEM, we proposemore » that these twinned crystals form via selective dissolution and an ion-exchange reaction accompanied by oxidation of a parent crystal of CoO, a material with cubic symmetry. This template crystal serves to nucleate the growth of four LiCoO{sub 2} twin crystals and to convert a highly anisotropic, layered material into a pseudo-3-dimensional, isotropic material.« less

Ikaite crystal distribution in Arctic winter sea ice and implications for CO2 system dynamics

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Søgaard, D. H.; Cooper, M.; Pućko, M.; Lennert, K.; Papakyriakou, T. N.; Wang, F.; Geilfus, N. X.; Glud, R. N.; Ehn, J.; McGinnnis, D. F.; Attard, K.; Sievers, J.; Deming, J. W.; Barber, D.

2012-12-01

The precipitation of ikaite (CaCO3·6H2O) in polar sea ice is critical to the efficiency of the sea ice-driven carbon pump and potentially important to the global carbon cycle, yet the spatial and temporal occurrence of ikaite within the ice is poorly known. We report unique observations of ikaite in unmelted ice and vertical profiles of ikaite abundance and concentration in sea ice for the crucial season of winter. Ice was examined from two locations: a 1 m thick land-fast ice site and a 0.3 m thick polynya site, both in the Young Sound area (74° N, 20° W) of NE Greenland. Ikaite crystals, ranging in size from a few µm to 700 µm were observed to concentrate in the interstices between the ice platelets in both granular and columnar sea ice. In vertical sea-ice profiles from both locations, ikaite concentration determined from image analysis, decreased with depth from surfaceice values of 700-900 µmol kg-1 ice (~ 25 × 106 crystals kg-1) to bottom-layer values of 100-200 µmol kg-1 ice (1-7 × 106 kg-1), all of which are much higher (4-10 times) than those reported in the few previous studies. Direct measurements of total alkalinity (TA) in surface layers fell within the same range as ikaite concentration whereas TA concentrations in bottom layers were twice as high. This depth-related discrepancy suggests interior ice processes where ikaite crystals form in surface sea ice layers and partly dissolved in bottom layers. From these findings and model calculations we relate sea ice formation and melt to observed pCO2 conditions in polar surface waters, and hence, the air-sea CO2 flux.

Sr and Pb isotopic geochemistry of feldspars and implications for the growth of megacrysts in plutonic settings.

NASA Astrophysics Data System (ADS)

Munnikhuis, J.; Glazner, A. F.; Coleman, D. S.; Mills, R. D.

2015-12-01

Why megacrystic textures develop in silicic igneous rocks is still unknown. One hypothesis is that these crystals nucleate early in a magma chamber with a high liquid content. A supportive observation of this hypothesis is areas in plutons with high concentrations of megacrysts suggesting flow sorting. Another group of hypotheses suggest megacrystic textures form during protracted late-stage coarsening in a low-melt, interlocked matrix due to either thermal oscillations from incremental pluton emplacement, or Ostwald ripening. Isotopic analyses of large, euhedral K-feldspar megacrysts from the Cretaceous intrusive suites of the Sierra Nevada batholith (SNB) provide new insight into their origin. Megacrysts from the SNB reach the decimeter scale, are Or rich (85-90%), are perthitic, and host mineral inclusions of nearly all phases in the host rock. In-situ micro-drilling of transects, from core to rim, of the alkali feldspars provides material for Sr and Pb isotopic analyses by thermal ionization mass spectrometry (TIMS). Preliminary 87Sr/86Sr(i) isotopic data from samples from the Cathedral Peak Granodiorite, of the Tuolumne Intrusive Suite range from 0.706337 to 0.706452 (~1.6ɛSr) near the cores, whereas a sawtooth pattern with larger variability, 0.706179 to 0.706533 (~5ɛSr), occurs nears the rims. We interpret these preliminary data to indicate that the late portion of growth (i.e. crystal rim) was dominated by either cannibalism of small K-feldspar crystals with isotopic variability, or by addition of isotopically diverse late components to the magma. By comparing the Sr and Pb isotopic stratigraphy of megacrysts from a variety of rock matrices and different granitoids in the SNB isotopic trends can be evaluated to determine if crystals sizes are dependent on disequilibrium processes or grow at a steady state.

New crystal forms of Diocleinae lectins in the presence of different dimannosides

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

Moreno, Frederico Bruno Mendes Batista; Bezerra, Gustavo Arruda; Oliveira, Taianá Maia de

2006-11-01

The crystallization and preliminary X-ray data of Canavalia gladiata lectin (CGL) and C. maritima lectin (CML) complexed with Man(α1-2)Man(α1)OMe, Man(α1-3)Man(α1)OMe and Man(α1-4)Man(α1)OMe in two crystal forms [the complexes with Man(α1-3)Man(α1)OMe and Man(α1-4)Man(α1)OMe crystallized in space group P3{sub 2} and those with Man(α1-2)Man(α1)OMe crystallized in space group I222], which differed from those of the native proteins (P2{sub 1}2{sub 1}2 for CML and C222 for CGL), are reported. Studying the interactions between lectins and sugars is important in order to explain the differences observed in the biological activities presented by the highly similar proteins of the Diocleinae subtribe. Here, the crystallization andmore » preliminary X-ray data of Canavalia gladiata lectin (CGL) and C. maritima lectin (CML) complexed with Man(α1-2)Man(α1)OMe, Man(α1-3)Man(α1)OMe and Man(α1-4)Man(α1)OMe in two crystal forms [the complexes with Man(α1-3)Man(α1)OMe and Man(α1-4)Man(α1)OMe crystallized in space group P3{sub 2} and those with Man(α1-2)Man(α1)OMe crystallized in space group I222], which differed from those of the native proteins (P2{sub 1}2{sub 1}2 for CML and C222 for CGL), are reported. The crystal complexes of ConA-like lectins with Man(α1-4)Man(α1)OMe are reported here for the first time.« less

Metallic dielectric photonic crystals and methods of fabrication

DOEpatents

Chou, Jeffrey Brian; Kim, Sang-Gook

2017-12-05

A metallic-dielectric photonic crystal is formed with a periodic structure defining a plurality of resonant cavities to selectively absorb incident radiation. A metal layer is deposited on the inner surfaces of the resonant cavities and a dielectric material fills inside the resonant cavities. This photonic crystal can be used to selectively absorb broadband solar radiation and then reemit absorbed radiation in a wavelength band that matches the absorption band of a photovoltaic cell. The photonic crystal can be fabricated by patterning a sacrificial layer with a plurality of holes, into which is deposited a supporting material. Removing the rest of the sacrificial layer creates a supporting structure, on which a layer of metal is deposited to define resonant cavities. A dielectric material then fills the cavities to form the photonic crystal.

Neutron imaging systems utilizing lithium-containing semiconductor crystals

DOEpatents

Stowe, Ashley C.; Burger, Arnold

2017-04-25

A neutron imaging system, including: a plurality of Li-III-VI.sub.2 semiconductor crystals arranged in an array, wherein III represents a Group III element and VI represents a Group VI element; and electronics operable for detecting and a charge in each of the plurality of crystals in the presence of neutrons and for imaging the neutrons. Each of the crystals is formed by: melting the Group III element; adding the Li to the melted Group III element at a rate that allows the Li and Group III element to react, thereby providing a single phase Li-III compound; and adding the Group VI element to the single phase Li-III compound and heating. Optionally, each of the crystals is also formed by doping with a Group IV element activator.

Crystallization by Particle Attachment in Synthetic, Biogenic, and Geologic Environments

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

De Yoreo, James J.; Gilbert, Pupa U.; Sommerdijk, Nico

Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. These non-classical pathways to crystallization are diverse, in contrast to classical models that consider the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle attachment processes and show that multiple pathways result from the interplay of free energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects; particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemblemore » behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems and patterns of mineralization in natural environments.« less

Metallic dielectric photonic crystals and methods of fabrication

DOEpatents

Chou, Jeffrey Brian; Kim, Sang-Gook

2016-12-20

A metallic-dielectric photonic crystal is formed with a periodic structure defining a plurality of resonant cavities to selectively absorb incident radiation. A metal layer is deposited on the inner surfaces of the resonant cavities and a dielectric material fills inside the resonant cavities. This photonic crystal can be used to selectively absorb broadband solar radiation and then reemit absorbed radiation in a wavelength band that matches the absorption band of a photovoltaic cell. The photonic crystal can be fabricated by patterning a sacrificial layer with a plurality of holes, into which is deposited a supporting material. Removing the rest of the sacrificial layer creates a supporting structure, on which a layer of metal is deposited to define resonant cavities. A dielectric material then fills the cavities to form the photonic crystal.

COMMUNITY REACTIONS TO CAMPAIGNS ADDRESSING CRYSTAL METHAMPHETAMINE USE AMONG GAY AND BISEXUAL MEN IN NEW YORK CITY*

PubMed Central

NANÍN, JOSÉ E.; PARSONS, JEFFREY T.; BIMBI, DAVID S.; GROV, CHRISTIAN; BROWN, JUSTIN T.

2007-01-01

Crystal methamphetamine (aka “crystal meth”) use with high-risk sex has become an emerging health problem for gay and bisexual men in New York City since the late 1990s. Public health campaigns were eventually developed to encourage gay and bisexual men to avoid or reconsider using crystal meth. Reactions to three campaigns were measured with a cross-sectional survey administered in 2004. Among an ethnically-diverse sample of 971 gay and bisexual men, 61.8% reported seeing the campaigns. Those who reported ever using crystal meth, recent use, and recent use with sex were significantly more likely to have seen the campaigns. In general, white men, HIV-negative men, and men not currently using crystal meth responded more positively to the campaigns than their counterparts; yet, more men of color reported having discussions with partners and friends about their crystal use as a result of these campaigns. Implications for researchers and practitioners are discussed. PMID:17533803

Forisome Based Smart Materials

DTIC Science & Technology

2015-03-31

different temperature and humidity conditions to stimulate crystal formation and we were able to generate crystals (Fig. 3). Staing of crystal...natural forisomes to dope the solution with a nucleation site unfortunately without success. SEO proteins have 11 cysteines that may form sulfide

Effects of impurities on crystal growth in fructose crystallization

NASA Astrophysics Data System (ADS)

Chu, Y. D.; Shiau, L. D.; Berglund, K. A.

1989-10-01

The influence of impurities on the crystallization of anhydrous fructose from aqueous solution was studied. The growth kinetics of fructose crystals in the fructose-water-glucose and fructose-water-difructose dianhydrides systems were investigated using photomicroscopic contact nucleation techniques. Glucose is the major impurity likely to be present in fructose syrup formed during corn wet milling, while several difructose dianhydrides are formed in situ under crystallization conditions and have been proposed as a cause in the decrease of overall yields. Both sets of impurities were found to cause inhibition of crystal growth, but the mechanisms responsible in each case are different. It was found that the presence of glucose increases the solubility of fructose in water and thus lowers the supersaturation of the solution. This is probably the main effect responsible for the decrease of crystal growth. Since the molecular structures of difructose dianhydrides are similar to that of fructose, they are probably "tailor-made" impurities. The decrease of crystal growth is probably caused by the incorporation of these impurities into or adsorption to the crystal surface which would accept fructose molecules in the orientation that existed in the difructose dianhydride.

A Kinetic Study of the Effect of Basicity on the Mold Fluxes Crystallization

NASA Astrophysics Data System (ADS)

Zhou, Lejun; Wang, Wanlin; Ma, Fanjun; Li, Jin; Wei, Juan; Matsuura, Hiroyuki; Tsukihashi, Fumitaka

2012-04-01

The effect of basicity on the mold fluxes crystallization was investigated in this article. The time-temperature-transformation (TTT) diagrams and continuous-cooling-transformation (CCT) diagrams of mold fluxes with different basicity were constructed by using single, hot thermocouple technology (SHTT). The results showed that with the increase of basicity, the incubation time of isothermal crystallization became shorter, the crystallization temperature was getting higher, and the critical cooling rate of continuous cooling crystallization became faster. The X-ray diffraction analysis suggested that calcium silicate (CaO·SiO2) was precipitated at the upper part of the TTT diagram and cuspidine (Ca4Si2O7F2) was formed at the lower part, when the basicity of mold fluxes was within 1.0 to 1.2. However, when basicity was 0.8, only the cuspidine phase was formed. A kinetic study of isothermal crystallization process indicated that the increase of the basicity tended to enhance the mold flux crystallization, and the crystallization activation energy became smaller. The crystallization mechanism of cupsidine was changing from one-dimensional growth to three-dimensional growth with a constant number of nuclei, when the basicity of mold fluxes varied from 0.8 to 1.2.

Metastable liquid-liquid transition in a molecular model of water

NASA Astrophysics Data System (ADS)

Palmer, Jeremy C.; Martelli, Fausto; Liu, Yang; Car, Roberto; Panagiotopoulos, Athanassios Z.; Debenedetti, Pablo G.

2014-06-01

Liquid water's isothermal compressibility and isobaric heat capacity, and the magnitude of its thermal expansion coefficient, increase sharply on cooling below the equilibrium freezing point. Many experimental, theoretical and computational studies have sought to understand the molecular origin and implications of this anomalous behaviour. Of the different theoretical scenarios put forward, one posits the existence of a first-order phase transition that involves two forms of liquid water and terminates at a critical point located at deeply supercooled conditions. Some experimental evidence is consistent with this hypothesis, but no definitive proof of a liquid-liquid transition in water has been obtained to date: rapid ice crystallization has so far prevented decisive measurements on deeply supercooled water, although this challenge has been overcome recently. Computer simulations are therefore crucial for exploring water's structure and behaviour in this regime, and have shown that some water models exhibit liquid-liquid transitions and others do not. However, recent work has argued that the liquid-liquid transition has been mistakenly interpreted, and is in fact a liquid-crystal transition in all atomistic models of water. Here we show, by studying the liquid-liquid transition in the ST2 model of water with the use of six advanced sampling methods to compute the free-energy surface, that two metastable liquid phases and a stable crystal phase exist at the same deeply supercooled thermodynamic condition, and that the transition between the two liquids satisfies the thermodynamic criteria of a first-order transition. We follow the rearrangement of water's coordination shell and topological ring structure along a thermodynamically reversible path from the low-density liquid to cubic ice. We also show that the system fluctuates freely between the two liquid phases rather than crystallizing. These findings provide unambiguous evidence for a liquid-liquid transition in the ST2 model of water, and point to the separation of time scales between crystallization and relaxation as being crucial for enabling it.

Metastable liquid-liquid transition in a molecular model of water.

PubMed

Palmer, Jeremy C; Martelli, Fausto; Liu, Yang; Car, Roberto; Panagiotopoulos, Athanassios Z; Debenedetti, Pablo G

2014-06-19

Liquid water's isothermal compressibility and isobaric heat capacity, and the magnitude of its thermal expansion coefficient, increase sharply on cooling below the equilibrium freezing point. Many experimental, theoretical and computational studies have sought to understand the molecular origin and implications of this anomalous behaviour. Of the different theoretical scenarios put forward, one posits the existence of a first-order phase transition that involves two forms of liquid water and terminates at a critical point located at deeply supercooled conditions. Some experimental evidence is consistent with this hypothesis, but no definitive proof of a liquid-liquid transition in water has been obtained to date: rapid ice crystallization has so far prevented decisive measurements on deeply supercooled water, although this challenge has been overcome recently. Computer simulations are therefore crucial for exploring water's structure and behaviour in this regime, and have shown that some water models exhibit liquid-liquid transitions and others do not. However, recent work has argued that the liquid-liquid transition has been mistakenly interpreted, and is in fact a liquid-crystal transition in all atomistic models of water. Here we show, by studying the liquid-liquid transition in the ST2 model of water with the use of six advanced sampling methods to compute the free-energy surface, that two metastable liquid phases and a stable crystal phase exist at the same deeply supercooled thermodynamic condition, and that the transition between the two liquids satisfies the thermodynamic criteria of a first-order transition. We follow the rearrangement of water's coordination shell and topological ring structure along a thermodynamically reversible path from the low-density liquid to cubic ice. We also show that the system fluctuates freely between the two liquid phases rather than crystallizing. These findings provide unambiguous evidence for a liquid-liquid transition in the ST2 model of water, and point to the separation of time scales between crystallization and relaxation as being crucial for enabling it.

Probing Core Processes in the Earth and Small Bodies Using Paleomagnetism

NASA Astrophysics Data System (ADS)

Fu, R. R.; Weiss, B. P.; Lima, E. A.; Glenn, D. R.; Kehayias, P.; Walsworth, R. L.

2015-12-01

Convective motion in the cores of differentiated metal-silicate bodies may sustain a global dynamo magnetic field. Progressive crystallization in a dynamo-generating core is expected to play a central role in determining the observable properties of the hosted magnetic field. Importantly, the release of light elements and latent heat during core crystallization is a key source of entropy for sustaining core convection. Therefore, the persistence and intensity of a dynamo magnetic field depend directly on the extent and style of core crystallization. We present and discuss paleomagnetic data from the Earth and asteroid-sized bodies to characterize internally generated magnetic fields during the early histories of these objects. In the case of the Earth, recent and ongoing paleomagnetic experiments of zircons from the Jack Hills of Australia can potentially constrain the existence and intensity of the geodynamo before 3.5 Ga. If robust, such measurements hold strong implications for the energy budget of the Earth's early core and the dynamics of the early mantle. We will discuss both recently published and preliminary results and assess carefully the challenges and uncertainties of paleomagnetic experimentation on ancient zircon samples. In the case of small bodies, several classes of meteorites record ancient magnetic fields likely produced by core dynamos on their parent bodies. Data from the CV carbonaceous chondrites and pallasites indicate that dynamos in planetesimal-sized bodies persisted for a broad range of timescales between ~10 My and >100 My. Meanwhile, measurements of the angrite group of achondrites show that their earliest-forming members crystallized in an almost non-magnetic environment, suggesting a delayed onset of the planetesimal dynamo until several My after initial differentiation. We will discuss the possible causes for this observed diversity of small body dynamo properties, including the role of core crystallization and the distribution of short-lived radioisotopes.

A new polymorph of 4'-hydroxyvalerophenone revealed by thermoanalytical and X-ray diffraction studies

NASA Astrophysics Data System (ADS)

Lopes, Cátia S. D.; Bernardes, Carlos E. S.; Piedade, M. Fátima M.; Diogo, Hermínio P.; da Piedade, Manuel E. Minas

2017-04-01

A new polymorph of 1-(4-hydroxyphenyl)pentan-1-one (4'-hydroxyvalerophenone, HVP) was identified by using differential scanning calorimetry, hot stage microscopy, and X-ray powder diffraction. This novel crystal form (form II) was obtained by crystallization from melt. It has a fusion temperature of T fus = 324.3 ± 0.2 K and an enthalpy of fusion Δfus H m o = 18.14±0.18 kJ·mol-1. These values are significantly lower than those observed for the previously known phase (form I, monoclinic, space group P21/ c, T fus = 335.6 ± 0.7 K; Δfus H m o = 26.67±0.04 kJ·mol-1), which can be prepared by crystallization from ethanol. The results here obtained, therefore, suggest that form I is thermodynamically more stable than the newly identified form II and, furthermore, that the two polymorphs are monotropically related.

Formation of Hadean granites by melting of igneous crust

NASA Astrophysics Data System (ADS)

Burnham, A. D.; Berry, A. J.

2017-06-01

The oldest known samples of Earth, with ages of up to 4.4 Gyr, are detrital zircon grains in meta-sedimentary rocks of the Jack Hills in Australia. These zircons offer insights into the magmas from which they crystallized, and, by implication, igneous activity and tectonics in the first 500 million years of Earth’s history, the Hadean eon. However, the compositions of these magmas and the relative contributions of igneous and sedimentary components to their sources have not yet been resolved. Here we compare the trace element concentrations of the Jack Hills zircons to those of zircons from the locality where igneous (I-) and sedimentary (S-) type granites were first distinguished. We show that the Hadean zircons crystallized predominantly from I-type magmas formed by melting of a reduced, garnet-bearing igneous crust. Further, we propose that both the phosphorus content of zircon and the ratio of phosphorus to rare earth elements can be used to distinguish between detrital zircon grains from I- and S-type sources. These elemental discriminants provide a new geochemical tool to assess the relative contributions of primeval magmatism and melting of recycled sediments to the continents over geological time.

Free and ATP-bound structures of Ap4A hydrolase from Aquifex aeolicus V5.

PubMed

Jeyakanthan, Jeyaraman; Kanaujia, Shankar Prasad; Nishida, Yuya; Nakagawa, Noriko; Praveen, Surendran; Shinkai, Akeo; Kuramitsu, Seiki; Yokoyama, Shigeyuki; Sekar, Kanagaraj

2010-02-01

Asymmetric diadenosine tetraphosphate (Ap(4)A) hydrolases degrade the metabolite Ap(4)A back into ATP and AMP. The three-dimensional crystal structure of Ap(4)A hydrolase (16 kDa) from Aquifex aeolicus has been determined in free and ATP-bound forms at 1.8 and 1.95 A resolution, respectively. The overall three-dimensional crystal structure of the enzyme shows an alphabetaalpha-sandwich architecture with a characteristic loop adjacent to the catalytic site of the protein molecule. The ATP molecule is bound in the primary active site and the adenine moiety of the nucleotide binds in a ring-stacking arrangement equivalent to that observed in the X-ray structure of Ap(4)A hydrolase from Caenorhabditis elegans. Binding of ATP in the active site induces local conformational changes which may have important implications in the mechanism of substrate recognition in this class of enzymes. Furthermore, two invariant water molecules have been identified and their possible structural and/or functional roles are discussed. In addition, modelling of the substrate molecule at the primary active site of the enzyme suggests a possible path for entry and/or exit of the substrate and/or product molecule.

Highly sensitive quartz crystal microbalance based biosensor using Au dendrite structure

NASA Astrophysics Data System (ADS)

Asai, Naoto; Terasawa, Hideaki; Shimizu, Tomohiro; Shingubara, Shoso; Ito, Takeshi

2018-02-01

A Au dendrite structure was obtained by only electroplating under a suitable potential. A blanch like nanostructure was formed along the crystal orientation. In this study, we attempted to fabricate a Au dendrite structure on the electrode of a quartz crystal by electroplating to increase the specific surface area. We estimated the effective surface area by cyclic voltammetry (CV) and monitored the frequency shift induced by antigen-antibody interaction by the quartz crystal microbalance (QCM) method. The dendrite structure with the largest surface area was formed under -0.95 V for 5 min. In the measurement of the antigen-antibody interaction, the frequency shifts of 40, 80, and 110 Hz were obtained with the dendrite structured QCM chips formed at the above potential for 1, 1.5, and 2.0 min, respectively. The sensitivity was improved compared with that QCM chip having a flat surface electrode.

Modeling solid-state transformations occurring in dissolution testing.

PubMed

Laaksonen, Timo; Aaltonen, Jaakko

2013-04-15

Changes in the solid-state form can occur during dissolution testing of drugs. This can often complicate interpretation of results. Additionally, there can be several mechanisms through which such a change proceeds, e.g. solvent-mediated transformation or crystal growth within the drug material itself. Here, a mathematical model was constructed to study the dissolution testing of a material, which undergoes such changes. The model consisted of two processes: the recrystallization of the drug from a supersaturated liquid state caused by the dissolution of the more soluble solid form and the crystal growth of the stable solid form at the surface of the drug formulation. Comparison to experimental data on theophylline dissolution showed that the results obtained with the model matched real solid-state changes and that it was able to distinguish between cases where the transformation was controlled either by solvent-mediated crystallization or solid-state crystal growth. Copyright © 2013 Elsevier B.V. All rights reserved.