The application and use of chemical space mapping to interpret crystallization screening results

PubMed Central

Snell, Edward H.; Nagel, Ray M.; Wojtaszcyk, Ann; O’Neill, Hugh; Wolfley, Jennifer L.; Luft, Joseph R.

2008-01-01

Macromolecular crystallization screening is an empirical process. It often begins by setting up experiments with a number of chemically diverse cocktails designed to sample chemical space known to promote crystallization. Where a potential crystal is seen a refined screen is set up, optimizing around that condition. By using an incomplete factorial sampling of chemical space to formulate the cocktails and presenting the results graphically, it is possible to readily identify trends relevant to crystallization, coarsely sample the phase diagram and help guide the optimization process. In this paper, chemical space mapping is applied to both single macromolecules and to a diverse set of macromolecules in order to illustrate how visual information is more readily understood and assimilated than the same information presented textually. PMID:19018100

The application and use of chemical space mapping to interpret crystallization screening results.

PubMed

Snell, Edward H; Nagel, Ray M; Wojtaszcyk, Ann; O'Neill, Hugh; Wolfley, Jennifer L; Luft, Joseph R

2008-12-01

Macromolecular crystallization screening is an empirical process. It often begins by setting up experiments with a number of chemically diverse cocktails designed to sample chemical space known to promote crystallization. Where a potential crystal is seen a refined screen is set up, optimizing around that condition. By using an incomplete factorial sampling of chemical space to formulate the cocktails and presenting the results graphically, it is possible to readily identify trends relevant to crystallization, coarsely sample the phase diagram and help guide the optimization process. In this paper, chemical space mapping is applied to both single macromolecules and to a diverse set of macromolecules in order to illustrate how visual information is more readily understood and assimilated than the same information presented textually.

Precession technique and electron diffractometry as new tools for crystal structure analysis and chemical bonding determination.

PubMed

Avilov, A; Kuligin, K; Nicolopoulos, S; Nickolskiy, M; Boulahya, K; Portillo, J; Lepeshov, G; Sobolev, B; Collette, J P; Martin, N; Robins, A C; Fischione, P

2007-01-01

We have developed a new fast electron diffractometer working with high dynamic range and linearity for crystal structure determinations. Electron diffraction (ED) patterns can be scanned serially in front of a Faraday cage detector; the total measurement time for several hundred ED reflections can be tens of seconds having high statistical accuracy for all measured intensities (1-2%). This new tool can be installed to any type of TEM without any column modification and is linked to a specially developed electron beam precession "Spinning Star" system. Precession of the electron beam (Vincent-Midgley technique) reduces dynamical effects allowing also use of accurate intensities for crystal structure analysis. We describe the technical characteristics of this new tool together with the first experimental results. Accurate measurement of electron diffraction intensities by electron diffractometer opens new possibilities not only for revealing unknown structures, but also for electrostatic potential determination and chemical bonding investigation. As an example, we present detailed atomic bonding information of CaF(2) as revealed for the first time by precise electron diffractometry.

High throughput screening using acoustic droplet ejection to combine protein crystals and chemical libraries on crystallization plates at high density

DOE PAGES

Teplitsky, Ella; Joshi, Karan; Ericson, Daniel L.; ...

2015-07-01

We describe a high throughput method for screening up to 1728 distinct chemicals with protein crystals on a single microplate. Acoustic droplet ejection (ADE) was used to co-position 2.5 nL of protein, precipitant, and chemicals on a MiTeGen in situ-1 crystallization plate™ for screening by co-crystallization or soaking. ADE-transferred droplets follow a precise trajectory which allows all components to be transferred through small apertures in the microplate lid. The apertures were large enough for 2.5 nL droplets to pass through them, but small enough so that they did not disrupt the internal environment created by the mother liquor. Using thismore » system, thermolysin and trypsin crystals were efficiently screened for binding to a heavy-metal mini-library. Fluorescence and X-ray diffraction were used to confirm that each chemical in the heavy-metal library was correctly paired with the intended protein crystal. Moreover, a fragment mini-library was screened to observe two known lysozyme We describe a high throughput method for screening up to 1728 distinct chemicals with protein crystals on a single microplate. Acoustic droplet ejection (ADE) was used to co-position 2.5 nL of protein, precipitant, and chemicals on a MiTeGen in situ-1 crystallization plate™ for screening by co-crystallization or soaking. ADE-transferred droplets follow a precise trajectory which allows all components to be transferred through small apertures in the microplate lid. The apertures were large enough for 2.5 nL droplets to pass through them, but small enough so that they did not disrupt the internal environment created by the mother liquor. Using this system, thermolysin and trypsin crystals were efficiently screened for binding to a heavy-metal mini-library. Fluorescence and X-ray diffraction were used to confirm that each chemical in the heavy-metal library was correctly paired with the intended protein crystal. A fragment mini-library was screened to observe two known

Analysis of synthetic diamond single crystals by X-ray topography and double-crystal diffractometry

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

Prokhorov, I. A., E-mail: igor.prokhorov@mail.ru; Ralchenko, V. G.; Bolshakov, A. P.

2013-12-15

Structural features of diamond single crystals synthesized under high pressure and homoepitaxial films grown by chemical vapor deposition (CVD) have been analyzed by double-crystal X-ray diffractometry and topography. The conditions of a diffraction analysis of diamond crystals using Ge monochromators have been optimized. The main structural defects (dislocations, stacking faults, growth striations, second-phase inclusions, etc.) formed during crystal growth have been revealed. The nitrogen concentration in high-pressure/high-temperature (HPHT) diamond substrates is estimated based on X-ray diffraction data. The formation of dislocation bundles at the film-substrate interface in the epitaxial structures has been revealed by plane-wave topography; these dislocations are likelymore » due to the relaxation of elastic macroscopic stresses caused by the lattice mismatch between the substrate and film. The critical thicknesses of plastic relaxation onset in CVD diamond films are calculated. The experimental techniques for studying the real diamond structure in optimizing crystal-growth technology are proven to be highly efficient.« less

Damage and recovery of skin barrier function after glycolic acid chemical peeling and crystal microdermabrasion.

PubMed

Song, Ji Youn; Kang, Hyun A; Kim, Mi-Yeon; Park, Young Min; Kim, Hyung Ok

2004-03-01

Superficial chemical peeling and microdermabrasion have become increasingly popular methods for producing facial rejuvenation. However, there are few studies reporting the skin barrier function changes after these procedures. To evaluate objectively the degree of damage visually and the time needed for the skin barrier function to recover after glycolic acid peeling and aluminum oxide crystal microdermabrasion using noninvasive bioengineering methods. Superficial chemical peeling using 30%, 50%, and 70% glycolic acid and aluminum oxide crystal microdermabrasion were used on the volar forearm of 13 healthy women. The skin response was measured by a visual observation and using an evaporimeter, corneometer, and colorimeter before and after peeling at set time intervals. Both glycolic acid peeling and aluminum oxide crystal microdermabrasion induced significant damage to the skin barrier function immediately after the procedure, and the degree of damage was less severe after the aluminum oxide crystal microdermabrasion compared with glycolic acid peeling. The damaged skin barrier function had recovered within 24 hours after both procedures. The degree of erythema induction was less severe after the aluminum oxide crystal microdermabrasion compared with the glycolic acid peeling procedure. The degree of erythema induced after the glycolic acid peeling procedure was not proportional to the peeling solution concentration used. The erythema subsided within 1 day after the aluminum oxide crystal microdermabrasion procedure and within 4 days after the glycolic acid peeling procedure. These results suggest that the skin barrier function is damaged after the glycolic acid peeling and aluminum oxide crystal microdermabrasion procedure but recovers within 1 to 4 days. Therefore, repeating the superficial peeling procedure at 2-week intervals will allow sufficient time for the damaged skin to recover its barrier function.

Optical and chemical analysis of iron in Luna 20 plagioclase.

NASA Technical Reports Server (NTRS)

Bell, P. M.; Mao, H. K.

1973-01-01

Review of analytical data on the iron content of Luna 20 anorthitic plagioclase, obtained by a highly sensitive technique for measuring polarized absorption related to crystal-field splittings and by automated electron microprobe analysis of oriented single crystals. The iron content is found to range from a few hundredths to a few tenths of a weight per cent from crystal to crystal. The optical and chemical properties of the iron appear to be caused by postcrystallization migration and exsolution. Postcrystallization effects may obscure evidence of the original oxidation state and iron concentration of these crystals.

Surface force analysis of glycine adsorption on different crystal surfaces of titanium dioxide (TiO2).

PubMed

Ganbaatar, Narangerel; Imai, Kanae; Yano, Taka-Aki; Hara, Masahiko

2017-01-01

Surface force analysis with atomic force microscope (AFM) in which a single amino acid residue was mounted on the tip apex of AFM probe was carried out for the first time at the molecular level on titanium dioxide (TiO 2 ) as a representative mineral surface for prebiotic chemical evolution reactions. The force analyses on surfaces with three different crystal orientations revealed that the TiO 2 (110) surface has unique characteristics for adsorbing glycine molecules showing different features compared to those on TiO 2 (001) and (100). To examine this difference, we investigated thermal desorption spectroscopy (TDS) and the interaction between the PEG cross-linker and the three TiO 2 surfaces. Our data suggest that the different single crystal surfaces would provide different chemical evolution field for amino acid molecules.

Near-equilibrium chemical vapor deposition of high-quality single-crystal graphene directly on various dielectric substrates.

PubMed

Chen, Jianyi; Guo, Yunlong; Jiang, Lili; Xu, Zhiping; Huang, Liping; Xue, Yunzhou; Geng, Dechao; Wu, Bin; Hu, Wenping; Yu, Gui; Liu, Yunqi

2014-03-05

By using near-equilibrium chemical vapor deposition, it is demonstrated that high-quality single-crystal graphene can be grown on dielectric substrates. The maximum size is about 11 μm. The carrier mobility can reach about 5650 cm(2) V(-1) s(-1) , which is comparable to those of some metal-catalyzed graphene crystals, reflecting the good quality of the graphene lattice. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermotropic Liquid Crystal-Assisted Chemical and Biological Sensors

PubMed Central

Honaker, Lawrence W.; Usol’tseva, Nadezhda; Mann, Elizabeth K.

2017-01-01

In this review article, we analyze recent progress in the application of liquid crystal-assisted advanced functional materials for sensing biological and chemical analytes. Multiple research groups demonstrate substantial interest in liquid crystal (LC) sensing platforms, generating an increasing number of scientific articles. We review trends in implementing LC sensing techniques and identify common problems related to the stability and reliability of the sensing materials as well as to experimental set-ups. Finally, we suggest possible means of bridging scientific findings to viable and attractive LC sensor platforms. PMID:29295530

Magnetorheological finishing with chemically modified fluids for studying material removal of single-crystal ZnS

NASA Astrophysics Data System (ADS)

Salzman, S.; Romanofsky, H. J.; Clara, Y. I.; Giannechini, L. J.; West, Garrett J.; Lambropoulos, J. C.; Jacobs, S. D.

2013-09-01

Magnetorheological finishing (MRF) of polycrystalline, chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and zinc selenide (ZnSe) can leave millimeter-size artifacts on the part surface. These pebble-like features come from the anisotropic mechanical and chemical properties of the ceramic material and from the CVD growth process itself. The resulting surface texture limits the use of MRF for polishing aspheric and other complex shapes using these important infrared (IR) ceramics. An investigation of the individual contributions of chemistry and mechanics to polishing of other polycrystalline ceramics has been employed in the past to overcome similar material anisotropy problems. The approach taken was to study the removal process for the different single-crystal orientations that comprise the ceramic, making adjustments to mechanics (polishing abrasive type and concentration) and polishing slurry chemistry (primarily pH) to equalize the removal rate for all crystal orientations. Polishing with the modified slurry was shown to prevent the development of surface texture. Here we present mechanical (microhardness testing) and chemical (acid etching) studies performed on the four single-crystal orientations of ZnS: 100, 110, 111, and 311. We found that the (111) plane is 35% to 55% harder and 30% to 40% more resistant to chemical etching than the other three planes. This relatively high degree of variation in these properties can help to explain the surface texture developed from MRF of the polycrystalline material. Theoretical calculations of microhardness, planar, and bond densities are presented and compared with the experimental data. Here surface characterization of these single-crystal orientations of ZnS for material removal and roughness with chemically modified MR fluids at various pH levels between pH 4 and pH 6 are presented for the first time.

Two-Dimensional Photonic Crystals for Sensitive Microscale Chemical and Biochemical Sensing

PubMed Central

Miller, Benjamin L.

2015-01-01

Photonic crystals – optical devices able to respond to changes in the refractive index of a small volume of space – are an emerging class of label-free chemical-and bio-sensors. This review focuses on one class of photonic crystal, in which light is confined to a patterned planar material layer of sub-wavelength thickness. These devices are small (on the order of tens to 100s of microns square), suitable for incorporation into lab-on-a-chip systems, and in theory can provide exceptional sensitivity. We introduce the defining characteristics and basic operation of two-dimensional photonic crystal sensors, describe variations of their basic design geometry, and summarize reported detection results from chemical and biological sensing experiments. PMID:25563402

Comparative analysis of thermal behavior, isothermal crystallization kinetics and polymorphism of palm oil fractions.

PubMed

Zhang, Xia; Li, Lin; Xie, He; Liang, Zhili; Su, Jianyu; Liu, Guoqin; Li, Bing

2013-01-15

Thermal behavior of palm stearin (PS) and palm olein (PO) was explored by monitoring peak temperature transitions by differential scanning calorimetry (DSC). The fatty acid composition (FAC), isothermal crystallization kinetics studied by pulsed Nuclear Magnetic Resonance (pNMR) and isothermal microstructure were also compared. The results indicated that the fatty acid composition had an important influence on the crystallization process. PS and PO both exhibited more multiple endotherms than exotherms which showed irregular peak shapes. An increasing in cooling rate, generally, was associated with an increase in peak size. Application of the Avaimi equation to isothermal crystallization of PS and PO revealed different nucleation and growth mechanisms based on the Avrami exponents. PS quickly reached the end of crystallization because of more saturated triacylglycerol (TAG). The Avrami index of PS were the same as PO under the same isothermal condition at lower temperatrue, indicating that the crystallization mechanism of the two samples based on super-cooling state were the same. According to the polarized light microscope (PLM) images, crystal morphology of PS and PO was different. With the temperature increased, the structure of crystal network of both PS and PO gradually loosened.

Pediatric susceptibility to 18 industrial chemicals: a comparative analysis of newborn with young animals.

PubMed

Hasegawa, R; Hirata-Koizumi, M; Dourson, M; Parker, A; Hirose, A; Nakai, S; Kamata, E; Ema, M

2007-04-01

We comprehensively re-analyzed the toxicity data for 18 industrial chemicals from repeated oral exposures in newborn and young rats, which were previously published. Two new toxicity endpoints specific to this comparative analysis were identified, the first, the presumed no observed adverse effect level (pNOAEL) was estimated based on results of both main and dose-finding studies, and the second, the presumed unequivocally toxic level (pUETL) was defined as a clear toxic dose giving similar severity in both newborn and young rats. Based on the analyses of both pNOAEL and pUETL ratios between the different ages, newborn rats demonstrated greater susceptibility (at most 8-fold) to nearly two thirds of these 18 chemicals (mostly phenolic substances), and less or nearly equal sensitivity to the other chemicals. Exceptionally one chemical only showed toxicity in newborn rats. In addition, Benchmark Dose Lower Bound (BMDL) estimates were calculated as an alternative endpoint. Most BMDLs were comparable to their corresponding pNOAELs and the overall correlation coefficient was 0.904. We discussed how our results can be incorporated into chemical risk assessment approaches to protect pediatric health from direct oral exposure to chemicals.

Towards true 3D textural analysis; using your crystal mush wisely.

NASA Astrophysics Data System (ADS)

Jerram, D. A.; Morgan, D. J.; Pankhurst, M. J.

2014-12-01

The crystal cargo that is found in volcanic and plutonic rocks contains a wealth of information about magmatic mush processes, crystallisation history, crystal entrainment and recycling. Phenocryst populations predominantly record episodes of growth/nucleation and bulk geochemical changes within an evolving crystal-melt body. Ante- and xeno-crysts provide useful clues to the nature of mush interaction with wall rock and with principal magma(s). Furthermore, crystal evolutions (core to rim) record pathways through pressure, temperature and compositional space. These can often illustrate complex recycling within systems, describing the plumbing architecture. Understanding this architecture underpins our knowledge of how igneous systems can interact with the crust, grow, freeze, re-mobilise and prime for eruption. Initially, 2D studies produced corrected 3D crystal size distributions to help provide information about nucleation and residence times. It immediately became clear that crystal shape is an important factor in determining the confidence placed upon 3D reconstructions of 2D data. Additionally studies utilised serial sections of medium- to coarse-grain-size populations which allowed 3D reconstruction using modelling software to be improved, since size and shape etc. can be directly constrained. Finally the advent of textural studies using X-ray tomography has revolutionised the way in which we can inspect the crystal cargo in mushy systems, allowing us to image in great detail crystal packing arrangements, 3D CSDs, shapes and orientations etc. The latest most innovative studies use X-ray micro-computed tomography to rapidly characterise chemical populations within the crystal cargo, adding a further dimension to this approach, and implies the ability to untangle magmatic chemical components to better understand their individual and combined evolution. In this contribution key examples of the different types of textural analysis techniques in 2D and 3D

Fragment-Based Electronic Structure Approach for Computing Nuclear Magnetic Resonance Chemical Shifts in Molecular Crystals.

PubMed

Hartman, Joshua D; Beran, Gregory J O

2014-11-11

First-principles chemical shielding tensor predictions play a critical role in studying molecular crystal structures using nuclear magnetic resonance. Fragment-based electronic structure methods have dramatically improved the ability to model molecular crystal structures and energetics using high-level electronic structure methods. Here, a many-body expansion fragment approach is applied to the calculation of chemical shielding tensors in molecular crystals. First, the impact of truncating the many-body expansion at different orders and the role of electrostatic embedding are examined on a series of molecular clusters extracted from molecular crystals. Second, the ability of these techniques to assign three polymorphic forms of the drug sulfanilamide to the corresponding experimental (13)C spectra is assessed. This challenging example requires discriminating among spectra whose (13)C chemical shifts differ by only a few parts per million (ppm) across the different polymorphs. Fragment-based PBE0/6-311+G(2d,p) level chemical shielding predictions correctly assign these three polymorphs and reproduce the sulfanilamide experimental (13)C chemical shifts with 1 ppm accuracy. The results demonstrate that fragment approaches are competitive with the widely used gauge-invariant projector augmented wave (GIPAW) periodic density functional theory calculations.

Crystal-chemical characteristics of nontronites from bottom sediments of Pacific ocean

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

Palchik, N. A., E-mail: nadezhda@igm.nsc.ru; Moroz, T. N.; Grigorieva, T. N.

A crystal-chemical analysis of the nontronite samples formed in deep-water sediments of the underwater Juan-de-Fuca ridge in the Pacific ocean has been performed using powder X-ray diffraction, IR spectroscopy, and Mössbauer spectroscopy. A comparison with the previously investigated nontronites from different regions of the Sea of Okhotsk showed that the structural features of these formations are due to the difference in the physicochemical parameters of their crystallization. The values of the basal interplanar spacing d{sub 001} (within 11–13 Å) in the samples analyzed are determined by the degree of hydration and cation filling of the interlayer space, while the differencesmore » in the IR spectra are due to isomorphic substitutions in the structure. The character of cation distribution and the nature and concentration of stacking faults in nontronite structures are determined. The differences in the composition, structure, and properties of nontronites of different origin are confirmed by theoretical calculations of their structural parameters.« less

Recognizing chemicals in patents: a comparative analysis.

PubMed

Habibi, Maryam; Wiegandt, David Luis; Schmedding, Florian; Leser, Ulf

2016-01-01

Recently, methods for Chemical Named Entity Recognition (NER) have gained substantial interest, driven by the need for automatically analyzing todays ever growing collections of biomedical text. Chemical NER for patents is particularly essential due to the high economic importance of pharmaceutical findings. However, NER on patents has essentially been neglected by the research community for long, mostly because of the lack of enough annotated corpora. A recent international competition specifically targeted this task, but evaluated tools only on gold standard patent abstracts instead of full patents; furthermore, results from such competitions are often difficult to extrapolate to real-life settings due to the relatively high homogeneity of training and test data. Here, we evaluate the two state-of-the-art chemical NER tools, tmChem and ChemSpot, on four different annotated patent corpora, two of which consist of full texts. We study the overall performance of the tools, compare their results at the instance level, report on high-recall and high-precision ensembles, and perform cross-corpus and intra-corpus evaluations. Our findings indicate that full patents are considerably harder to analyze than patent abstracts and clearly confirm the common wisdom that using the same text genre (patent vs. scientific) and text type (abstract vs. full text) for training and testing is a pre-requisite for achieving high quality text mining results.

Growth, structural, optical, mechanical and quantum chemical analysis of unidirectional grown bis(guanidinium) 5-sulfosalicylate (BGSSA) single crystal

NASA Astrophysics Data System (ADS)

Sreedevi, R.; Saravana Kumar, G.; Amarsingh Bhabu, K.; Balu, T.; Murugakoothan, P.; Rajasekaran, T. R.

2018-02-01

Bis(guanidinium) 5-sulfosalicylate single crystal was grown by using Sankaranarayanan-Ramasamy (SR) method from the solution of methanol and water in equimolar ratio. Good quality crystal with 50 mm length and 10 mm in diameter was grown. The grown crystal was subjected to single crystal X-ray diffraction analysis to confirm the crystal structure and it was found to be orthorhombic. UV-Vis-NIR spectroscopic study revealed that the SR method grown crystal had good optical transparency with wide optical band gap of 4.4 eV. The presence of the functional groups and modes of vibrations were identified by FTIR spectroscopy recorded in the range 4000-400 cm-1. The mechanical strength of the grown crystal was confirmed using Vickers microhardness tester by applying load from 25 g to 100 g. Density functional theory (DFT) method with B3LYP/6-31-G (d,p) level basis set was employed and hence the optimized molecular geometry, first order hyperpolarizability, dipole moment, thermodynamic functions, molecular electrostatic potential and frontier molecular orbital analysis of the grown BGSSA sample was computed and analysed.

Exceptional enhancement of Raman scattering on silver chlorobromide nanocube photonic crystals: chemical and photonic contributions

DOE PAGES

Li, Zheng; Gosztola, David J.; Sun, Cheng-Jun; ...

2015-02-02

Photonic crystals made from self-assembly of mono-dispersed AgCl xBr 1-x nanocubes, which are not plasmonically active, have been discovered to exceptionally enhance Raman scattering of molecules chemically adsorbed on their surfaces. Comprehensive control measurements and X-ray absorption near-edge structure spectroscopy indicate that the Raman enhancement on the AgCl xBr 1-x nanocube photonic crystals is primarily ascribed to the chemical enhancement mechanism associated with the chemical interactions between adsorbing molecules and the AgCl xBr 1-x surfaces. In addition, the ordering of the AgCl xBr 1-x nanocubes in the photonic crystals can selectively reflect Raman scattering back to the detector at themore » bandgap position of the photonic crystals to provide additional enhancement, i.e., photonic mode enhancement. The thiophenol molecules adsorbed on the AgCl 0.44Br 0.56 nanocube photonic crystals exhibit astonishingly strong Raman signals that are on the same order of magnitude as those recorded from the thiophenol molecules adsorbed on the assembled Ag nanocubes.« less

Single-crystal silicon optical fiber by direct laser crystallization

DOE PAGES

Ji, Xiaoyu; Lei, Shiming; Yu, Shih -Ying; ...

2016-12-05

Semiconductor core optical fibers with a silica cladding are of great interest in nonlinear photonics and optoelectronics applications. Laser crystallization has been recently demonstrated for crystallizing amorphous silicon fibers into crystalline form. Here we explore the underlying mechanism by which long single-crystal silicon fibers, which are novel platforms for silicon photonics, can be achieved by this process. Using finite element modeling, we construct a laser processing diagram that reveals a parameter space within which single crystals can be grown. Utilizing this diagram, we illustrate the creation of single-crystal silicon core fibers by laser crystallizing amorphous silicon deposited inside silica capillarymore » fibers by high-pressure chemical vapor deposition. The single-crystal fibers, up to 5.1 mm long, have a very welldefined core/cladding interface and a chemically pure silicon core that leads to very low optical losses down to ~0.47-1dB/cm at the standard telecommunication wavelength (1550 nm). Furthermore, tt also exhibits a photosensitivity that is comparable to bulk silicon. Creating such laser processing diagrams can provide a general framework for developing single-crystal fibers in other materials of technological importance.« less

An Experiment with Manifold Purposes: The Chemical Reactivity of Crystal Defects upon Crystal Dissolution.

ERIC Educational Resources Information Center

Lazzarini, Annaluisa Fantola; Lazzarini, Ennio

1983-01-01

Background information and procedures are provided for an experiment designed to introduce (1) crystal defects and their reactivity upon crystal dissolution; (2) hydrates electron and its reactivity; (3) application of radiochemical method of analysis; and (4) the technique of competitive kinetics. Suggested readings and additional experiments are…

Improving Student Results in the Crystal Violet Chemical Kinetics Experiment

ERIC Educational Resources Information Center

Kazmierczak, Nathanael; Vander Griend, Douglas A.

2017-01-01

Despite widespread use in general chemistry laboratories, the crystal violet chemical kinetics experiment frequently suffers from erroneous student results. Student calculations for the reaction order in hydroxide often contain large asymmetric errors, pointing to the presence of systematic error. Through a combination of "in silico"…

Comparing Chemistry to Outcome: The Development of a Chemical Distance Metric, Coupled with Clustering and Hierarchal Visualization Applied to Macromolecular Crystallography

PubMed Central

Bruno, Andrew E.; Ruby, Amanda M.; Luft, Joseph R.; Grant, Thomas D.; Seetharaman, Jayaraman; Montelione, Gaetano T.; Hunt, John F.; Snell, Edward H.

2014-01-01

Many bioscience fields employ high-throughput methods to screen multiple biochemical conditions. The analysis of these becomes tedious without a degree of automation. Crystallization, a rate limiting step in biological X-ray crystallography, is one of these fields. Screening of multiple potential crystallization conditions (cocktails) is the most effective method of probing a proteins phase diagram and guiding crystallization but the interpretation of results can be time-consuming. To aid this empirical approach a cocktail distance coefficient was developed to quantitatively compare macromolecule crystallization conditions and outcome. These coefficients were evaluated against an existing similarity metric developed for crystallization, the C6 metric, using both virtual crystallization screens and by comparison of two related 1,536-cocktail high-throughput crystallization screens. Hierarchical clustering was employed to visualize one of these screens and the crystallization results from an exopolyphosphatase-related protein from Bacteroides fragilis, (BfR192) overlaid on this clustering. This demonstrated a strong correlation between certain chemically related clusters and crystal lead conditions. While this analysis was not used to guide the initial crystallization optimization, it led to the re-evaluation of unexplained peaks in the electron density map of the protein and to the insertion and correct placement of sodium, potassium and phosphate atoms in the structure. With these in place, the resulting structure of the putative active site demonstrated features consistent with active sites of other phosphatases which are involved in binding the phosphoryl moieties of nucleotide triphosphates. The new distance coefficient, CDcoeff, appears to be robust in this application, and coupled with hierarchical clustering and the overlay of crystallization outcome, reveals information of biological relevance. While tested with a single example the potential applications

Structural, quantum chemical, vibrational and thermal studies of a hydrogen bonded zwitterionic co-crystal (nicotinic acid: pyrogallol)

NASA Astrophysics Data System (ADS)

Prabha, E. Arockia Jeya Yasmi; Kumar, S. Suresh; Athimoolam, S.; Sridhar, B.

2017-02-01

In the present work, a new co-crystal of nicotinic acid with pyrogallol (NICPY) has been grown in the zwitterionic form and the corresponding structural, vibrational, thermal, solubility and anti-cancer characteristics have been reported. The single crystal X-ray diffraction analysis confirms that the structural molecular packing of the crystal stabilized through N-H⋯O and O-H⋯O hydrogen bond. The stabilization energy of the hydrogen bond motifs were calculated in the solid state. Vibrational spectral studies such as Fourier transform-infrared (FT-IR) and FT-Raman were adopted to understand the zwitterionic co-crystalline nature of the compound, which has been compared with theoretically calculated vibrational frequencies. The thermal stability of the grown co-crystal was analyzed by TG/DTA study. The solubility of the NICPY co-crystal was investigated in water at different temperature and compared with that of the nicotinic acid, which is the parent compound of NICPY co-crystal. The grown crystals were treated with human cervical cancer cell line (HeLa) to analyze the cytotoxicity of NICPY crystals and compared with the parent compound, which shows that NICPY has moderate activity against human cervical cancer cell line.

Purification, crystallization and preliminary X-ray analysis of phycocyanin and phycoerythrin from Porphyra yezoensis Ueda

PubMed Central

Cai, Chuner; Wu, Lian; Li, Chunxia; He, Peimin; Li, Jie; Zhou, Jiahai

2011-01-01

Porphyra yezoensis is one of the most important and widely cultured seaweeds in China. Phycobiliproteins exhibit excellent spectroscopic properties and play versatile roles in the biomedical, food, cosmetics and chemical synthetic dye industries. Here, the purification and crystallization of phycoerythrin and phycocyanin, two phycobiliproteins extracted from P. yezoensis, are described. Using a novel protocol including co-precipitation with ammonium sulfate and hydroxyapatite column chromatography, both phycobiliproteins were produced on a large scale with improved quality and yield compared with those previously reported. Native PAGE analysis indicated that phycoerythrin and phycocyanin exist as (αβ)3 heterohexamers in solution. The crystals of phycoerythrin diffracted to 2.07 Å resolution and belonged to space group R3. The unit-cell parameters referred to hexagonal axes are a = b = 187.7, c = 59.7 Å, with nine (αβ)2 heterotetramers per unit cell. The crystals of phycocyanin diffracted to 2.70 Å resolution in space group P21. Matthews coefficient analysis shows that 10–19 (αβ) heterodimers of phycocyanin in the asymmetric unit would be reasonable. A self-rotation function calculation clarified this ambiguity and indicated that 12 (αβ) heterodimers of phycocyanin are assembled in the asymmetric unit. PMID:21543866

Crystallization, Optical and Chemical Properties of Fluoride Glasses

NASA Technical Reports Server (NTRS)

Doremus, R. H.

1985-01-01

Fluoride glasses have great promise as infrared optical components, especially fibers, because they are transparent to 8 micrometers and higher. In order to optimize properties, different glass compositions are needed. Some are hard to form in a container, and may possibly be formable in a containerless furnace. Understanding of crystallization with and without a container could lead to glasses with optimum properties. Chemical durability (attack by water) can limit or extend the applicability of fluoride glasses. Progress to date is given.

Analysis of Crystallization Kinetics

NASA Technical Reports Server (NTRS)

Kelton, Kenneth F.

1997-01-01

A realistic computer model for polymorphic crystallization (i.e., initial and final phases with identical compositions), which includes time-dependent nucleation and cluster-size-dependent growth rates, is developed and tested by fits to experimental data. Model calculations are used to assess the validity of two of the more common approaches for the analysis of crystallization data. The effects of particle size on transformation kinetics, important for the crystallization of many systems of limited dimension including thin films, fine powders, and nanoparticles, are examined.

Elemental distribution analysis of urinary crystals.

PubMed

Fazil Marickar, Y M; Lekshmi, P R; Varma, Luxmi; Koshy, Peter

2009-10-01

Various crystals are seen in human urine. Some of them, particularly calcium oxalate dihydrate, are seen normally. Pathological crystals indicate crystal formation initiating urinary stones. Unfortunately, many of the relevant crystals are not recognized in light microscopic analysis of the urinary deposit performed in most of the clinical laboratories. Many crystals are not clearly identifiable under the ordinary light microscopy. The objective of the present study was to perform scanning electron microscopic (SEM) assessment of various urinary deposits and confirm the identity by elemental distribution analysis (EDAX). 50 samples of urinary deposits were collected from urinary stone clinic. Deposits containing significant crystalluria (more than 10 per HPF) were collected under liquid paraffin in special containers and taken up for SEM studies. The deposited crystals were retrieved with appropriate Pasteur pipettes, and placed on micropore filter paper discs. The fluid was absorbed by thicker layers of filter paper underneath and discs were fixed to brass studs. They were then gold sputtered to 100 A and examined under SEM (Jeol JSM 35C microscope). When crystals were seen, their morphology was recorded by taking photographs at different angles. At appropriate magnification, EDAX probe was pointed to the crystals under study and the wave patterns analyzed. Components of the crystals were recognized by utilizing the data. All the samples analyzed contained significant number of crystals. All samples contained more than one type of crystal. The commonest crystals encountered included calcium oxalate monohydrate (whewellite 22%), calcium oxalate dihydrate (weddellite 32%), uric acid (10%), calcium phosphates, namely, apatite (4%), brushite (6%), struvite (6%) and octocalcium phosphate (2%). The morphological appearances of urinary crystals described were correlated with the wavelengths obtained through elemental distribution analysis. Various urinary crystals that

Single Crystal Membranes

NASA Technical Reports Server (NTRS)

Stormont, R. W.; Morrison, A.

1974-01-01

Single crystal a- and c-axis tubes and ribbons of sodium beta-alumina and sodium magnesium beta-alumina were grown from sodium oxide rich melts. Additional experiments grew ribbon crystals containing sodium magnesium beta, beta double prime, beta triple prime, and beta quadruple prime. A high pressure crystal growth chamber, sodium oxide rich melts, and iridium for all surfaces in contact with the melt were combined with the edge-defined, film-fed growth technique to grow the single crystal beta-alumina tubes and ribbons. The crystals were characterized using metallographic and X-ray diffraction techniques, and wet chemical analysis was used to determine the sodium, magnesium, and aluminum content of the grown crystals.

Crystallization and Melt Removal at Arenal Volcano, Polytopic Vector Analysis

NASA Astrophysics Data System (ADS)

Hidalgo, P. J.; Vogel, T. A.; Bolge, L. L.; Ehrlich, R.; Alvarado, G. E.

2007-12-01

Tephra sequences ET3 and ET4 from Arenal volcano in Costa Rica have recently been interpreted to be a product of crystal fractionation by Bolge and coworkers in a series of papers (2004, 2006). The two tephra units are part of a sequence of 22 tephra units that represent a 7000 year span of the Arenal volcano activity. The tephro- stratigraphy has been described extensively by Melson (1982; 1994). The ET3 and ET4 tephras were interpreted (based on major- and trace-element, isotopic analyses of whole rocks and microchemical analyses of individual phases) as clear evidence of crystal separation by gravity settling (Bolge et al., 2004, 2006). The lower ET4 tephra sequence (andesitic and crystal poor) and the upper ET3 tephra (basaltic and crystal rich) represent an inverted snapshot of the magma chamber with contrasting geochemical properties. The ET3 sequence (deeper part of the magma chamber) has nearly constant composition with only a few elements varying stratigraphically (best represented by CaO). This is consistent with gradually decreasing amounts of melt in the upper part of ET3. The lower ET4 tephra (upper part of the magma chamber) contains large chemical gradients in both incompatible and compatible elements. In the present study we use whole-rock geochemical data from the recent tephra sequences ET3 and ET4 as inputs to Polytopic Vector Analysis (PVA) (for a review of this method see Vogel and coworkers, in press). With this method we produce a three end member solution that is consistent with crystallization of Olivine, plagioclase and pyroxene from the most mafic end member (EM1) resulting in a crystal rich mush zone. As crystallization progresses the compositions of the liquids are driven towards an intermediate end member (EM3), which has an intermediate composition liquid. At EM3 composition, rapid depletion of FeO, MgO and TiO2 by crystallization of Fe-Ti oxides, rapidly drives the liquid composition towards the silicic EM1 (incompatible element

Carbon agent chemical vapor transport growth of Ga2O3 crystal

NASA Astrophysics Data System (ADS)

Jie, Su; Tong, Liu; Jingming, Liu; Jun, Yang; Guiying, Shen; Yongbiao, Bai; Zhiyuan, Dong; Youwen, Zhao

2016-10-01

Beta-type gallium oxide (β-Ga2O3) is a new attractive material for optoelectronic devices. Different methods had been tried to grow high quality β-Ga2O3 crystals. In this work, crystal growth of Ga2O3 has been carried out by chemical vapor transport (CVT) method in a closed quartz tube using C as transport agent and sapphire wafer as seed. The CVT mass flux has been analyzed by theoretical calculations based on equilibrium thermodynamics and 1D diffusional mass transport. The crystal growth experimental results are in agreement with the theoretical predictions. Influence factors of Ga2O3 crystal growth, such as temperature distribution, amount of C as transport agent used, have also been discussed. Structural (XRD) and optical (Raman spectroscopy, photoluminescence spectrum) properties of the CVT-Ga2O3 crystal are presented. Project supported by the National Natural Science Foundation of China (Nos. 61474104, 61504131).

Pyroxenes as recorders of lunar basalt petrogenesis - Chemical trends due to crystal-liquid interaction.

NASA Technical Reports Server (NTRS)

Bence, A. E.; Papike, J. J.

1972-01-01

Review of the crystallization histories suggested by the chemical, crystallographic, morphological, and paragenetic relationships observed in pyroxenes from basalts collected on the Apollo 11, 12, 14, 15, and Luna 16 missions. Although the final stages of lunar basalt crystallization appear to be rapid near-surface events, the initial stages are shown to vary considerably among the different basalt types.

Improved Electrostatic Embedding for Fragment-Based Chemical Shift Calculations in Molecular Crystals.

PubMed

Hartman, Joshua D; Balaji, Ashwin; Beran, Gregory J O

2017-12-12

Fragment-based methods predict nuclear magnetic resonance (NMR) chemical shielding tensors in molecular crystals with high accuracy and computational efficiency. Such methods typically employ electrostatic embedding to mimic the crystalline environment, and the quality of the results can be sensitive to the embedding treatment. To improve the quality of this embedding environment for fragment-based molecular crystal property calculations, we borrow ideas from the embedded ion method to incorporate self-consistently polarized Madelung field effects. The self-consistent reproduction of the Madelung potential (SCRMP) model developed here constructs an array of point charges that incorporates self-consistent lattice polarization and which reproduces the Madelung potential at all atomic sites involved in the quantum mechanical region of the system. The performance of fragment- and cluster-based 1 H, 13 C, 14 N, and 17 O chemical shift predictions using SCRMP and density functionals like PBE and PBE0 are assessed. The improved embedding model results in substantial improvements in the predicted 17 O chemical shifts and modest improvements in the 15 N ones. Finally, the performance of the model is demonstrated by examining the assignment of the two oxygen chemical shifts in the challenging γ-polymorph of glycine. Overall, the SCRMP-embedded NMR chemical shift predictions are on par with or more accurate than those obtained with the widely used gauge-including projector augmented wave (GIPAW) model.

Hydrogen bonds in betaine-acid (1:1) crystals revealed by Raman and 13C chemical shift tensors

NASA Astrophysics Data System (ADS)

Ilczyszyn, Marek; Ilczyszyn, Maria M.

2017-06-01

H-bonds of five betaine-acid (1:1) crystals are considered by analysis of tensors based on the Raman scissoring mode and 13C chemical shift of the betaine -CO1O2- carboxylate group. The leading structural factor in these systems is the strongest H-bond linking the betaine and the acidic moieties, (O1⋯H-O)com. The Raman and NMR tensors are strongly related to its character and to the R(O1⋯O)com distance. Very high molecular polarizability variation due to the scissoring vibration was found for the betaine-selenious acid crystal. The probable reason is modest network of H-bonds in this case and relatively high proton polarizability of these bonds.

Struvite crystal growth inhibition by trisodium citrate and the formation of chemical complexes in growth solution

NASA Astrophysics Data System (ADS)

Prywer, Jolanta; Mielniczek-Brzóska, Ewa; Olszynski, Marcin

2015-05-01

Effect of trisodium citrate on the crystallization of struvite was studied. To evaluate such an effect an experiment of struvite growth from artificial urine was performed. The investigations are related to infectious urinary stones formation. The crystallization process was induced by the addition of aqueous ammonia solution to mimic the bacterial activity. The spectrophotometric results demonstrate that trisodium citrate increases induction time with respect to struvite formation and decreases the growth efficiency of struvite. The inhibitory effect of trisodium citrate on the nucleation and growth of struvite is explained in base of chemical speciation analysis. Such an analysis demonstrates that the inhibitory effect is related with the fact that trisodium citrate binds NH4 + and Mg2+ ions in the range of pH from 7 to 9.5 characteristic for struvite precipitation. The most important is the MgCit- complex whose concentration strongly depends on an increase in pH rather than on an increase in citrate concentrations.

Quantitative analysis of tridymite and cristobalite crystallized in rice husk ash by heating.

PubMed

Shinohara, Yasushi; Kohyama, Norihiko

2004-04-01

The quantities of two forms of crystalline silica, tridymite and cristobalite, in heated rice husk ash (RHA) samples were determined by X-ray diffraction (XRD) and chemical methods. Two RHA samples, containing 93% SiO2 and 2-3% K2O, were prepared from charcoaled rice husk products and heated to above 900 degrees C. The crystalline silica made up over 60-80% of the total silica in the heated RHA samples based on the XRD analysis. The crystalline phases in the two samples were somewhat different: The sample heated in the temperature range of 900 to 1,200 degrees C contained 52-62% cristobalite and 10-17% tridymite, but the other sample heated at a comparable temperature, above 1,100 degrees C, contained 46-66% tridymite and 37-16% cristobalite. Based on a correlation of lower tridymite crystallization temperature with higher potassium content, it was concluded that higher potassium levels were responsible for this difference. The pyrophosphoric acid analysis did not give exact results in the evaluation of total crystalline silica content in these RHA samples. As the combustion of rice husk was considered to cover the demands for energy and silica resource in Asian countries, cristobalite and tridymite crystallized in RHA by burning of rice husk should be assessed precisely by XRD analysis and the airborne dust in relevant workplace be controlled.

Morphological and ultrastructural comparative analysis of bone tissue after Er:YAG laser and surgical drill osteotomy.

PubMed

Panduric, Dragana Gabric; Juric, Ivona Bago; Music, Svetozar; Molčanov, Krešimir; Sušic, Mato; Anic, Ivica

2014-07-01

The purpose of this study was to analyze morphological, chemical, and crystallographic changes of bone tissue after osteotomy performed with an erbium:yttrium-aluminium-garnet (Er:YAG) laser and a low speed pilot drill. Bone blocks were prepared from porcine ribs, and on each block, two tunnel preparations were performed using the Er:YAG laser (pulse energy: 1000 mJ, pulse duration: 300 μs, pulse repetition rate: 20 Hz) or the low-speed surgical pilot drill. The morphological changes of the cortical and the spongious surface of the tunnel preparations were analyzed under the field emission scanning electron microscopy (FE-SEM) at low and high resolution. The distribution and the level of chemical elements in the treated surfaces were evaluated by qualitative and semiquantitative energy dispersive x-ray analysis (SEM-EDX). Diffraction x-ray analysis was used to detect any differences and thermally induced modifications of hydroxyapatite crystals. FE-SEM revealed sharp edges of the Er:YAG preparations, with empty intertrabecular spaces and no signs of carbonization. In the drill group, the surface of the preparations was smooth, completely covered with smear layer and microcracks, and with hairy-like irregularities on the edges. SEM-EDX analysis did not reveal any differences in the number of specific chemical elements between the laser and the drill group. There were no thermally induced modifications of hydroxyapatite crystal structure in the bone tissue in either group. The Er:YAG laser ablation did not cause any chemical or crystallographic changes of the bone tissue. Compared with the drill, Er:YAG laser created well-defined edges of the preparations, and cortical bone had no smear layer.

Chemical composition, crystal size and lattice structural changes after incorporation of strontium into biomimetic apatite.

PubMed

Li, Z Y; Lam, W M; Yang, C; Xu, B; Ni, G X; Abbah, S A; Cheung, K M C; Luk, K D K; Lu, W W

2007-03-01

Recently, strontium (Sr) as ranelate compound has become increasingly popular in the treatment of osteoporosis. However, the lattice structure of bone crystal after Sr incorporation is yet to be extensively reported. In this study, we synthesized strontium-substituted hydroxyapatite (Sr-HA) with different Sr content (0.3%, 1.5% and 15% Sr-HA in mole ratio) to simulate bone crystals incorporated with Sr. The changes in chemical composition and lattice structure of apetite after synthetic incorporation of Sr were evaluated to gain insight into bone crystal changes after incorporation of Sr. X-ray diffraction (XRD) patterns revealed that 0.3% and 1.5% Sr-HA exhibited single phase spectrum, which was similar to that of HA. However, 15% Sr-HA induced the incorporation of HPO4(2-) and more CO3(2-), the crystallinity reduced dramatically. Transmission electron microscopy (TEM) images showed that the crystal length and width of 0.3% and 1.5% Sr-HA increased slightly. Meanwhile, the length and width distribution were broadened and the aspect ratio decreased from 10.68+/-4.00 to 7.28+/-2.80. The crystal size and crystallinity of 15% Sr-HA dropped rapidly, which may suggest that the fundamental crystal structure is changed. The findings from this work indicate that current clinical dosage which usually results in Sr incorporation of below 1.5% may not change chemical composition and lattice structure of bone, while it will broaden the bone crystal size distribution and strengthen the bone.

Comparative analysis of surface wax in mature fruits between Satsuma mandarin (Citrus unshiu) and 'Newhall' navel orange (Citrus sinensis) from the perspective of crystal morphology, chemical composition and key gene expression.

PubMed

Wang, Jinqiu; Hao, Haohao; Liu, Runsheng; Ma, Qiaoli; Xu, Juan; Chen, Feng; Cheng, Yunjiang; Deng, Xiuxin

2014-06-15

Surface wax of mature Satsuma mandarin (Citrus unshiu) and 'Newhall' navel orange (Citrus sinensis) was analysed by crystal morphology, chemical composition, and gene expression levels. The epicuticular and total waxes of both citrus cultivars were mostly composed of aldehydes, alkanes, fatty acids and primary alcohols. The epicuticular wax accounted for 80% of the total wax in the Newhall fruits and was higher than that in the Satsuma fruits. Scanning electron microscopy showed that larger and more wax platelets were deposited on the surface of Newhall fruits than on the Satsuma fruits. Moreover, the expression levels of genes involved in the wax formation were consistent with the biochemical and crystal morphological analyses. These diversities of fruit wax between the two cultivars may contribute to the differences of fruit postharvest storage properties, which can provide important information for the production of synthetic wax for citrus fruits. Copyright © 2013 Elsevier Ltd. All rights reserved.

Crystallization Kinetics of a Solid Oxide Fuel Cell Seal Glass by Differential Thermal Analysis

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Gamble, Eleanor A.

2005-01-01

Crystallization kinetics of a barium calcium aluminosilicate glass (BCAS), a sealant material for planar solid oxide fuel cells, have been investigated by differential thermal analysis (DTA). From variation of DTA peak maximum temperature with heating rate, the activation energy for glass crystallization was calculated to be 259 kJ/mol. Development of crystalline phases on thermal treatments of the glass at various temperatures has been followed by powder x-ray diffraction. Microstructure and chemical composition of the crystalline phases were investigated by scanning electron microscopy and energy dispersive spectroscopic (EDS) analysis. BaSiO3 and hexacelsian (BaAl2Si2O8) were the primary crystalline phases whereas monoclinic celsian (BaAl2Si2O8) and (Ba(x), Ca(y))SiO4 were also detected as minor phases. Needle-shaped BaSiO3 crystals are formed first, followed by the formation of other phases at longer times of heat treatments. The glass does not fully crystallize even after long term heat treatments at 750 to 900 C.

Comparing Crystals

ERIC Educational Resources Information Center

Sharp, Janet; Hoiberg, Karen; Chumbley, Scott

2003-01-01

This standard lesson on identifying salt and sugar crystals expands into an opportunity for students to develop their observation, questioning, and modeling skills. Although sugar and salt may look similar, students discovered that they looked very different under a magnifying glass and behaved differently when dissolved in water. In addition,…

Carboxylic acids in crystallization of macromolecules: learning from successful crystallization experiments.

PubMed

Offermann, Lesa R; He, John Z; Mank, Nicholas J; Booth, William T; Chruszcz, Maksymilian

2014-03-01

The production of macromolecular crystals suitable for structural analysis is one of the most important and limiting steps in the structure determination process. Often, preliminary crystallization trials are performed using hundreds of empirically selected conditions. Carboxylic acids and/or their salts are one of the most popular components of these empirically derived crystallization conditions. Our findings indicate that almost 40 % of entries deposited to the Protein Data Bank (PDB) reporting crystallization conditions contain at least one carboxylic acid. In order to analyze the role of carboxylic acids in macromolecular crystallization, a large-scale analysis of the successful crystallization experiments reported to the PDB was performed. The PDB is currently the largest source of crystallization data, however it is not easily searchable. These complications are due to a combination of a free text format, which is used to capture information on the crystallization experiments, and the inconsistent naming of chemicals used in crystallization experiments. Despite these difficulties, our approach allows for the extraction of over 47,000 crystallization conditions from the PDB. Initially, the selected conditions were investigated to determine which carboxylic acids or their salts are most often present in crystallization solutions. From this group, selected sets of crystallization conditions were analyzed in detail, assessing parameters such as concentration, pH, and precipitant used. Our findings will lead to the design of new crystallization screens focused around carboxylic acids.

Crystal Data

National Institute of Standards and Technology Data Gateway

SRD 3 NIST Crystal Data (PC database for purchase)   NIST Crystal Data contains chemical, physical, and crystallographic information useful to characterize more than 237,671 inorganic and organic crystalline materials. The data include the standard cell parameters, cell volume, space group number and symbol, calculated density, chemical formula, chemical name, and classification by chemical type.

Introducing uncertainty analysis of nucleation and crystal growth models in Process Analytical Technology (PAT) system design of crystallization processes.

PubMed

Samad, Noor Asma Fazli Abdul; Sin, Gürkan; Gernaey, Krist V; Gani, Rafiqul

2013-11-01

This paper presents the application of uncertainty and sensitivity analysis as part of a systematic model-based process monitoring and control (PAT) system design framework for crystallization processes. For the uncertainty analysis, the Monte Carlo procedure is used to propagate input uncertainty, while for sensitivity analysis, global methods including the standardized regression coefficients (SRC) and Morris screening are used to identify the most significant parameters. The potassium dihydrogen phosphate (KDP) crystallization process is used as a case study, both in open-loop and closed-loop operation. In the uncertainty analysis, the impact on the predicted output of uncertain parameters related to the nucleation and the crystal growth model has been investigated for both a one- and two-dimensional crystal size distribution (CSD). The open-loop results show that the input uncertainties lead to significant uncertainties on the CSD, with appearance of a secondary peak due to secondary nucleation for both cases. The sensitivity analysis indicated that the most important parameters affecting the CSDs are nucleation order and growth order constants. In the proposed PAT system design (closed-loop), the target CSD variability was successfully reduced compared to the open-loop case, also when considering uncertainty in nucleation and crystal growth model parameters. The latter forms a strong indication of the robustness of the proposed PAT system design in achieving the target CSD and encourages its transfer to full-scale implementation. Copyright © 2013 Elsevier B.V. All rights reserved.

Crystallization dynamics in glass-forming systems

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

Cullinan, Timothy Edward

Crystallization under far-from-equilibrium conditions is investigated for two different scenarios: crystallization of the metallic glass alloy Cu 50Zr 50 and solidification of a transparent organic compound, o-terphenyl. For Cu 50Zr 50, crystallization kinetics are quanti ed through a new procedure that directly fits thermal analysis data to the commonly utilized JMAK model. The phase evolution during crystallization is quantified through in-situ measurements (HEXRD, DSC) and ex-situ microstructural analysis (TEM, HRTEM). The influence of chemical partitioning, diffusion, and crystallographic orientation on this sequence are examined. For o-terphenyl, the relationship between crystal growth velocity and interface undercooling is systematically studied via directionalmore » solidification.« less

Comparative analysis of chemical similarity methods for modular natural products with a hypothetical structure enumeration algorithm.

PubMed

Skinnider, Michael A; Dejong, Chris A; Franczak, Brian C; McNicholas, Paul D; Magarvey, Nathan A

2017-08-16

Natural products represent a prominent source of pharmaceutically and industrially important agents. Calculating the chemical similarity of two molecules is a central task in cheminformatics, with applications at multiple stages of the drug discovery pipeline. Quantifying the similarity of natural products is a particularly important problem, as the biological activities of these molecules have been extensively optimized by natural selection. The large and structurally complex scaffolds of natural products distinguish their physical and chemical properties from those of synthetic compounds. However, no analysis of the performance of existing methods for molecular similarity calculation specific to natural products has been reported to date. Here, we present LEMONS, an algorithm for the enumeration of hypothetical modular natural product structures. We leverage this algorithm to conduct a comparative analysis of molecular similarity methods within the unique chemical space occupied by modular natural products using controlled synthetic data, and comprehensively investigate the impact of diverse biosynthetic parameters on similarity search. We additionally investigate a recently described algorithm for natural product retrobiosynthesis and alignment, and find that when rule-based retrobiosynthesis can be applied, this approach outperforms conventional two-dimensional fingerprints, suggesting it may represent a valuable approach for the targeted exploration of natural product chemical space and microbial genome mining. Our open-source algorithm is an extensible method of enumerating hypothetical natural product structures with diverse potential applications in bioinformatics.

Comparative Analysis of Hexagonal Solid Silica and Nitro-benzene Filled Hollow Core Photonic Crystal Fiber

NASA Astrophysics Data System (ADS)

Shahiruddin; Singh, Dharmendra K.; Hassan, M. A.

2018-02-01

A comparative study of five ring solid core and nitrobenzene filled hollow core liquid filled photonic crystal fiber (PCF) are presented. Considering the same structure, one is used as solid silica and another one is filled with nitrobenzene in the core. Here the paper elaborates the confinement loss, dispersion properties and birefringence of an index-guiding PCF with asymmetric cladding designed and analyzed by the finite-element method. The proposed structure shows the low confinement loss in case of solid silica, negative dispersion in nitrobenzene filled hollow core PCF and high birefringence in both the cases. The calculated values shows flat zero confinement loss in 0.7 µm to 1.54 µm range, flat zero dispersion is achieved in solid core and -2000 ps/km-nm in nitrobenzene filled hollow core PCF and high birefringence in the range of 10-3 in nitrobenzene filled hollow core PCF. Results show the relative analysis at different air fill fraction.

Increasing dissolution of trospium chloride by co-crystallization with urea

NASA Astrophysics Data System (ADS)

Skořepová, Eliška; Hušák, Michal; Čejka, Jan; Zámostný, Petr; Kratochvíl, Bohumil

2014-08-01

The search for various solid forms of an active pharmaceutical ingredient (API) is an important step in drug development. Our aim was to prepare co-crystals of trospium chloride, an anticholinergic drug used for the treatment of incontinence, and to investigate if they have advantageous properties for drug formulation. Phase identification was done by powder X-ray diffraction and single-crystal X-ray diffraction. The chemical composition was verified by solution NMR and the dissolution rate of the prepared phases was studied by IDR (intrinsic dissolution rate). For further analysis of phase stability and transitions, combined thermal analysis and temperature-resolved X-ray powder diffraction were used. Urea was selected as a co-crystallization partner. Trospium chloride urea (1:1) co-crystal was prepared by a solvent evaporation. From single-crystal data, the co-crystal structure was solved in a space group P21/c and compared to previously published structures of trospium chloride. Intrinsic dissolution rate revealed that the co-crystal dissolves 32% faster than pure API. However, its low thermal and pressure stability makes it a challenging choice for the final drug formulation.

Epicuticular Wax Crystals of Wollemia nobilis: Morphology and Chemical Composition

PubMed Central

Dragota, Simona; Riederer, Markus

2007-01-01

Background and Aims The morphology of the epicuticular leaf waxes of Wollemia nobilis (Araucariaceae) was studied with special emphasis on the relationship between the microstructure of epicuticular wax crystals and their chemical composition. Wollemia nobilis is a unique coniferous tree of the family Araucariaceae and is of very high scientific value as it is the sole living representative of an ancient genus, which until 1994 was known only from fossils. Methods Scanning electron microscopy (SEM), gas chromatography (GC) combined with mass spectrometry (GC–MS) and nuclear magnetic resonance spectroscopy (NMR) were used for characterizing the morphology and the chemical structure of the epicuticular wax layer of W. nobilis needles. Key Results The main component of the leaf epicuticular wax of W. nobilis is nonacosan-10-ol. This secondary alcohol together with nonacosane diols is responsible for the tubular habit of the epicuticular wax crystals. Scanning electron micrographs revealed differences in the fine structure of adaxial and abaxial leaf surfaces that could be explained by gas chromatographic studies after selective mechanical removal of the waxes. Conclusions SEM investigations established the tubular crystalline microstructure of the epicuticular wax of W. nobilis leaves. GC–MS and NMR experiments showed that nonacosan-10-ol is the major constituent of the epicuticular wax of W. nobilis leaves. PMID:17611192

Crystal growth, structure analysis and characterisation of 2 - (1, 3 - dioxoisoindolin - 2 - yl) acetic acid single crystal

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

Sankari, R. Siva, E-mail: sivasankari.sh@act.edu.in; Perumal, Rajesh Narayana

2014-04-24

Single crystal of dielectric material 2 - (1, 3 - dioxoisoindolin - 2 - yl) acetic acid has been grown by slow evaporation solution growth method. The grown crystal was harvested in 25 days. The crystal structure was analyzed by Single crystal X - ray diffraction. UV-vis-NIR analysis was performed to examine the optical property of the grown crystal. The thermal property of the grown crystal was studied by thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The dielectric measurements were carried out and the dielectric constant was calculated and plotted at all frequencies.

A strategic approach to physico-chemical analysis of bis (thiourea) lead chloride - A reliable semi-organic nonlinear optical crystal

NASA Astrophysics Data System (ADS)

Rajagopalan, N. R.; Krishnamoorthy, P.; Jayamoorthy, K.

2017-03-01

Good quality crystals of bis thiourea lead chloride (BTLC) have been grown by slow evaporation method from aqueous solution. Orthorhombic structure and Pna21 space group of the crystals have been identified by single crystal X-ray diffraction. Studies on nucleation kinetics of grown BTLC has been carried out from which meta-stable zone width, induction period, free energy change, critical radius, critical number and growth rate have been calculated. The experimental values of interfacial surface energy for the crystal growth process have been compared with theoretical models. Ultra violet transmittance studies resulted in a high transmittance and wide band gap energy suggested the required optical transparency of the crystal. The second harmonic generation (SHG) and phase matching nature of the crystal have been justified by Kurtz-Perry method. The SHG nature of the crystal has been further attested by the higher values of theoretical hyper polarizability. The dielectric nature of the crystals at different temperatures with varying frequencies has been thoroughly studied. The activation energy values of the electrical process have been calculated from ac conductivity study. Solid state parameters including valence electron plasma energy, Penn gap, Fermi energy and polarisability have been unveiled by theoretical approach and correlated with the crystal's SHG efficiency. The values of hardness number, elastic stiffness constant, Meyer's Index, minimum level of indentation load, load dependent constant, fracture toughness, brittleness index and corrected hardness obtained from Vicker's hardness test clearly showed that the BTLC crystal has good mechanical stability required for NLO device fabrication.

Benchmark fragment-based (1)H, (13)C, (15)N and (17)O chemical shift predictions in molecular crystals.

PubMed

Hartman, Joshua D; Kudla, Ryan A; Day, Graeme M; Mueller, Leonard J; Beran, Gregory J O

2016-08-21

The performance of fragment-based ab initio(1)H, (13)C, (15)N and (17)O chemical shift predictions is assessed against experimental NMR chemical shift data in four benchmark sets of molecular crystals. Employing a variety of commonly used density functionals (PBE0, B3LYP, TPSSh, OPBE, PBE, TPSS), we explore the relative performance of cluster, two-body fragment, and combined cluster/fragment models. The hybrid density functionals (PBE0, B3LYP and TPSSh) generally out-perform their generalized gradient approximation (GGA)-based counterparts. (1)H, (13)C, (15)N, and (17)O isotropic chemical shifts can be predicted with root-mean-square errors of 0.3, 1.5, 4.2, and 9.8 ppm, respectively, using a computationally inexpensive electrostatically embedded two-body PBE0 fragment model. Oxygen chemical shieldings prove particularly sensitive to local many-body effects, and using a combined cluster/fragment model instead of the simple two-body fragment model decreases the root-mean-square errors to 7.6 ppm. These fragment-based model errors compare favorably with GIPAW PBE ones of 0.4, 2.2, 5.4, and 7.2 ppm for the same (1)H, (13)C, (15)N, and (17)O test sets. Using these benchmark calculations, a set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided and their robustness assessed using statistical cross-validation. We demonstrate the utility of these approaches and the reported scaling parameters on applications to 9-tert-butyl anthracene, several histidine co-crystals, benzoic acid and the C-nitrosoarene SnCl2(CH3)2(NODMA)2.

Comparative structural analysis of human DEAD-box RNA helicases.

PubMed

Schütz, Patrick; Karlberg, Tobias; van den Berg, Susanne; Collins, Ruairi; Lehtiö, Lari; Högbom, Martin; Holmberg-Schiavone, Lovisa; Tempel, Wolfram; Park, Hee-Won; Hammarström, Martin; Moche, Martin; Thorsell, Ann-Gerd; Schüler, Herwig

2010-09-30

DEAD-box RNA helicases play various, often critical, roles in all processes where RNAs are involved. Members of this family of proteins are linked to human disease, including cancer and viral infections. DEAD-box proteins contain two conserved domains that both contribute to RNA and ATP binding. Despite recent advances the molecular details of how these enzymes convert chemical energy into RNA remodeling is unknown. We present crystal structures of the isolated DEAD-domains of human DDX2A/eIF4A1, DDX2B/eIF4A2, DDX5, DDX10/DBP4, DDX18/myc-regulated DEAD-box protein, DDX20, DDX47, DDX52/ROK1, and DDX53/CAGE, and of the helicase domains of DDX25 and DDX41. Together with prior knowledge this enables a family-wide comparative structural analysis. We propose a general mechanism for opening of the RNA binding site. This analysis also provides insights into the diversity of DExD/H- proteins, with implications for understanding the functions of individual family members.

Comparative Structural Analysis of Human DEAD-Box RNA Helicases

PubMed Central

Schütz, Patrick; Karlberg, Tobias; van den Berg, Susanne; Collins, Ruairi; Lehtiö, Lari; Högbom, Martin; Holmberg-Schiavone, Lovisa; Tempel, Wolfram; Park, Hee-Won; Hammarström, Martin; Moche, Martin; Thorsell, Ann-Gerd; Schüler, Herwig

2010-01-01

DEAD-box RNA helicases play various, often critical, roles in all processes where RNAs are involved. Members of this family of proteins are linked to human disease, including cancer and viral infections. DEAD-box proteins contain two conserved domains that both contribute to RNA and ATP binding. Despite recent advances the molecular details of how these enzymes convert chemical energy into RNA remodeling is unknown. We present crystal structures of the isolated DEAD-domains of human DDX2A/eIF4A1, DDX2B/eIF4A2, DDX5, DDX10/DBP4, DDX18/myc-regulated DEAD-box protein, DDX20, DDX47, DDX52/ROK1, and DDX53/CAGE, and of the helicase domains of DDX25 and DDX41. Together with prior knowledge this enables a family-wide comparative structural analysis. We propose a general mechanism for opening of the RNA binding site. This analysis also provides insights into the diversity of DExD/H- proteins, with implications for understanding the functions of individual family members. PMID:20941364

Comparing Alternatives For Replacing Harmful Chemicals

NASA Technical Reports Server (NTRS)

Cruit, W.; Schutzenhofer, S.; Goldberg, B.; Everhart, K.

1995-01-01

Methodology developed to provide guidance for replacement of industrial chemicals that must be phased out by law because they are toxic and/or affect environment adversely. Chemicals and processes ranked numerically. Applies mostly to chemicals contributing to depletion of ozone in upper atmosphere; some other harmful chemicals included. Quality function deployment matrix format provides convenient way to compare alternative processes and chemicals. Overall rating at bottom of each process-and-chemical column indicates relative advantage.

The importance of proper crystal-chemical and geometrical reasoning demonstrated using layered single and double hydroxides

PubMed Central

Richardson, Ian G.

2013-01-01

Atomistic modelling techniques and Rietveld refinement of X-ray powder diffraction data are widely used but often result in crystal structures that are not realistic, presumably because the authors neglect to check the crystal-chemical plausibility of their structure. The purpose of this paper is to reinforce the importance and utility of proper crystal-chemical and geometrical reasoning in structural studies. It is achieved by using such reasoning to generate new yet fundamental information about layered double hydroxides (LDH), a large, much-studied family of compounds. LDH phases are derived from layered single hydroxides by the substitution of a fraction (x) of the divalent cations by trivalent. Equations are derived that enable calculation of x from the a parameter of the unit cell and vice versa, which can be expected to be of widespread utility as a sanity test for extant and future structure determinations and computer simulation studies. The phase at x = 0 is shown to be an α form of divalent metal hydroxide rather than the β polymorph. Crystal-chemically sensible model structures are provided for β-Zn(OH)2 and Ni- and Mg-based carbonate LDH phases that have any trivalent cation and any value of x, including x = 0 [i.e. for α-M(OH)2·mH2O phases]. PMID:23719702

Synthesis and crystal structure analysis of uranyl triple acetates

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

Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com; Department of Chemistry, Samara National Research University, 443086 Samara; Serezhkina, Larisa B.

2016-12-15

Single crystals of triple acetates NaR[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O (R=Mg, Co, Ni, Zn), well-known for their use as reagents for sodium determination, were grown from aqueous solutions and their structural and spectroscopic properties were studied. Crystal structures of the mentioned phases are based upon (Na[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}){sup 2–} clusters and [R(H{sub 2}O){sub 6}]{sup 2+} aqua-complexes. The cooling of a single crystal of NaMg[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O from 300 to 100 K leads to a phase transition from trigonal to monoclinic crystal system. Intermolecular interactions between the structural units and their mutual packing were studiedmore » and compared from the point of view of the stereoatomic model of crystal structures based on Voronoi-Dirichlet tessellation. Using this method we compared the crystal structures of the triple acetates with Na[UO{sub 2}(CH{sub 3}COO){sub 3}] and [R(H{sub 2}O){sub 6}][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} and proposed reasons of triple acetates stability. Infrared and Raman spectra were collected and their bands were assigned. - Graphical abstract: Single crystals of uranium based triple acetates, analytical reagents for sodium determination, were synthesized and structurally, spectroscopically and topologically characterized. The structures were compared with the structures of compounds from preceding families [M(H{sub 2}O){sub 6})][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} (M = Mg, Co, Ni, Zn) and Na[UO{sub 2}(CH{sub 3}COO){sub 3}]. Analysis was performed with the method of molecular Voronoi-Dirichlet polyhedra to reveal a large contribution of the hydrogen bonds into intermolecular interactions which can be a reason of low solubility of studied complexes.« less

Synthesis, crystal structures and spectroscopic properties of triazine-based hydrazone derivatives; a comparative experimental-theoretical study.

PubMed

Arshad, Muhammad Nadeem; Bibi, Aisha; Mahmood, Tariq; Asiri, Abdullah M; Ayub, Khurshid

2015-04-03

We report here a comparative theoretical and experimental study of four triazine-based hydrazone derivatives. The hydrazones are synthesized by a three step process from commercially available benzil and thiosemicarbazide. The structures of all compounds were determined by using the UV-Vis., FT-IR, NMR (1H and 13C) spectroscopic techniques and finally confirmed unequivocally by single crystal X-ray diffraction analysis. Experimental geometric parameters and spectroscopic properties of the triazine based hydrazones are compared with those obtained from density functional theory (DFT) studies. The model developed here comprises of geometry optimization at B3LYP/6-31G (d, p) level of DFT. Optimized geometric parameters of all four compounds showed excellent correlations with the results obtained from X-ray diffraction studies. The vibrational spectra show nice correlations with the experimental IR spectra. Moreover, the simulated absorption spectra also agree well with experimental results (within 10-20 nm). The molecular electrostatic potential (MEP) mapped over the entire stabilized geometries of the compounds indicated their chemical reactivates. Furthermore, frontier molecular orbital (electronic properties) and first hyperpolarizability (nonlinear optical response) were also computed at the B3LYP/6-31G (d, p) level of theory.

Analysis of submicron-sized niflumic acid crystals prepared by electrospray crystallization.

PubMed

Ambrus, Rita; Radacsi, Norbert; Szunyogh, Tímea; van der Heijden, Antoine E D M; Ter Horst, Joop H; Szabó-Révész, Piroska

2013-03-25

Interest in submicron-sized drug particles has emerged from both laboratory and industrial perspectives in the last decade. Production of crystals in the nano size scale offers a novel way to particles for drug formulation solving formulation problems of drugs with low solubility in class II of the Biopharmaceutical Classification System. In this work niflumic acid nanoparticles with a size range of 200-800nm were produced by the novel crystallization method, electrospray crystallization. Their properties were compared to those from evaporative and anti-solvent crystallizations, using the same organic solvent, acetone. There is a remarkable difference in the product crystal size depending on the applied methods. The size and morphology were analyzed by scanning electron microscopy and laser diffraction. The structure of the samples was investigated using differential scanning calorimetry, Fourier-transformed infrared spectroscopy and X-ray powder diffraction. The particles produced using electrospray crystallization process were probably changing from amorphous to crystalline state after the procedure. Copyright © 2012 Elsevier B.V. All rights reserved.

Flowsheet Analysis of U-Pu Co-Crystallization Process as a New Reprocessing System

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

Shunji Homma; Jun-ichi Ishii; Jiro Koga

2006-07-01

A new fuel reprocessing system by U-Pu co-crystallization process is proposed and examined by flowsheet analysis. This reprocessing system is based on the fact that hexavalent plutonium in nitric acid solution is co-crystallized with uranyl nitrate, whereas it is not crystallized when uranyl nitrate does not exist in the solution. The system consists of five steps: dissolution of spent fuel, plutonium oxidation, U-Pu co-crystallization as a co-decontamination, re-dissolution of the crystals, and U re-crystallization as a U-Pu separation. The system requires a recycling of the mother liquor from the U-Pu co-crystallization step and the appropriate recycle ratio is determined bymore » flowsheet analysis such that the satisfactory decontamination is achieved. Further flowsheet study using four different compositions of LWR spent fuels demonstrates that the constant ratio of plutonium to uranium in mother liquor from the re-crystallization step is achieved for every composition by controlling the temperature. It is also demonstrated by comparing to the Purex process that the size of the plant based on the proposed system is significantly reduced. (authors)« less

Modeling Conformal Growth in Photonic Crystals and Comparing to Experiment

NASA Astrophysics Data System (ADS)

Brzezinski, Andrew; Chen, Ying-Chieh; Wiltzius, Pierre; Braun, Paul

2008-03-01

Conformal growth, e.g. atomic layer deposition (ALD), of materials such as silicon and TiO2 on three dimensional (3D) templates is important for making photonic crystals. However, reliable calculations of optical properties as a function of the conformal growth, such as the optical band structure, are hampered by difficultly in accurately assessing a deposited material's spatial distribution. A widely used approximation ignores ``pinch off'' of precursor gas and assumes complete template infilling. Another approximation results in non-uniform growth velocity by employing iso-intensity surfaces of the 3D interference pattern used to create the template. We have developed an accurate model of conformal growth in arbitrary 3D periodic structures, allowing for arbitrary surface orientation. Results are compared with the above approximations and with experimentally fabricated photonic crystals. We use an SU8 polymer template created by 4-beam interference lithography, onto which various amounts of TiO2 are grown by ALD. Characterization is performed by analysis of cross-sectional scanning electron micrographs and by solid angle resolved optical spectroscopy.

Semiconducting molecular crystals: Bulk in-gap states modified by structural and chemical defects

NASA Astrophysics Data System (ADS)

Haas, S.; Krellner, C.; Goldmann, C.; Pernstich, K. P.; Gundlach, D. J.; Batlogg, B.

2007-03-01

Charge transport in organic molecular crystals is strongly influenced by the density of localized in-gap states (traps). Thus, a profound knowledge of the defect states' origin is essential. Temperature-dependent space-charge limited current (TD-SCLC) spectroscopy was used as a powerful tool to quantitatively study the density of states (DOS) in high-quality rubrene and pentacene single crystals. In particular, changes of the DOS due to intentionally induced chemical and structural defects were monitored. For instance, the controlled exposure of pentacene and rubrene to x-ray radiation results in a broad over-all increase of the DOS. Namely, the ionizing radiation induces a variety of both chemical and structural defects. On the other hand, exposure of rubrene to UV-excited oxygen is reflected in a sharp peak in the DOS, whereas in a similar experiment with pentacene oxygen acts as a dopant, and possible defects are metastable on the time-scale of the measurement, thus leaving the extracted DOS virtually unchanged.

Vibrational spectra and natural bond orbital analysis of organic crystal L-prolinium picrate

NASA Astrophysics Data System (ADS)

Edwin, Bismi; Amalanathan, M.; Hubert Joe, I.

2012-10-01

Vibrational spectral analysis and quantum chemical computations based on density functional theory (DFT) have been performed on the organic crystal L-prolinium picrate (LPP). The equilibrium geometry, various bonding features and harmonic vibrational wavenumbers of LPP have been investigated using B3LYP method. The calculated molecular geometry has been compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with the aid of VEDA 4 program. The various intramolecular interactions confirming the biological activity of the compound have been exposed by natural bond orbital analysis. The distribution of Mulliken atomic charges and bending of natural hybrid orbitals associated with hydrogen bonding also reflects the presence of intramolecular hydrogen bonding thereby enhancing bioactivity. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and low value of energy gap indicates electron transport in the molecule and thereby bioactivity. Vibrational analysis reveals the presence of strong O-H⋯O and N-H⋯O interaction between L-prolinium and picrate ions providing evidence for the charge transfer interaction between the donor and acceptor groups and is responsible for its bioactivity.

Conformational, structural, vibrational and quantum chemical analysis on 4-aminobenzohydrazide and 4-hydroxybenzohydrazide--a comparative study.

PubMed

Arjunan, V; Jayaprakash, A; Carthigayan, K; Periandy, S; Mohan, S

2013-05-01

Experimental and theoretical quantum chemical studies were carried out on 4-hydroxybenzohydrazide (4HBH) and 4-aminobenzohydrazide (4ABH) using FTIR and FT-Raman spectral data. The structural characteristics and vibrational spectroscopic analysis were carried performed by quantum chemical methods with the hybrid exchange-correlation functional B3LYP using 6-31G(**), 6-311++G(**) and aug-cc-pVDZ basis sets. The most stable conformer of the title compounds have been determined from the analysis of potential energy surface. The stable molecular geometries, electronic and thermodynamic parameters, IR intensities, harmonic vibrational frequencies, depolarisation ratio and Raman intensities have been computed. Molecular electrostatic potential and frontier molecular orbitals were constructed to understand the electronic properties. The potential energy distributions (PEDs) were calculated to explain the mixing of fundamental modes. The theoretical geometrical parameters and the fundamental frequencies were compared with the experimental. The interactions of hydroxy and amino group substitutions on the characteristic vibrations of the ring and hydrazide group have been analysed. Copyright © 2013 Elsevier B.V. All rights reserved.

Enhanced NMR Discrimination of Pharmaceutically Relevant Molecular Crystal Forms through Fragment-Based Ab Initio Chemical Shift Predictions.

PubMed

Hartman, Joshua D; Day, Graeme M; Beran, Gregory J O

2016-11-02

Chemical shift prediction plays an important role in the determination or validation of crystal structures with solid-state nuclear magnetic resonance (NMR) spectroscopy. One of the fundamental theoretical challenges lies in discriminating variations in chemical shifts resulting from different crystallographic environments. Fragment-based electronic structure methods provide an alternative to the widely used plane wave gauge-including projector augmented wave (GIPAW) density functional technique for chemical shift prediction. Fragment methods allow hybrid density functionals to be employed routinely in chemical shift prediction, and we have recently demonstrated appreciable improvements in the accuracy of the predicted shifts when using the hybrid PBE0 functional instead of generalized gradient approximation (GGA) functionals like PBE. Here, we investigate the solid-state 13 C and 15 N NMR spectra for multiple crystal forms of acetaminophen, phenobarbital, and testosterone. We demonstrate that the use of the hybrid density functional instead of a GGA provides both higher accuracy in the chemical shifts and increased discrimination among the different crystallographic environments. Finally, these results also provide compelling evidence for the transferability of the linear regression parameters mapping predicted chemical shieldings to chemical shifts that were derived in an earlier study.

Enhanced NMR Discrimination of Pharmaceutically Relevant Molecular Crystal Forms through Fragment-Based Ab Initio Chemical Shift Predictions

PubMed Central

2016-01-01

Chemical shift prediction plays an important role in the determination or validation of crystal structures with solid-state nuclear magnetic resonance (NMR) spectroscopy. One of the fundamental theoretical challenges lies in discriminating variations in chemical shifts resulting from different crystallographic environments. Fragment-based electronic structure methods provide an alternative to the widely used plane wave gauge-including projector augmented wave (GIPAW) density functional technique for chemical shift prediction. Fragment methods allow hybrid density functionals to be employed routinely in chemical shift prediction, and we have recently demonstrated appreciable improvements in the accuracy of the predicted shifts when using the hybrid PBE0 functional instead of generalized gradient approximation (GGA) functionals like PBE. Here, we investigate the solid-state 13C and 15N NMR spectra for multiple crystal forms of acetaminophen, phenobarbital, and testosterone. We demonstrate that the use of the hybrid density functional instead of a GGA provides both higher accuracy in the chemical shifts and increased discrimination among the different crystallographic environments. Finally, these results also provide compelling evidence for the transferability of the linear regression parameters mapping predicted chemical shieldings to chemical shifts that were derived in an earlier study. PMID:27829821

Local crystal/chemical structures at iron sites in amorphous, magnetic, and nanocrystalline materials

NASA Astrophysics Data System (ADS)

Clark, Ted Michael

Order-disorder phenomena have been examined by means of Mossbauer spectroscopy in a variety of materials, including (a) tektites and other silicate glasses, (b) magnetic materials such as natural and synthetic magnetoplumbite, M-type hexagonal ferrites and magnetite, and (c) nanocrystalline zinc ferrite. A methodology has been established for the analysis of the local crystal/chemical structures of iron in tektites and its application has reconfirmed a low ferric/ferrous ratio of approximately 0.10 for tektites. Additionally, a greater degree of submirocscopic heterogeneity has been established for Muong Nong tektites in comparison with splash form tektites. The dynamics of the 2b site in hexagonal ferrites has been studied above and below the Curie temperature for magnetoplumbite and its synthetic analogs, and also for polycrystalline and oriented single-crystals of MeFesb{12}Osb{19} (Me=Ba, Sr, Pb). Cation ordering on this site is shown to be dependent on the thermal history of the material, while the dynamic disorder of the 2b site for the end-member hexagonal ferrites is shown to be influenced by the divalent heavy metal species, Me. The influence of chemical composition on the morphology of magnetite has been shown to depend on the site preference of impurity cations: Substitutional impurities with tetrahedral site preferences are postulated to result in the seldom-observed cubic habit. Based on the cation distributions of bulk and nanocrystalline material it is held that the enhanced magnetic moments and susceptibilities of nanocrystalline zinc ferrite are shown to be consistent with surface phenomena, independent of synthesis methodology, and contrary to claims of special effects resulting from a particular synthesis methodology.

Crystal Growth of Graphene Films and Graphene Nanoribbons via Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Jacobberger, Robert Michael

Graphene is a two-dimensional carbon allotrope that has exceptional properties, including high charge carrier mobility, thermal conductivity, mechanical strength, and flexibility. Graphene is a semimetal, prohibiting its use in semiconductor applications in which a bandgap is required. However, graphene can be transformed from a semimetal into a semiconductor if it is confined into one-dimensional nanoribbons narrower than 10 nm with well-defined armchair edges. In this work, we study the crystal growth of graphene via chemical vapor deposition (CVD), which is the most promising method to produce graphene films on the industrial scale. We explore the growth of isolated graphene crystals, continuous graphene films, and narrow graphene nanoribbons with armchair edges. We gain key insight into the critical growth parameters and mechanisms that influence the crystal morphology, orientation, defect density, and evolution, providing an empirical understanding of the diverse growth behaviors observed in literature. Using this knowledge, we synthesize graphene with remarkably low pinhole density and achieve high-quality graphene at 750 °C on Cu(111), which is over 250 °C lower than the temperature typically used to grow graphene on copper from methane. We also describe our breakthrough in graphene nanoribbon synthesis. Highly anisotropic nanoribbons are formed on Ge(001) if an exceptionally slow growth rate is used. The nanoribbons are self-defining with predominantly smooth armchair edges, are self-aligning, and have tunable width to < 10 nm. High-performance field-effect transistors incorporating these nanoribbons as channels display high conductance modulation > 10,000 and high conductance > 5 muS. This directional and anisotropic growth enables the fabrication of semiconducting nanoribbons directly on conventional semiconductor wafers and, thus, promises to allow the integration of nanoribbons into future hybrid integrated circuits. We additionally report our

An extended chemical analysis of gallstone.

PubMed

Chandran, P; Kuchhal, N K; Garg, P; Pundir, C S

2007-09-01

Chemical composition of gall stones is essential for aetiopathogensis of gallstone disease. We have reported quantitative chemical analysis of total cholesterol bilirubin, calcium, iron and inorganic phosphate in 120 gallstones from haryana. To extend this chemical analysis of gall stones by studying more cases and by analyzing more chemical constituents. A quantitative chemical analysis of total cholesterol, total bilirubin, fatty acids, triglycerides, phospholipids, bile acids, soluble proteins, sodium potassium, magnesium, copper, oxalate and chlorides of biliary calculi (52 cholesterol, 76 mixed and 72 pigment) retrieved from surgical operation of 200 patients from Haryana state was carried out. Total cholesterol as the major component and total bilirubin, phospholipids, triglycerides, bile acids, fatty acids (esterified), soluble protein, calcium, magnesium, iron, copper, sodium, potassium, inorganic phosphate, oxalate and chloride as minor components were found in all types of calculi. The cholesterol stones had higher content of total cholesterol, phospholipids, fatty acids (esterified), inorganic phosphate and copper compared to mixed and pigment stones. The mixed stones had higher content of iron and triglycerides than to cholesterol and pigment stones. The pigment stones were richer in total bilirubin, bile acids, calcium, oxalate, magnesium, sodium, potassium, chloride and soluble protein compared to cholesterol and mixed stones. Although total cholesterol was a major component of cholesterol, mixed and pigment gall stone in Haryana, the content of most of the other lipids, cations and anions was different in different gall stones indicating their different mechanism of formation.

The 5S rRNA loop E: chemical probing and phylogenetic data versus crystal structure.

PubMed

Leontis, N B; Westhof, E

1998-09-01

A significant fraction of the bases in a folded, structured RNA molecule participate in noncanonical base pairing interactions, often in the context of internal loops or multi-helix junction loops. The appearance of each new high-resolution RNA structure provides welcome data to guide efforts to understand and predict RNA 3D structure, especially when the RNA in question is a functionally conserved molecule. The recent publication of the crystal structure of the "Loop E" region of bacterial 5S ribosomal RNA is such an event [Correll CC, Freeborn B, Moore PB, Steitz TA, 1997, Cell 91:705-712]. In addition to providing more examples of already established noncanonical base pairs, such as purine-purine sheared pairings, trans-Hoogsteen UA, and GU wobble pairs, the structure provides the first high-resolution views of two new purine-purine pairings and a new GU pairing. The goal of the present analysis is to expand the capabilities of both chemical probing and phylogenetic analysis to predict with greater accuracy the structures of RNA molecules. First, in light of existing chemical probing data, we investigate what lessons could be learned regarding the interpretation of this widely used method of RNA structure probing. Then we analyze the 3D structure with reference to molecular phylogeny data (assuming conservation of function) to discover what alternative base pairings are geometrically compatible with the structure. The comparisons between previous modeling efforts and crystal structures show that the intricate involvements of ions and water molecules in the maintenance of non-Watson-Crick pairs render the process of correctly identifying the interacting sites in such pairs treacherous, except in cases of trans-Hoogsteen A/U or sheared A/G pairs for the adenine N1 site. The phylogenetic analysis identifies A/A, A/C, A/U and C/A, C/C, and C/U pairings isosteric with sheared A/G, as well as A/A and A/C pairings isosteric with both G/U and G/G bifurcated pairings

Phenylacetic acid co-crystals with acridine, caffeine, isonicotinamide and nicotinamide: Crystal structures, thermal analysis, FTIR spectroscopy and Hirshfeld surface analysis

NASA Astrophysics Data System (ADS)

Amombo Noa, Francoise M.; Jacobs, Ayesha

2017-07-01

Co-crystals of phenylacetic acid (PAA) with acridine (ACR), caffeine (CAF), isonicotinamide (INM) and nicotinamide (NAM) have been successfully prepared and characterised by single crystal X-ray diffraction, FTIR spectroscopy, thermal analysis and Hirshfeld surface analysis. The ACR, INM and NAM co-crystals with PAA exhibit the carboxylic acid-pyridine heterosynthon. Furthermore the amide-amide supramolecular homosynthon is observed in the PAA co-crystals with INM and NAM as well as Nsbnd H⋯O interactions between the acid and the respective base. The CAF co-crystal exhibits hydrogen bonding between the imidazole nitrogen and the COOH group of the PAA. The compounds demonstrate different stoichiometries; for PAA·ACR and PAA·INM a 1:1 ratio is displayed, a 2:1 in 2PAA·CAF and a 2:2 in the case of 2PAA·2NAM.

Growth of single crystals of BaFe12O19 by solid state crystal growth

NASA Astrophysics Data System (ADS)

Fisher, John G.; Sun, Hengyang; Kook, Young-Geun; Kim, Joon-Seong; Le, Phan Gia

2016-10-01

Single crystals of BaFe12O19 are grown for the first time by solid state crystal growth. Seed crystals of BaFe12O19 are buried in BaFe12O19+1 wt% BaCO3 powder, which are then pressed into pellets containing the seed crystals. During sintering, single crystals of BaFe12O19 up to ∼130 μm thick in the c-axis direction grow on the seed crystals by consuming grains from the surrounding polycrystalline matrix. Scanning electron microscopy-energy dispersive spectroscopy analysis shows that the single crystal and the surrounding polycrystalline matrix have the same chemical composition. Micro-Raman scattering shows the single crystal to have the BaFe12O19 structure. The optimum growth temperature is found to be 1200 °C. The single crystal growth behavior is explained using the mixed control theory of grain growth.

Chemical speciation using high energy resolution PIXE spectroscopy in the tender X-ray range

NASA Astrophysics Data System (ADS)

Kavčič, Matjaž; Petric, Marko; Vogel-Mikuš, Katarina

2018-02-01

High energy resolution X-ray emission spectroscopy employing wavelength dispersive (WDS) crystal spectrometers can provide energy resolution on the level of core-hole lifetime broadening of the characteristic emission lines. While crystal spectrometers have been traditionally used in combination with electron excitation for major and minor element analysis, they have been rarely considered in proton induced X-ray emission (PIXE) trace element analysis mainly due to low detection efficiency. Compared to the simplest flat crystal WDS spectrometer the efficiency can be improved by employing cylindrically or even spherically curved crystals in combination with position sensitive X-ray detectors. When such spectrometer is coupled to MeV proton excitation, chemical bonding effects are revealed in the high energy resolution spectra yielding opportunity to extend the analytical capabilities of PIXE technique also towards chemical state analysis. In this contribution we will focus on the high energy resolution PIXE (HR-PIXE) spectroscopy in the tender X-ray range performed in our laboratory with our home-built tender X-ray emission spectrometer. Some general properties of high energy resolution PIXE spectroscopy in the tender X-ray range are presented followed by an example of sulfur speciation in biological tissue illustrating the capabilities as well as limitations of HR-PIXE method used for chemical speciation in the tender X-ray range.

Single crystal growth and surface chemical stability of KPb2Br5

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Isaenko, L. I.; Kesler, V. G.; Tarasova, A. Yu.

2011-03-01

Single crystal of KPb2Br5 has been grown using the Bridgman technique. Initially the synthesis of stoichiometric KPb2Br5 compound was performed from high purity bromide salts. Electronic structure of KPb2Br5 has been determined with X-ray photoelectron spectroscopy for powdered sample fabricated by grinding in air. Drastic chemical interaction of KPb2Br5 with atmosphere has not been detected. Chemical bonding in potassium- and lead-containing bromides is considered using binding energy differences ΔK=(BE K 2p3/2-BE Br 3d) and ΔPb=(BE Pb 4f7/2-BE Br 3d), respectively, as representative parameters.

Compositional analysis of dilute nitride doped indium antimonide bulk crystal by VDS technique

NASA Astrophysics Data System (ADS)

Deshpande, Manisha; Maske, Dilip; Choudhari, Rashmi; Arora, Brij Mohan; Gadkari, Dattatray

2016-05-01

Dilute nitrides are suitable materials for fabrication of devices in detection of long wavelength infrared region. Dilute nitride doped Indium antimonide bulk crystals were grown using vertical directional solidification technique. The compositional characteristics of the crystals were carried out using EDS. The analysis was simulated and compared with observations using DTSA II software for accuracy. The ingots have uniform composition of Indium and Antimony. The actual nitrogen composition measured using EDS was 0.136% for doped nitrogen composition 0.1% except near conical end where it was 0.1%. The study of bonding between nitrogen, Indium and antimony was carried out using SIMS. The analysis shows strong presence of In-N bonding along with In-Sb bonds which indicates nitrogen has replaced antimony atoms in crystal lattice.

The Crystal-Chemical Effect of REE Separation in Minerals: Causes and Practical Values

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.

2018-03-01

Contrast variations in the type of REE distribution from a distinctly negative mode to a positive mode is revealed in zonal fluorites of Eastern Transbaikal, with a pronounced decrease in the Ce/Y ratios in successive zones of increasing Y accompanied by a gradual decrease in the temperature and salinity of fluid inclusions in the fluorites. It is assumed that these facts are caused by the appearance of nm-size phases of REE minerals characterized by various crystalline structures and demonstrating selective concentrations of lanthanides, i.e., exhibiting a crystal-chemical differentiation of REEs that is widespread in the processes of mineral formation. Based on this natural mechanism, the development of a procedure of selective REE extraction from the concentrates is proposed. The primary laboratory experiments resulted in the discovery of the difference in REE concentrations in the sediment and filtrate with the separation coefficient varying by a factor of 76. The results obtained allow one to expect a true separation possibility for Nd along with the medium and heavy REEs. In view of the data obtained, the crystalline-chemical separation of REEs has some advantages compared to the processes currently used, especially extraction.

Advanced Protein Crystallization Facility (APCF)

NASA Technical Reports Server (NTRS)

1998-01-01

This section of the Life and Microgravity Spacelab (LMS) publication contains articles entitled: (1) Crystallization of EGFR-EGF; (2) Crystallization of Apocrustacyanin C1; (3) Crystallization and X-ray Analysis of 5S rRNA and the 5S rRNA Domain A; (4) Growth of Lysozyme Crystals at Low Nucleation Density; (5) Comparative Analysis of Aspartyl tRNA-synthetase and Thaumatin Crystals Grown on Earth and In Microgravity; (6) Lysosome Crystal Growth in the Advanced Protein Crystallization Facility Monitored via Mach-Zehnder Interferometry and CCD Video; (7) Analysis of Thaumatin Crystals Grown on Earth and in Microgravity; (8) Crystallization of the Nucleosome Core Particle; (9) Crystallization of Photosystem I; (10) Mechanism of Membrane Protein Crystal Growth: Bacteriorhodopsin-mixed Micelle Packing at the Consolution Boundary, Stabilized in Microgravity; (11) Crystallization in a Microgravity Environment of CcdB, a Protein Involved in the Control of Cell Death; and (12) Crystallization of Sulfolobus Solfataricus

Devitrification and delayed crazing of SiO2 on single-crystal silicon and chemically vapor-deposited silicon nitride

NASA Technical Reports Server (NTRS)

Choi, Doo Jin; Scott, William D.

1987-01-01

The linear growth rate of cristobalite was measured in thin SiO2 films on silicon and chemically vapor-deposited silicon nitride. The presence of trace impurities from alumina furnace tubes greatly increased the crystal growth rate. Under clean conditions, the growth rate was still 1 order-of-magnitude greater than that for internally nucleated crystals in bulk silica. Crystallized films cracked and lifted from the surface after exposure to atmospheric water vapor. The crystallization and subsequent crazing and lifting of protective SiO2 films on silicon nitride should be considered in long-term applications.

Crystals in light.

PubMed

Kahr, Bart; Freudenthal, John; Gunn, Erica

2010-05-18

molecules. Luminophores were used as guests in crystals to reveal aspects of growth mechanisms by labeling surface structures such as steps and kinks. New methods were adopted for measuring and imaging the optical rotatory power of crystals. Chiroptical anisotropies can now be compared with the results of quantum chemical calculations that have emerged in the past 10 years. The rapid determination of the optical rotation and circular dichroism tensors of molecules in crystals, and the interpretation of these anisotropies, remains a subject of future research. Polycrystalline patterns that form far from equilibrium challenged the quantitative interpretation of micrographs when heterogeneities along the optical path and obliquely angled interfaces played large roles. Resulting "artifacts" were nevertheless incisive probes of polycrystalline texture and mesoscale chemistry in simple substances grown far from equilibrium or in biopathological crystals such as Alzheimer's amyloid plaques.

Compositional analysis of dilute nitride doped indium antimonide bulk crystal by VDS technique

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

Deshpande, Manisha, E-mail: manishauj@gmail.com; Department of Physics, Mithibai College, Vile Parle; Maske, Dilip

2016-05-06

Dilute nitrides are suitable materials for fabrication of devices in detection of long wavelength infrared region. Dilute nitride doped Indium antimonide bulk crystals were grown using vertical directional solidification technique. The compositional characteristics of the crystals were carried out using EDS. The analysis was simulated and compared with observations using DTSA II software for accuracy. The ingots have uniform composition of Indium and Antimony. The actual nitrogen composition measured using EDS was 0.136% for doped nitrogen composition 0.1% except near conical end where it was 0.1%. The study of bonding between nitrogen, Indium and antimony was carried out using SIMS.more » The analysis shows strong presence of In-N bonding along with In-Sb bonds which indicates nitrogen has replaced antimony atoms in crystal lattice.« less

Persistent hydrogen bonding in polymorphic crystal structures.

PubMed

Galek, Peter T A; Fábián, László; Allen, Frank H

2009-02-01

The significance of hydrogen bonding and its variability in polymorphic crystal structures is explored using new automated structural analysis methods. The concept of a chemically equivalent hydrogen bond is defined, which may be identified in pairs of structures, revealing those types of bonds that may persist, or not, in moving from one polymorphic form to another. Their frequency and nature are investigated in 882 polymorphic structures from the Cambridge Structural Database. A new method to compare conformations of equivalent molecules is introduced and applied to derive distinct subsets of conformational and packing polymorphs. The roles of chemical functionality and hydrogen-bond geometry in persistent interactions are systematically explored. Detailed structural comparisons reveal a large majority of persistent hydrogen bonds that are energetically crucial to structural stability.

Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids.

PubMed

Pindelska, Edyta; Sokal, Agnieszka; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Kolodziejski, Waclaw

2014-11-01

In this work, three polycrystalline materials containing co-crystals of theophylline with malonic, maleic, and glutaric acids were studied using (13)C, (15)N and (1)H solid-state NMR and FT-IR spectroscopy. The NMR assignments were supported by gauge including projector augmented waves (GIPAW) calculations of chemical shielding, performed using X-ray determined geometry. The experimental (13)C cross polarization/magic angle spinning (CP/MAS) NMR results and the calculated isotropic chemical shifts were in excellent agreement. A rapid and convenient method for theophylline co-crystals crystal structure analysis has been proposed for co-crystals, which are potentially new APIs. Copyright © 2014 Elsevier B.V. All rights reserved.

High-throughput crystallization screening.

PubMed

Skarina, Tatiana; Xu, Xiaohui; Evdokimova, Elena; Savchenko, Alexei

2014-01-01

Protein structure determination by X-ray crystallography is dependent on obtaining a single protein crystal suitable for diffraction data collection. Due to this requirement, protein crystallization represents a key step in protein structure determination. The conditions for protein crystallization have to be determined empirically for each protein, making this step also a bottleneck in the structure determination process. Typical protein crystallization practice involves parallel setup and monitoring of a considerable number of individual protein crystallization experiments (also called crystallization trials). In these trials the aliquots of purified protein are mixed with a range of solutions composed of a precipitating agent, buffer, and sometimes an additive that have been previously successful in prompting protein crystallization. The individual chemical conditions in which a particular protein shows signs of crystallization are used as a starting point for further crystallization experiments. The goal is optimizing the formation of individual protein crystals of sufficient size and quality to make them suitable for diffraction data collection. Thus the composition of the primary crystallization screen is critical for successful crystallization.Systematic analysis of crystallization experiments carried out on several hundred proteins as part of large-scale structural genomics efforts allowed the optimization of the protein crystallization protocol and identification of a minimal set of 96 crystallization solutions (the "TRAP" screen) that, in our experience, led to crystallization of the maximum number of proteins.

Characterization of a defective PbWO4 crystal cut along the a-c crystallographic plane: structural assessment and a novel photoelastic stress analysis

NASA Astrophysics Data System (ADS)

Montalto, L.; Natali, P. P.; Daví, F.; Mengucci., P.; Paone, N.; Rinaldi, D.

2017-12-01

Among scintillators, the PWO is one of the most widely used, for instance in CMS calorimeter at CERN and PANDA project. Crystallographic structure and chemical composition as well as residual stress condition, are indicators of homogeneity and good quality of the crystal. In this paper, structural characterization of a defective PbWO4 (PWO) crystal has been performed by X-ray Diffraction (XRD), Energy Dispersive Spectroscopy (EDS) and Photoelasticity in the unusual (a, c) crystallographic plane. XRD and EDS analysis have been used to investigate crystallographic orientation and chemical composition, while stress distribution, which indicates macroscopic inhomogeneities and defects, has been obtained by photoelastic approaches, in Conoscopic and Sphenoscopic configuration. Since the sample is cut along the (a, c) crystallographic plane, a new method is proposed for the interpretation of the fringe pattern. The structural analysis has detected odds from the nominal lattice dimension, which can be attributed to the strong presence of Pb and W. A strong inhomogeneity over the crystal sample has been revealed by the photoelastic inspection. The results give reliability to the proposed procedure which is exploitable in crystals with other structures.

Development of speckle-free channel-cut crystal optics using plasma chemical vaporization machining for coherent x-ray applications.

PubMed

Hirano, Takashi; Osaka, Taito; Sano, Yasuhisa; Inubushi, Yuichi; Matsuyama, Satoshi; Tono, Kensuke; Ishikawa, Tetsuya; Yabashi, Makina; Yamauchi, Kazuto

2016-06-01

We have developed a method of fabricating speckle-free channel-cut crystal optics with plasma chemical vaporization machining, an etching method using atmospheric-pressure plasma, for coherent X-ray applications. We investigated the etching characteristics to silicon crystals and achieved a small surface roughness of less than 1 nm rms at a removal depth of >10 μm, which satisfies the requirements for eliminating subsurface damage while suppressing diffuse scattering from rough surfaces. We applied this method for fabricating channel-cut Si(220) crystals for a hard X-ray split-and-delay optical system and confirmed that the crystals provided speckle-free reflection profiles under coherent X-ray illumination.

Vibrational and structural investigation of SOUL protein single crystals by using micro-Raman spectroscopy

NASA Astrophysics Data System (ADS)

Rossi, Barbara; Giarola, Marco; Mariotto, Gino; Ambrosi, Emmanuele; Monaco, Hugo L.

2010-05-01

Protein SOUL is a new member of the recently discovered putative heme-binding protein family called SOUL/HEBP and, to date, no structural information exists for this protein. Here, micro-Raman spectroscopy is used to study the vibrational properties of single crystals obtained from recombinant protein SOUL by means of two different optimization routes. This spectroscopic approach offers the valuable advantage of the in-situ collection of experimental data from protein crystals, placed onto a hanging-drop plate, under the same conditions used to grow the crystals. By focusing on the regions of amides I and III bands, some secondary structure characteristic features have been recognized. Moreover, some side-chain marker bands were observed in the Raman spectra of SOUL crystals and the unambiguous assignment of these peaks inferred by comparing the experimental Raman spectra of pure amino acids and their Raman intensities computed using quantum chemical calculations. Our comparative analysis allows to get a deeper understanding of the side-chain environments and of the interactions involving these specific amino acids in the two different SOUL crystals.

Chemical conversion of cisplatin and carboplatin with histidine in a model protein crystallized under sodium iodide conditions

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

Tanley, Simon W. M.; Helliwell, John R., E-mail: john.helliwell@manchester.ac.uk

Crystals of HEWL with cisplatin and HEWL with carboplatin grown in sodium iodide conditions both show a partial chemical transformation of cisplatin or carboplatin to a transiodoplatin (PtI{sub 2}X{sub 2}) form. The binding is only at the N{sup δ} atom of His15. A further Pt species (PtI{sub 3}X) is also seen, in both cases bound in a crevice between symmetry-related protein molecules. Cisplatin and carboplatin are platinum anticancer agents that are used to treat a variety of cancers. Previous X-ray crystallographic studies of carboplatin binding to histidine in hen egg-white lysozyme (HEWL) showed a partial chemical conversion of carboplatin tomore » cisplatin owing to the high sodium chloride concentration used in the crystallization conditions. Also, the co-crystallization of HEWL with carboplatin in sodium bromide conditions resulted in the partial conversion of carboplatin to the transbromoplatin form, with a portion of the cyclobutanedicarboxylate (CBDC) moiety still present. The results of the co-crystallization of HEWL with cisplatin or carboplatin in sodium iodide conditions are now reported in order to determine whether the cisplatin and carboplatin converted to the iodo form, and whether this took place in a similar way to the partial conversion of carboplatin to cisplatin in NaCl conditions or to transbromoplatin in NaBr conditions as seen previously. It is reported here that a partial chemical transformation has taken place to a transplatin form for both ligands. The NaI-grown crystals belonged to the monoclinic space group P2{sub 1} with two molecules in the asymmetric unit. The chemically transformed cisplatin and carboplatin bind to both His15 residues, i.e. in each asymmetric unit. The binding is only at the N{sup δ} atom of His15. A third platinum species is also seen in both conditions bound in a crevice between symmetry-related molecules. Here, the platinum is bound to three I atoms identified based on their anomalous difference electron

Protein Crystals as Novel Catalytic Materials.

PubMed

Margolin, Alexey L.; Navia, Manuel A.

2001-06-18

In this era of molecular biology, protein crystallization is often considered to be a necessary first step in obtaining structural information through X-ray diffraction analysis. In a different light, protein crystals can also be thought of as materials, whose chemical and physical properties make them broadly attractive and useful across a larger spectrum of disciplines. The full potential of these protein crystalline materials has been severely restricted in practice, however, both by their inherent fragility, and by strongly held skepticism concerning their routine and predictable growth, formulation, and practical application. Fortunately, these problems have turned out to be solvable. A systematic exploration of the biophysics and biochemistry of protein crystallization has shown that one can dependably create new protein crystalline materials more or less at will. In turn, these crystals can be readily strengthened, both chemically and mechanically, to make them suitable for practical commercialization. Today, these novel materials are used as industrial catalysts on a commercial scale, in bioremediation and "green chemistry" applications, and in enantioselective chromatography of pharmaceuticals and fine chemicals. In the near future, their utility will expand, to include the purification of protein drugs, formulation of direct protein therapeutics, and development of adjuvant-less vaccines.

Structural, chemical and physical properties of pure and La3+ doped L-Threonine acetate crystals

NASA Astrophysics Data System (ADS)

Senthamizhan, A.; Sambathkumar, K.; Nithiyanantham, S.; Venkatachalapathy, M.; Rajkamal, N.

2017-12-01

The pure and La3+ doped L- Threonine crystals can be grown by slow evaporation techniques. The crystal structure were examined through X-Ray diffraction (XRD) analysis, confirmed the P212121 system. The quantitative nature of dopant can be analyzed with Inductively Coupled Plasma (ICP) study. The Fourier Transform Infra-Red (FTIR) and Fourier Transform (FT- Raman) investigations yields the possible stretching/bonding with their functional groups and the qualitative/quantitative nature of both crystals is analyzed. The optical behavior of crystals can be studied through Ultra Violet (UV) - Visible spectrometer. The mechanical, thermal and decomposition studies can be carried out through Vickers hardness test, Thermo Gravometric Analysis (TGA) and Differential Thermal Analysis (DTA). The Non Linear Optical (NLO) properties are found more than Potassium Phosphate (KDP) through Kurtz powders technique. The dielectric and optical absorption studies for both pure and L-doped crystals were studied and interpreted all the properties. The La3+ dopant increases the properties are investigated.

Synthesis, crystal structure, NLO and Hirshfeld surface analysis of 1,2,3-triazolyl chalcone single crystal

NASA Astrophysics Data System (ADS)

Shruthi, C.; Ravindrachary, V.; Guruswamy, B.; Lokanath, N. K.; Kumara, Karthik; Goveas, Janet

2018-05-01

Needle shaped brown coloured single crystal of the title compound was grown by slow evaporation technique using methanol as solvent. The grown crystal was characterized using FT-IR, Single crystal XRD, UV-visible and NLO studies. Crystal structure was confirmed by FT-IR study and the functional groups were identified. XRD study reveals that the crystal belongs to orthorhombic crystal system with pnaa space group and the corresponding cell parameters were calculated. UV-visible spectrum shows that the crystal is transparent in the entire visible region and absorption takes place in the UV-range. NLO efficiency of the crystal obtained 0.66 times that of urea was determined by SHG test. The intermolecular interaction and percentage contribution of each individual atom in the crystal lattice was quantized using Hirshfeld surface and 2D finger print analysis.

Electronic structure and pair potential energy analysis of 4-n-methoxy-4′-cyanobiphenyl: A nematic liquid crystal

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

Sharma, Dipendra, E-mail: d-11sharma@rediffmail.com; Tiwari, S. N., E-mail: sntiwari123@rediffmail.com; Dwivedi, M. K., E-mail: dwivedi-ji@gmail.com

2016-05-06

Electronic structure properties of 4-n-methoxy-4′-cyanobiphenyl, a pure nematic liquid crystal have been examined using an ab‒initio, HF/6‒31G(d,p) technique with GAMESS program. Conformational and charge distribution analysis have been carried out. MEP, HOMO and LUMO surfaces have been scanned. Ionization potential, electron affinity, electronegativity, global hardness and softness of the liquid crystal molecule have been calculated. Further, stacking, side by side and end to end interactions between a molecular pair have been evaluated. Results have been used to elucidate the physico-chemical and liquid crystalline properties of the system.

Crystal growth and characterization of third order nonlinear optical piperazinium bis(4-hydroxybenzenesulphonate) (P4HBS) single crystal

NASA Astrophysics Data System (ADS)

Pichan, Karuppasamy; Muthu, Senthil Pandian; Perumalsamy, Ramasamy

2017-09-01

The organic single crystal of piperazinium bis(4-hydroxybenzenesulphonate) (P4HBS) was grown by slow evaporation solution technique (SEST) at room temperature. The lattice parameters of the grown crystal were confirmed by single crystal X-ray diffraction analysis. Functional groups of P4HBS crystal were confirmed by FTIR spectrum analysis. The optical quality of the grown crystal was identified by the UV-Vis NIR spectrum analysis. The grown crystal has good optical transmittance in the range of 410-1100 nm. In photoluminescence spectrum, sharp emission peaks are observed, which indicates the ultraviolet (UV) emission. The photoconductivity study reveals that the grown crystal has negative photoconductive nature. The thermal behaviour of the P4HBS crystal was investigated by thermogravimetric and differential thermal analysis (TG-DTA). The mechanical stability of grown crystal was analyzed and the indentation size effect (ISE) was explained by Hays-Kendall's (HK) approach and proportional specimen resistance model (PSRM). Chemical etching study was carried out and the etch pit density (EPD) was calculated. The dielectric constant (ε‧) and dielectric loss (tan δ) as a function of frequency were measured for the grown crystal. The solid state parameters such as valence electron, plasma energy, Penn gap and Fermi energy were evaluated theoretically for the P4HBS using the empirical relation. The estimated values are used to calculate the electronic polarizability. The third-order nonlinear optical properties such as nonlinear refractive index (n2), absorption co-efficient (β) and susceptibility (χ(3)) were studied by Z-scan technique at 632.8 nm using He-Ne laser.

Nanoscale arrays of antimony telluride single crystals by selective chemical vapor deposition

PubMed Central

Huang, Ruomeng; Benjamin, Sophie L.; Gurnani, Chitra; Wang, Yudong; Hector, Andrew L.; Levason, William; Reid, Gillian; De Groot, C. H. (Kees)

2016-01-01

Arrays of individual single nanocrystals of Sb2Te3 have been formed using selective chemical vapor deposition (CVD) from a single source precursor. Crystals are self-assembled reproducibly in confined spaces of 100 nm diameter with pitch down to 500 nm. The distribution of crystallite sizes across the arrays is very narrow (standard deviation of 15%) and is affected by both the hole diameter and the array pitch. The preferred growth of the crystals in the <1 1 0> orientation along the diagonal of the square holes strongly indicates that the diffusion of adatoms results in a near thermodynamic equilibrium growth mechanism of the nuclei. A clear relationship between electrical resistivity and selectivity is established across a range of metal selenides and tellurides, showing that conductive materials result in more selective growth and suggesting that electron donation is of critical importance for selective deposition. PMID:27283116

Crystal Structure and Crystal Chemistry of Some Common REE Minerals and Nanpingite

NASA Astrophysics Data System (ADS)

Ni, Yunxiang

1995-01-01

Part I. Crystal structure and crystal chemistry of fluorocarbonate minerals. The crystal structure of bastnasite-(Ce) have been solved in P-62c and refined to R = 0.018. The structure is composed of (001) (CeF) layers interspersed with (CO_3) layers in a 1:1 ratio. The Ce atom is coordinated in rm CeO_6F_3 polyhedra. The atomic arrangement of synchysite-(Ce) has been solved and refined to R = 0.036 with a monoclinic space group C2/c. It possesses a (001) layer structure, with layers of (Ca) and (CeF) separated by layers of carbonate groups. The layers stack in a manner analogous to C2/c muscovite. Polytypism similar to the micas may exist in synchysite. The crystal structures of cordylite-(Ce) have been solved in P6 _3/mmc and refined to R = 0.023. The structure and chemical formula are different from those deduced by Oftedal. The formula is rm MBaCe_2(CO _3)_4F, where M is rm Na^+, Ca^{2+}_{1/2 }+ O_{1/2}, or any solution. The presence of (NaF) layer in the structure is the key difference from the Oftedal's structure. This redefinition of the chemical formula and crystal structure of cordylite will be proposed to IMA-CNMMN. Part II. Crystal structure and crystal chemistry of monazite-xenotime series. Monazite is monoclinic, P2 _1/n, and xenotime is isostructural with zircon (I4_1/amd). Both atomic arrangements are based on (001) chains of intervening phosphate tetrahedra and RE polyhedra, with a REO_8 polyhedron in xenotime that accommodates HRE (Tb - Lu) and a REO_9 polyhedron in monazite that preferentially incorporates LRE (La - Gd). As the structure "transforms" from xenotime to monazite, the crystallographic properties are comparable along the (001) chains, with structural adjustments of 2.2 A along (010) to accommodate the different size RE atoms. Part III. Crystal structure of nanpingite-2M _2, the Cs end-member of muscovite. The crystal structure of nanpingite has been refined to R = 0.058. Compared to K^+ in muscovite, the largest interlayer Cs^+ in

Nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization without chemical additions.

PubMed

Song, Yong-Hui; Qiu, Guang-Lei; Yuan, Peng; Cui, Xiao-Yu; Peng, Jian-Feng; Zeng, Ping; Duan, Liang; Xiang, Lian-Cheng; Qian, Feng

2011-06-15

Anaerobically digested swine wastewater contains high concentrations of phosphorus (P) and nitrogen (N). A pilot-scale experiment was carried out for nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization. In the pilot plant, a sequencing batch reactor (SBR) and a continuous-flow reactor with struvite accumulation devices were designed and employed. The wastewater pH value was increased by CO(2) stripping, and the struvite crystallization process was performed without alkali and Mg(2+) additions. Results of the long-term operation of the system showed that, both reactors provided up to 85% P removal and recovery over wide ranges of aeration times (1.0-4.0 h), hydraulic retention times (HRT) (6.0-15.0 h) and temperatures (0-29.5°C) for an extended period of 247 d, in which approximate 30% of P was recovered by the struvite accumulation devices. However, 40-90% of NH(4)(+)-N removed was through air stripping instead of being immobilized in the recovered solids. The recovered products were detected and analyzed by scanning electron microscope (SEM), X-ray diffraction (XRD) and chemical methods, which were proved to be struvite with purity of more than 90%. This work demonstrated the feasibility and effects of nutrients removal and recovery from anaerobically digested swine wastewater by struvite crystallization without chemical additions. Copyright © 2011 Elsevier B.V. All rights reserved.

Adaptation of in-situ microscopy for crystallization processes

NASA Astrophysics Data System (ADS)

Bluma, A.; Höpfner, T.; Rudolph, G.; Lindner, P.; Beutel, S.; Hitzmann, B.; Scheper, T.

2009-08-01

In biotechnological and pharmaceutical engineering, the study of crystallization processes gains importance. An efficient analytical inline sensor could help to improve the knowledge about these processes in order to increase efficiency and yields. The in-situ microscope (ISM) is an optical sensor developed for the monitoring of bioprocesses. A new application for this sensor is the monitoring in downstream processes, e.g. the crystallization of proteins and other organic compounds. This contribution shows new aspects of using in-situ microscopy to monitor crystallization processes. Crystals of different chemical compounds were precipitated from supersaturated solutions and the crystal growth was monitored. Exemplified morphological properties and different forms of crystals could be distinguished on the basis of offline experiments. For inline monitoring of crystallization processes, a special 0.5 L stirred tank reactor was developed and equipped with the in-situ microscope. This reactor was utilized to carry out batch experiments for crystallizations of O-acetylsalicyclic acid (ASS) and hen egg white lysozyme (HEWL). During the whole crystallization process, the in-situ microscope system acquired images directly from the crystallization broth. For the data evaluation, an image analysis algorithm was developed and implemented in the microscope analysis software.

Growth of tungsten oxide nanostructures by chemical solution deposition

NASA Astrophysics Data System (ADS)

Jin, L. H.; Bai, Y.; Li, C. S.; Wang, Y.; Feng, J. Q.; Lei, L.; Zhao, G. Y.; Zhang, P. X.

2018-05-01

Tungsten oxide nanostructures were fabricated on LaAlO3 (00l) substrates by a simple chemical solution deposition. The decomposition behavior and phase formation of ammonium tungstate precursor were characterized by thermal analysis and X-ray diffraction. Moreover, the morphology and chemical state of nanostructures were analyzed by scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectra. The effects of crystallization temperature on the formation of nanodots and nanowires were investigated. The results indicated that the change of nanostructures had close relationship with the crystallization temperature during the chemical solution deposition process. Under higher crystallization temperature, the square-like dots transformed into the dome-like nanodots and nanowires. Moreover high density well-ordered nanodots could be obtained on the substrate with the further increase of crystallization temperature. It also suggested that this simple chemical solution process could be used to adjust the nanostructures of tungsten oxide compounds on substrate.

Single crystal and optical ceramic multicomponent garnet scintillators: A comparative study

NASA Astrophysics Data System (ADS)

Wu, Yuntao; Luo, Zhaohua; Jiang, Haochuan; Meng, Fang; Koschan, Merry; Melcher, Charles L.

2015-04-01

Multicomponent garnet materials can be made in optical ceramic as well as single crystal form due to their cubic crystal structure. In this work, high-quality Gd3Ga3Al2O12:0.2 at% Ce (GGAG:Ce) single crystal and (Gd,Lu)3Ga3Al2O12:1 at% Ce (GLuGAG:Ce) optical ceramics were fabricated by the Czochralski method and a combination of hot isostatic pressing (HIPing) and annealing treatment, respectively. Under optical and X-ray excitation, the GLuGAG:Ce optical ceramic exhibits a broad Ce3+ transition emission centered at 550 nm, while the emission peak of the GGAG:Ce single crystal is centered at 540 nm. A self-absorption effect in GLuGAG:Ce optical ceramic results in this red-shift of the Ce3+ emission peak compared to that in the GGAG:Ce single crystal. The light yield under 662 keV γ-ray excitation was 45,000±2500 photons/MeV and 48,200±2410 photons/MeV for the GGAG:Ce single crystal and GLuGAG:Ce optical ceramic, respectively. An energy resolution of 7.1% for 662 keV γ-rays was achieved in the GLuGAG:Ce optical ceramic with a Hamamatsu R6231 PMT, which is superior to the value of 7.6% for a GGAG:Ce single crystal. Scintillation decay time measurements under 137Cs irradiation show two exponential decay components of 58 ns (47%) and 504 ns (53%) for the GGAG:Ce single crystal, and 84 ns (76%) and 148 ns (24%) for the GLuGAG:Ce optical ceramic. The afterglow level after X-ray cutoff in the GLuGAG:Ce optical ceramic is at least one order of magnitude lower than in the GGAG:Ce single crystal.

Understanding Crystal Populations: The Role of Textural Analysis in Determining Magmatic Timescales

NASA Astrophysics Data System (ADS)

Jerram, D. A.

2006-12-01

Crystal populations in igneous rocks that erupt at the Earths surface act as records of magma chamber processes at depth, predominantly recording episodes of growth/nucleation and geochemical changes within the host body. Detailed inspection of such crystal populations, however, reveals a complex crystal cargo that comprises crystals which have grown directly from the host, crystals that have spent one or more protracted periods being isolated from the host magma and crystals that originated from a completely different magma body and/or country rock. To further interrogate this crystal cargo we can use textural analysis techniques to fully quantify the crystal population and gather important information about the population, such as crystal morphology, spatial distribution and size relationships. When quantified, such data can be used to better constrain the different components of the resultant crystal population and how they relate to each other. Additionally, by combining textural analysis information with geochemical analysis, a powerful measure of magma timescales and magma chamber processes results. In this contribution the different types of textural analysis techniques in 2D and 3D are introduced with examples from both plutonic and volcanic systems presented to highlight the roll of this approach to quantifying magma timescales.

Inverse Opal Photonic Crystals as an Optofluidic Platform for Fast Analysis of Hydrocarbon Mixtures.

PubMed

Xu, Qiwei; Mahpeykar, Seyed Milad; Burgess, Ian B; Wang, Xihua

2018-06-13

Most of the reported optofluidic devices analyze liquid by measuring its refractive index. Recently, the wettability of liquid on various substrates has also been used as a key sensing parameter in optofluidic sensors. However, the above-mentioned techniques face challenges in the analysis of the relative concentration of components in an alkane hydrocarbon mixture, as both refractive indices and wettabilities of alkane hydrocarbons are very close. Here, we propose to apply volatility of liquid as the key sensing parameter, correlate it to the optical property of liquid inside inverse opal photonic crystals, and construct powerful optofluidic sensors for alkane hydrocarbon identification and analysis. We have demonstrated that via evaporation of hydrocarbons inside the periodic structure of inverse opal photonic crystals and observation of their reflection spectra, an inverse opal film could be used as a fast-response optofluidic sensor to accurately differentiate pure hydrocarbon liquids and relative concentrations of their binary and ternary mixtures in tens of seconds. In these 3D photonic crystals, pure chemicals with different volatilities would have different evaporation rates and can be easily identified via the total drying time. For multicomponent mixtures, the same strategy is applied to determine the relative concentration of each component simply by measuring drying time under different temperatures. Using this optofluidic sensing platform, we have determined the relative concentrations of ternary hydrocarbon mixtures with the difference of only one carbon between alkane hydrocarbons, which is a big step toward detailed hydrocarbon analysis for practical use.

Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes

NASA Astrophysics Data System (ADS)

Baitinger, Michael; Böhme, Bodo; Ormeci, Alim; Grin, Yuri

Clathrates represent a family of inorganic materials called cage compounds. The key feature of their crystal structures is a three-dimensional (host) framework bearing large cavities (cages) with 20-28 vertices. These polyhedral cages bear—as a rule—guest species. Depending on the formal charge of the framework, clathrates are grouped in anionic, cationic and neutral. While the bonding in the framework is of (polar) covalent nature, the guest-host interaction can be ionic, covalent or even van-der Waals, depending on the chemical composition of the clathrates. The chemical composition and structural features of the cationic clathrates can be described by the enhanced Zintl concept, whereas the composition of the anionic clathrates deviates often from the Zintl counts, indicating additional atomic interactions in comparison with the ionic-covalent Zintl model. These interactions can be visualized and studied by applying modern quantum chemical approaches such as electron localizability.

A Canonical Analysis of Career Choice Crystallization and Vocational Maturity.

ERIC Educational Resources Information Center

Blustein, David L.

1988-01-01

Administered measures of vocational maturity and career choice crystallization to 158 community college students. Used canonical analysis to identify relationships between age, gender, career choice crystallization, and vocational maturity. Analysis yielded one significant canonical root, indicating most shared variance between variables was…

Synthesis, characterization, crystal structure and quantum chemical investigations of three novel coumarin-benzenesulfonohydrazide derivatives

NASA Astrophysics Data System (ADS)

Chethan Prathap, K. N.; Lokanath, N. K.

2018-04-01

Coumarin derivatives are an important class of heterocyclic compounds due to their physical and biological properties. Coumarin derivatives have been identified with many significant electro-optical properties and biological activities. Three novel coumarin derivatives containing benzene sulfonohydrazide group were synthesized by condensation reaction. The synthesized compounds were characterized by various spectroscopic techniques (Mass, 1H/13C NMR and FTIR). Thermal and optical properties were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and UV-Vis spectroscopic studies. Finally their structures were confirmed by single crystal X-ray diffraction (XRD) studies. The three compounds exhibit diverse intermolecular interactions, as observed by the crystal packing and Hirshfeld surface analysis. Further, their structures were optimized by density functional theory (DFT) calculations using B3LYP hybrid functionals with 6-311G+(d,p) level basis set. The Mulliken charge, molecular electrostatic potential (MEP), frontier molecular orbitals (HOMO-LUMO) were investigated. The experimentally determined parameters were compared with those calculated theoretically and they complement each other with a very good correlation. The transitions among the molecular orbitals were investigated using time-dependent density functional theory (TD-DFT) and the electronic absorption spectra obtained showed very good agreement with the experimentally measured UV-Vis spectra. Furthermore, non-linear optical (NLO) properties were investigated by calculating polarizabilities and hyperpolarizabilities. All three compounds exhibit significantly high hyperpolarizabilities compared to the reference material urea, which makes them potential candidates for NLO applications.

Improving the chemical compatibility of sealing glass for solid oxide fuel cells: Blocking the reactive species by controlled crystallization

NASA Astrophysics Data System (ADS)

Zhang, Teng; Zou, Qi; Zeng, Fanrong; Wang, Shaorong; Tang, Dian; Yang, Hiswen

2012-10-01

The chemical compatibility of sealing glass is of great importance for Solid oxide fuel cell (SOFC). In this work, the interfacial reaction between sealing glass and Cr-containing interconnect alloy is characterized by reacting Cr2O3 powders with a representative SrO-containing glass crystallized by different heat-treatment schedules. The crystalline structure and crystalline content of sealing glass are determined by X-ray diffraction. The results show that the fraction of Cr6+ decreases from 39.8 ± 1.9% for quenched glass to 8.2 ± 0.4% for glass crystallized at 900 °C for 2 h. In addition, the interfacial reaction can be further reduced with increasing crystallization temperature and time as well as the addition of nucleation agent (TiO2). The formation of some Sr-containing crystalline phases, Sr2SiO4 and Sr(TiO3), contributes to the improvement of chemical compatibility of sealing glass, in agreement with the results of thermodynamic calculations.

Effect of Crystal Orientation on Analysis of Single-Crystal, Nickel-Based Turbine Blade Superalloys

NASA Technical Reports Server (NTRS)

Swanson, G. R.; Arakere, N. K.

2000-01-01

High-cycle fatigue-induced failures in turbine and turbopump blades is a pervasive problem. Single-crystal nickel turbine blades are used because of their superior creep, stress rupture, melt resistance, and thermomechanical fatigue capabilities. Single-crystal materials have highly orthotropic properties making the position of the crystal lattice relative to the part geometry a significant and complicating factor. A fatigue failure criterion based on the maximum shear stress amplitude on the 24 octahedral and 6 cube slip systems is presented for single-crystal nickel superalloys (FCC crystal). This criterion greatly reduces the scatter in uniaxial fatigue data for PWA 1493 at 1,200 F in air. Additionally, single-crystal turbine blades used in the Space Shuttle main engine high pressure fuel turbopump/alternate turbopump are modeled using a three-dimensional finite element (FE) model. This model accounts for material orthotrophy and crystal orientation. Fatigue life of the blade tip is computed using FE stress results and the failure criterion that was developed. Stress analysis results in the blade attachment region are also presented. Results demonstrate that control of crystallographic orientation has the potential to significantly increase a component's resistance to fatigue crack growth without adding additional weight or cost.

Single crystal growth and characterization of pure and sodium-modified copper tartrate

NASA Astrophysics Data System (ADS)

Quasim, I.; Firdous, A.; Want, B.; Khosa, S. K.; Kotru, P. N.

2008-12-01

Single crystal growth of pure and modified copper tartrate crystals bearing composition (Cu) x(Na) yC 4H 4O 6· nH 2O (where x=1, 0.77, 0.65; y=0, 0.23, 0.35) is achieved using gel technique. The optimum conditions required for the growth of these crystals are worked out. The morphological development of these crystals is studied using optical and scanning electron microscopy. The dominant habit faces of the grown copper tartrate crystals are (0 0 1) and (1 1 1). Calculation of the cell parameters using CRYSFIRE software suggests that the pure copper tartrate crystal belongs to orthorhombic system with space group P2 1/c whereas the modified copper tartrate falls under tetragonal system with the space group P4 2/nbc. The external morphological development is shown to remain unaffected in the modified copper tartrate. The stoichiometric composition of the crystals is established by EDAX analysis, CH analysis, FTIR spectroscopy and thermoanalytical techniques. Thermal analysis of the grown crystals suggests that pure copper tartrate is thermally stable up to 42.84 °C whereas the modified copper tartrate crystals are stable only up to 33.11 and 25.11 °C. Calculation of the percentage weight loss from the thermogram supplemented by EDAX/CH analysis and FTIR spectroscopy suggest that the chemical formula of pure copper tartrate crystal is CuC 4H 4O 6·3H 2O whereas the chemical formula for the modified copper tartrate crystals is (Cu) 0.77(Na) 0.23C 4H 4O 6·3H 2O and (Cu) 0.65(Na) 0.35 C 4H 4O 6·H 2O.

Structural and quantum chemical analysis of exciton coupling in homo- and heteroaggregate stacks of merocyanines

NASA Astrophysics Data System (ADS)

Bialas, David; Zitzler-Kunkel, André; Kirchner, Eva; Schmidt, David; Würthner, Frank

2016-09-01

Exciton coupling is of fundamental importance and determines functional properties of organic dyes in (opto-)electronic and photovoltaic devices. Here we show that strong exciton coupling is not limited to the situation of equal chromophores as often assumed. Quadruple dye stacks were obtained from two bis(merocyanine) dyes with same or different chromophores, respectively, which dimerize in less-polar solvents resulting in the respective homo- and heteroaggregates. The structures of the quadruple dye stacks were assigned by NMR techniques and unambiguously confirmed by single-crystal X-ray analysis. The heteroaggregate stack formed from the bis(merocyanine) bearing two different chromophores exhibits remarkably different ultraviolet/vis absorption bands compared with those of the homoaggregate of the bis(merocyanine) comprising two identical chromophores. Quantum chemical analysis based on an extension of Kasha's exciton theory appropriately describes the absorption properties of both types of stacks revealing strong exciton coupling also between different chromophores within the heteroaggregate.

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.

Chem I Supplement: Liquid Crystals--The Chameleon Chemicals.

ERIC Educational Resources Information Center

Brown, Glenn H.

1983-01-01

Presents information relevant to everyday life so as to stimulate student interest in the properties of the two basic types of liquid crystals: thermotropic and lyotropic. Describes the applications of liquid crystals to electronics, biomedicine, and polymer science and appraises the future of liquid crystal research. (JM)

Crystal-field analysis of U3+ ions in K2LaX5 (X=Cl, Br or I) single crystals

NASA Astrophysics Data System (ADS)

Karbowiak, M.; Edelstein, N.; Gajek, Z.; Drożdżyński, J.

1998-11-01

An analysis of low temperature absorption spectra of U3+ ions doped in K2LaX5 (X=Cl, Br or I) single crystals is reported. The energy levels of the U3+ ion in the single crystals were assigned and fitted to a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions at the Cs symmetry site. An analysis of the nephelauxetic effect and crystal-field splittings in the series of compounds is also reported.

Electric propulsion reliability: Statistical analysis of on-orbit anomalies and comparative analysis of electric versus chemical propulsion failure rates

NASA Astrophysics Data System (ADS)

Saleh, Joseph Homer; Geng, Fan; Ku, Michelle; Walker, Mitchell L. R.

2017-10-01

With a few hundred spacecraft launched to date with electric propulsion (EP), it is possible to conduct an epidemiological study of EP's on orbit reliability. The first objective of the present work was to undertake such a study and analyze EP's track record of on orbit anomalies and failures by different covariates. The second objective was to provide a comparative analysis of EP's failure rates with those of chemical propulsion. Satellite operators, manufacturers, and insurers will make reliability- and risk-informed decisions regarding the adoption and promotion of EP on board spacecraft. This work provides evidence-based support for such decisions. After a thorough data collection, 162 EP-equipped satellites launched between January 1997 and December 2015 were included in our dataset for analysis. Several statistical analyses were conducted, at the aggregate level and then with the data stratified by severity of the anomaly, by orbit type, and by EP technology. Mean Time To Anomaly (MTTA) and the distribution of the time to (minor/major) anomaly were investigated, as well as anomaly rates. The important findings in this work include the following: (1) Post-2005, EP's reliability has outperformed that of chemical propulsion; (2) Hall thrusters have robustly outperformed chemical propulsion, and they maintain a small but shrinking reliability advantage over gridded ion engines. Other results were also provided, for example the differentials in MTTA of minor and major anomalies for gridded ion engines and Hall thrusters. It was shown that: (3) Hall thrusters exhibit minor anomalies very early on orbit, which might be indicative of infant anomalies, and thus would benefit from better ground testing and acceptance procedures; (4) Strong evidence exists that EP anomalies (onset and likelihood) and orbit type are dependent, a dependence likely mediated by either the space environment or differences in thrusters duty cycles; (5) Gridded ion thrusters exhibit both

X-ray texture analysis of paper coating pigments and the correlation with chemical composition analysis

NASA Astrophysics Data System (ADS)

Roine, J.; Tenho, M.; Murtomaa, M.; Lehto, V.-P.; Kansanaho, R.

2007-10-01

The present research experiments the applicability of x-ray texture analysis in investigating the properties of paper coatings. The preferred orientations of kaolin, talc, ground calcium carbonate, and precipitated calcium carbonate particles used in four different paper coatings were determined qualitatively based on the measured crystal orientation data. The extent of the orientation, namely, the degree of the texture of each pigment, was characterized quantitatively using a single parameter. As a result, the effect of paper calendering is clearly seen as an increase on the degree of texture of the coating pigments. The effect of calendering on the preferred orientation of kaolin was also evident in an independent energy dispersive spectrometer analysis on micrometer scale and an electron spectroscopy for chemical analysis on nanometer scale. Thus, the present work proves x-ray texture analysis to be a potential research tool for characterizing the properties of paper coating layers.

Survey and analysis of crystal polymorphism in organic structures

PubMed Central

Kaur, Ramanpreet

2018-01-01

With the intention of producing the most comprehensive treatment of the prevalence of crystal polymorphism among structurally characterized materials, all polymorphic compounds flagged as such within the Cambridge Structural Database (CSD) are analysed and a list of crystallographically characterized organic polymorphic compounds is assembled. Classifying these structures into subclasses of anhydrates, salts, hydrates, non-hydrated solvates and cocrystals reveals that there are significant variations in polymorphism prevalence as a function of crystal type, a fact which has not previously been recognized in the literature. It is also shown that, as a percentage, polymorphic entries are decreasing temporally within the CSD, with the notable exception of cocrystals, which continue to rise at a rate that is a constant fraction of the overall entries. Some phenomena identified that require additional scrutiny include the relative prevalence of temperature-induced phase transitions among organic salts and the paucity of polymorphism in crystals with three or more chemical components. PMID:29765601

Soft x-ray measurements using photoconductive type-IIa and single-crystal chemical vapor deposited diamond detectors

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

Moore, A. S.; Bentley, C. D.; Foster, J. M.

2008-10-15

Photoconductive detectors (PCDs) are routinely used alongside vacuum x-ray diodes (XRDs) to provide an alternative x-ray flux measurement at laser facilities such as HELEN at AWE Aldermaston, UK, and Omega at the Laboratory for Laser Energetics. To evaluate diamond PCDs as an alternative to XRD arrays, calibration measurements made at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory are used to accurately calculate the x-ray flux from a laser-heated target. This is compared to a flux measurement using the Dante XRD diagnostic. Estimates indicate that the photoinduced conductivity from measurements made at Omega are too large, and calculationsmore » using the radiometric calibrations made at the NSLS agree with this hypothesis. High-purity, single-crystal, chemical vapor deposited (CVD) diamond samples are compared to natural type-IIa PCDs and show promising high resistivity effects, the corollary of which preliminary results show is a slower response time.« 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

Method for solid state crystal growth

DOEpatents

Nolas, George S.; Beekman, Matthew K.

2013-04-09

A novel method for high quality crystal growth of intermetallic clathrates is presented. The synthesis of high quality pure phase crystals has been complicated by the simultaneous formation of both clathrate type-I and clathrate type-II structures. It was found that selective, phase pure, single-crystal growth of type-I and type-II clathrates can be achieved by maintaining sufficient partial pressure of a chemical constituent during slow, controlled deprivation of the chemical constituent from the primary reactant. The chemical constituent is slowly removed from the primary reactant by the reaction of the chemical constituent vapor with a secondary reactant, spatially separated from the primary reactant, in a closed volume under uniaxial pressure and heat to form the single phase pure crystals.

Crystal structure and theoretical studies of derivative of imidazo-1,2,4-triazine

NASA Astrophysics Data System (ADS)

Dybała, Izabela; Sztanke, Krzysztof

2016-09-01

In this study, we present the result of X-ray structure analysis of methyl [8-(3-chlorophenyl)-4-oxo-2,3,4,6,7,8-heksahydroimidazo[2,1-c][1,2,4]triazin-3-yl]acetate (1). The molecule conformation is flat, with a chlorophenyl substituent and the ester moiety lying in the plain of the heterobicyclic scaffold. Its conformation is stabilized by an intramolecular Nsbnd H…O hydrogen bond. Within the crystalline structure of 1, molecules associate with one another by weak Csbnd H…O, Csbnd H…Cl and Csbnd H…π bonds. The molecular and crystal structure of 1 was compared with the previously described structurally similar compound possessing the same bicyclic rigid core and similar chemical nature of the functional ester moiety. Very interesting differences in molecules geometry and association were observed. Non-covalent bonds within the crystals are additionally visualized by determination of Hirshfeld surfaces. Moreover, the quantum chemical calculation for 1 in the gas phase were carried out. The DFT calculation methods was used to optimize of molecule geometry and obtain molecular energy profiles with respect to selected torsion angles. The quantum chemical conformational analysis that was carried out for compound 1 in the gas phase suggests that in the solid state the molecules adopt the minimum energy conformation.

Likelihood of atom-atom contacts in crystal structures of halogenated organic compounds.

PubMed

Jelsch, Christian; Soudani, Sarra; Ben Nasr, Cherif

2015-05-01

The likelihood of occurrence of intermolecular contacts in crystals of halogenated organic compounds has been analysed statistically using tools based on the Hirshfeld surface. Several families of small halogenated molecules (containing organic F, Cl, Br or I atoms) were analysed, based on chemical composition and aromatic or aliphatic character. The behaviour of crystal contacts was also probed for molecules containing O or N. So-called halogen bonding (a halogen making short interactions with O or N, or a π interaction with C) is generally disfavoured, except when H is scarce on the molecular surface. Similarly, halogen⋯halogen contacts are more rare than expected, except for molecules that are poor in H. In general, the H atom is found to be the preferred partner of organic halogen atoms in crystal structures. On the other hand, C⋯C interactions in parallel π-stacking have a high propensity to occur in halogenated aromatic molecules. The behaviour of the four different halogen species (F, Cl, Br, I) is compared in several chemical composition contexts. The analysis tool can be refined by distinguishing several types for a given chemical species, such as H atoms bound to O or C. Such distinction shows, for instance, that C-H⋯Cl and O-H⋯O are the preferred interactions in compounds containing both O and Cl.

Silicon nanostructure arrays prepared by single step metal assisted chemical etching from single crystal wafer

NASA Astrophysics Data System (ADS)

Sarkar, Kalyan; Das, Debajyoti

2018-04-01

Arrays of silicon nanostructures have been produced by single step Metal Assisted Chemical Etching (MACE) of single crystal Si-wafers at room temp and normal atmospheric condition. By studying optical and structural properties of the silicon nanowire like structures synthesized by Ag catalyst assisted chemical etching, a significant change in the reflectance spectra has been obtained leading to a gross reduction in reflectance from ˜31% to less than 1%. In comparison with bulk c-Si, the surface areas of the nanostructured samples have been increased significantly with the etching time, leading to an efficient absorption of light, favorable for photovoltaic applications.

Influence of the chemical composition of rapidly quenched amorphous alloys (Ni, Fe, Cr)-B-Si on its crystallization process

NASA Astrophysics Data System (ADS)

Elmanov, G.; Dzhumaev, P.; Ivanitskaya, E.; Skrytnyi, V.; Ruslanov, A.

2016-04-01

This paper presents results of research of the structure and phase transformations during the multistage crystallization of the metallic glasses with the compositions Ni71,5Cr6,8Fe2,7B11,9Si7,1 and Ni63,4Cr7,4Fe4,3Mn0,8B15,6Si8,5 labeled as AWS BNi-2 according to American Welding Society. Differential scanning calorimetry (DSC), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis (EDX) were used as experimental research methods. The influence of the alloys chemical composition (boron, manganese and iron) on the temperatures and the exothermic heat effects of phase transformations, as well as on the phase composition of alloys at three stages of crystallization was analyzed. We present a thermodynamic explanation of the observed heat effects. It has been shown that manganese has the main influence on the phase transformations temperatures and heat effects in these two alloys. It is also assumed that at the final crystallization stage simultaneously with the formation of phases Ni3B and β1-Ni3Si should occur the nucleation of borides of CrB type with high Cr and low Si content.

A Rare Case of Anal and Perianal Chemical Burn in a Child due to Potassium Permanganate Crystals.

PubMed

Dash, Suvashis; Bhojani, Jatin; Sharma, Sharadendu

2018-02-09

Many chemicals used as medical treatments can cause chemical burns as an untoward side effect. One of such chemicals is potassium permanganate. It is a caustic chemical used as a disinfectant. The most common sites of burn by potassium permanganate are exposed sites like the face and hands. Chemical burns in the perianal and anal region are rare in clinical practice and even sparser in the pediatric age group. In this article, we report a case of perianal and anal chemical burn in an 18-month-old, male child, caused by potassium permanganate crystal applied wrongly for the treatment of pinworm infestation. As a chemical burn in this region can have serious complications, it is necessary to be vigilant when using such chemicals in these cases. Early and timely management in such cases leads to good outcomes. This is the first of such cases of chemical burn caused by potassium permanganate in the anal and perianal region.

Optical analysis of crystal growth

NASA Technical Reports Server (NTRS)

Workman, Gary L.; Passeur, Andrea; Harper, Sabrina

1994-01-01

Processing and data reduction of holographic images from Spacelab presents some interesting challenges in determining the effects of microgravity on crystal growth processes. Evaluation of several processing techniques, including the Computerized Holographic Image Processing System and the image processing software ITEX150, will provide fundamental information for holographic analysis of the space flight data.

Crystal Engineering for Low Defect Density and High Efficiency Hybrid Chemical Vapor Deposition Grown Perovskite Solar Cells.

PubMed

Ng, Annie; Ren, Zhiwei; Shen, Qian; Cheung, Sin Hang; Gokkaya, Huseyin Cem; So, Shu Kong; Djurišić, Aleksandra B; Wan, Yangyang; Wu, Xiaojun; Surya, Charles

2016-12-07

Synthesis of high quality perovskite absorber is a key factor in determining the performance of the solar cells. We demonstrate that hybrid chemical vapor deposition (HCVD) growth technique can provide high level of versatility and repeatability to ensure the optimal conditions for the growth of the perovskite films as well as potential for batch processing. It is found that the growth ambient and degree of crystallization of CH 3 NH 3 PbI 3 (MAPI) have strong impact on the defect density of MAPI. We demonstrate that HCVD process with slow postdeposition cooling rate can significantly reduce the density of shallow and deep traps in the MAPI due to enhanced material crystallization, while a mixed O 2 /N 2 carrier gas is effective in passivating both shallow and deep traps. By careful control of the perovskite growth process, a champion device with power conversion efficiency of 17.6% is achieved. Our work complements the existing theoretical studies on different types of trap states in MAPI and fills the gap on the theoretical analysis of the interaction between deep levels and oxygen. The experimental results are consistent with the theoretical predictions.

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.

Synthesis, crystal growth and characterization of a phase matchable nonlinear optical single crystal: p-chloro dibenzylideneacetone

NASA Astrophysics Data System (ADS)

Ravindra, H. J.; John Kiran, A.; Nooji, Satheesha Rai; Dharmaprakash, S. M.; Chandrasekharan, K.; Kalluraya, Balakrishna; Rotermund, Fabian

2008-05-01

Good quality single crystals of p-chloro dibenzylideneacetone (CDBA) of size 13 mm×8 mm×2 mm were grown by slow evaporation solution growth technique. The grown crystals were confirmed by elemental analysis, Fourier transform infrared (FTIR) analysis and single crystal X-ray diffraction techniques. From the thermo gravimetric/differential thermal (TG/DT) analysis, the CDBA was found to be thermally stable up to 250 °C. The mechanical stability of the crystal is comparable with that of the other reported chalcones. The lower optical cut-off wavelength for this crystal was observed at 440 nm. The laser damage threshold of the crystal was 0.6 GW/cm 2 at 532 nm. The second harmonic generation conversion efficiency of the powder sample of CDBA was found to be 4.5 times greater than that of urea. We also demonstrate the existence of the phase matching property in this crystal using Kurtz powder technique.

Suspect Screening Analysis of Chemicals in Consumer Products.

PubMed

Phillips, Katherine A; Yau, Alice; Favela, Kristin A; Isaacs, Kristin K; McEachran, Andrew; Grulke, Christopher; Richard, Ann M; Williams, Antony J; Sobus, Jon R; Thomas, Russell S; Wambaugh, John F

2018-03-06

A two-dimensional gas chromatography-time-of-flight/mass spectrometry (GC×GC-TOF/MS) suspect screening analysis method was used to rapidly characterize chemicals in 100 consumer products-which included formulations (e.g., shampoos, paints), articles (e.g., upholsteries, shower curtains), and foods (cereals)-and therefore supports broader efforts to prioritize chemicals based on potential human health risks. Analyses yielded 4270 unique chemical signatures across the products, with 1602 signatures tentatively identified using the National Institute of Standards and Technology 2008 spectral database. Chemical standards confirmed the presence of 119 compounds. Of the 1602 tentatively identified chemicals, 1404 were not present in a public database of known consumer product chemicals. Reported data and model predictions of chemical functional use were applied to evaluate the tentative chemical identifications. Estimated chemical concentrations were compared to manufacturer-reported values and other measured data. Chemical presence and concentration data can now be used to improve estimates of chemical exposure, and refine estimates of risk posed to human health and the environment.

Optical and dielectric studies of KH2PO4 crystal influenced by organic ligand of citric acid and L-valine: A single crystal growth and comparative study

NASA Astrophysics Data System (ADS)

Anis, Mohd; Hakeem, D. A.; Muley, G. G.

In the present study pure, citric acid (CA) and L-valine (LV) doped potassium dihydrogen phosphate (KDP) crystals have been grown with the aim to investigate the nonlinear optical applications facilitated by UV-visible, third order nonlinear optical (TONLO) and dielectric properties. The structural parameters of grown crystals have been confirmed by single crystal X-ray diffraction analysis. The enhancement in optical transparency of KDP crystal due to addition of CA and LV has been examined within 200-900 nm by means of UV-visible spectral analysis. In addition, the transmittance data have been used to evaluate the effect of dopants on reflectance, refractive index and extinction coefficient of grown crystals in the visible region. The Z-scan analysis has been performed at 632.8 nm to identify the nature of photoinduced nonlinear refraction and nonlinear absorption in doped KDP crystals. The influence of π-bonded ligand of dopant CA and LV on TONLO susceptibility (χ3), refractive index (n2) and absorption coefficient (β) of KDP crystals has been evaluated to discuss laser assisted device applications. The decrease in dielectric constant and dielectric loss of KDP crystal due to addition of CA and LV has been explored using the temperature dependent dielectric studies.

Growth of propyl-p-hydroxybenzoate single crystals and its characterizations

NASA Astrophysics Data System (ADS)

Karunagaran, N.; Ramasamy, P.

2012-06-01

Single crystals of Propyl-p-hydroxybenzoate (PHB) crystals have been grown by slow evaporation solution technique (SEST) using methanol as a solvent. The PHB single crystal of dimension up to 27×16×8 mm3 has been grown in a period of 18 days at room temperature. The optical transparency of the grown PHB crystal has been measured on (212) plane by UV-Vis-NIR spectrophotometer. The crystal has 60% of transparency in the entire visible region. The thermo gravimetric analysis (TG) and differential thermal analysis (DTA) studies reveal that the crystal is thermally stable up to 99°C. The mechanical strength of the grown PHB crystal is measured using Vickers microhardness tester. The chemical etching studies were carried out on (212) plane using methanol etchant. The laser damage threshold of PHB crystal is 1.3 GW/cm2. The dielectric properties have been investigated. The birefringence value is found to be 0.10148 at the wavelength of 504 nm. The refractive index of grown PHB single crystal is 1.6753.

Gold nanoparticle capture within protein crystal scaffolds.

PubMed

Kowalski, Ann E; Huber, Thaddaus R; Ni, Thomas W; Hartje, Luke F; Appel, Karina L; Yost, Jarad W; Ackerson, Christopher J; Snow, Christopher D

2016-07-07

DNA assemblies have been used to organize inorganic nanoparticles into 3D arrays, with emergent properties arising as a result of nanoparticle spacing and geometry. We report here the use of engineered protein crystals as an alternative approach to biologically mediated assembly of inorganic nanoparticles. The protein crystal's 13 nm diameter pores result in an 80% solvent content and display hexahistidine sequences on their interior. The hexahistidine sequence captures Au25(glutathione)∼17 (nitrilotriacetic acid)∼1 nanoclusters throughout a chemically crosslinked crystal via the coordination of Ni(ii) to both the cluster and the protein. Nanoparticle loading was validated by confocal microscopy and elemental analysis. The nanoparticles may be released from the crystal by exposure to EDTA, which chelates the Ni(ii) and breaks the specific protein/nanoparticle interaction. The integrity of the protein crystals after crosslinking and nanoparticle capture was confirmed by single crystal X-ray crystallography.

Growth and microtopographic study of CuInSe{sub 2} single crystals

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

Chauhan, Sanjaysinh M.; Chaki, Sunil, E-mail: sunilchaki@yahoo.co.in; Deshpande, M. P.

2016-05-23

The CuInSe{sub 2} single crystals were grown by chemical vapour transport (CVT) technique using iodine as transporting agent. The elemental composition of the as-grown CuInSe{sub 2} single crystals was determined by energy dispersive analysis of X-ray (EDAX). The unit cell crystal structure and lattice parameters were determined by X-ray diffraction (XRD) technique. The surface microtopographic study of the as-grown CuInSe{sub 2} single crystals surfaces were done to study the defects, growth mechanism, etc. of the CVT grown crystals.

Metal nanoinks as chemically stable surface enhanced scattering (SERS) probes for the analysis of blue BIC ballpoint pens.

PubMed

Alyami, A; Saviello, D; McAuliffe, M A P; Mirabile, A; Lewis, L; Iacopino, D

2017-06-07

Metal nanoinks constituted by Ag nanoparticles and Au nanorods were employed as probes for the Surface Enhanced Raman Scattering (SERS) analysis of a blue BIC ballpoint pen. The dye components of the pen ink were first separated by thin layer chromatography (TLC) and subsequently analysed by SERS at illumination wavelengths of 514 nm and 785 nm. Compared to normal Raman conditions, enhanced spectra were obtained for all separated spots, allowing easy identification of phthalocyanine Blue 38 and triarylene crystal violet in the ink mixture. A combination of effects such as molecular resonance, electromagnetic and chemical effects were the contributing factors to the generation of spectra enhanced compared to normal Raman conditions. Enhancement factors (EFs) between 5 × 10 3 and 3 × 10 6 were obtained, depending on the combination of SERS probes and laser illumination used. In contrast to previous conflicting reports, the metal nanoinks were chemically stable, allowing the collection of reproducible spectra for days after deposition on TLC plates. In addition and in advance to previously reported SERS probes, no need for additional aggregating agents or correction of electrostatic charge was necessary to induce the generation of enhanced SERS spectra.

Chemical consequences of compaction within the freezing front of a crystallizing magma ocean

NASA Astrophysics Data System (ADS)

Hier-Majumder, S.; Hirschmann, M. M.

2013-12-01

develop a simple 1-D model of melt retention in the freezing front of a crystallizing magma ocean, and apply it to the thermal and chemical evolution of the early Earth.

Crystallization mechanisms of acicular crystals

NASA Astrophysics Data System (ADS)

Puel, François; Verdurand, Elodie; Taulelle, Pascal; Bebon, Christine; Colson, Didier; Klein, Jean-Paul; Veesler, Stéphane

2008-01-01

In this contribution, we present an experimental investigation of the growth of four different organic molecules produced at industrial scale with a view to understand the crystallization mechanism of acicular or needle-like crystals. For all organic crystals studied in this article, layer-by-layer growth of the lateral faces is very slow and clear, as soon as the supersaturation is high enough, there is competition between growth and surface-activated secondary nucleation. This gives rise to pseudo-twinned crystals composed of several needle individuals aligned along a crystallographic axis; this is explained by regular over- and inter-growths as in the case of twinning. And when supersaturation is even higher, nucleation is fast and random. In an industrial continuous crystallization, the rapid growth of needle-like crystals is to be avoided as it leads to fragile crystals or needles, which can be partly broken or totally detached from the parent crystals especially along structural anisotropic axis corresponding to weaker chemical bonds, thus leading to slower growing faces. When an activated mechanism is involved such as a secondary surface nucleation, it is no longer possible to obtain a steady state. Therefore, the crystal number, size and habit vary significantly with time, leading to troubles in the downstream processing operations and to modifications of the final solid-specific properties. These results provide valuable information on the unique crystallization mechanisms of acicular crystals, and show that it is important to know these threshold and critical values when running a crystallizer in order to obtain easy-to-handle crystals.

Comparative study of glycine single crystals with additive of potassium nitrate in different concentration ratios

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

Gujarati, Vivek P., E-mail: vivekgujarati@gmail.com; Deshpande, M. P., E-mail: vishwadeshpande@yahoo.co.in; Patel, Kamakshi R.

2016-05-06

Semi-organic crystals of Glycine Potassium Nitrate (GPN) with potential applications in Non linear optics (NLO) were grown using slow evaporation technique. Glycine and Potassium Nitrate were taken in three different concentration ratios of 3:1, 2:1 and 1:1 respectively. We checked the solubility of the material in distilled water at different temperatures and could observe the growth of crystals in 7 weeks time. Purity of the grown crystals was confirmed by Energy Dispersive X-ray Analysis (EDAX) and CHN analysis. GSN Powder X-ray diffraction pattern was recorded to confirm the crystalline nature. To confirm the applications of grown crystals in opto-electronics field,more » UV-Vis-NIR study was carried out. Dielectric properties of the samples were studied in between the frequency range 1Hz to 100 KHz.« less

Microstructure and conductivity of in-situ polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) crystals

NASA Astrophysics Data System (ADS)

Liu, Jinglin; Ouyang, Liangqi; Wu, Jinghang; Kuo, Chin-Chen; Wei, Bin; Martin, David

2013-03-01

Conjugated polymers are widely used in organic solar cells, biomedical devices, and chemical sensors. Both chemical and electrochemical methods have been developed for preparing conducting polymers, but the extent of crystalline order is usually modest. Here we synthesized highly-ordered brominated (3,4-ethylenedioxythiophene) (EDOT-Br) monomer crystals via electrochemical methods. The kinetics of the synthesis was studied with a Quartz Crystal Microbalance (QCM) and Cyclic Voltammetry (CV). The chemical structure of the EDOT-Br monomer has been confirmed by Nuclear Magnetic Resonance (NMR), Ultraviolet-Visible Spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), and Mass Spectrometry (MS). The EDOT-Br monomer crystals can be in-situ polymerized into highly ordered PEDOT conjugated polymer crystals by annealing at temperatures below the EDOT-Br melting point. The crystalline structure was studied by optical microscopy, electron microscopy and X-Ray analysis. The conductivity and electrochemical properties of both the EDOT-Br monomer and corresponding PEDOT polymer crystals were examined with electrochemical impedance spectroscopy (EIS) and CV. This work was supported by NSF, DMR- 1103027.

Cross correlation of chemical profiles in minerals: Technical issues and numerical methods

NASA Astrophysics Data System (ADS)

Probst, Line; Caricchi, Luca; Gander, Martin; Wallace, Glen; Sheldrake, Tom

2017-04-01

Crystals grown in magma reservoirs and develop chemical zoning because of the lack of re-equilibration when thermodynamic conditions change. Therefore, the study of chemical zoning in minerals offers the opportunity to reconstruct the pre-eruptive conditions and the temporal evolution of magma reservoirs. We are building a quantitative method that allows the comparison between zonation patterns within minerals. The aim of this method is to identify if similar crystal have partially similar zonation patterns and thus shared a part of their growth history. Our method is based on the correlation method developed first by G. Wallace and G. Bergantz (2004). Here we present some technical issues linked to the use of a numerical method to compare crystals within their textural context in thin sections. The first issue is related to the acquisition of chemical profiles from images of thin sections (e.g. BSE or cathodoluminescence images). We present a new procedure that significantly improves both image and profile processing. A second issue is related to the random orientation of crystals in a thin section. The software we are building takes in account different orientation of crystals by applying different stretching factors to chemical profiles. Thus the automated selection of the best stretching factor is crucial for the rest of the procedure. The last point is the significance level, the threshold above which the correlation between two profiles is considered as real (and not random). This threshold must also be carefully defined and justified. All these points were studied with statistical analysis and we present results leading to a more reliable and robust method. [1] Wallace, G.S. and Bergantz, G.W., 2004. Constraints on mingling of crystal populations from off-center zoning profiles: A statistical approach. American Mineralogist, vol. 89 (1), pp. 64-73. [2] Wallace, G.S. and Bergantz, G.W., 2004. Reconciling heterogeneity in crystal zoning data: An application of

Frequency conversion of cw chemical HF laser radiation in nonlinear crystals

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

Klement'ev, V.M.; Kolpakov, Y.G.; Pecherskii, Y.Y.

1977-07-01

A description is given of a cw chemical HF laser and its characteristics. The results are reported of investigations of the efficiency of conversion of the HF laser radiation into second harmonics and combination frequencies in LiNbO/sub 3/, LiIO/sub 3/, and Ag/sub 3/AsS/sub 3/ crystals. The most efficient conversion was achieved in proustite (Ag/sub 3/AsS/sub 3/) when the second-harmonic power was approx.3..mu..W and the fundamental-frequency power was approx.100 mW. Twenty-one emission lines were obtained in the 1.39--1.49 ..mu.. range. The HF laser radiation was converted to the visible range (0.522--0.516 ..mu..).

Boron Arsenide and Boron Phosphide for High Temperature and Luminescent Devices. [semiconductor devices - crystal growth/crystal structure

NASA Technical Reports Server (NTRS)

Chu, T. L.

1975-01-01

The crystal growth of boron arsenide and boron phosphide in the form of bulk crystals and epitaxial layers on suitable substrates is discussed. The physical, chemical, and electrical properties of the crystals and epitaxial layers are examined. Bulk crystals of boron arsenide were prepared by the chemical transport technique, and their carrier concentration and Hall mobility were measured. The growth of boron arsenide crystals from high temperature solutions was attempted without success. Bulk crystals of boron phosphide were also prepared by chemical transport and solution growth techniques. Techniques required for the fabrication of boron phosphide devices such as junction shaping, diffusion, and contact formation were investigated. Alloying techniques were developed for the formation of low-resistance ohmic contacts to boron phosphide. Four types of boron phosphide devices were fabricated: (1) metal-insulator-boron phosphide structures, (2) Schottky barriers; (3) boron phosphide-silicon carbide heterojunctions; and (4) p-n homojunctions. Easily visible red electroluminescence was observed from both epitaxial and solution grown p-n junctions.

Synthesis, characterization, single crystal X-ray and DFT analysis of disubstituted phosphorodithioates

NASA Astrophysics Data System (ADS)

Kour, Mandeep; Kumar, Sandeep; Feddag, Ahmed; Andotra, Savit; Chouaih, Abdelkader; Gupta, Vivek K.; Kant, Rajni; Pandey, Sushil K.

2018-04-01

Disubstituted phosphorodithioates of the type [{(2,5-CH3)2C6H3O}2PS2HNEt3] (1) and [{(3,5-CH3)2C6H3O)2(PS2)}2] (2) were synthesized and characterized by IR and NMR (1H,13C and 31P) spectroscopic studies and as single crystal X-ray analysis. The compound 1 crystallizes in monoclinic space group P21/c whereas compound 2 crystallizes in triclinic space group Pbar1. The X-ray analysis reveals that in compound 1 phosphorus atom is coordinated to the two S and two O atoms to form tetrahedral geometry. The structure is stabilized by cation-anion Nsbnd H⋯S hydrogen bonded interactions. In compound 2, the two phosphorus atoms have a distorted tetrahedral geometry coordinated to two (3,5-CH3)2C6H3O groups. The molecule possesses a crystallographic center of symmetry and consists of zig-zag array of Sdbnd Psbnd Ssbnd Ssbnd Pdbnd S linkages with two diphenyldithiophosphate moieties in the trans configuration. Molecular geometries, HOMO-LUMO analysis and molecular electrostatic potential of compounds 1 and 2 are investigated by theoretical calculations using B3LYP functional with the 6-311G basis combination set in the ground state and compared with the experimental values.

Crystal Chemical Controls on Equation of State

NASA Astrophysics Data System (ADS)

Thompson, R. M.; McCarthy, A. C.; Downs, R. T.

2007-12-01

Minerals are known to compress through a number of mechanisms, ranging from polyhedral distortion to electronic transitions. Two mechanisms which can produce significant volume decreases are angle-bending and bond compression. The crystal chemical effects of these two mechanisms have been studied and documented for years. With more recent advances in theory and software enabling the accurate determination of bonding topologies, M-O bonding to bridging oxygens has been shown to modify compressibility by changing angle-bending force constants. Minerals that compress mainly through angle-bending tend be soft. Good examples are quartz and cristobalite, minerals composed solely of corner-sharing silicate tetrahedra with bulk moduli of 37 and 12 GPa, respectively. Rock salt structured oxides must compress strictly by bond compression, and are much stiffer - lime and periclase have bulk moduli of 111 and 156 GPa, respectively. Feldspars have bulk moduli intermediate to the above examples. Based solely on the presence of Al-O-Si angles, theoretically softer than Si-O-Si angles, feldspars should be softer than quartz or cristobalite, but the T-O-T angles are stiffened by bonds to interstitial cations. The number and nature of these bonds affects compressibility sufficiently to create exceptions to Bridgman's law, which correlates bulk modulus with ambient unit cell volume in isostructural materials. In this paper, we present new high-pressure refinements of the crystal structures of jadeite, aegirine, and NaGa- clinopyroxene. Bulk moduli of these pyroxenes and all other end-member clinopyroxenes we could find in the literature (19 total) are plotted vs. unit cell volumes to test Bridgman's law. The data fall along two trends, each of which is separately consistent with Bridgman's law. Pyroxenes in one trend are dramatically stiffer than those in the other trend, with bulk moduli that differ by approximately 40 GPa. The only difference between the topologies of the

Crysalis: an integrated server for computational analysis and design of protein crystallization.

PubMed

Wang, Huilin; Feng, Liubin; Zhang, Ziding; Webb, Geoffrey I; Lin, Donghai; Song, Jiangning

2016-02-24

The failure of multi-step experimental procedures to yield diffraction-quality crystals is a major bottleneck in protein structure determination. Accordingly, several bioinformatics methods have been successfully developed and employed to select crystallizable proteins. Unfortunately, the majority of existing in silico methods only allow the prediction of crystallization propensity, seldom enabling computational design of protein mutants that can be targeted for enhancing protein crystallizability. Here, we present Crysalis, an integrated crystallization analysis tool that builds on support-vector regression (SVR) models to facilitate computational protein crystallization prediction, analysis, and design. More specifically, the functionality of this new tool includes: (1) rapid selection of target crystallizable proteins at the proteome level, (2) identification of site non-optimality for protein crystallization and systematic analysis of all potential single-point mutations that might enhance protein crystallization propensity, and (3) annotation of target protein based on predicted structural properties. We applied the design mode of Crysalis to identify site non-optimality for protein crystallization on a proteome-scale, focusing on proteins currently classified as non-crystallizable. Our results revealed that site non-optimality is based on biases related to residues, predicted structures, physicochemical properties, and sequence loci, which provides in-depth understanding of the features influencing protein crystallization. Crysalis is freely available at http://nmrcen.xmu.edu.cn/crysalis/.

Investigations on nucleation, HRXRD, optical, piezoelectric, polarizability and Z-scan analysis of L-arginine maleate dihydrate single crystals

NASA Astrophysics Data System (ADS)

Sakthy Priya, S.; Alexandar, A.; Surendran, P.; Lakshmanan, A.; Rameshkumar, P.; Sagayaraj, P.

2017-04-01

An efficient organic nonlinear optical single crystal of L-arginine maleate dihydrate (LAMD) has been grown by slow evaporation solution technique (SEST) and slow cooling technique (SCT). The crystalline perfection of the crystal was examined using high-resolution X-ray diffractometry (HRXRD) analysis. Photoluminescence study confirmed the optical properties and defects level in the crystal lattice. Electromechanical behaviour was observed using piezoelectric co-efficient (d33) analysis. The photoconductivity analysis confirmed the negative photoconducting nature of the material. The dielectric constant and loss were measured as a function of frequency with varying temperature and vice-versa. The laser damage threshold (LDT) measurement was carried out using Nd:YAG Laser with a wavelength of 1064 nm (Focal length is 35 cm) and the obtained results showed that LDT value of the crystal is high compared to KDP crystal. The high laser damage threshold of the grown crystal makes it a potential candidate for second and higher order nonlinear optical device application. The third order nonlinear optical parameters of LAMD crystal is determined by open-aperture and closed-aperture studies using Z-scan technique. The third order linear and nonlinear optical parameters such as the nonlinear refractive index (n2), two photon absorption coefficient (β), Real part (Reχ3) and imaginary part (Imχ3) of third-order nonlinear optical susceptibility are calculated.

Expression, purification, crystallization and preliminary X-ray analysis of tannase from Lactobacillus plantarum.

PubMed

Wu, Mingbo; Peng, Xiaohong; Wen, Hua; Wang, Qin; Chen, Qianming; McKinstry, William J; Ren, Bin

2013-04-01

Tannase catalyses the hydrolysis of the galloyl ester bond of tannins to release gallic acid. It belongs to the serine esterases and has wide applications in the food, feed, beverage, pharmaceutical and chemical industries. The tannase from Lactobacillus plantarum was cloned, expressed and purified. The protein was crystallized by the sitting-drop vapour-diffusion method with microseeding. The crystals belonged to space group P1, with unit-cell parameters a = 46.5, b = 62.8, c = 83.8 Å, α = 70.4, β = 86.0, γ = 79.4°. Although the enzyme exists mainly as a monomer in solution, it forms a dimer in the asymmetric unit of the crystal. The crystals diffracted to beyond 1.60 Å resolution using synchrotron radiation and a complete data set was collected to 1.65 Å resolution.

a Study of the Synchrotron Laue Method for Quantitative Crystal Structure Analysis.

NASA Astrophysics Data System (ADS)

Gomez de Anderez, Dora M.

1990-01-01

Available from UMI in association with The British Library. Quantitative crystal structure analyses have been carried out on small molecule crystals using synchrotron radiation and the Laue method. A variety of single crystal structure determinations and associated refinements are used and compared with the monochromatic analyses. The new molecular structure of 7-amino-5-bromo -4-methyl-2-oxo-1,2,3,4-tetrahidro-1, 6 -naphthyridine-8-carbonitrile (C_{10 }H_9ON_4 Br.H_2O) has been determined, first using monochromatic Mo Kalpha radiation and a four-circle diffractometer, then using synchrotron Laue diffraction photography. The structure refinements showed a R-factor of 4.97 and 14.0% for the Mo Kalpha and Laue data respectively. The molecular structure of (S)-2-chloro-2-fluoro-N-((S)-1-phenylethyl) ethanamide, (C_{10}H _{11}ClFNO), has been determined using the same crystal throughout for X-ray monochromatic analyses (Mo Kalpha and Cu K alpha) followed by synchrotron Laue data collection. The Laue and monochromatic data compare favourably. The R -factors (on F) were 6.23, 6.45 and 8.19% for the Mo K alpha, Cu Kalpha and Laue data sets respectively. The molecular structure of 3-(5-hydroxy-3-methyl-1-phenylpyrazol-4-yl)-1,3-diphenyl -prop- 2-en-1-one, (C_{25 }H_{20}N _2O_2) has been determined using the synchrotron Laue method. The results compare very well with Mo Kalpha monochromatic data. The R-factors (on F) were 4.60 and 5.29% for Mo Kalpha and Laue analysis respectively. The Laue method is assessed in locating the 20 hydrogen atoms in this structure. The structure analysis of the benzil compound ((C_6H_5 O.CO_2)) is carried out using the synchrotron Laue method firstly at room temperature and secondly at low temperature -114 ^circC. The structure shows an R-factor (on F) of 13.06% and 6.85% for each data set respectively. The synchrotron Laue method was used to collect data for ergocalciferol (Vitamin D_2). The same crystal was also used to record oscillation

Antiswarming: Structure and dynamics of repulsive chemically active particles

NASA Astrophysics Data System (ADS)

Yan, Wen; Brady, John F.

2017-12-01

Chemically active Brownian particles with surface catalytic reactions may repel each other due to diffusiophoretic interactions in the reaction and product concentration fields. The system behavior can be described by a "chemical" coupling parameter Γc that compares the strength of diffusiophoretic repulsion to Brownian motion, and by a mapping to the classical electrostatic one component plasma (OCP) system. When confined to a constant-volume domain, body-centered cubic (bcc) crystals spontaneously form from random initial configurations when the repulsion is strong enough to overcome Brownian motion. Face-centered cubic (fcc) crystals may also be stable. The "melting point" of the "liquid-to-crystal transition" occurs at Γc≈140 for both bcc and fcc lattices.

Thermodynamic analysis and purifying an amorphous phase of frozen crystallization centers

NASA Astrophysics Data System (ADS)

Lysov, V. I.; Tsaregradskaya, T. L.; Turkov, O. V.; Saenko, G. V.

2017-12-01

The possibility of dissolving frozen crystallization centers in amorphous alloys of the Fe-B system is considered by means of thermodynamic calculations. This can in turn improve the thermal stability of an amorphous alloy. The effect isothermal annealing has on the thermal stability of multicomponent amorphous alloys based on iron is investigated via the highly sensitive dilatometric technique, measurements of microsolidity, and electron microscopic investigations. The annealing temperature is determined empirically on the basis of the theses of the thermodynamic theory of the high temperature stability of multicomponent amorphous alloys, according to which there exists a range of temperatures that is characterized by a negative difference between the chemical potentials of phases in a heterogeneous amorphous matrix-frozen crystallization centers system. The thermodynamic condition of the possible dissolution of frozen crystallization centers is thus met. It is shown that introducing regimes of thermal processing allows us to expand the ranges of the thermal stability of iron-based amorphous alloys by 20-40 K through purifying an amorphous matrix of frozen crystallization centers. This conclusion is proved via electron microscopic investigations.

Analysis of Pfizer compounds in EPA's ToxCast chemicals-assay space.

PubMed

Shah, Falgun; Greene, Nigel

2014-01-21

The U.S. Environmental Protection Agency (EPA) launched the ToxCast program in 2007 with the goal of evaluating high-throughput in vitro assays to prioritize chemicals that need toxicity testing. Their goal was to develop predictive bioactivity signatures for toxic compounds using a set of in vitro assays and/or in silico properties. In 2009, Pfizer joined the ToxCast initiative by contributing 52 compounds with preclinical and clinical data for profiling across the multiple assay platforms available. Here, we describe the initial analysis of the Pfizer subset of compounds within the ToxCast chemical (n = 1814) and in vitro assay (n = 486) space. An analysis of the hit rate of Pfizer compounds in the ToxCast assay panel allowed us to focus our mining of assays potentially most relevant to the attrition of our compounds. We compared the bioactivity profile of Pfizer compounds to other compounds in the ToxCast chemical space to gain insights into common toxicity pathways. Additionally, we explored the similarity in the chemical and biological spaces between drug-like compounds and environmental chemicals in ToxCast and compared the in vivo profiles of a subset of failed pharmaceuticals having high similarity in both spaces. We found differences in the chemical and biological spaces of pharmaceuticals compared to environmental chemicals, which may question the applicability of bioactivity signatures developed exclusively based on the latter to drug-like compounds if used without prior validation with the ToxCast Phase-II chemicals. Finally, our analysis has allowed us to identify novel interactions for our compounds in particular with multiple nuclear receptors that were previously not known. This insight may help us to identify potential liabilities with future novel compounds.

Comparative analysis of 2D spatio-temporal visualisation techniques for the pulsed THz-radiation field using an electro-optic crystal

NASA Astrophysics Data System (ADS)

Ushakov, A. A.; Chizhov, P. A.; Bukin, V. V.; Garnov, S. V.; Savel'ev, A. B.

2018-05-01

Two 2D techniques for visualising the field of pulsed THz radiation ('shadow' and 'interferometric'), which are based on the linear electro-optical effect with application of a ZnTe detector crystal 1 × 1 cm in size, are compared. The noise level and dynamic range for the aforementioned techniques are analysed and their applicability limits are discussed.

The proposed biosynthesis of procyanidins by the comparative chemical analysis of five Camellia species using LC-MS

PubMed Central

Zhang, Liang; Tai, Yuling; Wang, Yijun; Meng, Qilu; Yang, Yunqiu; Zhang, Shihua; Yang, Hua; Zhang, Zhengzhu; Li, Daxiang; Wan, Xiaochun

2017-01-01

The genus Camellia (C.) contains many species, including C. sinensis, C. assamica, and C. taliensis, C. gymnogyna and C. tachangensis. The polyphenols of C. sinensis and C. assamica are flavan-3-ols monomers and their dimers and trimmers. However, the biosynthesis of procyanidins in Camellia genus remains unclear. In the present study, a comparative chemical analysis of flavan-3-ols, flavan-3-ols glycoside and procyanidins was conducted by high performance liquid chromatography (HPLC) and liquid chromatography diode array detection coupled with triple-quadrupole mass-spectrometry (LC-DAD-QQQ-MS). The results showed that C. tachangensis had a significant higher contents of (-)-epicatechin (EC) and (-)-epigallocatechin (EGC) compared with C. sinensis (p < 0.001). By contrast, higher levels of galloylated catechins were detected in C. sinensis. LC-DAD-MS/MS indicated that the main secondary metabolites of C. tachangensis were non-galloylated catechins, procyanidin dimers and trimers. Furthermore, (-)-epicatechin glucose (EC-glucose) and (-)-epigallocatechin glucose (EGC-glucose) were also abundant in C. tachangensis. A correlation analysis of EC-glucose and procyanidins dimers was conducted in five Camellia species. The levels of EC-glucose were closely related to the procyanidin dimers content. Thus, it was suggested that EC-glucose might be an important substrate for the biosynthesis of procyanidins. PMID:28383067

Crystal-Chemical Correlations in Chromites from Kimberlitic and Non-Kimberlitic Sources.

NASA Astrophysics Data System (ADS)

Freckelton, C. N.; Flemming, R. L.

2009-05-01

This study explores the utility of micro X-ray diffraction (μXRD) as a tool for diamond exploration, as a compliment to current industry-standard techniques such as electron probe microanalysis (EPMA). Here we examine chromite. As one of the first phases to crystallize in mantle rocks, it is a useful indicator of upper mantle magmatic conditions in rocks that have been sampled by kimberlites. In addition, chromite does not alter easily from chemical and physical weathering processes. As such, chromite is a useful kimberlite indicator mineral in diamond exploration. We present correlations between crystal structure (unit cell) and chemical composition of chromite, (Fe,Mg)[Cr, Al]2O4, using correlated μXRD and EPMA data for 133 chromites from a three source locations: Two kimberlite sources and one non-kimberlitic source from an Archean granite/greenstone terrain. Quantitative analysis was performed using Electron Probe Microanalysis (EPMA) at Mineral Services, South Africa, prior to the loan of the samples. Randomly-oriented chromite grains, approximately 500 μm in diameter, were analyzed as previously mounted for EPMA. Micro X-ray-diffraction was performed using a Bruker D8-Discover Diffractometer, with θ-θ geometry, with CuKα radiation, operating at 40 kV and 40 mA, with nominal beam diameter of 500 μm. The data were collected in omega scan mode. Two dimensional General Area Detector Diffraction System (GADDS) images were collected for 20 minutes per image, and integrated to produce one-dimensional plots of intensity versus 2θ, for subsequent unit cell refinement using CELREF. Although all samples in this study were considered to be 'chromite', a plot of Cr/(Cr+Al) versus Fe2+/(Fe2++Mg) shows extensive substitution among four dominant members: chromite (FeCr2O4), magnesio-chromite (MgCr2O4), spinel (MgAl2O4), and hercynite (FeAl2O4), where Mg and Fe2+ substitute for one another on the tetrahedral site, and Cr and Al substitute for one another on the

SEMICONDUCTOR MATERIALS: Chemical etching of a GaSb crystal incorporated with Mn grown by the Bridgman method under microgravity conditions

NASA Astrophysics Data System (ADS)

Xiaofeng, Chen; Nuofu, Chen; Jinliang, Wu; Xiulan, Zhang; Chunlin, Chai; Yude, Yu

2009-08-01

A GaSb crystal incorporated with Mn has been grown by the Bridgman method on the Polizon facility onboard the FOTON-M3 spacecraft. Structural defects and growth striations have been successfully revealed by the chemical etching method. By calculating various parameters of the convection, the striation patterns can be explained, and the critical value of the Taylor number, which characterizes the convective condition of the rotating magnetic field induced azimuthal flow, was shown. The stresses generated during crystal growth can be reflected by the observations of etch pit distribution and other structural defects. Suggestions for improving the space experiment to improve the quality of the crystal are given.

Preparation, crystal structure, vibrational spectral and density functional studies of bis (4-nitrophenol)-2,4,6-triamino-1,3,5-triazine monohydrate

NASA Astrophysics Data System (ADS)

Kanagathara, N.; Marchewka, M. K.; Drozd, M.; Renganathan, N. G.; Gunasekaran, S.; Anbalagan, G.

2013-10-01

An organic-organic salt, bis (4-nitrophenol) 2,4,6-triamino 1,3,5-triazine monohydrate (BNPM) has been prepared by slow evaporation technique at room temperature. Single crystal X-ray diffraction analysis reveals that the compound crystallizes in triclinic system with centrosymmetric space group P-1. IR and Raman spectra of BNPM have been recorded and analyzed. The study has been extended to confocal Raman spectral analysis. Band assignments have been made for the melamine and p-nitrophenol molecules. Vibrational spectra have also been discussed on the basis of quantum chemical density functional theory calculations using Firefly (PC GAMESS) Version 7.1 G. Vibrational frequencies are calculated and scaled values are compared with the experimental one. The Mulliken charges, HOMO-LUMO orbital energies are calculated and analyzed. The chemical structure of the compound was established by 1H NMR and 13C NMR spectra.

Crysalis: an integrated server for computational analysis and design of protein crystallization

PubMed Central

Wang, Huilin; Feng, Liubin; Zhang, Ziding; Webb, Geoffrey I.; Lin, Donghai; Song, Jiangning

2016-01-01

The failure of multi-step experimental procedures to yield diffraction-quality crystals is a major bottleneck in protein structure determination. Accordingly, several bioinformatics methods have been successfully developed and employed to select crystallizable proteins. Unfortunately, the majority of existing in silico methods only allow the prediction of crystallization propensity, seldom enabling computational design of protein mutants that can be targeted for enhancing protein crystallizability. Here, we present Crysalis, an integrated crystallization analysis tool that builds on support-vector regression (SVR) models to facilitate computational protein crystallization prediction, analysis, and design. More specifically, the functionality of this new tool includes: (1) rapid selection of target crystallizable proteins at the proteome level, (2) identification of site non-optimality for protein crystallization and systematic analysis of all potential single-point mutations that might enhance protein crystallization propensity, and (3) annotation of target protein based on predicted structural properties. We applied the design mode of Crysalis to identify site non-optimality for protein crystallization on a proteome-scale, focusing on proteins currently classified as non-crystallizable. Our results revealed that site non-optimality is based on biases related to residues, predicted structures, physicochemical properties, and sequence loci, which provides in-depth understanding of the features influencing protein crystallization. Crysalis is freely available at http://nmrcen.xmu.edu.cn/crysalis/. PMID:26906024

Crystal Growth Technology

NASA Astrophysics Data System (ADS)

Scheel, Hans J.; Fukuda, Tsuguo

2004-06-01

This volume deals with the technologies of crystal fabrication, of crystal machining, and of epilayer production and is the first book on industrial and scientific aspects of crystal and layer production. The major industrial crystals are treated: Si, GaAs, GaP, InP, CdTe, sapphire, oxide and halide scintillator crystals, crystals for optical, piezoelectric and microwave applications and more. Contains 29 contributions from leading crystal technologists covering the following topics:

General aspects of crystal growth technology Silicon Compound semiconductors Oxides and halides Crystal machining Epitaxy and layer deposition Scientific and technological problems of production and machining of industrial crystals are discussed by top experts, most of them from the major growth industries and crystal growth centers. In addition, it will be useful for the users of crystals, for teachers and graduate students in materials sciences, in electronic and other functional materials, chemical and metallurgical engineering, micro-and optoelectronics including nanotechnology, mechanical engineering and precision-machining, microtechnology, and in solid-state sciences.

• Expression, purification, crystallization and preliminary X-ray analysis of tannase from Lactobacillus plantarum

  PubMed Central

  Wu, Mingbo; Peng, Xiaohong; Wen, Hua; Wang, Qin; Chen, Qianming; McKinstry, William J.; Ren, Bin

  2013-01-01

  Tannase catalyses the hydrolysis of the galloyl ester bond of tannins to release gallic acid. It belongs to the serine esterases and has wide applications in the food, feed, beverage, pharmaceutical and chemical industries. The tannase from Lactobacillus plantarum was cloned, expressed and purified. The protein was crystallized by the sitting-drop vapour-diffusion method with microseeding. The crystals belonged to space group P1, with unit-cell paramters a = 46.5, b = 62.8, c = 83.8 Å, α = 70.4, β = 86.0, γ = 79.4°. Although the enzyme exists mainly as a monomer in solution, it forms a dimer in the asymmetric unit of the crystal. The crystals diffracted to beyond 1.60 Å resolution using synchrotron radiation and a complete data set was collected to 1.65 Å resolution. PMID:23545659

• Topological Characterization of Carbon Graphite and Crystal Cubic Carbon Structures.

  PubMed

  Siddiqui, Wei Gao Muhammad Kamran; Naeem, Muhammad; Rehman, Najma Abdul

  2017-09-07

  Graph theory is used for modeling, designing, analysis and understanding chemical structures or chemical networks and their properties. The molecular graph is a graph consisting of atoms called vertices and the chemical bond between atoms called edges. In this article, we study the chemical graphs of carbon graphite and crystal structure of cubic carbon. Moreover, we compute and give closed formulas of degree based additive topological indices, namely hyper-Zagreb index, first multiple and second multiple Zagreb indices, and first and second Zagreb polynomials.

• Effect of medicinal plants on the crystallization of cholesterol

  NASA Astrophysics Data System (ADS)

  Saraswathi, N. T.; Gnanam, F. D.

  1997-08-01

  One of the least desirable calcifications in the human body is the mineral deposition in atherosclerosis plaques. These plaques principally consist of lipids such as cholesterol, cholesteryl esters, phospholipids and triglycerides. Chemical analysis of advanced plaques have shown the presence of considerable amounts of free cholesterol identified as cholesterol monohydrate crystals. Cholesterol has been crystallized in vitro. The extracts of some of the Indian medicinal plants detailed below were used as additives to study their effect on the crystallization behaviour of cholesterol. It has been found that many of the herbs have inhibitory effect on the crystallization such as nucleation, crystal size and habit modification. The inhibitory effect of the plants are graded as Commiphora mughul > Aegle marmeleos > Cynoden dactylon > Musa paradisiaca > Polygala javana > Alphinia officinarum > Solanum trilobatum > Enicostemma lyssopifolium.

• Chemical disorder influence on magnetic state of optimally-doped La0.7Ca0.3MnO3

  NASA Astrophysics Data System (ADS)

  Rozenberg, E.; Auslender, M.; Shames, A. I.; Jung, G.; Felner, I.; Tsindlekht, M. I.; Mogilyansky, D.; Sominski, E.; Gedanken, A.; Mukovskii, Ya. M.; Gorodetsky, G.

  2011-10-01

  X-band electron magnetic resonance and dc/ac magnetic measurements have been employed to study the effects of chemical disorder on magnetic ordering in bulk and nanometer-sized single crystals and bulk ceramics of optimally-doped La0.7Ca0.3MnO3 manganite. The magnetic ground state of bulk samples appeared to be ferromagnetic with the lower Curie temperature and higher magnetic homogeneity in the vicinity of the ferromagnetic-paramagnetic phase transition in the crystal, as compared with those characteristics in the ceramics. The influence of technological driven "macroscopic" fluctuations of Ca-dopant level in crystal and "mesoscopic" disorder within grain boundary regions in ceramics was proposed to be responsible for these effects. Surface spin disorder together with pronounced inter-particle interactions within agglomerated nano-sample results in well defined core/shell spin configuration in La0.7Ca0.3MnO3 nano-crystals. The analysis of the electron paramagnetic resonance data enlightened the reasons for the observed difference in the magnetic order. Lattice effects dominate the first-order nature of magnetic phase transition in bulk samples. However, mesoscale chemical disorder seems to be responsible for the appearance of small ferromagnetic polarons in the paramagnetic state of bulk ceramics. The experimental results and their analysis indicate that a chemical/magnetic disorder has a strong impact on the magnetic state even in the case of mostly stable optimally hole-doped manganites.

• Crystal growth and characterization of semi-organic 2-amino-5-nitropyridinium bromide (2A5NPBr) single crystals for third-order nonlinear optical (NLO) applications

  NASA Astrophysics Data System (ADS)

  Vediyappan, Sivasubramani; Arumugam, Raja; Pichan, Karuppasamy; Kasthuri, Ramachandran; Muthu, Senthil Pandian; Perumal, Ramasamy

  2017-12-01

  Semi-organic nonlinear optical (NLO) 2-amino-5-nitropyridinium bromide (2A5NPBr) single crystals have been grown by slow evaporation solution technique (SEST) with the growth period of 60 days. The single-crystal XRD analysis confirms the unit cell parameters of the grown crystal. The crystallinity of grown 2A5NPBr was analyzed by powder X-ray diffraction (PXRD) measurement. The presence of functional groups of 2A5NPBr crystal was confirmed by Fourier transform infrared (FTIR) spectrum analysis. The optical transmittance of the grown crystal was analyzed by UV-Vis-NIR analysis. It shows good transparency in the visible and NIR region and it is favorable for nonlinear optical (NLO) device applications. The chemical etching study was carried out and it reveals that the grown crystal has less dislocation density. The photoconductivity study reveals that the grown crystal possesses positive photoconductive nature. The thermal stability of the crystal has been investigated by thermogravimetric (TG) and differential thermal analysis (DTA). The dielectric constant and dielectric loss as a function of frequency were measured. The electronic polarizability (α) of 2A5NPBr molecule has been calculated theoretically by different ways such as Penn analysis, Clausius-Mossotti relation, Lorentz-Lorenz equation, optical bandgap, and coupled dipole method (CDM). The obtained values of electronic polarizability (α) are in good agreement with each other. Laser damage threshold (LDT) of 2A5NPBr crystal has been measured using Nd:YAG laser with the wavelength of 1064 nm. Third-order nonlinear optical property of the grown crystal was studied by Z-scan technique using He-Ne laser of wavelength 632.8 nm.

Optical emission diagnostics of plasmas in chemical vapor deposition of single-crystal diamond

DOE PAGES

Hemawan, Kadek W.; Hemley, Russell J.

2015-08-03

Here, a key aspect of single crystal diamond growth via microwave plasma chemical vapor deposition is in-process control of the local plasma-substrate environment, that is, plasma gas phase concentrations of activated species at the plasma boundary layer near the substrate surface. Emission spectra of the plasma relative to the diamond substrate inside the microwave plasma reactor chamber have been analyzed via optical emission spectroscopy. The spectra of radical species such as CH, C 2, and H (Balmer series) important for diamond growth were found to be more depndent on operating pressure than on microwave power. Plasma gas temperatures were calculatedmore » from measurements of the C 2 Swan band (d 3Π → a 3Π transition) system. The plasma gas temperature ranges from 2800 to 3400 K depending on the spatial location of the plasma ball, microwave power and operating pressure. Addition of Ar into CH 4 + H 2 plasma input gas mixture has little influence on the Hα, Hβ, and Hγ intensities and single-crystal diamond growth rates.« less

Crystal Thermoelasticity at Extreme Loading Rates and Pressures: Analysis of Higher-Order Energy Potentials

DTIC Science & Technology

2015-07-01

ARL-RP-0526 ● JULY 2015 US Army Research Laboratory Crystal Thermoelasticity at Extreme Loading Rates and Pressures : Analysis of...ARL-RP-0526 ● JULY 2015 US Army Research Laboratory Crystal Thermoelasticity at Extreme Loading Rates and Pressures : Analysis of...2015 4. TITLE AND SUBTITLE Crystal Thermoelasticity at Extreme Loading Rates and Pressures : Analysis of Higher-Order Energy Potentials 5a. CONTRACT

Influence of encapsulated functional lipids on crystal structure and chemical stability in solid lipid nanoparticles: Towards bioactive-based design of delivery systems.

PubMed

Salminen, Hanna; Gömmel, Christina; Leuenberger, Bruno H; Weiss, Jochen

2016-01-01

We investigated the influence of physicochemical properties of encapsulated functional lipids--vitamin A, β-carotene and ω-3 fish oil--on the structural arrangement of solid lipid nanoparticles (SLN). The relationship between the crystal structure and chemical stability of the incorporated bioactive lipids was evaluated with different emulsifier compositions of a saponin-rich, food-grade Quillaja extract alone or combined with high-melting or low-melting lecithins. The major factors influencing the structural arrangement and chemical stability of functional lipids in solid lipid dispersions were their solubility in the aqueous phase and their crystallization temperature in relation to that of the carrier lipid. The results showed that the stabilization of the α-subcell crystals in the lattice of the carrier lipid is a key parameter for forming stable solid lipid dispersions. This study contributes to a better understanding of SLN as a function of the bioactive lipid. Copyright © 2015 Elsevier Ltd. All rights reserved.

Advances in food crystallization.

PubMed

Hartel, Richard W

2013-01-01

Crystals often play an important role in food product quality and shelf life. Controlling crystallization to obtain the desired crystal content, size distribution, shape, and polymorph is key to manufacturing products with desired functionality and shelf life. Technical developments in the field have improved the tools with which we study and characterize crystals in foods. These developments also help our understanding of the physico-chemical phenomena that govern crystallization and improve our ability to control it during processing and storage. In this review, some of the more important recent developments in measuring and controlling crystallization are discussed.

Determining Kinetic Parameters for Isothermal Crystallization of Glasses

NASA Technical Reports Server (NTRS)

Ray, C. S.; Zhang, T.; Reis, S. T.; Brow, R. K.

2006-01-01

Non-isothermal crystallization techniques are frequently used to determine the kinetic parameters for crystallization in glasses. These techniques are experimentally simple and quick compared to the isothermal techniques. However, the analytical models used for non-isothermal data analysis, originally developed for describing isothermal transformation kinetics, are fundamentally flawed. The present paper describes a technique for determining the kinetic parameters for isothermal crystallization in glasses, which eliminates most of the common problems that generally make the studies of isothermal crystallization laborious and time consuming. In this technique, the volume fraction of glass that is crystallized as a function of time during an isothermal hold was determined using differential thermal analysis (DTA). The crystallization parameters for the lithium-disilicate (Li2O.2SiO2) model glass were first determined and compared to the same parameters determined by other techniques to establish the accuracy and usefulness of the present technique. This technique was then used to describe the crystallization kinetics of a complex Ca-Sr-Zn-silicate glass developed for sealing solid oxide fuel cells.

Flexural Plate Wave Devices for Chemical Analysis

DTIC Science & Technology

1991-04-16

Naval Research Laboratory Washi..gton. DC 20375-5000 NRL Memorandum Report 6815 AD-A234 129 Flexural Plate Wave Devices for Chemical Analysis JAY W...4. TITLE AND SUBTITLE S. FUNDING NUMBERS Flexural Plate Wave Devices for Chemical Analysis 6. AUTHOR(S) 61-1638-01 Jay W. Grate. Stuart W. Wenzel... ANALYSIS INTRODUCTION Flexural plate wave (FPW) devices offer many attractive features for chemical analysis (1-9). As gravimetric sensors for chemical

Intermolecular shielding contributions studied by modeling the 13C chemical-shift tensors of organic single crystals with plane waves

PubMed Central

Johnston, Jessica C.; Iuliucci, Robbie J.; Facelli, Julio C.; Fitzgerald, George; Mueller, Karl T.

2009-01-01

In order to predict accurately the chemical shift of NMR-active nuclei in solid phase systems, magnetic shielding calculations must be capable of considering the complete lattice structure. Here we assess the accuracy of the density functional theory gauge-including projector augmented wave method, which uses pseudopotentials to approximate the nodal structure of the core electrons, to determine the magnetic properties of crystals by predicting the full chemical-shift tensors of all 13C nuclides in 14 organic single crystals from which experimental tensors have previously been reported. Plane-wave methods use periodic boundary conditions to incorporate the lattice structure, providing a substantial improvement for modeling the chemical shifts in hydrogen-bonded systems. Principal tensor components can now be predicted to an accuracy that approaches the typical experimental uncertainty. Moreover, methods that include the full solid-phase structure enable geometry optimizations to be performed on the input structures prior to calculation of the shielding. Improvement after optimization is noted here even when neutron diffraction data are used for determining the initial structures. After geometry optimization, the isotropic shift can be predicted to within 1 ppm. PMID:19831448

Multivariate Quantitative Chemical Analysis

NASA Technical Reports Server (NTRS)

Kinchen, David G.; Capezza, Mary

1995-01-01

Technique of multivariate quantitative chemical analysis devised for use in determining relative proportions of two components mixed and sprayed together onto object to form thermally insulating foam. Potentially adaptable to other materials, especially in process-monitoring applications in which necessary to know and control critical properties of products via quantitative chemical analyses of products. In addition to chemical composition, also used to determine such physical properties as densities and strengths.

Microscopy and Chemical Inversing Techniques to Determine the Photonic Crystal Structure of Iridescent Beetle Scales in the Cerambycidae Family

NASA Astrophysics Data System (ADS)

Richey, Lauren; Gardner, John; Standing, Michael; Jorgensen, Matthew; Bartl, Michael

2010-10-01

Photonic crystals (PCs) are periodic structures that manipulate electromagnetic waves by defining allowed and forbidden frequency bands known as photonic band gaps. Despite production of PC structures operating at infrared wavelengths, visible counterparts are difficult to fabricate because periodicities must satisfy the diffraction criteria. As part of an ongoing search for naturally occurring PCs [1], a three-dimensional array of nanoscopic spheres in the iridescent scales of the Cerambycidae insects A. elegans and G. celestis has been found. Such arrays are similar to opal gemstones and self-assembled colloidal spheres which can be chemically inverted to create a lattice-like PC. Through a chemical replication process [2], scanning electron microscopy analysis, sequential focused ion beam slicing and three-dimensional modeling, we analyzed the structural arrangement of the nanoscopic spheres. The study of naturally occurring structures and their inversing techniques into PCs allows for diversity in optical PC fabrication. [1] J.W. Galusha et al., Phys. Rev. E 77 (2008) 050904. [2] J.W. Galusha et al., J. Mater. Chem. 20 (2010) 1277.

Iron single crystal growth from a lithium-rich melt

NASA Astrophysics Data System (ADS)

Fix, M.; Schumann, H.; Jantz, S. G.; Breitner, F. A.; Leineweber, A.; Jesche, A.

2018-03-01

α -Fe single crystals of rhombic dodecahedral habit were grown from a Li84N12Fe∼3 melt. Crystals of several millimeter along a side form at temperatures around T ≈ 800 ° C. Upon further cooling the growth competes with the formation of Fe-doped Li3N. The b.c.c. structure and good sample quality of α -Fe single crystals were confirmed by X-ray and electron diffraction as well as magnetization measurements and chemical analysis. A nitrogen concentration of 90 ppm was detected by means of carrier gas hot extraction. Scanning electron microscopy did not reveal any sign of iron nitride precipitates.

Crystal Structure Prediction via Deep Learning.

PubMed

Ryan, Kevin; Lengyel, Jeff; Shatruk, Michael

2018-06-06

We demonstrate the application of deep neural networks as a machine-learning tool for the analysis of a large collection of crystallographic data contained in the crystal structure repositories. Using input data in the form of multi-perspective atomic fingerprints, which describe coordination topology around unique crystallographic sites, we show that the neural-network model can be trained to effectively distinguish chemical elements based on the topology of their crystallographic environment. The model also identifies structurally similar atomic sites in the entire dataset of ~50000 crystal structures, essentially uncovering trends that reflect the periodic table of elements. The trained model was used to analyze templates derived from the known binary and ternary crystal structures in order to predict the likelihood to form new compounds that could be generated by placing elements into these structural templates in combinatorial fashion. Statistical analysis of predictive performance of the neural-network model, which was applied to a test set of structures never seen by the model during training, indicates its ability to predict known elemental compositions with a high likelihood of success. In ~30% of cases, the known compositions were found among top-10 most likely candidates proposed by the model. These results suggest that the approach developed in this work can be used to effectively guide the synthetic efforts in the discovery of new materials, especially in the case of systems composed of 3 or more chemical elements.

Growth, structural, optical, piezoelectric and etching analysis of L-lysine p-nitrophenolate monohydrate single crystals

NASA Astrophysics Data System (ADS)

Alexandar, A.; Lakshmanan, A.; Sakthy Priya, S.; Surendran, P.; Rameshkumar, P.

2017-09-01

Nonlinear optical single crystals of L-lysine p-nitrophenolate monohydrate (LLPNP) were grown in aqueous solution by the slow evaporation solution technique (SEST). The grown crystals were subjected to powder X-ray diffraction analysis, (PXRD) and it was found that the title compound was crystallized in the orthorhombic crystal system with noncentrosymmetric space group of P212121. The vibrational frequencies of various functional groups present in the crystal were analyzed using the FTIR spectrum with a wavenumber range between 450 cm-1 and 4000 cm-1. The microhardness analysis of the sample revealed that the crystal belongs to the soft material category. Piezoelectric analysis was performed to measure the value of the piezoelectric (d33) coefficient. Blue light emission of the material was confirmed using the photoluminescence spectrum. Thermal stability of the grown crystal was analyzed using a melting point apparatus and it was found that the LLPNP is stable upto 175∘C. Etching analysis was performed at various durations, in order to identify the surface properties of the LLPNP crystal.

Berkeley Screen: a set of 96 solutions for general macromolecular crystallization

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

Pereira, Jose H.; McAndrew, Ryan P.; Tomaleri, Giovani P.

Using statistical analysis of the Biological Macromolecular Crystallization Database, combined with previous knowledge about crystallization reagents, a crystallization screen called the Berkeley Screen has been created. Correlating crystallization conditions and high-resolution protein structures, it is possible to better understand the influence that a particular solution has on protein crystal formation. Ions and small molecules such as buffers and precipitants used in crystallization experiments were identified in electron density maps, highlighting the role of these chemicals in protein crystal packing. The Berkeley Screen has been extensively used to crystallize target proteins from the Joint BioEnergy Institute and the Collaborative Crystallography programmore » at the Berkeley Center for Structural Biology, contributing to several Protein Data Bank entries and related publications. The Berkeley Screen provides the crystallographic community with an efficient set of solutions for general macromolecular crystallization trials, offering a valuable alternative to the existing commercially available screens. The Berkeley Screen provides an efficient set of solutions for general macromolecular crystallization trials.« less

Berkeley Screen: a set of 96 solutions for general macromolecular crystallization

DOE PAGES

Pereira, Jose H.; McAndrew, Ryan P.; Tomaleri, Giovani P.; ...

2017-09-05

Using statistical analysis of the Biological Macromolecular Crystallization Database, combined with previous knowledge about crystallization reagents, a crystallization screen called the Berkeley Screen has been created. Correlating crystallization conditions and high-resolution protein structures, it is possible to better understand the influence that a particular solution has on protein crystal formation. Ions and small molecules such as buffers and precipitants used in crystallization experiments were identified in electron density maps, highlighting the role of these chemicals in protein crystal packing. The Berkeley Screen has been extensively used to crystallize target proteins from the Joint BioEnergy Institute and the Collaborative Crystallography programmore » at the Berkeley Center for Structural Biology, contributing to several Protein Data Bank entries and related publications. The Berkeley Screen provides the crystallographic community with an efficient set of solutions for general macromolecular crystallization trials, offering a valuable alternative to the existing commercially available screens. The Berkeley Screen provides an efficient set of solutions for general macromolecular crystallization trials.« less

Optimizing Associative Experimental Design for Protein Crystallization Screening

PubMed Central

Dinç, Imren; Pusey, Marc L.; Aygün, Ramazan S.

2016-01-01

The goal of protein crystallization screening is the determination of the main factors of importance to crystallizing the protein under investigation. One of the major issues about determining these factors is that screening is often expanded to many hundreds or thousands of conditions to maximize combinatorial chemical space coverage for maximizing the chances of a successful (crystalline) outcome. In this paper, we propose an experimental design method called “Associative Experimental Design (AED)” and an optimization method includes eliminating prohibited combinations and prioritizing reagents based on AED analysis of results from protein crystallization experiments. AED generates candidate cocktails based on these initial screening results. These results are analyzed to determine those screening factors in chemical space that are most likely to lead to higher scoring outcomes, crystals. We have tested AED on three proteins derived from the hyperthermophile Thermococcus thioreducens, and we applied an optimization method to these proteins. Our AED method generated novel cocktails (count provided in parentheses) leading to crystals for three proteins as follows: Nucleoside diphosphate kinase (4), HAD superfamily hydrolase (2), Nucleoside kinase (1). After getting promising results, we have tested our optimization method on four different proteins. The AED method with optimization yielded 4, 3, and 20 crystalline conditions for holo Human Transferrin, archaeal exosome protein, and Nucleoside diphosphate kinase, respectively. PMID:26955046

Anharmonic vibrational spectroscopy, NBO charges and global chemical reactivity studies on the charge transfer PDCA-.AHMP+ single crystal using DFT calculations

NASA Astrophysics Data System (ADS)

Faizan, Mohd; Afroz, Ziya; Bhat, Sheeraz Ahmad; Alam, Mohamad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-04-01

The charge transfer (CT) complex of the 2-amino-4-hydroxy-6-methylpyrimidine and 2,3 pyrazinedicarboxylic acid (PDCA-.AHMP+) was synthesized and its single crystal was grown by solution method. The structure of the crystalline complex has been investigated by single crystal X-ray diffraction (SCXRD). The vibrational features of the complex have been studied with the help of FTIR spectra and DFT computation. The anharmonic corrections in vibrational frequencies are made using the GVPT2 method at B3LYP/6-311++G(d,p) level of theory. The frontier molecular orbitals and global chemical reactivity have been calculated to understand the pharmacological aspect of the synthesized crystal. Furthermore, Hirshfeld electrostatic potential (ESP) surface, void space in the crystal structure and natural as well as Mulliken atomic charges are studied.

SymDex: increasing the efficiency of chemical fingerprint similarity searches for comparing large chemical libraries by using query set indexing.

PubMed

Tai, David; Fang, Jianwen

2012-08-27

The large sizes of today's chemical databases require efficient algorithms to perform similarity searches. It can be very time consuming to compare two large chemical databases. This paper seeks to build upon existing research efforts by describing a novel strategy for accelerating existing search algorithms for comparing large chemical collections. The quest for efficiency has focused on developing better indexing algorithms by creating heuristics for searching individual chemical against a chemical library by detecting and eliminating needless similarity calculations. For comparing two chemical collections, these algorithms simply execute searches for each chemical in the query set sequentially. The strategy presented in this paper achieves a speedup upon these algorithms by indexing the set of all query chemicals so redundant calculations that arise in the case of sequential searches are eliminated. We implement this novel algorithm by developing a similarity search program called Symmetric inDexing or SymDex. SymDex shows over a 232% maximum speedup compared to the state-of-the-art single query search algorithm over real data for various fingerprint lengths. Considerable speedup is even seen for batch searches where query set sizes are relatively small compared to typical database sizes. To the best of our knowledge, SymDex is the first search algorithm designed specifically for comparing chemical libraries. It can be adapted to most, if not all, existing indexing algorithms and shows potential for accelerating future similarity search algorithms for comparing chemical databases.

Analysis of co-crystallized free phytosterols with triacylglycerols as a functional food ingredient.

PubMed

Acevedo, Nuria C; Franchetti, Danielle

2016-07-01

This research focuses on the analysis of mixtures of free phytosterols (FPSs) with fully hydrogenated soybean oil (FHSO):soybean oil (SO) mixtures as a potential zero-trans substitute for various types of shortenings. Oil binding capacity as well as the thermal, rheological and structural properties of FHSO:SO blends containing 0, 20 and 25wt.% β-sitosterol or stigmasterol were investigated in this study. Differential interference contrast (DIC) microscopy and wide angle X-ray diffraction (WAXRD) revealed that co-crystallization of FPSs with FHSO:SO blends occurred. Polymorphic forms were characterized as a mixture of β' and β for all samples. The addition of FPSs decreased oil loss (OL) of FHSO:SO samples. Melting profiles of the prepared FPS-TAG (triacylglycerol) blends were extended to higher temperatures compared to a commercial shortening. Rheological properties were comparable to those of commercial puff pastry shortening suggesting that FPS-TAG blends may be acceptable for bakery applications. FPSs co-crystallized with FHSO and SO may be a suitable trans-fat free substitute for a number of types of shortening, including puff pastry shortening. The manufacturing of co-crystallized /FPS-TAG matrices will possibly bring large economic benefits as their functionalization can potentially be achieved by using existing simple shear processing. Copyright © 2016 Elsevier Ltd. All rights reserved.

In situ crystal chemical study of solid diamond inclusions from Quaternary alluvial deposit in the Siberian craton

NASA Astrophysics Data System (ADS)

Dera, P. K.; Manghnani, M. H.; Hushur, A.; Sobolev, N. V.; Logvinova, A. M.; Newville, M.; Lanzirotti, A.

2013-12-01

Kimberlites belong to rare rock type available only within the Earth's cratonic areas and have been a subject of detailed studies because of the great depth of their origin in the mantle. Kimberlitic diamonds often contain pristine inclusions derived from significant depths with different histories of their origins. Many of kimberlitic diamonds were formed in ultramafic (peridotitic) and mafic (eclogitic) environments of the upper mantle. Thus far only a handful of comprehensive in situ studies including single-crystal X-ray diffraction characterization of pristine diamond solid inclusions have been reported (e.g. Kunz et al. 2001, Nestola et al. 2011). In this study five single-crystal solid inclusions from diamonds found in the Quaternary alluvial deposit in NW of the Siberian craton have been investigated using a combination of in situ single-crystal X-ray diffraction, Raman spectroscopy, synchrotron X-ray microfluorescence and X-ray Absorption Near Edge Spectroscopy (XANES). The grains were identified to be a suite of major upper mantle minerals including olivine, enstatite orthopyroxene (opx), C2/c omphacite clinopyroxene (cpx) and majoritic garnet (two grains), indicating eclogitic origin. All five inclusions are chemically homogeneous, do not show compositional zoning, and exhibit very similar major element chemistry, with significant amounts of Mn2+, Ni2+ and Cr3+ incorporated into the crystal structures, suggesting common geologic origin. All samples were studied in situ, while still embedded in the diamond crystals. High quality single-crystal X-ray diffraction data was collected at the Advanced Photon Source, Argonne National Laboratory to reveal details of the crystal structures and provide crystal chemical information. Some of the structural characteristics of the solid inclusions were found to be fairly uncommon, e.g. the orthoenstatite exhibits an unusually high Ca2+ content (Carlson et al. 1988), and omphacite occurs as the less common C2/c

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

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Reid, Ray D. (Inventor)

2009-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor)

2013-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic chemical analysis methods and apparatus

NASA Technical Reports Server (NTRS)

Reid, Ray D. (Inventor); Hug, William F. (Inventor)

2010-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. Chemical analysis instruments employed in some embodiments include capillary and gel plane electrophoresis, capillary electrochromatography, high performance liquid chromatography, flow cytometry, flow cells for liquids and aerosols, and surface detection instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted simultaneously with native fluorescence spectroscopy to provide high levels of sensitivity and specificity in the same instrument.

Effect of Li and NH4 doping on the crystal perfection, second harmonic generation efficiency and laser damage threshold of potassium pentaborate crystals

NASA Astrophysics Data System (ADS)

Vigneshwaran, A. N.; Kalainathan, S.; Raja, C. Ramachandra

2018-03-01

Potassium pentaborate (KB5) is an excellent nonlinear optical material especially in the UV region. In this work, Li and NH4 doped KB5 crystals were grown using slow evaporation solution growth method. The incorporation of dopant has been confirmed and analysed by Energy dispersive X-ray analysis (EDAX), Inductively coupled plasma (ICP) analysis and Raman spectroscopy. The crystalline perfection of pure and doped KB5 crystals was studied by High resolution X-ray diffraction (HRXRD) analysis. Structural grain boundaries were observed in doped crystals. Second harmonic generation was confirmed for pure and doped crystals and output values revealed the enhancement of SHG efficiency in doped crystals. Resistance against laser damage was carried out using 1064 nm Nd-YAG laser of pulse width 10 ns. The laser damage threshold value is increased in Li doped crystal and decreased in NH4 doped crystal when compared to pure KB5 crystal.

Non-isothermal crystallization of poly(etheretherketone) aromatic polymer composite

NASA Technical Reports Server (NTRS)

Cebe, Peggy

1988-01-01

The nonisothermal crystallization kinetics of PEEK APC-2 and of 450G neat resin PEEK material were compared using a differential scanning calorimeter to monitor heat flow during crystallization; the effects of cooling rate on the crystallization temperature, the degree of crystallinity, and the conversion rate were investigated. A modified Avrami (1940) analysis was used to describe nonisothermal crystallization kinetics. It was found that, compared with the 450G neat resin PEEK, the nonisothermal crystallization of the PEEK APC-2 composite is characterized by higher initiation temperature, higher heat flow maximum temperature, and greater relative conversion by primary processes.

Insight into the Near-Conduction Band States at the Crystallized Interface between GaN and SiN x Grown by Low-Pressure Chemical Vapor Deposition.

PubMed

Liu, Xinyu; Wang, Xinhua; Zhang, Yange; Wei, Ke; Zheng, Yingkui; Kang, Xuanwu; Jiang, Haojie; Li, Junfeng; Wang, Wenwu; Wu, Xuebang; Wang, Xianping; Huang, Sen

2018-06-12

Constant-capacitance deep-level transient Fourier spectroscopy is utilized to characterize the interface between a GaN epitaxial layer and a SiN x passivation layer grown by low-pressure chemical vapor deposition (LPCVD). A near-conduction band (NCB) state E LP ( E C - E T = 60 meV) featuring a very small capture cross section of 1.5 × 10 -20 cm -2 was detected at 70 K at the LPCVD-SiN x /GaN interface. A partially crystallized Si 2 N 2 O thin layer was detected at the interface by high-resolution transmission electron microscopy. Based on first-principles calculations of crystallized Si 2 N 2 O/GaN slabs, it was confirmed that the NCB state E LP mainly originates from the strong interactions between the dangling bonds of gallium and its vicinal atoms near the interface. The partially crystallized Si 2 N 2 O interfacial layer might also give rise to the very small capture cross section of the E LP owing to the smaller lattice mismatch between the Si 2 N 2 O and GaN epitaxial layer and a larger mean free path of the electron in the crystallized portion compared with an amorphous interfacial layer.

Comparative study on ATR-FTIR calibration models for monitoring solution concentration in cooling crystallization

NASA Astrophysics Data System (ADS)

Zhang, Fangkun; Liu, Tao; Wang, Xue Z.; Liu, Jingxiang; Jiang, Xiaobin

2017-02-01

In this paper calibration model building based on using an ATR-FTIR spectroscopy is investigated for in-situ measurement of the solution concentration during a cooling crystallization process. The cooling crystallization of L-glutamic Acid (LGA) as a case is studied here. It was found that using the metastable zone (MSZ) data for model calibration can guarantee the prediction accuracy for monitoring the operating window of cooling crystallization, compared to the usage of undersaturated zone (USZ) spectra for model building as traditionally practiced. Calibration experiments were made for LGA solution under different concentrations. Four candidate calibration models were established using different zone data for comparison, by using a multivariate partial least-squares (PLS) regression algorithm for the collected spectra together with the corresponding temperature values. Experiments under different process conditions including the changes of solution concentration and operating temperature were conducted. The results indicate that using the MSZ spectra for model calibration can give more accurate prediction of the solution concentration during the crystallization process, while maintaining accuracy in changing the operating temperature. The primary reason of prediction error was clarified as spectral nonlinearity for in-situ measurement between USZ and MSZ. In addition, an LGA cooling crystallization experiment was performed to verify the sensitivity of these calibration models for monitoring the crystal growth process.

A chemical model for generating the sources of mare basalts - Combined equilibrium and fractional crystallization of the lunar magmasphere

NASA Technical Reports Server (NTRS)

Snyder, Gregory A.; Taylor, Lawrence A.; Neal, Clive R.

1992-01-01

A chemical model for simulating the sources of the lunar mare basalts was developed by considering a modified mafic cumulate source formed during the combined equilibrium and fractional crystallization of a lunar magma ocean (LMO). The parameters which influence the initial LMO and its subsequent crystallization are examined, and both trace and major elements are modeled. It is shown that major elements tightly constrain the composition of mare basalt sources and the pathways to their creation. The ability of this LMO model to generate viable mare basalt source regions was tested through a case study involving the high-Ti basalts.

RNA Crystallization

NASA Technical Reports Server (NTRS)

Golden, Barbara L.; Kundrot, Craig E.

2003-01-01

RNA molecules may be crystallized using variations of the methods developed for protein crystallography. As the technology has become available to syntheisize and purify RNA molecules in the quantities and with the quality that is required for crystallography, the field of RNA structure has exploded. The first consideration when crystallizing an RNA is the sequence, which may be varied in a rational way to enhance crystallizability or prevent formation of alternate structures. Once a sequence has been designed, the RNA may be synthesized chemically by solid-state synthesis, or it may be produced enzymatically using RNA polymerase and an appropriate DNA template. Purification of milligram quantities of RNA can be accomplished by HPLC or gel electrophoresis. As with proteins, crystallization of RNA is usually accomplished by vapor diffusion techniques. There are several considerations that are either unique to RNA crystallization or more important for RNA crystallization. Techniques for design, synthesis, purification, and crystallization of RNAs will be reviewed here.

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

Crystal Cargo Characterization: Unravelling Granite Petrogenesis through Combined MicroXRF Imaging and In-situ Analyses.

NASA Astrophysics Data System (ADS)

McLeod, C. L.; Brown, K.; Brydon, R.; Haley, M.; Hill, T.; Shaulis, B.; Tronnes, R. G.

2017-12-01

Advances in the capabilities of microanalysis over the past several decades have promoted a redefinition of traditional petrological terminology. This has allowed a more accurate evaluation of a samples petrogenetic history. For example, the term "phenocryst", specifically describes crystals that grew from the liquid that solidified into the groundmass. Evolving from this idea is the term xenocryst, referring to crystals that did not originate in the magma but were gathered by it, and antecrysts, which crystallized from a progenitor of the magma that solidified into the groundmass. Through identification of a magmas different, and distinct, crystal populations, the petrogenetic history of a magmatic rock can therefore be unraveled. This approach has been widely applied to terrestrial volcanic systems throughout the past several decades. This study presents results from a combined microimaging and in-situ microanalytical investigation of granitic magmas crystal cargoes in order to unravel how granitic batholiths are constructed. 27 lithological units from two granite batholiths in the Oslo Rift, Norway form the basis of this investigation. Micro X-Ray Fluorescence (µXRF) mapping of major elements and selected trace elements is used in order to chemically map each granitic unit, identify any characteristic growth zoning, and compare the crystal cargoes of the different units. Major and trace elemental abundances of the major phases (feldspars, biotite, amphibole) and minor phases (apatite and titanite) are to be quantified through electron microprobe analysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) respectively. Through chemically fingerprinting the crystal cargoes of these Oslo Rift granitic magmas, the open vs. closed nature of granitic, intrusive, magmatic systems will be investigated. Within the context of the Oslo Rift, this study also offers an opportunity to evaluate the processes inherent to granitoid magmatism

Crystals in Urine Test: MedlinePlus Lab Test Information

MedlinePlus

... medlineplus.gov/labtests/crystalsinurinetest.html Crystals in Urine Test To use the sharing features on this page, ... enable JavaScript. What is a Crystals in Urine Test? Your urine contains many chemicals. Sometimes these chemicals ...

Chemical Sensing in Process Analysis.

ERIC Educational Resources Information Center

Hirschfeld, T.; And Others

1984-01-01

Discusses: (1) rationale for chemical sensors in process analysis; (2) existing types of process chemical sensors; (3) sensor limitations, considering lessons of chemometrics; (4) trends in process control sensors; and (5) future prospects. (JN)

Q-space analysis of light scattering by ice crystals

NASA Astrophysics Data System (ADS)

Heinson, Yuli W.; Maughan, Justin B.; Ding, Jiachen; Chakrabarti, Amitabha; Yang, Ping; Sorensen, Christopher M.

2016-12-01

Q-space analysis is applied to extensive simulations of the single-scattering properties of ice crystals with various habits/shapes over a range of sizes. The analysis uncovers features common to all the shapes: a forward scattering regime with intensity quantitatively related to the Rayleigh scattering by the particle and the internal coupling parameter, followed by a Guinier regime dependent upon the particle size, a complex power law regime with incipient two dimensional diffraction effects, and, in some cases, an enhanced backscattering regime. The effects of significant absorption on the scattering profile are also studied. The overall features found for the ice crystals are similar to features in scattering from same sized spheres.

Stress-induced crystal transition of poly(butylene succinate) studied by terahertz and low-frequency Raman spectroscopy and quantum chemical calculation

NASA Astrophysics Data System (ADS)

Tatsuoka, Seika; Sato, Harumi

2018-05-01

We measured terahertz (THz) and low-frequency Raman spectra of Poly (butylene succinate) (PBS) which shows the crystal transition from α to β by stretching. For the assignment of the absorption peaks in the low-frequency region, we performed quantum chemical calculations with Cartesian-coordinate tensor transfer (CCT) method. Four major peaks appeared in the THz spectra of PBS at around 58, 76, 90, and 100 cm-1, and in the low-frequency Raman spectra a peak was observed at 88 cm-1. The THz peak at 100 cm-1 and the Raman peak at 88 cm-1 show a shift to a lower wavenumber region with increasing temperature. The quantum chemical calculation of β crystal form reveals the new peak appears above 100 cm-1. It was found that two kinds of peaks overlapped at around 100 cm-1 in the THz spectra of PBS. One of them can be assigned to a weak hydrogen bond between the C=O and CH2 groups in the intermolecular chains, which is perpendicular to the molecular chain of the α crystal form. Another one showed a parallel polarization which can be assigned to the intramolecular interaction between O (ether) and H-C groups in the β crystal form. The position of the peak at around 100 cm-1 in the perpendicular polarization changed to a lower wavenumber region with stretching, because of the weakening of the intermolecular hydrogen bonding by increasing the interatomic distances. On the other hand, that of the parallel polarization shifts to a higher wavenumber region because of the shortening of the interatomic distance from α to β crystal form (the strength of the intramolecular hydrogen bonding became stronger) by stretching.

On the tungsten single crystal coatings achieved by chemical vapor transportation deposition

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

Shi, J.Q.; Shen, Y.B.; Yao, S.Y.

2016-12-15

The tungsten single crystal has many excellent properties, namely a high melting point, high anti-creeping strength. Chemical vapor transportation deposition (CVTD) is a possible approach to achieve large-sized W single crystals for high-temperature application such as the cathode of a thermionic energy converter. In this work, CVTD W coatings were deposited on the monocrystalline molybdenum substrate (a tube with < 111 > axial crystalline orientation) using WCl{sub 6} as a transport medium. The microstructures of the coatings were investigated by a scanning electron microscope (SEM) and electron backscatter diffraction (EBSD). The as-deposited coatings are hexagonal prisms—rough surfaces perpendicular to with alternating hill-like bulges and pits at the side edges of the prisms, and flat surfaces perpendicular to < 112 > with arc-shaped terraces at the side faces. This can be explained by two-dimensional nucleation -mediated lateral growth model. Some parts of the coatings contain hillocks of an exotic morphology (noted as “abnormal growth”). The authors hypothesize that the abnormal growth is likely caused by the defects of the Mo substrate, which facilitate W nucleation sites, cause orientation difference, and may even form boundaries in the coatings. A dislocation density of 10{sup 6} to 10{sup 7} (counts/cm{sup 2}) was revealed by an etch-pit method and synchrotron X-ray diffraction. As the depositing temperature rises, the dislocation density decreases, and no sub-boundaries are found on samples deposited over 1300 °C, as a result of atom diffusion and dislocation climbing. - Highlights: •The varied growth rate causes the different morphologies of different planes. •The W coating is a single crystal when only single hillocks appear. •The (110) plane tends to have the lowest dislocation density. •The dislocation density tends to decrease as the temperature increases.« less

Overexpression, crystallization and preliminary X-ray crystallographic analysis of the phosphotriesterase from Mycobacterium tuberculosis.

PubMed

Zhang, Liang; Chen, Ruyi; Dong, Zhe; Li, Xin

2013-01-01

Organophosphates (OPs) are extremely toxic compounds that are used as insecticides or even as chemical warfare agents. Phosphotriesterases (PHPs) are responsible for the detoxification of OPs by catalysing their degradation. Almost 100 PHP structures have been solved to date, yet the crystal structure of the phosphotriesterase from Mycobacterium tuberculosis (mPHP) remains unavailable. This study reports the first crystallization of mPHP. The crystal belonged to space group C222(1), with unit-cell parameters a = 68.03, b = 149.60, c = 74.23 Å, α = β = γ = 90°. An analytical ultracentrifugation experiment suggested that mPHP exists as a dimer in solution, even though one molecule is calculated to be present in the asymmetric unit according to the structural data.

Overexpression, crystallization and preliminary X-ray crystallographic analysis of the phosphotriesterase from Mycobacterium tuberculosis

PubMed Central

Zhang, Liang; Chen, Ruyi; Dong, Zhe; Li, Xin

2013-01-01

Organophosphates (OPs) are extremely toxic compounds that are used as insecticides or even as chemical warfare agents. Phosphotriesterases (PHPs) are responsible for the detoxification of OPs by catalysing their degradation. Almost 100 PHP structures have been solved to date, yet the crystal structure of the phosphotriesterase from Mycobacterium tuberculosis (mPHP) remains unavailable. This study reports the first crystallization of mPHP. The crystal belonged to space group C2221, with unit-cell parameters a = 68.03, b = 149.60, c = 74.23 Å, α = β = γ = 90°. An analytical ultracentrifugation experiment suggested that mPHP exists as a dimer in solution, even though one molecule is calculated to be present in the asymmetric unit according to the structural data. PMID:23295488

Transient rheology of crystallizing andesitic magmas

NASA Astrophysics Data System (ADS)

de Biasi, L. J.; Chevrel, M. O.; Hanson, J. B.; Cimarelli, C.; Lavallée, Y.; Dingwell, D. B.

2012-04-01

), crystallization of large, tabular plagioclase begins, inducing a significantly stronger increase in apparent viscosity until thermo-chemical equilibration is achieved. After continued stirring the apparent viscosity slightly decreases, likely due to increasing crystal alignment. The analysis of pre-equilibrium quenched samples indicates that crystals nucleate and grow preferentially in proximity to both the spindle and the crucible wall. Furthermore, decreasing the stirring rate (aka strain rate) results in an increase in the apparent viscosity, which evidences the non-Newtonian characteristics of the magmatic suspension. In conclusion, these experiments indicate that natural andesitic magmas undergo significant rheological changes at the onset of crystallization. The observed thermo-chemical variations elucidate a transient viscosity, which deserves consideration into all problems of magma transport. Reference: Vona, A., Romano, C., Dingwell, D.B., Giordano, D. 2011. The rheology of crystal-bearing basaltic magmas from Stromboli and Etna. Geochim. Cosmochim. Acta, 75, 3214-3236.

Reliability analysis of single crystal NiAl turbine blades

NASA Technical Reports Server (NTRS)

Salem, Jonathan; Noebe, Ronald; Wheeler, Donald R.; Holland, Fred; Palko, Joseph; Duffy, Stephen; Wright, P. Kennard

1995-01-01

As part of a co-operative agreement with General Electric Aircraft Engines (GEAE), NASA LeRC is modifying and validating the Ceramic Analysis and Reliability Evaluation of Structures algorithm for use in design of components made of high strength NiAl based intermetallic materials. NiAl single crystal alloys are being actively investigated by GEAE as a replacement for Ni-based single crystal superalloys for use in high pressure turbine blades and vanes. The driving force for this research lies in the numerous property advantages offered by NiAl alloys over their superalloy counterparts. These include a reduction of density by as much as a third without significantly sacrificing strength, higher melting point, greater thermal conductivity, better oxidation resistance, and a better response to thermal barrier coatings. The current drawback to high strength NiAl single crystals is their limited ductility. Consequently, significant efforts including the work agreement with GEAE are underway to develop testing and design methodologies for these materials. The approach to validation and component analysis involves the following steps: determination of the statistical nature and source of fracture in a high strength, NiAl single crystal turbine blade material; measurement of the failure strength envelope of the material; coding of statistically based reliability models; verification of the code and model; and modeling of turbine blades and vanes for rig testing.

Crystallization tendency of active pharmaceutical ingredients following rapid solvent evaporation--classification and comparison with crystallization tendency from undercooled melts.

PubMed

Van Eerdenbrugh, Bernard; Baird, Jared A; Taylor, Lynne S

2010-09-01

In this study, the crystallization behavior of a variety of compounds was studied following rapid solvent evaporation using spin coating. Initial screening to determine model compound suitability was performed using a structurally diverse set of 51 compounds in three different solvent systems [dichloromethane (DCM), a 1:1 (w/w) dichloromethane/ethanol mixture (MIX), and ethanol (EtOH)]. Of this starting set of 153 drug-solvent combinations, 93 (40 compounds) were selected for further evaluation based on solubility, chemical solution stability, and processability criteria. These systems were spin coated and their crystallization was monitored using polarized light microscopy (7 days, dry conditions). The crystallization behavior of the samples could be classified as rapid (Class I: 39 cases), intermediate (Class II: 23 cases), or slow (Class III: 31 cases). The solvent system employed influenced the classification outcome for only four of the compounds. The various compounds showed very diverse crystallization behavior. Upon comparison of classification results with those of a previous study, where cooling from the melt was used as a preparation technique, a good similarity was found whereby 68% of the cases were identically classified. Multivariate analysis was performed using a set of relevant physicochemical compound characteristics. It was found that a number of these parameters tended to differ between the different classes. These could be further interpreted in terms of the nature of the crystallization process. Additional multivariate analysis on the separate classes of compounds indicated some potential in predicting the crystallization tendency of a given compound.

Spectroscopic, quantum chemical calculation and molecular docking of dipfluzine

NASA Astrophysics Data System (ADS)

Srivastava, Karnica; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Wang, Jing

2016-12-01

Molecular structure and vibrational analysis of dipfluzine (C27H29FN2O) were presented using FT-IR and FT-Raman spectroscopy and quantum chemical calculations. The theoretical ground state geometry and electronic structure of dipfluzine are optimized by the DFT/B3LYP/6-311++G (d,p) method and compared with those of the crystal data. The 1D potential energy scan was performed by varying the dihedral angle using B3LYP functional at 6-31G(d,p) level of theory and thus the most stable conformer of the compound were determined. Molecular electrostatic potential surface (MEPS), frontier orbital analysis and electronic reactivity descriptor were used to predict the chemical reactivity of molecule. Energies of intra- and inter-molecular hydrogen bonds in molecule and their electronic aspects were investigated by natural bond orbital (NBO). To find out the anti-apoptotic activity of the title compound molecular docking studies have been performed against protein Fas.

Spectral, electron microscopic and chemical investigations of gamma-induced purple color zonings in amethyst crystals from the Dursunbey-Balıkesir region of Turkey

NASA Astrophysics Data System (ADS)

Hatipoğlu, Murat; Kibar, Rana; Çetin, Ahmet; Can, Nurdoğan; Helvacı, Cahit; Derin, H.

2011-07-01

Amethyst crystals on matrix specimens from the Dursunbey-Balıkesir region in Turkey have five representative purple color zonings: dark purple, light purple, lilac, orchid, and violet. The purple color zonings have been analyzed with optical absorption spectra in the visible wavelength region, chemical full trace element analyses (inductively coupled plasma-atomic emission spectroscopy and inductively coupled plasma-mass spectroscopy), and scanning electron microscopic images with high magnification. It can be proposed that the production of the purple color in amethyst crystals is due to three dominant absorption bands centered at 375, 530, and 675 nm, respectively. In addition, the purple color zonings are also due to four minor absorption bands centered at 435, 480, 620, and 760 nm. X-ray diffraction graphics of the investigated amethyst crystals indicate that these crystals are composed of a nearly pure alpha-quartz phase and do not include any moganite silica phase and/or other mineral implications. Trace element analyses of the amethyst crystals show five representative purple color zonings, suggesting that the absorption bands can be mainly attributed to extrinsic defects (chemical impurities). However, another important factor that influences all structural defects in amethyst is likely to be the gamma irradiation that exists during amethyst crystallization and its inclusion in host materials. This gamma irradiation originates from the large underlying intrusive granitoid body in the region of amethyst formation. Irradiation modifies the valence values of the impurity elements in the amethyst crystals. It is observed that the violet-colored amethyst crystals have the most stable and the least reversible coloration when exposed to strong light sources. This situation can be related to the higher impurity content of Fe (2.50 ppm), Co (3.1 ppm), Ni (38 ppm), Cu (17.9 ppm), Zn (10 ppm), Zr (3.9 ppm), and Mo (21.8 ppm).

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Lane, Arthur L. (Inventor); Bhartia, Rohit (Inventor); Reid, Ray D. (Inventor)

2017-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

Spectroscopic Chemical Analysis Methods and Apparatus

NASA Technical Reports Server (NTRS)

Hug, William F. (Inventor); Lane, Arthur L. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor)

2018-01-01

Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

The density and compositional analysis of titanium doped sapphire single crystal grown by the Czocharlski method

NASA Astrophysics Data System (ADS)

Kusuma, H. H.; Ibrahim, Z.; Othaman, Z.

2018-03-01

Titanium doped sapphire (Ti:Al2O3) crystal has attracted attention not only as beautiful gemstones, but also due to their applications as high power laser action. It is very important crystal for tunable solid state laser. Ti:Al2O3 crystals have been success grown using the Czocharlski method with automatic diameter control (ADC) system. The crystals were grown with different pull rates. The structure of the crystal was characterized with X-Ray Diffraction (XRD). The density of the crystal was measurement based on the Archimedes principle and the chemical composition of the crystal was confirmed by the Energy Dispersive X-ray (EDX) Spectroscopy. The XRD patterns of crystals are showed single main peak with a high intensity. Its shows that the samples are single crystal. The Ti:Al2O3 grown with different pull rate will affect the distribution of the concentration of dopant Ti3+ and densities on the sapphire crystals boules as well on the crystal growth process. The increment of the pull rate will increase the percentage distribution of Ti3+ and on the densities of the Ti:Al2O3 crystal boules. This may be attributed to the speed factor of the pull rate of the crystal that then caused changes in the heat flow in the furnace and then causes the homogeneities is changed of species distribution of atoms along crystal.

Preparation and Analysis of RNA Crystals

NASA Technical Reports Server (NTRS)

Todd, Paul

2000-01-01

The crystallization of RiboNucleic Acids (RNA) was studied from the standpoint of mechanisms of crystal growth in three tasks: (1) preparation of high-quality crystals of oligonuclotides for X-ray diffraction, (2) finding pathways to the growth of high-quality crystals for X-ray diffraction and (3) investigation of mechanisms of action of inertial acceleration on crystal growth. In these tasks: (1) RNA crystals were prepared and studied by X-ray diffraction; (2) a pathway to high-quality crystals was discovered and characterized; a combination of kinetic and equilibrium factors could be optimized as described below; and (3) an interplay between purity and gravity was found in a combination of space and ground experiments with nucleic acids and proteins. Most significantly, the rate of concentration of precipitant and RNA can be controlled by membrane-based methods of water removal or by diffusion of multivalent cations across an interface stabilized by a membrane. Oligonucleotide solutions are electrokinetically stabilized colloids, and crystals can form by the controlled addition of multivalent cations.

Quantitative Schlieren analysis applied to holograms of crystals grown on Spacelab 3

NASA Technical Reports Server (NTRS)

Brooks, Howard L.

1986-01-01

In order to extract additional information about crystals grown in the microgravity environment of Spacelab, a quantitative schlieren analysis technique was developed for use in a Holography Ground System of the Fluid Experiment System. Utilizing the Unidex position controller, it was possible to measure deviation angles produced by refractive index gradients of 0.5 milliradians. Additionally, refractive index gradient maps for any recorded time during the crystal growth were drawn and used to create solute concentration maps for the environment around the crystal. The technique was applied to flight holograms of Cell 204 of the Fluid Experiment System that were recorded during the Spacelab 3 mission on STS 51B. A triglycine sulfate crystal was grown under isothermal conditions in the cell and the data gathered with the quantitative schlieren analysis technique is consistent with a diffusion limited growth process.

Unifying Approach to Analytical Chemistry and Chemical Analysis: Problem-Oriented Role of Chemical Analysis.

ERIC Educational Resources Information Center

Pardue, Harry L.; Woo, Jannie

1984-01-01

Proposes an approach to teaching analytical chemistry and chemical analysis in which a problem to be resolved is the focus of a course. Indicates that this problem-oriented approach is intended to complement detailed discussions of fundamental and applied aspects of chemical determinations and not replace such discussions. (JN)

Defined PEG smears as an alternative approach to enhance the search for crystallization conditions and crystal-quality improvement in reduced screens

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

Chaikuad, Apirat, E-mail: apirat.chaikuad@sgc.ox.ac.uk; Knapp, Stefan; Johann Wolfgang Goethe-University, Building N240 Room 3.03, Max-von-Laue-Strasse 9, 60438 Frankfurt am Main

An alternative strategy for PEG sampling is suggested through the use of four newly defined PEG smears to enhance chemical space in reduced screens with a benefit towards protein crystallization. The quest for an optimal limited set of effective crystallization conditions remains a challenge in macromolecular crystallography, an issue that is complicated by the large number of chemicals which have been deemed to be suitable for promoting crystal growth. The lack of rational approaches towards the selection of successful chemical space and representative combinations has led to significant overlapping conditions, which are currently present in a multitude of commercially availablemore » crystallization screens. Here, an alternative approach to the sampling of widely used PEG precipitants is suggested through the use of PEG smears, which are mixtures of different PEGs with a requirement of either neutral or cooperatively positive effects of each component on crystal growth. Four newly defined smears were classified by molecular-weight groups and enabled the preservation of specific properties related to different polymer sizes. These smears not only allowed a wide coverage of properties of these polymers, but also reduced PEG variables, enabling greater sampling of other parameters such as buffers and additives. The efficiency of the smear-based screens was evaluated on more than 220 diverse recombinant human proteins, which overall revealed a good initial crystallization success rate of nearly 50%. In addition, in several cases successful crystallizations were only obtained using PEG smears, while various commercial screens failed to yield crystals. The defined smears therefore offer an alternative approach towards PEG sampling, which will benefit the design of crystallization screens sampling a wide chemical space of this key precipitant.« less

The plug-based nanovolume Microcapillary Protein Crystallization System (MPCS)

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

Gerdts, Cory J.; Elliott, Mark; Lovell, Scott

2012-02-08

The Microcapillary Protein Crystallization System (MPCS) embodies a new semi-automated plug-based crystallization technology which enables nanolitre-volume screening of crystallization conditions in a plasticware format that allows crystals to be easily removed for traditional cryoprotection and X-ray diffraction data collection. Protein crystals grown in these plastic devices can be directly subjected to in situ X-ray diffraction studies. The MPCS integrates the formulation of crystallization cocktails with the preparation of the crystallization experiments. Within microfluidic Teflon tubing or the microfluidic circuitry of a plastic CrystalCard, {approx}10-20 nl volume droplets are generated, each representing a microbatch-style crystallization experiment with a different chemical composition.more » The entire protein sample is utilized in crystallization experiments. Sparse-matrix screening and chemical gradient screening can be combined in one comprehensive 'hybrid' crystallization trial. The technology lends itself well to optimization by high-granularity gradient screening using optimization reagents such as precipitation agents, ligands or cryoprotectants.« less

Comparative study between chemical and atmospheric pressure plasma jet cleaning on glass substrate

NASA Astrophysics Data System (ADS)

Elfa, Rizan Rizon; Ahmad, Mohd Khairul; Fhong, Soon Chin; Sahdan, Mohd Zainizan; Nayan, Nafarizal

2017-01-01

The atmospheric pressure plasma jet with low frequency and argon as working gas is presented in this paper to demonstrate its application for glass substrate clean and modification. The glass substrate clean by atmospheric pressure plasma jet is an efficient method to replace other substrate clean method. A comparative analysis is done in this paper between substrate cleaned by chemical and plasma treatment methods. Water contact angle reading is taken for a different method of substrate clean and period of treatment. Under the plasma treatment, the sample shows low surface adhesion due to having the surface property of super hydrophilic surface 7.26°. This comparative analysis is necessary in the industrial application for cost production due to sufficient time and method of substrate clean.

Reduced-Pressure Chemical Vapor Deposition Growth of Isolated Ge Crystals and Suspended Layers on Micrometric Si Pillars.

PubMed

Skibitzki, Oliver; Capellini, Giovanni; Yamamoto, Yuji; Zaumseil, Peter; Schubert, Markus Andreas; Schroeder, Thomas; Ballabio, Andrea; Bergamaschini, Roberto; Salvalaglio, Marco; Miglio, Leo; Montalenti, Francesco

2016-10-05

In this work, we demonstrate the growth of Ge crystals and suspended continuous layers on Si(001) substrates deeply patterned in high aspect-ratio pillars. The material deposition was carried out in a commercial reduced-pressure chemical vapor deposition reactor, thus extending the "vertical-heteroepitaxy" technique developed by using the peculiar low-energy plasma-enhanced chemical vapor deposition reactor, to widely available epitaxial tools. The growth process was thoroughly analyzed, from the formation of small initial seeds to the final coalescence into a continuous suspended layer, by means of scanning and transmission electron microscopy, X-ray diffraction, and μ-Raman spectroscopy. The preoxidation of the Si pillar sidewalls and the addition of hydrochloric gas in the reactants proved to be key to achieve highly selective Ge growth on the pillars top only, which, in turn, is needed to promote the formation of a continuous Ge layer. Thanks to continuum growth models, we were able to single out the different roles played by thermodynamics and kinetics in the deposition dynamics. We believe that our findings will open the way to the low-cost realization of tens of micrometers thick heteroepitaxial layer (e.g., Ge, SiC, and GaAs) on Si having high crystal quality.

Effects of crystallization interfaces on irradiated ferroelectric thin films

NASA Astrophysics Data System (ADS)

Brewer, S. J.; Williams, S. C.; Cress, C. D.; Bassiri-Gharb, N.

2017-11-01

This work investigates the role of crystallization interfaces and chemical heterogeneity in the radiation tolerance of chemical solution-deposited lead zirconate titanate (PZT) thin films. Two sets of PZT thin films were fabricated with crystallization performed at (i) every deposited layer or (ii) every three layers. The films were exposed to a range of 60Co gamma radiation doses, between 0.2 and 20 Mrad, and their functional response was compared before and after irradiation. The observed trends indicate enhancements of dielectric, ferroelectric, and piezoelectric responses at low radiation doses and degradation of the same at higher doses. Response enhancements are expected to result from low-dose (≤2 Mrad), ionizing radiation-induced charging of internal interfaces—an effect that results in neutralization of pre-existing internal bias in the samples. At higher radiation doses (>2 Mrad), accumulation and self-ordering of radiation-modified, mobile, oxygen vacancy-related defects contribute to degradation of dielectric, ferroelectric, and piezoelectric properties, exacerbated in the samples with more crystallization layers, potentially due to increased defect accumulation at these internal interfaces. These results suggest that the interaction between radiation and crystallization interfaces is multifaceted—the effects of ionization, domain wall motion, point defect mobility, and microstructure are considered.

Single-crystal and polycrystalline diamond erosion studies in Pilot-PSI

NASA Astrophysics Data System (ADS)

Kogut, D.; Aussems, D.; Ning, N.; Bystrov, K.; Gicquel, A.; Achard, J.; Brinza, O.; Addab, Y.; Martin, C.; Pardanaud, C.; Khrapak, S.; Cartry, G.

2018-03-01

Diamond is a promising candidate for enhancing the negative-ion surface production in the ion sources for neutral injection in fusion reactors; hence evaluation of its reactivity towards hydrogen plasma is of high importance. Single crystal and polycrystalline diamond samples were exposed in Pilot-PSI with the D+ flux of (4‒7)·1024 m-2s-1 and the impact energy of 7-9 eV per deuteron at different surface temperatures; under such conditions physical sputtering is negligible, however chemical sputtering is important. Net chemical sputtering yield Y = 9.7·10-3 at/ion at 800 °C was precisely measured ex-situ using a protective platinum mask (5 × 10 × 2 μm) deposited beforehand on a single crystal followed by the post-mortem analysis using Transmission Electron Microscopy (TEM). The structural properties of the exposed diamond surface were analyzed by Raman spectroscopy and X-ray Photoelectron Spectroscopy (XPS). Gross chemical sputtering yields were determined in-situ by means of optical emission spectroscopy of the molecular CH A-X band for several surface temperatures. A bell-shaped dependence of the erosion yield versus temperature between 400 °C and 1200 °C was observed, with a maximum yield of ∼1.5·10-2 at/ion attained at 900 °C. The yields obtained for diamond are relatively high (0.5-1.5)·10-2 at/ion, comparable with those of graphite. XPS analysis shows amorphization of diamond surface within 1 nm depth, in a good agreement with molecular dynamics (MD) simulation. MD was also applied to study the hydrogen impact energy threshold for erosion of [100] diamond surface at different temperatures.

Crystallization and preliminary X-ray analysis of pyruvate kinase from Bacillus stearothermophilus

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

Suzuki, Kenichiro; Ito, Sohei; Shimizu-Ibuka, Akiko

2005-08-01

This report describes the crystallization and X-ray diffraction data collection of three types (wild-type, W416F/V435W and C9S/C268S) of B. stearothermophilus. Crystals of C9S/C268S belonged to space group P6{sub 2}22 and diffracted to a resolution of 2.4 Å. Pyruvate kinase (PK) from a moderate thermophile, Bacillus stearothermophilus (BstPK), is an allosteric enzyme activated by AMP and ribose 5-phosphate but not by fructose 1,6-bisphosphate (FBP). However, almost all other PKs are activated by FBP. The wild-type and W416F/V435W mutant BstPKs were crystallized by the hanging-drop vapour-diffusion method. However, they were unsuitable for structural analysis because their data sets exhibited low completeness. Amore » crystal suitable for structural analysis was obtained using C9S/C268S enzyme. The crystal belonged to space group P6{sub 2}22, with unit-cell parameters a = b = 145.97, c = 118.03 Å.« less

Solvent screening for a hard-to-dissolve molecular crystal.

PubMed

Maiti, A; Pagoria, P F; Gash, A E; Han, T Y; Orme, C A; Gee, R H; Fried, L E

2008-09-01

Materials with a high-degree of inter- and intra-molecular hydrogen bonding generally have limited solubility in conventional organic solvents. This presents a problem for the dissolution, manipulation and purification of these materials. Using a state-of-the-art density-functional-theory based quantum chemical solvation model we systematically evaluated solvents for a known hydrogen-bonded molecular crystal. This, coupled with direct solubility measurements, uncovered a class of ionic liquids involving fluoride anions that possess more than two orders of magnitude higher solvation power as compared with the best conventional solvents. The crystal structure of one such ionic liquid, determined by X-ray diffraction spectroscopy, indicates that F- ions are stabilized through H-bonded chains with water. The presence of coordinating water in such ionic liquids seems to facilitate the dissolution process by keeping the chemical activity of the F- ions in check.

A multistep single-crystal-to-single-crystal bromodiacetylene dimerization

NASA Astrophysics Data System (ADS)

Hoheisel, Tobias N.; Schrettl, Stephen; Marty, Roman; Todorova, Tanya K.; Corminboeuf, Clémence; Sienkiewicz, Andrzej; Scopelliti, Rosario; Schweizer, W. Bernd; Frauenrath, Holger

2013-04-01

Packing constraints and precise placement of functional groups are the reason that organic molecules in the crystalline state often display unusual physical or chemical properties not observed in solution. Here we report a single-crystal-to-single-crystal dimerization of a bromodiacetylene that involves unusually large atom displacements as well as the cleavage and formation of several bonds. Density functional theory computations support a mechanism in which the dimerization is initiated by a [2 + 1] photocycloaddition favoured by the nature of carbon-carbon short contacts in the crystal structure. The reaction proceeded up to the theoretical degree of conversion without loss of crystallinity, and it was also performed on a preparative scale with good yield. Moreover, it represents the first synthetic pathway to (E)-1,2-dibromo-1,2-diethynylethenes, which could serve as synthetic intermediates for the preparation of molecular carbon scaffolds. Our findings both extend the scope of single-crystal-to-single-crystal reactions and highlight their potential as a synthetic tool for complex transformations.

Crystal structure, chemical composition, and extended defects of the high-Tc (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta compounds.

PubMed

Eibl, O

1995-02-15

This paper summarizes results obtained by high-resolution transmission electron microscopy on the crystal structure and microstructure of the (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta high-Tc superconducting oxides. The experimental basis for the work presented here are high-resolution structure images obtained at ultra-thin (3 nm) areas of carefully prepared transmission electron microscope (TEM) samples. The analysis was carried out on a 400 kV TEM equipped with a pole piece yielding 0.17 nm point-to-point resolution. From the images obtained the projected crystal potential of the cations can be extracted directly, as confirmed by detailed image simulation. Structural analysis of the oxygen sublattice remains an unsolved problem by high-resolution TEM (HRTEM), mainly because of the small scattering factors, and thus the contribution of the oxygen sublattice to the image contrast is small. The (BiPb)2Sr2Ca(n)-1CunO4 + 2n + delta phases are modulated structures that can be understood as an average structure plus a superimposed displacement field. The crystal structure consists of BiO double layers and perovskite-type cuboids (containing Sr, Ca, Cu, and O), which are sandwiched between the BiO double layers. The displacement field can be directly analyzed by HRTEM, and the largest displacement amplitudes of 70 pm were determined for the Bi atoms in the n = 1 compound. The chemical composition of the n = 2 and n = 3 compounds was determined by EDX in the TEM for the cation sublattice. A significant (Ca + Sr) deficiency (approximately 10%) with respect to Cu was found. The (Sr + Ca)/Cu mole fraction ratio was 1.31 for the Bi-2212 phase and 1.14 for the Bi(Pb)-2223 phase. The oxygen content cannot be determined by EDX in the TEM with the accuracy necessary for a correlation with electrical and superconducting properties. The defect structure present in these materials, that is, intergrown lamellae with different crystal structures and equal or different chemical

Ground-based research of crystal growth of II-VI compound semiconductors by physical vapor transport

NASA Technical Reports Server (NTRS)

Volz, M. P.; Gillies, D. C.; Szofran, F. R.; Lehoczky, S. L.; Su, Ching-Hua; Sha, Yi-Gao; Zhou, W.; Dudley, M.; Liu, Hao-Chieh; Brebrick, R. F.;

Novel trace chemical detection algorithms: a comparative study

NASA Astrophysics Data System (ADS)

Raz, Gil; Murphy, Cara; Georgan, Chelsea; Greenwood, Ross; Prasanth, R. K.; Myers, Travis; Goyal, Anish; Kelley, David; Wood, Derek; Kotidis, Petros

2017-05-01

Algorithms for standoff detection and estimation of trace chemicals in hyperspectral images in the IR band are a key component for a variety of applications relevant to law-enforcement and the intelligence communities. Performance of these methods is impacted by the spectral signature variability due to presence of contaminants, surface roughness, nonlinear dependence on abundances as well as operational limitations on the compute platforms. In this work we provide a comparative performance and complexity analysis of several classes of algorithms as a function of noise levels, error distribution, scene complexity, and spatial degrees of freedom. The algorithm classes we analyze and test include adaptive cosine estimator (ACE and modifications to it), compressive/sparse methods, Bayesian estimation, and machine learning. We explicitly call out the conditions under which each algorithm class is optimal or near optimal as well as their built-in limitations and failure modes.

High resolution Physio-chemical Tissue Analysis: Towards Non-invasive In Vivo Biopsy

NASA Astrophysics Data System (ADS)

Xu, Guan; Meng, Zhuo-Xian; Lin, Jian-Die; Deng, Cheri X.; Carson, Paul L.; Fowlkes, J. Brian; Tao, Chao; Liu, Xiaojun; Wang, Xueding

2016-02-01

Conventional gold standard histopathologic diagnosis requires information of both high resolution structural and chemical changes in tissue. Providing optical information at ultrasonic resolution, photoacoustic (PA) technique could provide highly sensitive and highly accurate tissue characterization noninvasively in the authentic in vivo environment, offering a replacement for histopathology. A two-dimensional (2D) physio-chemical spectrogram (PCS) combining micrometer to centimeter morphology and chemical composition simultaneously can be generated for each biological sample with PA measurements at multiple optical wavelengths. This spectrogram presents a unique 2D “physio-chemical signature” for any specific type of tissue. Comprehensive analysis of PCS, termed PA physio-chemical analysis (PAPCA), can lead to very rich diagnostic information, including the contents of all relevant molecular and chemical components along with their corresponding histological microfeatures, comparable to those accessible by conventional histology. PAPCA could contribute to the diagnosis of many diseases involving diffusive patterns such as fatty liver.

The polymorphic weddellite crystals in three species of Cephalocereus (Cactaceae).

PubMed

Bárcenas-Argüello, María-Luisa; Gutiérrez-Castorena, Ma C-del-Carmen; Terrazas, Teresa

2015-10-01

Mineral inclusions in plant cells are genetically regulated, have an ecological function and are used as taxonomic characters. In Cactaceae, crystals in epidermal and cortical tissues have been reported; however, few studies have conducted chemical and morphological analyses on these crystals, and even fewer have reported non-mineral calcium to determine its systematic value. Cephalocereus apicicephalium, C. totolapensis and C. nizandensis are Cactaceae species endemic to the Isthmus of Tehuantepec, Mexico with abundant epidermal prismatic crystals. In the present study, we characterize the mineral cell inclusions, including their chemical composition and their morphology, for three species of Cephalocereus. Crystals of healthy branches of the three species were isolated and studied. The crystals were identified by X-ray diffraction (XRD), their morphology was described using a petrographic and scanning electron microscope (SEM), and their elemental composition was measured with Energy Dispersive X-ray (EDXAR). The three species synthesized weddellite with different degrees of hydration depending on the species. The optical properties of calcium oxalate crystals were different from the core, which was calcium carbonate. We observed a large diversity of predominantly spherical forms with SEM. EDXAR analysis detected different concentrations of Ca and significant amounts of elements, such as Si, Mg, Na, K, Cl, and Fe, which may be related to the edaphic environment of these cacti. The occurrence of weddellite is novel for the genus according to previous reports. The morphological diversity of the crystals may be related to their elemental composition and may be a source of phylogenetic characters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Optical Basicity and Nepheline Crystallization in High Alumina Glasses

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

Rodriguez, Carmen P.; McCloy, John S.; Schweiger, M. J.

2011-02-25

The purpose of this study was to find compositions that increase waste loading of high-alumina wastes beyond what is currently acceptable while avoiding crystallization of nepheline (NaAlSiO4) on slow cooling. Nepheline crystallization has been shown to have a large impact on the chemical durability of high-level waste glasses. It was hypothesized that there would be some composition regions where high-alumina would not result in nepheline crystal production, compositions not currently allowed by the nepheline discriminator. Optical basicity (OB) and the nepheline discriminator (ND) are two ways of describing a given complex glass composition. This report presents the theoretical and experimentalmore » basis for these models. They are being studied together in a quadrant system as metrics to explore nepheline crystallization and chemical durability as a function of waste glass composition. These metrics were calculated for glasses with existing data and also for theoretical glasses to explore nepheline formation in Quadrant IV (passes OB metric but fails ND metric), where glasses are presumed to have good chemical durability. Several of these compositions were chosen, and glasses were made to fill poorly represented regions in Quadrant IV. To evaluate nepheline formation and chemical durability of these glasses, quantitative X-ray diffraction (XRD) analysis and the Product Consistency Test were conducted. A large amount of quantitative XRD data is collected here, both from new glasses and from glasses of previous studies that had not previously performed quantitative XRD on the phase assemblage. Appendix A critically discusses a large dataset to be considered for future quantitative studies on nepheline formation in glass. Appendix B provides a theoretical justification for choice of the oxide coefficients used to compute the OB criterion for nepheline formation.« less

Fragment-based 13C nuclear magnetic resonance chemical shift predictions in molecular crystals: An alternative to planewave methods

NASA Astrophysics Data System (ADS)

Hartman, Joshua D.; Monaco, Stephen; Schatschneider, Bohdan; Beran, Gregory J. O.

2015-09-01

We assess the quality of fragment-based ab initio isotropic 13C chemical shift predictions for a collection of 25 molecular crystals with eight different density functionals. We explore the relative performance of cluster, two-body fragment, combined cluster/fragment, and the planewave gauge-including projector augmented wave (GIPAW) models relative to experiment. When electrostatic embedding is employed to capture many-body polarization effects, the simple and computationally inexpensive two-body fragment model predicts both isotropic 13C chemical shifts and the chemical shielding tensors as well as both cluster models and the GIPAW approach. Unlike the GIPAW approach, hybrid density functionals can be used readily in a fragment model, and all four hybrid functionals tested here (PBE0, B3LYP, B3PW91, and B97-2) predict chemical shifts in noticeably better agreement with experiment than the four generalized gradient approximation (GGA) functionals considered (PBE, OPBE, BLYP, and BP86). A set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided based on these benchmark calculations. Statistical cross-validation procedures are used to demonstrate the robustness of these fits.

Fragment-based (13)C nuclear magnetic resonance chemical shift predictions in molecular crystals: An alternative to planewave methods.

PubMed

Hartman, Joshua D; Monaco, Stephen; Schatschneider, Bohdan; Beran, Gregory J O

2015-09-14

We assess the quality of fragment-based ab initio isotropic (13)C chemical shift predictions for a collection of 25 molecular crystals with eight different density functionals. We explore the relative performance of cluster, two-body fragment, combined cluster/fragment, and the planewave gauge-including projector augmented wave (GIPAW) models relative to experiment. When electrostatic embedding is employed to capture many-body polarization effects, the simple and computationally inexpensive two-body fragment model predicts both isotropic (13)C chemical shifts and the chemical shielding tensors as well as both cluster models and the GIPAW approach. Unlike the GIPAW approach, hybrid density functionals can be used readily in a fragment model, and all four hybrid functionals tested here (PBE0, B3LYP, B3PW91, and B97-2) predict chemical shifts in noticeably better agreement with experiment than the four generalized gradient approximation (GGA) functionals considered (PBE, OPBE, BLYP, and BP86). A set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided based on these benchmark calculations. Statistical cross-validation procedures are used to demonstrate the robustness of these fits.

An Integrated Approach to Laser Crystal Development

NASA Technical Reports Server (NTRS)

Ries, Heidi R.

1996-01-01

Norfolk State University has developed an integrated research program in the area of laser crystal development, including crystal modeling, crystal growth, spectroscopy, and laser modeling. This research program supports a new graduate program in Chemical Physics, designed in part to address the shortage of minority scientists.

A simple 2D composite image analysis technique for the crystal growth study of L-ascorbic acid.

PubMed

Kumar, Krishan; Kumar, Virender; Lal, Jatin; Kaur, Harmeet; Singh, Jasbir

2017-06-01

This work was destined for 2D crystal growth studies of L-ascorbic acid using the composite image analysis technique. Growth experiments on the L-ascorbic acid crystals were carried out by standard (optical) microscopy, laser diffraction analysis, and composite image analysis. For image analysis, the growth of L-ascorbic acid crystals was captured as digital 2D RGB images, which were then processed to composite images. After processing, the crystal boundaries emerged as white lines against the black (cancelled) background. The crystal boundaries were well differentiated by peaks in the intensity graphs generated for the composite images. The lengths of crystal boundaries measured from the intensity graphs of composite images were in good agreement (correlation coefficient "r" = 0.99) with the lengths measured by standard microscopy. On the contrary, the lengths measured by laser diffraction were poorly correlated with both techniques. Therefore, the composite image analysis can replace the standard microscopy technique for the crystal growth studies of L-ascorbic acid. © 2017 Wiley Periodicals, Inc.

Crystallization and preliminary X-ray analysis of gamma-glutamyltranspeptidase from Escherichia coli K-12.

PubMed

Kumagai, H; Nohara, S; Suzuki, H; Hashimoto, W; Yamamoto, K; Sakai, H; Sakabe, K; Fukuyama, K; Sakabe, N

1993-12-20

gamma-Glutamyltranspeptidase (EC 2.3.2.2) from Escherichia coli K-12 has been purified and crystallized by means of vapor diffusion in hanging drops. Two kinds of crystals on cell dimensions were found for X-ray diffraction analysis, one from ammonium sulfate and the other from polyethylene glycol 6000 as precipitants. The crystals of the orthorhombic form grown in the presence of 15% polyethylene glycol and 20 mM sodium acetate buffer were chosen for further analysis. The crystals belonged to space group P2(1)2(1)2(1), with cell dimensions of a = 128.1, b = 129.9 and c = 79.2 A, and two molecules constitute an asymmetric unit. These crystals diffracted to 2.0 A resolution and were suitable for X-ray crystallographic studies.

KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal.

PubMed

Dong, Hui; Wang, Lili; Gao, Wei; Li, Xiaoyuan; Wang, Chao; Ji, Fang; Pan, Jinlong; Wang, Baorui

2017-03-09

A novel functional KH₂PO₄ (KDP) aqueous solution-in-oil (KDP aq/O) microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP) was prepared. The system, which consisted of decanol, Triton X-100, and KH₂PO₄ aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations ( c KDP ) were applied to replace water in the traditional water-in-oil (W/O) microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR) with the increasing of the c KDP . As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion ( c KDP was changed from 10 mM to 100 mM) as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR.

Controlled chemical modification of the internal surface of photonic crystal fibers for application as biosensitive elements

NASA Astrophysics Data System (ADS)

Pidenko, Sergey A.; Burmistrova, Natalia A.; Pidenko, Pavel S.; Shuvalov, Andrey A.; Chibrova, Anastasiya A.; Skibina, Yulia S.; Goryacheva, Irina Y.

2016-10-01

Photonic crystal fibers (PCF) are one of the most promising materials for creation of constructive elements for bio-, drug and contaminant sensing based on unique optical properties of the PCF as effective nanosized optical signal collectors. In order to provide efficient and controllable binding of biomolecules, the internal surface of glass hollow core photonic crystal fibers (HC-PCF) has been chemically modified with silanol groups and functionalized with (3-aminopropyl) triethoxysilane (APTES). The shift of local maxima in the HC-PCF transmission spectrum has been selected as a signal for estimating the amount of silanol groups on the HC-PCF inner surface. The relationship between amount of silanol groups on the HC-PCF inner surface and efficiency of following APTES functionalization has been evaluated. Covalent binding of horseradish peroxidase (chosen as a model protein) on functionalized PCF inner surface has been performed successively, thus verifying the possibility of creating a biosensitive element.

Chemical and Biological Sensing Using Diatom Photonic Crystal Biosilica With In-Situ Growth Plasmonic Nanoparticles.

PubMed

Kong, Xianming; Squire, Kenny; Li, Erwen; LeDuff, Paul; Rorrer, Gregory L; Tang, Suning; Chen, Bin; McKay, Christopher P; Navarro-Gonzalez, Rafael; Wang, Alan X

2016-12-01

In this paper, we described a new type of bioenabled nano-plasmonic sensors based on diatom photonic crystal biosilica with in-situ growth silver nanoparticles and demonstrated label-free chemical and biological sensing based on surface-enhanced Raman scattering (SERs) from complex samples. Diatoms are photosynthetic marine micro-organisms that create their own skeletal shells of hydrated amorphous silica, called frustules, which possess photonic crystal-like hierarchical micro- & nanoscale periodic pores. Our research shows that such hybrid plasmonic-biosilica nanostructures formed by cost-effective and eco-friendly bottom-up processes can achieve ultra-high limit of detection for medical applications, food sensing, water/air quality monitoring and geological/space research. The enhanced sensitivity comes from the optical coupling of the guided-mode resonance of the diatom frustules and the localized surface plasmons of the silver nanoparticles. Additionally, the nanoporous, ultra-hydrophilic diatom biosilica with large surface-to-volume ratio can concentrate more analyte molecules to the surface of the SERS substrates, which can help to detect biomolecules that cannot be easily adsorbed by metallic nanoparticles.

Explosive performance of HMX/NTO co-crystal

NASA Astrophysics Data System (ADS)

Li, J. C.; Jiao, Q. J.; Gong, Y. G.; Wang, Y. Y.; Liang, T.; Sun, J.

2018-01-01

A new co-crystal explosive of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) and 3-nitro-1, 2, 4-triazol-5-one (NTO) in a molar ratio of 1:1 has been prepared by solvent/anti-solvent method. The SEM photographs show that HMX/NTO co-crystals are distinctly different from HMX and NTO crystals. The co-crystals are prisms with well formed crystal surfaces. Thermal analysis results indicate the melting point of the co-crystal is 29.3 °Chigher than that of NTO. Moreover, the co-crystal exhibits a modified mechanical sensitivity. The characteristic height (H50) of impact sensitivity increases 14.8cm, and the explosion percentage (P) of friction sensitivity decreases by 40% compared with HMX. The HMX/NTO co-crystals possess good thermal property and low sensitivity, which mean huge advantages in blasting engineering.

A view inside the nature of protein crystals

NASA Astrophysics Data System (ADS)

Oswald, R.; Pietzsch, M.; Ulrich, J.

2017-07-01

In this work a fundamental analysis of protein crystal modifications was presented to compare and confirm the components of protein crystal modifications. The result is that a protein crystal contains besides the protein, the precipitant and water. A mass spectrometer coupled to a thermogravimetry device was used to confirm the different waters (free water -the chosen buffer- and bound water) inside the crystals. Here the biggest amount of water is the free water (the buffer) with an amount of approximately 35%. The bound water (in the sense of a hydrate) has only an amount of about 1-1.5%. Furthermore, an x-ray analysis to confirm the influence range of pH value on the stability of one crystal modification for the understanding of effects on dissolution mechanism of protein crystals was investigated. The crystals of the tetragonal modification crystallized at pH 4.7, 4.85, 5.0, 5.15 and 5.3 maintain according to the x-ray measurements the same lattice parameters. The measured data are discussed.

Direct determination of one-dimensional interphase structures using normalized crystal truncation rod analysis

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

Kawaguchi, Tomoya; Liu, Yihua; Reiter, Anthony

Here, a one-dimensional non-iterative direct method was employed for normalized crystal truncation rod analysis. The non-iterative approach, utilizing the Kramers–Kronig relation, avoids the ambiguities due to an improper initial model or incomplete convergence in the conventional iterative methods. The validity and limitations of the present method are demonstrated through both numerical simulations and experiments with Pt(111) in a 0.1 M CsF aqueous solution. The present method is compared with conventional iterative phase-retrieval methods.

Direct determination of one-dimensional interphase structures using normalized crystal truncation rod analysis

DOE PAGES

Kawaguchi, Tomoya; Liu, Yihua; Reiter, Anthony; ...

2018-04-20

Here, a one-dimensional non-iterative direct method was employed for normalized crystal truncation rod analysis. The non-iterative approach, utilizing the Kramers–Kronig relation, avoids the ambiguities due to an improper initial model or incomplete convergence in the conventional iterative methods. The validity and limitations of the present method are demonstrated through both numerical simulations and experiments with Pt(111) in a 0.1 M CsF aqueous solution. The present method is compared with conventional iterative phase-retrieval methods.

Hot spot formation and chemical reaction initiation in shocked HMX crystals with nanovoids: a large-scale reactive molecular dynamics study.

PubMed

Zhou, Tingting; Lou, Jianfeng; Zhang, Yangeng; Song, Huajie; Huang, Fenglei

2016-07-14

We report million-atom reactive molecular dynamic simulations of shock initiation of β-cyclotetramethylene tetranitramine (β-HMX) single crystals containing nanometer-scale spherical voids. Shock induced void collapse and subsequent hot spot formation as well as chemical reaction initiation are observed which depend on the void size and impact strength. For an impact velocity of 1 km s(-1) and a void radius of 4 nm, the void collapse process includes three stages; the dominant mechanism is the convergence of upstream molecules toward the centerline and the downstream surface of the void forming flowing molecules. Hot spot formation also undergoes three stages, and the principal mechanism is kinetic energy transforming to thermal energy due to the collision of flowing molecules on the downstream surface. The high temperature of the hot spot initiates a local chemical reaction, and the breakage of the N-NO2 bond plays the key role in the initial reaction mechanism. The impact strength and void size have noticeable effects on the shock dynamical process, resulting in a variation of the predominant mechanisms leading to void collapse and hot spot formation. Larger voids or stronger shocks result in more intense hot spots and, thus, more violent chemical reactions, promoting more reaction channels and generating more reaction products in a shorter duration. The reaction products are mainly concentrated in the developed hot spot, indicating that the chemical reactivity of the hmx crystal is greatly enhanced by void collapse. The detailed information derived from this study can aid a thorough understanding of the role of void collapse in hot spot formation and the chemical reaction initiation of explosives.

σ-Hole and π-Hole Synthon Mimicry in Third-Generation Crystal Engineering: Design of Elastic Crystals.

PubMed

Saha, Subhankar; Desiraju, Gautam R

2017-04-06

Designing elastic crystals is a difficult task and is of relevance in potential applications from materials to biology. Here, multi-step crystal engineering based on σ-hole and π-hole synthon mimicry is performed to obtain binary organic molecular crystals with a high degree of flexibility. A structural model is proposed based only on σ-hole-oriented type-II halogen bonds with their characteristic orthogonal geometry. These σ-hole contacts are then partly replaced by chemically and geometrically similar π-hole synthons to obtain new crystals in the second step. In the final step, all the σ-hole interactions are replaced with π-hole interactions and elastic crystals of non-halogenated compounds are obtained. All the crystals obtained according to our protocols are found to be elastic. When crystals that do not conform to the desired structure type appeared, they were found to be brittle. This underlines the role of orthogonal-type interactions, whether they are of the σ-hole or π-hole type, in achieving elasticity. This is the first report in which π-hole interactions are used for property engineering. This example may illustrate a new generation of crystal engineering in which a particular property is associated more with topological rather than chemical attributes, although the significance of the latter cannot be completely excluded. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystal Engineering of an nbo Topology Metal-Organic Framework for Chemical Fixation of CO₂ under Ambient Conditions

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

Gao, Wen-Yang; Chen, Yao; Niu, Youhong

Crystal engineering of the nbo metal–organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu₂(Cu-tactmb)(H₂O)₃(NO₃)₂]. This MOF demonstrates high catalytic activity for the chemical fixation of CO₂ into cyclic carbonates at room temperature under 1 atm pressure.

Can a fractionally crystallized magma ocean explain the thermo-chemical evolution of Mars?

NASA Astrophysics Data System (ADS)

Plesa, A.-C.; Tosi, N.; Breuer, D.

2014-10-01

The impact heat accumulated during the late stage of planetary accretion can melt a significant part or even the entire mantle of a terrestrial body, giving rise to a global magma ocean. The subsequent cooling of the interior causes the magma ocean to freeze from the core-mantle boundary (CMB) to the surface due to the steeper slope of the mantle adiabat compared to the slope of the solidus. Assuming fractional crystallization of the magma ocean, dense cumulates are produced close to the surface, largely due to iron enrichment in the evolving magma ocean liquid. A gravitationally unstable mantle thus forms, which is prone to overturn. We investigate the cumulate overturn and its influence on the thermal evolution of Mars using mantle convection simulations in 2D cylindrical geometry. We present a suite of simulations using different initial conditions and a strongly temperature-dependent viscosity. We assume that all radiogenic heat sources have been enriched during the freezing-phase of the magma ocean in the uppermost 50 km and that the initial steam-atmosphere created by the degassing of the freezing magma ocean was rapidly lost, implying that the surface temperature is set to present-day values. In this case, a stagnant lid quickly forms on top of the convective interior preventing the uppermost dense cumulates to sink, even when allowing for a plastic yielding mechanism. Below this dense stagnant lid, the mantle chemical gradient settles to a stable configuration. The convection pattern is dominated by small-scale structures, which are difficult to reconcile with the large-scale volcanic features observed over Mars' surface and partial melting ceases in less than 900 Ma. Assuming that the stagnant lid can break because of additional mechanisms and allowing the uppermost dense layer to overturn, a stable density gradient is obtained, with the densest material and the entire amount of heat sources lying above the CMB. This stratification leads to a strong

Magnetorheological finishing of chemical-vapor deposited zinc sulfide via chemically and mechanically modified fluids.

PubMed

Salzman, Sivan; Romanofsky, Henry J; Giannechini, Lucca J; Jacobs, Stephen D; Lambropoulos, John C

2016-02-20

We describe the anisotropy in the material removal rate (MRR) of the polycrystalline, chemical-vapor deposited zinc sulfide (ZnS). We define the polycrystalline anisotropy via microhardness and chemical erosion tests for four crystallographic orientations of ZnS: (100), (110), (111), and (311). Anisotropy in the MRR was studied under magnetorheological finishing (MRF) conditions. Three chemically and mechanically modified magnetorheological (MR) fluids at pH values of 4, 5, and 6 were used to test the MRR variations among the four single-crystal planes. When polishing the single-crystal planes and the polycrystalline with pH 5 and pH 6 MR fluids, variations were found in the MRR among the four single-crystal planes and surface artifacts were observed on the polycrystalline material. When polishing the single-crystal planes and the polycrystalline with the modified MR fluid at pH 4, however, minimal variation was observed in the MRR among the four orientations and a reduction in surface artifacts was achieved on the polycrystalline material.

Applications of the Cambridge Structural Database in organic chemistry and crystal chemistry.

PubMed

Allen, Frank H; Motherwell, W D Samuel

2002-06-01

The Cambridge Structural Database (CSD) and its associated software systems have formed the basis for more than 800 research applications in structural chemistry, crystallography and the life sciences. Relevant references, dating from the mid-1970s, and brief synopses of these papers are collected in a database, DBUse, which is freely available via the CCDC website. This database has been used to review research applications of the CSD in organic chemistry, including supramolecular applications, and in organic crystal chemistry. The review concentrates on applications that have been published since 1990 and covers a wide range of topics, including structure correlation, conformational analysis, hydrogen bonding and other intermolecular interactions, studies of crystal packing, extended structural motifs, crystal engineering and polymorphism, and crystal structure prediction. Applications of CSD information in studies of crystal structure precision, the determination of crystal structures from powder diffraction data, together with applications in chemical informatics, are also discussed.

Computerized Liquid Crystal Phase Identification by Neural Networks Analysis of Polarizing Microscopy Textures

NASA Astrophysics Data System (ADS)

Karaszi, Zoltan; Konya, Andrew; Dragan, Feodor; Jakli, Antal; CPIP/LCI; CS Dept. of Kent State University Collaboration

Polarizing optical microscopy (POM) is traditionally the best-established method of studying liquid crystals, and using POM started already with Otto Lehman in 1890. An expert, who is familiar with the science of optics of anisotropic materials and typical textures of liquid crystals, can identify phases with relatively large confidence. However, for unambiguous identification usually other expensive and time-consuming experiments are needed. Replacement of the subjective and qualitative human eye-based liquid crystal texture analysis with quantitative computerized image analysis technique started only recently and were used to enhance the detection of smooth phase transitions, determine order parameter and birefringence of specific liquid crystal phases. We investigate if the computer can recognize and name the phase where the texture was taken. To judge the potential of reliable image recognition based on this procedure, we used 871 images of liquid crystal textures belonging to five main categories: Nematic, Smectic A, Smectic C, Cholesteric and Crystal, and used a Neural Network Clustering Technique included in the data mining software package in Java ``WEKA''. A neural network trained on a set of 827 LC textures classified the remaining 44 textures with 80% accuracy.

Bulk crystal growth and their effective third order nonlinear optical properties of 2-(4-fluorobenzylidene) malononitrile (FBM) single crystal

NASA Astrophysics Data System (ADS)

Priyadharshini, A.; Kalainathan, S.

2018-04-01

2-(4-fluorobenzylidene) malononitrile (FBM), an organic third order nonlinear (TONLO) single crystal with the dimensions of 32 × 7 × 11 mm3, has been successfully grown in acetone solution by slow evaporation technique at 35 °C. The crystal system (triclinic), space group (P-1) and crystalline purity of the titular crystal were measured by single crystal and powder X-ray diffraction, respectively. The molecular weight and the multiple functional groups of the FBM material were confirmed through the mass and FT-IR spectral analysis. UV-Vis-NIR spectral study enroles that the FBM crystal exhibits excellent transparency (83%) in the entire visible and near infra-red region with a wide bandgap 2.90 eV. The low dielectric constant (εr) value of FBM crystal is appreciable for microelectronics industry applications. Thermal stability and melting point (130.09 °C) were ascertained by TGA-DSC analysis. The laser-induced surface damage threshold (LDT) value of FBM specimen is found to be 2.14 GW/cm2, it is fairly good compared to other reported NLO crystals. The third - order nonlinear optical character of the FBM crystal was confirmed through the typical single beam Z-scan technique. All these finding authorized that the organic crystal of FBM is favorably suitable for NLO applications.

Structural insights into the mycobacteria transcription initiation complex from analysis of X-ray crystal structures

DOE PAGES

Hubin, Elizabeth A.; Lilic, Mirjana; Darst, Seth A.; ...

2017-07-13

The mycobacteria RNA polymerase (RNAP) is a target for antimicrobials against tuberculosis, motivating structure/function studies. Here we report a 3.2 Å-resolution crystal structure of a Mycobacterium smegmatis (Msm) open promoter complex (RPo), along with structural analysis of the Msm RPo and a previously reported 2.76 Å-resolution crystal structure of an Msm transcription initiation complex with a promoter DNA fragment. We observe the interaction of the Msm RNAP α-subunit C-terminal domain (αCTD) with DNA, and we provide evidence that the a CTD may play a role in Mtb transcription regulation. Here, our results reveal the structure of an Actinobacteria-unique insert ofmore » the RNAP β' subunit. Finally, our analysis reveals the disposition of the N-terminal segment of Msm σ A, which may comprise an intrinsically disordered protein domain unique to mycobacteria. The clade-specific features of the mycobacteria RNAP provide clues to the profound instability of mycobacteria RPo compared with E. coli.« less

Structural insights into the mycobacteria transcription initiation complex from analysis of X-ray crystal structures

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

Hubin, Elizabeth A.; Lilic, Mirjana; Darst, Seth A.

The mycobacteria RNA polymerase (RNAP) is a target for antimicrobials against tuberculosis, motivating structure/function studies. Here we report a 3.2 Å-resolution crystal structure of a Mycobacterium smegmatis (Msm) open promoter complex (RPo), along with structural analysis of the Msm RPo and a previously reported 2.76 Å-resolution crystal structure of an Msm transcription initiation complex with a promoter DNA fragment. We observe the interaction of the Msm RNAP α-subunit C-terminal domain (αCTD) with DNA, and we provide evidence that the αCTD may play a role in Mtb transcription regulation. Our results reveal the structure of an Actinobacteria-unique insert of the RNAPmore » β' subunit. Finally, our analysis reveals the disposition of the N-terminal segment of Msm σA, which may comprise an intrinsically disordered protein domain unique to mycobacteria. The clade-specific features of the mycobacteria RNAP provide clues to the profound instability of mycobacteria RPo compared with E. coli.« less

Structural insights into the mycobacteria transcription initiation complex from analysis of X-ray crystal structures

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

Hubin, Elizabeth A.; Lilic, Mirjana; Darst, Seth A.

The mycobacteria RNA polymerase (RNAP) is a target for antimicrobials against tuberculosis, motivating structure/function studies. Here we report a 3.2 Å-resolution crystal structure of a Mycobacterium smegmatis (Msm) open promoter complex (RPo), along with structural analysis of the Msm RPo and a previously reported 2.76 Å-resolution crystal structure of an Msm transcription initiation complex with a promoter DNA fragment. We observe the interaction of the Msm RNAP α-subunit C-terminal domain (αCTD) with DNA, and we provide evidence that the a CTD may play a role in Mtb transcription regulation. Here, our results reveal the structure of an Actinobacteria-unique insert ofmore » the RNAP β' subunit. Finally, our analysis reveals the disposition of the N-terminal segment of Msm σ A, which may comprise an intrinsically disordered protein domain unique to mycobacteria. The clade-specific features of the mycobacteria RNAP provide clues to the profound instability of mycobacteria RPo compared with E. coli.« less

Concanavalin A-binding cholesterol crystallization inhibiting and promoting activity in bile from patients with Crohn's disease compared to patients with ulcerative colitis.

PubMed

Keulemans, Y C; Mok, K S; Slors, J F; Brink, M A; Gouma, D J; Tytgat, G N; Groen, A K

1999-10-01

Crohn's disease is a risk factor for gallstone formation. In contrast, patients with ulcerative colitis have an incidence of gallstone formation comparable to the general population. The reason for this difference is not known. The aim of this study was to elucidate the factors controlling cholesterol crystallization in gallbladder bile of Crohn's disease and ulcerative colitis patients. Gallbladder bile was obtained by aspiration during bowel resections (26 Crohn's disease patients, 20 ulcerative colitis patients). Biliary lipid composition, crystal detection time and the effect of extraction of the concanavalin A-binding fraction on crystal formation were determined. Cholesterol crystals were present in seven of the 26 bile samples of Crohn's disease-patients and one of the 20 ulcerative colitis patients. Four of the bile samples of Crohn's disease patients were fast nucleating. None of the 20 ulcerative colitis patients had fast nucleating bile. Lipid composition, total lipid concentration and CSI were not significantly different between the two groups. In Crohn's disease patients extraction of concanavalin A-binding fraction decreased crystallization in 10 bile samples but accelerated crystallization in one bile sample. In eight bile samples from ulcerative colitis patients crystallization increased after concanavalin A-binding fraction extraction. Compared to ulcerative colitis patients, gallbladder bile of Crohn's disease patients showed increased cholesterol crystallization despite comparable lipid composition and cholesterol saturation index. This difference is caused by increased cholesterol crystallization-promoting activity. Bile from ulcerative colitis patients contains a Con A-binding factor which inhibits cholesterol crystallization.

Photonic crystals at visible, x-ray, and terahertz frequencies

NASA Astrophysics Data System (ADS)

Prasad, Tushar

Photonic crystals are artificial structures with a periodically varying refractive index. This property allows photonic crystals to control the propagation of photons, making them desirable components for novel photonic devices. Photonic crystals are also termed as "semiconductors of light", since they control the flow of electromagnetic radiation similar to the way electrons are excited in a semiconductor crystal. The scale of periodicity in the refractive index determines the frequency (or wavelength) of the electromagnetic waves that can be manipulated. This thesis presents a detailed analysis of photonic crystals at visible, x-ray, and terahertz frequencies. Self-assembly and spin-coating methods are used to fabricate colloidal photonic crystals at visible frequencies. Their dispersion characteristics are examined through theoretical as well as experimental studies. Based on their peculiar dispersion property called the superprism effect, a sensor that can detect small quantities of chemical substances is designed. A photonic crystal that can manipulate x-rays is fabricated by using crystals of a non-toxic plant virus as templates. Calculations show that these metallized three-dimensional crystals can find utility in x-ray optical systems. Terahertz photonic crystal slabs are fabricated by standard lithographic and etching techniques. In-plane superprism effect and out-of-plane guided resonances are studied by terahertz time-domain spectroscopy, and verified by numerical simulations.

Studies on 2-amino-5-nitropyridinium nitrate (2A5NPN): A semi-organic third order nonlinear optical single crystal

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

Sivasubramani, V.; Pandian, Muthu Senthil, E-mail: senthilpandianm@ssn.edu.in; Ramasamy, P.

2016-05-23

2-amino-5-nitropyridinium nitrate (2A5NPN) is a semi-organic nonlinear optical crystal and optically good quality 2A5NPN single crystals were successfully grown by slow evaporation solution growth technique (SEST) at ambient temperature. The crystallographic structure of the grown crystal was determined by single crystal X-Ray diffraction analysis and it belongs to Monoclinic crystal system with centro symmetric crystalline nature. The crystallinity of the grown crystal was confirmed by powder X-ray diffraction analysis. The other physical properties of grown crystals are also characterized using TG-DTA, UV-Visible NIR, chemical etching, photoconductivity and Z-scan measurements. The Z-scan method reveals that the 2A5NPN crystal possesses multi photonmore » absorption behaviour and the significantly higher third order susceptibility and it is a promising potential NLO material.« less

Crystal growth of Bi{sub 2}Te{sub 3} and noble cleaved (0001) surface properties

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

Atuchin, V.V., E-mail: atuchin@thermo.isp.nsc.ru; Functional Electronics Laboratory, Tomsk State University, Tomsk 634050; Golyashov, V.A.

2016-04-15

A high quality Bi{sub 2}Te{sub 3} crystal has been grown by Bridgman method with the use of rotating heat field. The phase purity and bulk structural quality of the crystal have been verified by XRD analysis and rocking curve observation. The atomically smooth Bi{sub 2}Te{sub 3}(0001) surface with an excellent crystallographic quality is formed by cleavage in the air. The chemical and microstructural properties of the surface have been evaluated with RHEED, AFM, STM, SE and XPS. The Bi{sub 2}Te{sub 3}(0001) cleaved surface is formed by atomically smooth terraces with the height of the elemental step of ~1.04±0.1 nm, asmore » estimated by AFM. There is no surface oxidation process detected over a month keeping in the air at normal conditions, as shown by comparative core level photoelectron spectroscopy. - Graphical abstract: A high quality Bi{sub 2}Te{sub 3} crystal has been grown by Bridgman method with the use of rotating heat field and the Bi{sub 2}Te{sub 3}(0001) cleaved surface has been evaluated with RHEED, AFM, STM, SE and XPS. - Highlights: • High-quality Bi{sub 2}Te{sub 3} crystal of 10 mm in diameter and 50 mm long have been grown. • The high-purity cleaved Bi{sub 2}Te{sub 3}(0001) surface has been evaluated by RHEED, AFM, STM and XPS methods. • The Bi{sub 2}Te{sub 3} surface covered by atomically smooth (0001) terraces is chemically stable for a long time.« less

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.

Frequency doubling crystals

DOEpatents

Wang, Francis; Velsko, Stephan P.

1989-01-01

A systematic approach to the production of frequency conversion crystals is described in which a chiral molecule has attached to it a "harmonic generating unit" which contributes to the noncentrosymmetry of the molecule. Certain preferred embodiments of such harmonic generating units include carboxylate, guanadyly and imidazolyl units. Certain preferred crystals include L-arginine fluoride, deuterated L-arginine fluoride, L-arginine chloride monohydrate, L-arginine acetate, dithallium tartrate, ammonium N-acetyl valine, N-acetyl tyrosine and N-acetyl hydroxyproline. Chemical modifications of the chiral molecule, such as deuteration, halogenation and controlled counterion substitution are available to adapt the dispersive properties of a crystal in a particular wavelength region.

Study of the In2O3 molecule in the free state and in the crystal

NASA Astrophysics Data System (ADS)

Kaplan, Ilya G.; Miranda, Ulises; Trakhtenberg, Leonid I.

2018-03-01

The nanomaterials based on the In2O3 molecule are widely used as catalysts and sensors among other applications. In the present study, we discuss the possibility of using nanoclusters of In2O3 as molecular photomotors. A comparative analysis of the electronic structure of the In2O3 molecule in the free state and in the crystal is performed. For the free In2O3 molecule the geometry of its lowest structures, V-shape and linear, was optimised at the CCSD(T) level, which is the most precise computational method applied up to date to study In2O3. Using experimental crystallographic data, we determined the geometry of In2O3 in the crystal. It has a zigzag, not symmetric structure and possesses a dipole moment with magnitude slightly smaller than that of the V-structure of the free molecule (the linear structure due to its symmetry has no dipole moment). According to the Natural Atomic population analysis, the chemical structure of the linear In2O3 can be represented as O = In-O-In = O; the V-shaped molecule has the similar double- and single-bond structure. The construction of nanoclusters from ´bricksʼ of In2O3 with geometry extracted from crystal (or nanoclusters extracted directly from crystal) and their use as photo-driven molecular motors are discussed.

CERENA: ChEmical REaction Network Analyzer--A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics.

PubMed

Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J; Hasenauer, Jan

2016-01-01

Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/.

CERENA: ChEmical REaction Network Analyzer—A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics

PubMed Central

Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J.; Hasenauer, Jan

2016-01-01

Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/. PMID:26807911

Crystallization and preliminary crystallographic analysis of human common-type acylphosphatase

PubMed Central

Yeung, Rachel C. Y.; Lam, Sonia Y.; Wong, Kam-Bo

2006-01-01

Human acylphosphatase, an 11 kDa enzyme that catalyzes the hydrolysis of carboxyl phosphate bonds, has been studied extensively as a model system for amyloid-fibril formation. However, the structure is still not known of any isoform of human acylphosphatase. Here, the crystallization and preliminary X-­ray diffraction data analysis of human common-type acylphosphatase are reported. Crystals of human common-type acylphosphatase have been grown by the sitting-drop vapour-diffusion method at 289 K using polyethylene glycol 4000 as precipitant. Diffraction data were collected to 1.45 Å resolution at 100 K. The crystals belong to space group P212121, with unit-cell parameters a = 42.58, b = 47.23, c = 57.26 Å. PMID:16511269

(NZ)CH...O contacts assist crystallization of a ParB-like nuclease.

PubMed

Shaw, Neil; Cheng, Chongyun; Tempel, Wolfram; Chang, Jessie; Ng, Joseph; Wang, Xin-Yu; Perrett, Sarah; Rose, John; Rao, Zihe; Wang, Bi-Cheng; Liu, Zhi-Jie

2007-07-07

The major bottleneck for determination of 3 D structures of proteins using X-rays is the production of diffraction quality crystals. Often proteins are subjected to chemical modification to improve the chances of crystallization Here, we report the successful crystallization of a nuclease employing a reductive methylation protocol. The key to crystallization was the successful introduction of 44 new cohesive (NZ) CH...O contacts (3.2-3.7 A) by the addition of 2 methyl groups to the side chain amine nitrogen (NZ) of 9 lysine residues of the nuclease. The new contacts dramatically altered the crystallization properties of the protein, resulting in crystals that diffracted to 1.2 A resolution. Analytical ultracentrifugation analysis and thermodynamics results revealed a more compact protein structure with better solvent exclusion of buried Trp residues in the folded state of the methylated protein, assisting crystallization. In this study, introduction of novel cohesive (NZ)CH...O contacts by reductive methylation resulted in the crystallization of a protein that had previously resisted crystallization in spite of extensive purification and crystallization space screening. Introduction of (NZ)CH...O contacts could provide a solution to crystallization problems for a broad range of protein targets.

Defined PEG smears as an alternative approach to enhance the search for crystallization conditions and crystal-quality improvement in reduced screens

PubMed Central

Chaikuad, Apirat; Knapp, Stefan; von Delft, Frank

2015-01-01

The quest for an optimal limited set of effective crystallization conditions remains a challenge in macromolecular crystallography, an issue that is complicated by the large number of chemicals which have been deemed to be suitable for promoting crystal growth. The lack of rational approaches towards the selection of successful chemical space and representative combinations has led to significant overlapping conditions, which are currently present in a multitude of commercially available crystallization screens. Here, an alternative approach to the sampling of widely used PEG precipitants is suggested through the use of PEG smears, which are mixtures of different PEGs with a requirement of either neutral or cooperatively positive effects of each component on crystal growth. Four newly defined smears were classified by molecular-weight groups and enabled the preservation of specific properties related to different polymer sizes. These smears not only allowed a wide coverage of properties of these polymers, but also reduced PEG variables, enabling greater sampling of other parameters such as buffers and additives. The efficiency of the smear-based screens was evaluated on more than 220 diverse recombinant human proteins, which overall revealed a good initial crystallization success rate of nearly 50%. In addition, in several cases successful crystallizations were only obtained using PEG smears, while various commercial screens failed to yield crystals. The defined smears therefore offer an alternative approach towards PEG sampling, which will benefit the design of crystallization screens sampling a wide chemical space of this key precipitant. PMID:26249344

Defined PEG smears as an alternative approach to enhance the search for crystallization conditions and crystal-quality improvement in reduced screens.

PubMed

Chaikuad, Apirat; Knapp, Stefan; von Delft, Frank

2015-08-01

The quest for an optimal limited set of effective crystallization conditions remains a challenge in macromolecular crystallography, an issue that is complicated by the large number of chemicals which have been deemed to be suitable for promoting crystal growth. The lack of rational approaches towards the selection of successful chemical space and representative combinations has led to significant overlapping conditions, which are currently present in a multitude of commercially available crystallization screens. Here, an alternative approach to the sampling of widely used PEG precipitants is suggested through the use of PEG smears, which are mixtures of different PEGs with a requirement of either neutral or cooperatively positive effects of each component on crystal growth. Four newly defined smears were classified by molecular-weight groups and enabled the preservation of specific properties related to different polymer sizes. These smears not only allowed a wide coverage of properties of these polymers, but also reduced PEG variables, enabling greater sampling of other parameters such as buffers and additives. The efficiency of the smear-based screens was evaluated on more than 220 diverse recombinant human proteins, which overall revealed a good initial crystallization success rate of nearly 50%. In addition, in several cases successful crystallizations were only obtained using PEG smears, while various commercial screens failed to yield crystals. The defined smears therefore offer an alternative approach towards PEG sampling, which will benefit the design of crystallization screens sampling a wide chemical space of this key precipitant.

Pilonidal sinus disease surgery in children: the first study to compare crystallized phenol application to primary excision and closure.

PubMed

Ates, Ufuk; Ergun, Ergun; Gollu, Gulnur; Sozduyar, Sumeyye; Kologlu, Meltem; Cakmak, Murat; Dindar, Huseyin; Yagmurlu, Aydin

2018-03-01

Pilonidal sinus (PS) is an infectious and inflammatory disease of sacrococcygeal region. Current methods include; surgical excision with/without suturing the defect, rhomboid excision and flap and chemical substance application. In this study, crystallized phenol application was compared to excision and primary closure. This retrospective study included pediatric patients with PS who were treated with excision and primer closure technique and phenol application. The patients' medical data were analyzed retrospectively. This study included 117 patients with PS. There were 52 girls (44%) and 65 boys (56%). Mean age of children was 15.6 (12-20) years. Excision and primary closure were applied to 77 patients (66%) and phenol was applied to 40 patients (34%). The children in phenol group were discharged on the operation day; mean hospitalization time in the excision and primary closure group was 2.7 (1-14) days. Mean follow up was 44.6 (8-82) months for primary excision and closure group and 8.1 (1-19) months for phenol group. Although many surgical and non-surgical treatment modalities have been described for PS, the optimal one remains unknown. Limited with the retrospective nature of the data, crystallized phenol application seems a feasible minimal invasive alternative to primary closure of PS with lower recurrence and complication rates in children. Level III. Copyright © 2017 Elsevier Inc. All rights reserved.

Luminescence and radiation resistance of undoped NaI crystals

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

Shiran, N., E-mail: shiran@isc.kharkov.com; Boiaryntseva, I.; Gektin, A.

2014-11-15

Highlights: • The performance of NaI scintillators depends on luminescence properties. • A criterion of crystals’ purity level is radiation colorability at room temperature. • The traces of the most dangerous impurities were detected. • Crucial role in efficiency of pure NaI scintillator play the crystal perfection. - Abstract: Undoped NaI single crystal is an excellent scintillator at low temperature. However, scintillation parameters of different quality crystals vary in a wide range, significantly exceeding measurement error. Experimental data demonstrate the features of luminescence, radiation induced coloration, and afterglow dependence on the quality of nominally pure crystals. It is found thatmore » defects level that allows to elucidate artefacts introduced by traces of harmful impurities corresponds to 3 × 10{sup 15} cm{sup −3} that significantly overhead accuracy of chemical and absorption analysis. It is shown that special raw material treatment before and during the single crystal growth allows to reach NaI purity level that avoids impurities influence to the basic luminescence data.« less

Containerless processing of single crystals in low-G environment

NASA Technical Reports Server (NTRS)

Walter, H. U.

1974-01-01

Experiments on containerless crystal growth from the melt were conducted during Skylab missions SL3 and SL4 (Skylab Experiment M-560). Six samples of InSb were processed, one of them heavily doped with selenium. The concept of the experiment is discussed and related to general crystal growth methods and their merits as techniques for containerless processing in space. The morphology of the crystals obtained is explained in terms of volume changes associated with solidification and wetting conditions during solidification. All samples exhibit extremely well developed growth facets. Analysis by X-ray topographical methods and chemical etching shows that the crystals are of high structural perfection. Average dislocation density as revealed by etching is of the order of 100 per sq cm; no dislocation clusters could be observed in the space-grown samples. A sequence of striations that is observed in the first half of the selenium-doped sample is explained as being caused by periodic surface breakdown.

Crystallization and preliminary X-ray diffraction analysis of restriction endonuclease EcoRII

NASA Technical Reports Server (NTRS)

Karpova, E. A.; Meehan, E.; Pusey, M. L.; Chen, L.

1999-01-01

Crystals of the restriction endonuclease EcoRII have been obtained by the vapor-diffusion technique in the presence of ammonium sulfate or polyethylene glycol. The best crystals were grown with ammonium sulfate as a precipitant. Crystals with dimensions of up to 0.6 x 0. 6 x 0.6 mm have been observed. The crystals diffract to about 4.0 A resolution at a cryo-temperature of 100 K using a rotating-anode X-ray source and a Rigaku R-AXIS IV imaging-plate detector. The space group has been determined to be either I23 or I2(1)3, with unit-cell parameters a = b = c = 160.3 A, alpha = beta = gamma = 90 degrees. The crystal asymmetric unit contains two protein molecules, and self-rotation function analysis shows a pseudo-twofold symmetry relating the two monomers. Attempts to improve the resolution of crystal diffraction and to search for heavy-atom derivatives are under way.

Effect of Crystal Orientation on Fatigue Failure of Single Crystal Nickel Base Turbine Blade Superalloys

NASA Technical Reports Server (NTRS)

Arakere, Nagaraj K.; Swanson, Gregory R.

2000-01-01

High Cycle Fatigue (HCF) induced failures in aircraft gas-turbine engines is a pervasive problem affecting a wide range of components and materials. HCF is currently the primary cause of component failures in gas turbine aircraft engines. Turbine blades in high performance aircraft and rocket engines are increasingly being made of single crystal nickel superalloys. Single-crystal Nickel-base superalloys were developed to provide superior creep, stress rupture, melt resistance and thermomechanical fatigue capabilities over polycrystalline alloys previously used in the production of turbine blades and vanes. Currently the most widely used single crystal turbine blade superalloys are PWA 1480/1493 and PWA 1484. These alloys play an important role in commercial, military and space propulsion systems. PWA1493, identical to PWA1480, but with tighter chemical constituent control, is used in the NASA SSME (Space Shuttle Main Engine) alternate turbopump, a liquid hydrogen fueled rocket engine. Objectives for this paper are motivated by the need for developing failure criteria and fatigue life evaluation procedures for high temperature single crystal components, using available fatigue data and finite element modeling of turbine blades. Using the FE (finite element) stress analysis results and the fatigue life relations developed, the effect of variation of primary and secondary crystal orientations on life is determined, at critical blade locations. The most advantageous crystal orientation for a given blade design is determined. Results presented demonstrates that control of secondary and primary crystallographic orientation has the potential to optimize blade design by increasing its resistance to fatigue crack growth without adding additional weight or cost.

Fragment-based {sup 13}C nuclear magnetic resonance chemical shift predictions in molecular crystals: An alternative to planewave methods

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

Hartman, Joshua D.; Beran, Gregory J. O., E-mail: gregory.beran@ucr.edu; Monaco, Stephen

2015-09-14

We assess the quality of fragment-based ab initio isotropic {sup 13}C chemical shift predictions for a collection of 25 molecular crystals with eight different density functionals. We explore the relative performance of cluster, two-body fragment, combined cluster/fragment, and the planewave gauge-including projector augmented wave (GIPAW) models relative to experiment. When electrostatic embedding is employed to capture many-body polarization effects, the simple and computationally inexpensive two-body fragment model predicts both isotropic {sup 13}C chemical shifts and the chemical shielding tensors as well as both cluster models and the GIPAW approach. Unlike the GIPAW approach, hybrid density functionals can be used readilymore » in a fragment model, and all four hybrid functionals tested here (PBE0, B3LYP, B3PW91, and B97-2) predict chemical shifts in noticeably better agreement with experiment than the four generalized gradient approximation (GGA) functionals considered (PBE, OPBE, BLYP, and BP86). A set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided based on these benchmark calculations. Statistical cross-validation procedures are used to demonstrate the robustness of these fits.« less

Fourier transform infrared spectroscopy for analysis of kidney stones.

PubMed

Khan, Aysha Habib; Imran, Sheharbano; Talati, Jamsheer; Jafri, Lena

2018-01-01

To compare the results of a chemical method of kidney stone analysis with the results of Fourier transform infrared (FT-IR) spectroscopy. Kidney stones collected between June and October 2015 were simultaneously analyzed by chemical and FT-IR methods. Kidney stones (n=449) were collected from patients from 1 to 81 years old. Most stones were from adults, with only 11.5% from children (aged 3-16 years) and 1.5% from children aged <2 years. The male to female ratio was 4.6. In adults, the calcium oxalate stone type, calcium oxalate monohydrate (COM, n=224), was the most common crystal, followed by uric acid and calcium oxalate dihydrate (COD, n=83). In children, the most frequently occurring type was predominantly COD (n=21), followed by COM (n=11), ammonium urate (n=10), carbonate apatite (n=6), uric acid (n=4), and cystine (n=1). Core composition in 22 stones showed ammonium urate (n=2), COM (n=2), and carbonate apatite (n=1) in five stones, while uric acid crystals were detected (n=13) by FT-IR. While chemical analysis identified 3 stones as uric acid and the rest as calcium oxalate only. Agreement between the two methods was moderate, with a kappa statistic of 0.57 (95% confidence interval, 0.5-0.64). Disagreement was noted in the analysis of 77 stones. FT-IR analysis of kidney stones can overcome many limitations associated with chemical analysis.

KDP Aqueous Solution-in-Oil Microemulsion for Ultra-Precision Chemical-Mechanical Polishing of KDP Crystal

PubMed Central

Dong, Hui; Wang, Lili; Gao, Wei; Li, Xiaoyuan; Wang, Chao; Ji, Fang; Pan, Jinlong; Wang, Baorui

2017-01-01

A novel functional KH2PO4 (KDP) aqueous solution-in-oil (KDP aq/O) microemulsion system for KDP crystal ultra-precision chemical-mechanical polishing (CMP) was prepared. The system, which consisted of decanol, Triton X-100, and KH2PO4 aqueous solution, was available at room temperature. The functional KDP aq/O microemulsion system was systematically studied and applied as polishing solution to KDP CMP technology. In this study, a controlled deliquescent mechanism was proposed for KDP polishing with the KDP aq/O microemulsion. KDP aqueous solution, the chemical etchant in the polishing process, was caged into the micelles in the microemulsion, leading to a limitation of the reaction between the KDP crystal and KDP aqueous solution only if the microemulsion was deformed under the effect of the external force. Based on the interface reaction dynamics, KDP aqueous solutions with different concentrations (cKDP) were applied to replace water in the traditional water-in-oil (W/O) microemulsion. The practicability of the controlled deliquescent mechanism was proved by the decreasing material removal rate (MRR) with the increasing of the cKDP. As a result, the corrosion pits on the KDP surface were avoided to some degree. Moreover, the roughnesses of KDP with KDP aq/O microemulsion (cKDP was changed from 10 mM to 100 mM) as polishing solutions were smaller than that with the W/O microemulsion. The smallest surface root-mean-square roughness of 1.5 nm was obtained at a 30 mmol/L KDP aq solution, because of the most appropriate deliquescent rate and MRR. PMID:28772632

Comparative study of crystallization process in metallic melts using ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Debela, Tekalign T.; Wang, X. D.; Cao, Q. P.; Zhang, D. X.; Jiang, J. Z.

2017-05-01

The crystallization process of liquid metals is studied using ab initio molecular dynamics simulations. The evolution of short-range order during quenching in Pb and Zn liquids is compared with body-centered cubic (bcc) Nb and V, and hexagonal closed-packed (hcp) Mg. We found that the fraction and type of the short-range order depends on the system under consideration, in which the icosahedral symmetry seems to dominate in the body-centered cubic metals. Although the local atomic structures in stable liquids are similar, liquid hcp-like Zn, bcc-like Nb and V can be deeply supercooled far below its melting point before crystallization while the supercooled temperature range in liquid Pb is limited. Further investigations into the nucleation process reveal the process of polymorph selection. In the body-centered cubic systems, the polymorph selection occurs in the supercooled state before the nucleation is initiated, while in the closed-packed systems it starts at the time of onset of crystallization. Atoms with bcc-like lattices in all studied supercooled liquids are always detected before the polymorph selection. It is also found that the bond orientational ordering is strongly correlated with the crystallization process in supercooled Zn and Pb liquids.

Automated macromolecular crystallization screening

DOEpatents

Segelke, Brent W.; Rupp, Bernhard; Krupka, Heike I.

2005-03-01

An automated macromolecular crystallization screening system wherein a multiplicity of reagent mixes are produced. A multiplicity of analysis plates is produced utilizing the reagent mixes combined with a sample. The analysis plates are incubated to promote growth of crystals. Images of the crystals are made. The images are analyzed with regard to suitability of the crystals for analysis by x-ray crystallography. A design of reagent mixes is produced based upon the expected suitability of the crystals for analysis by x-ray crystallography. A second multiplicity of mixes of the reagent components is produced utilizing the design and a second multiplicity of reagent mixes is used for a second round of automated macromolecular crystallization screening. In one embodiment the multiplicity of reagent mixes are produced by a random selection of reagent components.

X-ray chemical analyzer for field applications

DOEpatents

Gamba, Otto O. M.

1977-01-01

A self-supporting portable field multichannel X-ray chemical analyzer system comprising a lightweight, flexibly connected, remotely locatable, radioisotope-excited sensing probe utilizing a cryogenically-cooled solid state semi-conductor crystal detector for fast in situ non-destructive, qualitative and quantitative analysis of elements in solid, powder, liquid or slurried form, utilizing an X-ray energy dispersive spectrometry technique.

Investigations on synthesis, growth and physicochemical properties of semi-organic NLO crystal bis(thiourea) ammonium nitrate for nonlinear frequency conversion

NASA Astrophysics Data System (ADS)

Anbarasi, A.; Ravi Kumar, S. M.; Sundar, G. J. Shanmuga; Mosses, M. Allen; Raj, M. Packiya; Prabhakaran, M.; Ravisankar, R.; Gunaseelan, R.

2017-10-01

Bis(thiourea) ammonium nitrate (BTAN), a new nonlinear optical crystal was grown successfully by slow evaporation technique using water as solvent at room temperature. The grown crystals were optically good quality with dimensions upto 10 × 6 × 3 mm3. Single crystal X-Ray diffraction analysis reveals that the crystal lattice is orthorhombic. From Powder X-ray diffraction analysis the diffraction planes have been indexed. The presence of the various functional groups of BTAN was identified through FTIR spectroscopic analysis. UV cut-off wavelength was observed from optical absorbance spectrum and it was found to be 240 nm. Second harmonic efficiency was determined using Kurtz powder method in comparison with KDP to confirm the nonlinearity of the material. Thermal analysis confirmed that grown crystal is thermally stable upto 184 °C. Microhardness studies show that hardness number (Hv) increases with load. Conductivity measurements such as dielectric, ac and photoconductivity were studied. Growth mechanism and surface features of the as grown single crystal was analysed by chemical etching analysis.

XRD, vibrational spectra and quantum chemical studies of an anticancer drug: 6-Mercaptopurine.

PubMed

Kumar, S Suresh; Athimoolam, S; Sridhar, B

2015-07-05

The single crystal of the hydrated anticancer drug, 6-Mercaptopurine (6-MP), has been grown by slow evaporation technique under room temperature. The structure was determined by single crystal X-ray diffraction. The vibrational spectral analysis was carried out using Laser Raman and FT-IR spectroscopy in the range of 3300-100 and 4000-400 cm(-1). The single crystal X-ray studies shows that the crystal packing is dominated by N-H⋯O and O-H⋯N classical hydrogen bonds leading to a hydrogen bonded ensemble. This classical hydrogen bonds were further connected through O-H⋯S hydrogen bond to form two primary ring R4(4)(16) and R4(4)(12) motifs. These two primary ring motifs are interlinked with each other to build a ladder like structure. These ladders are connected through N-H⋯N hydrogen bond along c-axis of the unit cell through chain C(5) motifs. Further, the strength of the hydrogen bonds is studied through vibrational spectral measurements. The shifting of bands due to the intermolecular interactions was also analyzed in the solid crystalline state. Geometrical optimizations of the drug molecule were done by Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The natural bond orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical hardness, electro-negativity and chemical potential of the molecule are carried out by HOMO-LUMO plot. In which, the frontier orbitals has lower band gap value indicating the possible pharmaceutical activity of the molecule. Copyright © 2015 Elsevier B.V. All rights reserved.

Impact of physical and chemical parameters on the hydroxyapatite nanopowder synthesized by chemical precipitation method

NASA Astrophysics Data System (ADS)

Thu Trang Pham, Thi; Phuong Nguyen, Thu; Pham, Thi Nam; Phuong Vu, Thi; Tran, Dai Lam; Thai, Hoang; Thanh Dinh, Thi Mai

2013-09-01

In this paper, the synthesis of hydroxyapatite (HAp) nanopowder was studied by chemical precipitation method at different values of reaction temperature, settling time, Ca/P ratio, calcination temperature, (NH4)2HPO4 addition rate, initial concentration of Ca(NO3)2 and (NH4)2HPO4. Analysis results of properties, morphology, structure of HAp powder from infrared (IR) spectra, x-ray diffraction (XRD), energy dispersive x-ray (EDX) spectra and scanning electron microscopy (SEM) indicated that the synthesized HAp powder had cylinder crystal shape with size less than 100 nm, single-phase structure. The variation of the synthesis conditions did not affect the morphology but affected the size of HAp crystals.

Dry-growth of silver single-crystal nanowires from porous Ag structure

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

Chen, Chuantong, E-mail: chenchuantong@sanken.osaka-u.ac.jp; Nagao, Shijo; Jiu, Jinting

A fabrication method of single crystal Ag nanowires in large scale is introduced without any chemical synthesis in wet processes, which usually generates fivefold twinned nanowires of fcc metals. Dense single-crystal nanowires grow on a mechanically polished surface of micro-porous Ag structure, which is created from Ag micro-particles. The diameter and the length of the nanowires can be controlled simply by changing the temperature and the time of the heating during the nanowire growth in air. Unique growth mechanism is described in detail, based on stress-induced migration accelerated by the micro-porous structure where the origin of Ag nanowires growth ismore » incubated. Transmission electron microscopy analysis on the single crystal nanowires is also presented. This simple method offered an alternative preparation for metallic nanowires, especially with the single crystal structure in numerous applications.« less

Kinetics and pathways for crystallization of amorphous mullite and YAG

NASA Astrophysics Data System (ADS)

Johnson, Bradley Richard

The crystallization behavior of quenched mullite (3Al2O 3•2SiO2) and YAG (Y3Al5O 12) composition glasses (made using containerless methods) were characterized with the ultimate goal of producing single crystal, structural, ceramic oxide fibers from these materials. The kinetics for crystallization were determined from thermal analysis experiments. From the results, time-temperature-transformation (TTT) curves were calculated. The crystallization pathways were determined by examining the crystal structure, microstructure, and chemical composition of heat treated specimens using x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A machine was also designed and built to facilitate controlled crystallization of amorphous fibers. Quenched, Y3Al5O12 composition beads crystallized at temperatures as low as 840°C. The as-received specimens contained a few, small YAG crystals, in addition to a mixture of different amorphous phases. The coexistence of two different amorphous phases of the same composition, but having different densities is termed polyamorphism, and this has been reported to occur in Y3Al5O12 composition quenched melts. Although various crystallization pathways have been reported for chemically synthesized YAG precursors, these specimens crystallized directly into YAG, which was the only phase formed. Quenched, 3Al2O3•2SiO2 composition mullite beads and fibers crystallized at temperatures as low as 920°C. Due to phase separation in the quenched melts, multiple phases with slightly different compositions and different crystallization activation energies crystallized. These phases were not equilibrium, 3:2 mullite, but metastable, alumina-rich, pseudotetragonal mullite. The residual, amorphous, silica-rich phase existed as numerous, 7--10 nm sized inclusions embedded within pseudotetragonal mullite. A large amount of internal strain was detected in pseudotetragonal mullite, and the source of this

Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass

NASA Technical Reports Server (NTRS)

Wiesner, Valerie L.; Bansal, Narottam P.

2015-01-01

The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.

Crystallization of sodium chloride from a concentrated calcium chloride-potassium chloride-sodium chloride solution in a CMSMPR crystallizer: Observation of crystal size distribution and model validation

NASA Astrophysics Data System (ADS)

Choi, Byung Sang

Compared to overwhelming technical data available in other advanced technologies, knowledge about particle technology, especially in particle synthesis from a solution, is still poor due to the lack of available equipment to study crystallization phenomena in a crystallizer. Recent technical advances in particle size measurement such as Coulter counter and laser light scattering have made in/ex situ study of some of particle synthesis, i.e., growth, attrition, and aggregation, possible with simple systems. Even with these advancements in measurement technology, to grasp fully the crystallization phenomena requires further theoretical and technical advances in understanding such particle synthesis mechanisms. Therefore, it is the motive of this work to establish the general processing parameters and to produce rigorous experimental data with reliable performance and characterization that rigorously account for the crystallization phenomena of nucleation, growth, aggregation, and breakage including their variations with time and space in a controlled continuous mixed-suspension mixed-product removal (CMSMPR) crystallizer. This dissertation reports the results and achievements in the following areas: (1) experimental programs to support the development and validation of the phenomenological models and generation of laboratory data for the purpose of testing, refining, and validating the crystallization process, (2) development of laboratory well-mixed crystallizer system and experimental protocols to generate crystal size distribution (CSD) data, (3) the effects of feed solution concentration, crystallization temperature, feed flow rate, and mixing speed, as well as different types of mixers resulting in the evolution of CSDs with time from a concentrated brine solution, (4) with statistically designed experiments the effects of processing variables on the resultant particle structure and CSD at steady state were quantified and related to each of those operating

Structure and vibrational spectra of melaminium bis(trifluoroacetate) trihydrate: FT-IR, FT-Raman and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Sangeetha, V.; Govindarajan, M.; Kanagathara, N.; Marchewka, M. K.; Gunasekaran, S.; Anbalagan, G.

Melaminium bis(trifluoroacetate) trihydrate (MTFA), an organic material has been synthesized and single crystals of MTFA have been grown by the slow solvent evaporation method at room temperature. X-ray powder diffraction analysis confirms that MTFA crystal belongs to the monoclinic system with space group P2/c. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional theory (DFT) B3LYP method with 6-311G(d,p) and 6-311++G(d,p) basis sets. The X-ray diffraction data have been compared with the data of optimized molecular structure. The theoretical results show that the crystal structure can be reproduced by optimized geometry and the vibrational frequencies show good agreement with the experimental values. The nuclear magnetic resonance (NMR) chemical shift of the molecule has been calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. HOMO-LUMO, and other related molecular and electronic properties are calculated. The Mulliken and NBO charges have also been calculated and interpreted.

A comparative study of the influence of buoyancy driven fluid flow on GaAs crystal growth

NASA Technical Reports Server (NTRS)

Kafalas, J. A.; Bellows, A. H.

1988-01-01

A systematic investigation of the effect of gravity driven fluid flow on GaAs crystal growth was performed. It includes GaAs crystal growth in the microgravity environment aboard the Space Shuttle. The program involves a controlled comparative study of crystal growth under a variety of earth based conditions with variable orientation and applied magnetic field in addition to the microgravity growth. Earth based growth will be performed under stabilizing as well as destabilizing temperature gradients. The boules grown in space and on earth will be fully characterized to correlate the degree of convection with the distribution of impurities. Both macro- and micro-segregation will be determined. The space growth experiment will be flown in a self-contained payload container through NASA's Get Away Special program.

Magnetorheological finishing of chemical-vapor deposited zinc sulfide via chemically and mechanically modified fluids

DOE PAGES

Salzman, Sivan; Romanofsky, Henry J.; Giannechini, Lucca J.; ...

2016-02-19

In this study, we describe the anisotropy in the material removal rate (MRR) of the polycrystalline, chemical-vapor deposited zinc sulfide (ZnS).We define the polycrystalline anisotropy via microhardness and chemical erosion tests for four crystallographic orientations of ZnS: (100), (110), (111), and (311). Anisotropy in the MRR was studied under magnetorheological finishing (MRF) conditions. Three chemically and mechanically modified magnetorheological (MR) fluids at pH values of 4, 5, and 6 were used to test the MRR variations among the four single-crystal planes. When polishing the single-crystal planes and the polycrystalline with pH 5 and pH 6MR fluids, variations were found inmore » the MRR among the four single-crystal planes and surface artifacts were observed on the polycrystalline material. When polishing the single-crystal planes and the polycrystalline with the modified MR fluid at pH 4, however, minimal variation was observed in the MRR among the four orientations and a reduction in surface artifacts was achieved on the polycrystalline material.« less

Anisotropic Strain Relaxation of Graphene by Corrugation on Copper Crystal Surfaces.

PubMed

Deng, Bing; Wu, Juanxia; Zhang, Shishu; Qi, Yue; Zheng, Liming; Yang, Hao; Tang, Jilin; Tong, Lianming; Zhang, Jin; Liu, Zhongfan; Peng, Hailin

2018-05-01

Corrugation is a ubiquitous phenomenon for graphene grown on metal substrates by chemical vapor deposition, which greatly affects the electrical, mechanical, and chemical properties. Recent years have witnessed great progress in controlled growth of large graphene single crystals; however, the issue of surface roughness is far from being addressed. Here, the corrugation at the interface of copper (Cu) and graphene, including Cu step bunches (CuSB) and graphene wrinkles, are investigated and ascribed to the anisotropic strain relaxation. It is found that the corrugation is strongly dependent on Cu crystallographic orientations, specifically, the packed density and anisotropic atomic configuration. Dense Cu step bunches are prone to form on loose packed faces due to the instability of surface dynamics. On an anisotropic Cu crystal surface, Cu step bunches and graphene wrinkles are formed in two perpendicular directions to release the anisotropic interfacial stress, as revealed by morphology imaging and vibrational analysis. Cu(111) is a suitable crystal face for growth of ultraflat graphene with roughness as low as 0.20 nm. It is believed the findings will contribute to clarifying the interplay between graphene and Cu crystal faces, and reducing surface roughness of graphene by engineering the crystallographic orientation of Cu substrates. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Circularly polarized Raman study on diamond structure crystals

NASA Astrophysics Data System (ADS)

Lee, Je-Ho; Kim, Sera; Seong, Maeng-Je

2018-01-01

Circularly polarized Raman and/or photoluminescence (PL) analyses have recently been very important in studying physical properties of many layered materials that were either mechanically exfoliated or grown by chemical-vapor-deposition (CVD) on silicon substrates. Since silicon Raman signal is always accompanied by the circularly polarized Raman and/or PL signal from the layered materials, observation of proper circularly polarized Raman selection rules on silicon substrates would be extremely good indicator that the circularly polarized Raman and/or PL measurements on the layered materials were done properly. We have performed circularly polarized Raman measurements on silicon substrates and compared the results with the Raman intensities calculated by using Raman tensors of the diamond crystal structure. Our experimental results were in excellent agreement with the calculation. Similar circularly polarized Raman analysis done on germanium substrate also showed good agreement.

Crystal growth, structural, optical, thermal, mechanical, laser damage threshold and electrical properties of triphenylphosphine oxide 4-nitrophenol (TP4N) single crystals for nonlinear optical applications

NASA Astrophysics Data System (ADS)

Karuppasamy, P.; Senthil Pandian, Muthu; Ramasamy, P.; Verma, Sunil

2018-05-01

The optically good quality single crystals of triphenylphosphine oxide 4-nitrophenol (TP4N) with maximum dimension of 15 × 10 × 5 mm3 were grown by slow evaporation solution technique (SEST) at room temperature. The cell dimensions of the grown TP4N crystal were confirmed by single crystal X-ray diffraction (SXRD) and the crystalline purity was confirmed and planes were indexed by powder X-ray diffraction (PXRD) analysis. Functional groups of TP4N crystal were confirmed by Fourier transform infrared (FTIR) spectral analysis. The optical transmittance of the grown crystal was determined by the UV-Vis NIR spectral analysis and it has good optical transparency in the entire visible region. The band tail (Urbach) energy of the grown crystal was analyzed and it appears to be minimum, which indicates that the TP4N has good crystallinity. The position of valence band (Ev) and conduction band (Ec) of the TP4N have been determined from the electron affinity energy (EA) and the ionization energy (EI) of its elements and using the optical band gap. The thermal behaviour of the grown crystal was investigated by thermogravimetric and differential thermal analysis (TG-DTA). Vickers microhardness analysis was carried out to identify the mechanical stability of the grown crystal and their indentation size effect (ISE) was explained by the Meyer's law (ML), Hays-Kendall's (HK) approach, proportional specimen resistance (PSR) model, modified PSR model (MPSR), elastic/plastic deformation (EPD) model and indentation induced cracking (IIC) model. Chemical etching study was carried out to find the etch pit density (EPD) of the grown crystal. Laser damage threshold (LDT) value was measured by using Nd:YAG laser (1064 nm). The dielectric permittivity (ε՛) and dielectric loss (tan δ) as a function of frequency was measured. The electronic polarizability (α) of the TP4N crystal was calculated. It is well matched to the value which was calculated from Clausius-Mossotti relation

Synthesis, crystal structure analysis, spectral investigations, DFT computations, Biological activities and molecular docking of methyl(2E)-2-{[N-(2-formylphenyl)(4-methylbenzene) sulfonamido]methyl}-3-(4-fluorophenyl)prop-2-enoate, a potential bioactive agent

NASA Astrophysics Data System (ADS)

Murugavel, S.; Vetri Velan, V.; Kannan, Damodharan; Bakthadoss, Manickam

2016-03-01

The title compound methyl(2E)-2-{[N-(2-formylphenyl) (4-methylbenzene)sulfonamido]methyl}-3-(4-fluorophenyl) prop-2-enoate (MFMSF) has been synthesized and single crystals were grown by slow evaporation solution growth technique at room temperature. The grown crystals were characterized by FTIR, 1H NMR, 13C NMR, and single crystal X-ray diffraction. In the crystal, molecules are linked by intermolecular C-H…O hydrogen bonds forming a two-dimensional supramolecular network along [110] direction. The molecular geometry was also optimized using density functional theory (DFT/B3LYP) method with the 6-311G (d,p) basis set in ground state and compared with the experimental data. The entire vibrational assignments of wave numbers were made on the basis of potential energy distribution (PED) by VEDA 4 programme. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. In addition, NLO, MEP, Mulliken, thermodynamic properties, HOMO and LUMO energy gap were theoretically predicted. The global chemical reactivity descriptors are calculated for MFMSF and used to predict their relative stability and reactivity. The antibacterial activity of the compound was also tested against various pathogens. The molecular docking studies concede that title compound may exhibit PBP-2X inhibitor activity.

Chemical and Thermal Analysis

NASA Technical Reports Server (NTRS)

Bulluck, J. W.; Rushing, R. A.; Thornton, C. P.

1996-01-01

Work has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution of the Coflon material using a dual detector Gel Permeation Analysis. Again these changes may result in variation in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-Ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Thermogravimetric Analysis, and Differential Scanning Calorimetry. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed in a modified Fluid G, which we will call G2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures, 70 C, 110 C, and 130 C. The primary purpose of the pressure tests in Fluid G2 was to further elucidate the aging mechanism of PVDF degradation.

Protein Crystallization.

PubMed

McPherson, Alexander

2017-01-01

Protein crystallization was discovered by chance nearly 200 years ago and was developed in the late nineteenth century as a powerful purification tool, and a demonstration of chemical purity. The crystallization of proteins, nucleic acids, and large biological complexes, such as viruses, depends on the creation of a solution that is supersaturated in the macromolecule, but exhibits conditions that do not significantly perturb its natural state. Supersaturation is produced through the addition of mild precipitating agents such as neutral salts or polymers, and by manipulation of various parameters that include temperature, ionic strength, and pH. Also important in the crystallization process are factors that can affect the structural state of the macromolecule, such as metal ions, inhibitors, cofactors, or other conventional small molecules. A variety of approaches have been developed that combine the spectrum of factors that effect and promote crystallization, and among the most widely used are vapor diffusion, dialysis, batch, and liquid-liquid diffusion. Successes in macromolecular crystallization have multiplied rapidly in recent years due to the advent of practical, easy-to-use screening kits, and the application of laboratory robotics.

Ultrasensitive quartz crystal microbalance sensors for detection of M13-Phages in liquids.

PubMed

Uttenthaler, E; Schräml, M; Mandel, J; Drost, S

2001-12-01

Quartz crystal microbalance (QCM) sensors are widely used for determining liquid properties or probing interfacial processes. For some applications the sensitivity of the QCM sensors typically used (5-20 MHz) is limited compared with other biosensor methods. In this study ultrasensitive QCM sensors with resonant frequencies from 39 to 110 MHz for measurements in the liquid phase are presented. The fundamental sensor effect of a QCM is the decrease of the resonant frequency of an oscillating quartz crystal due to the binding of mass on a coated surface during the measurement. The sensitivity of QCM sensors increases strongly with an increasing resonant frequency and, therefore, with a decreasing thickness of the sensitive area. The new kind of ultrasensitive QCM sensors used in this study is based on chemically milled shear mode quartz crystals which are etched only in the center of the blank, forming a thin quartz membrane with a thick, mechanically stable outer ring. An immunoassay using a virus specific monoclonal antibody and a M13-Phage showed an increase in the signal to noise ratio by a factor of more than 6 for 56 MHz quartz crystals compared with standard 19 MHz quartz crystals, the detection limit was improved by a factor of 200. Probing of acoustic properties of glycerol/water mixtures resulted in an increase in sensitivity, which is in very good agreement with theory. Chemically milled QCM sensors strongly improve the sensitivity in biosensing and probing of acoustic properties and, therefore, offer interesting new application fields for QCM sensors.

Quantitative Methods Based on Twisted Nematic Liquid Crystals for Mapping Surfaces Patterned with Bio/Chemical Functionality Relevant to Bioanalytical Assays

PubMed Central

Lowe, Aaron M.; Bertics, Paul J.; Abbott, Nicholas L.

2009-01-01

We report methods for the acquisition and analysis of optical images formed by thin films of twisted nematic liquid crystals (LCs) placed into contact with surfaces patterned with bio/chemical functionality relevant to surface-based assays. The methods are simple to implement and are shown to provide easily interpreted maps of chemical transformations on surfaces that are widely exploited in the preparation of analytic devices. The methods involve acquisition of multiple images of the LC as a function of the orientation of a polarizer; data analysis condenses the information present in the stack of images into a spatial map of the twist angle of the LC on the analytic surface. The potential utility of the methods is illustrated by mapping (i) the displacement of a monolayer formed from one alkanethiol on a gold film by a second thiol in solution, (ii) coadsorption of mixtures of amine-terminated and ethyleneglycol-terminated alkanethiols on gold films, which leads to a type of mixed monolayer that is widely exploited for immobilization of proteins on analytic surfaces, and (iii) patterns of antibodies printed onto surfaces. These results show that maps of the twist angle of the LC constructed from families of optical images can be used to reveal surface features that are not apparent in a single image of the LC film. Furthermore, the twist angles of the LC can be used to quantify the energy of interaction of the LC with the surface with a spatial resolution of <10 µm. When combined, the results described in this paper suggest non-destructive methods to monitor and validate chemical transformations on surfaces of the type that are routinely employed in the preparation of surface-based analytic technologies. PMID:18355089

VHH antibodies: Emerging reagents for the analysis of environmental chemicals

PubMed Central

Bever, Candace S.; Dong, Jie-Xian; Vasylieva, Natalia; Barnych, Bogdan; Cui, Yongliang; Xu, Zhen-Lin; Hammock, Bruce D.; Gee, Shirley J.

2016-01-01

A VHH antibody (or nanobody) is the antigen binding fragment of heavy chain only antibodies. Discovered nearly 25 years ago, they have been investigated for their use in clinical therapeutics and immunodiagnostics, and more recently for environmental monitoring applications. A new and valuable immunoreagent for the analysis of small molecular weight environmental chemicals, VHH will overcome many pitfalls encountered with conventional reagents. In the work so far, VHH antibodies often perform comparably to conventional antibodies for small molecule analysis, are amenable to numerous genetic engineering techniques, and show ease of adaption to other immunodiagnostic platforms for use in environmental monitoring. Recent reviews cover the structure and production of VHH antibodies as well as their use in clinical settings. However, no report focuses on the use of these VHH antibodies to small environmental chemicals (MW <1,500 Da). This review article summarizes the efforts made to produce VHHs to various environmental targets, compares the VHH-based assays with conventional antibody assays, and discusses the advantages and limitations in developing these new antibody reagents particularly to small molecule targets. PMID:27209591

Stability of (Fe-Tm-B) amorphous alloys: relaxation and crystallization phenomena

NASA Astrophysics Data System (ADS)

Zemčík, T.

1994-12-01

Fe-Tm-B base (TM=transition metal) amorphous alloys (metallic glasses) are thermodynamically metastable. This limits their use as otherwise favourable materials, e.g. magnetically soft, corrosion resistant and mechanically firm. By analogy of the mechanical strain-stress dependence, at a certain degree of thermal activation the amorphous structure reaches its limiting state where it changes its character and physical properties. Relaxation and early crystallization processes in amorphous alloys, starting already around 100°C, are reviewed involving subsequently stress relief, free volume shrinking, topological and chemical ordering, pre-crystallization phenomena up to partial (primary) crystallization. Two diametrically different examples are demonstrated from among the soft magnetic materials: relaxation and early crystallization processes in the Fe-Co-B metallic glasses and controlled crystallization of amorphous ribbons yielding rather modern nanocrystalline “Finemet” alloys where late relaxation and pre-crystallization phenomena overlap when forming extremely dispersive and fine-grained nanocrystals-in-amorphous-sauce structure. Mössbauer spectroscopy seems to be unique for magnetic and phase analysis of such complicated systems.

Crystallization and preliminary X-ray diffraction analysis of West Nile virus

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

Kaufmann, Barbel; Plevka, Pavel; Kuhn, Richard J.

2010-05-25

West Nile virus, a human pathogen, is closely related to other medically important flaviviruses of global impact such as dengue virus. The infectious virus was purified from cell culture using polyethylene glycol (PEG) precipitation and density-gradient centrifugation. Thin amorphously shaped crystals of the lipid-enveloped virus were grown in quartz capillaries equilibrated by vapor diffusion. Crystal diffraction extended at best to a resolution of about 25 {angstrom} using synchrotron radiation. A preliminary analysis of the diffraction images indicated that the crystals had unit-cell parameters a {approx_equal} b {approx_equal} 480 {angstrom}, {gamma} = 120{sup o}, suggesting a tight hexagonal packing of onemore » virus particle per unit cell.« less

Analysis of zinc binding sites in protein crystal structures.

PubMed

Alberts, I L; Nadassy, K; Wodak, S J

1998-08-01

The geometrical properties of zinc binding sites in a dataset of high quality protein crystal structures deposited in the Protein Data Bank have been examined to identify important differences between zinc sites that are directly involved in catalysis and those that play a structural role. Coordination angles in the zinc primary coordination sphere are compared with ideal values for each coordination geometry, and zinc coordination distances are compared with those in small zinc complexes from the Cambridge Structural Database as a guide of expected trends. We find that distances and angles in the primary coordination sphere are in general close to the expected (or ideal) values. Deviations occur primarily for oxygen coordinating atoms and are found to be mainly due to H-bonding of the oxygen coordinating ligand to protein residues, bidentate binding arrangements, and multi-zinc sites. We find that H-bonding of oxygen containing residues (or water) to zinc bound histidines is almost universal in our dataset and defines the elec-His-Zn motif. Analysis of the stereochemistry shows that carboxyl elec-His-Zn motifs are geometrically rigid, while water elec-His-Zn motifs show the most geometrical variation. As catalytic motifs have a higher proportion of carboxyl elec atoms than structural motifs, they provide a more rigid framework for zinc binding. This is understood biologically, as a small distortion in the zinc position in an enzyme can have serious consequences on the enzymatic reaction. We also analyze the sequence pattern of the zinc ligands and residues that provide elecs, and identify conserved hydrophobic residues in the endopeptidases that also appear to contribute to stabilizing the catalytic zinc site. A zinc binding template in protein crystal structures is derived from these observations.

Photonic crystal fiber long-period gratings for structural monitoring and chemical sensing

NASA Astrophysics Data System (ADS)

Tang, Jaw-Luen; Wang, Jian-Neng

2008-03-01

We present a simple, low-cost, temperature- and strain-insensitive long-period gratings (LPGs) written in photonic crystal fibers (PCFs) that can be used as sensitive chemical solution sensors or bend sensors for a variety of industrial applications, including civil engineering, aircraft, chemistry, food industry, and biosensing. Three different configurations of PCFs have been used for this study, including a polarization maintaining PCF, a large mode area PCF and an endlessly single mode PCF. These LPGs have been characterized for their sensitivity to temperature, strain, bending, and surrounding refractive index. Transmission spectra of the LPGs were found to exhibit negligible temperature and strain sensitivities, whereas possessing usable sensitivity to refractive index and bending. This type of PCF sensor could in principle be designed for optimum sensitivity to desired measurand(s), while minimizing or removing undesirable cross-sensitivities. The unique sensing features of PCFs are particularly suited for a wide variety of applications in smart structures, embedded materials, telecommunications and sensor systems.

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

40 CFR 761.253 - Chemical analysis.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Chemical analysis. 761.253 Section 761.253 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT... Sample Sites, Collecting Surface Samples, and Analyzing Standard PCB Wipe Samples § 761.253 Chemical...

Tracking and Motion Analysis of Crack Propagations in Crystals for Molecular Dynamics

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

Tsap, L V; Duchaineau, M; Goldgof, D B

2001-05-14

This paper presents a quantitative analysis for a discovery in molecular dynamics. Recent simulations have shown that velocities of crack propagations in crystals under certain conditions can become supersonic, which is contrary to classical physics. In this research, they present a framework for tracking and motion analysis of crack propagations in crystals. It includes line segment extraction based on Canny edge maps, feature selection based on physical properties, and subsequent tracking of primary and secondary wavefronts. This tracking is completely automated; it runs in real time on three 834-image sequences using forty 250 MHZ processors. Results supporting physical observations aremore » presented in terms of both feature tracking and velocity analysis.« less

Selective crystallization of calcium salts by poly(acrylate)-grafted chitosan.

PubMed

Neira-Carrillo, Andrónico; Yazdani-Pedram, Mehrdad; Retuert, Jaime; Diaz-Dosque, Mario; Gallois, Sebastien; Arias, José L

2005-06-01

The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration.

Comparative physico-chemical profiles of Tugaksheeree (Curcuma angustifolia Roxb. and Maranta arundinacea Linn.).

PubMed

Rajashekhara, N; Shukla, Vinay J; Ravishankar, B; Sharma, Parameshwar P

2013-10-01

Tugaksheeree is as an ingredient in many Ayurvedic formulations. The starch obtained from the rhizomes of two plants, is used as Tugaksheeree, Curcuma angustifolia (CA) Roxb. (Family: Zingiberaceae) and Maranta arundinacea (MA) Linn. (Family Marantaceae). In the present study, a comparative physico-analysis of both the drugs has been carried out. The results suggest that the starch from CA and MA has similar organoleptic characters. The percentage of starch content is higher in the rhizome of CA when compared with that of MA and the starch of MA is packed more densely than the starch in CA. The chemical constituents of both the starch and rhizomes are partially similar to each other. Hence, the therapeutic activities may be similar.

A probabilistic analysis of the crystal oscillator behavior at low drive levels

NASA Astrophysics Data System (ADS)

Shmaliy, Yuriy S.; Brendel, Rémi

2008-03-01

The paper discusses a probabilistic model of a crystal oscillator at low drive levels where the noise intensity is comparable with the oscillation amplitude. The stationary probability density of the oscillations envelope is derived and investigated for the nonlinear resonator loses. A stochastic explanation is given for the well-known phenomenon termed sleeping sickness associated with losing a facility of self-excitation by a crystal oscillator after a long storage without a power supply. It is shown that, with low drive levels leading to an insufficient feedback, a crystal oscillator generates the noise-induced oscillations rather than it absolutely "falls in sleep".

Synthesis and characterization of tetraacetonitrilolithiumhexafluorophosphate crystal

NASA Astrophysics Data System (ADS)

Li, Xuecong; Li, Xuanli; Zhang, Zhiye; Yang, Lin; Zhong, Benhe; Wang, Xinlong

2015-08-01

Tetraacetonitrilolithiumhexafluorophosphate (Li(CH3CN)4PF6) crystal is an important intermediate in the preparation of high purity lithium hexafluorophosphate electrolyte via a simple transformation method. In this study, the crystal parameters were determined by X-ray powder diffraction analysis, which showed that it belongs to the triclinic system with space group P1. FTIR spectral studies identified the characteristic absorption bands of Ctbnd N and PF6- in the synthesized complex. Chemical analysis, gas chromatography, and ICP-AES results showed that the elementary ratio of Li:P:F: CH3CN in the complex is approximately: 1:1:6:4. Furthermore, the geometric optimization structure of Li(CH3CN)4PF6 was obtained using GAUSSIAN 09 program on a B3LYP/6-31+G(d, p) level. In this structure, two acetonitrile ligands bind strongly with the Li+ ion, whereas the other two are weakly-coordinated with lithium. The results of solid-state 13C-, 31P-, and 19F-NMR spectra confirmed that this configuration is reasonable.

RBAP, a rhodamine B-based derivative: synthesis, crystal structure analysis, molecular simulation, and its application as a selective fluorescent chemical sensor for Sn2+.

PubMed

Bao, Xiaofeng; Cao, Xiaowei; Nie, Xuemei; Jin, Yanyan; Zhou, Baojing

2014-06-11

A new fluorescent chemosensor based on a Rhodamine B and a benzyl 3-aminopropanoate conjugate (RBAP) was designed, synthesized, and structurally characterized. Its single crystal structure was obtained and analyzed by X-ray analysis. In a MeOH/H2O (2:3, v/v, pH 5.95) solution RBAP exhibits a high selectivity and excellent sensitivity for Sn2+ ions in the presence of many other metal cations. The binding analysis using the Job's plot suggested the RBAP formed a 1:1 complex with Sn2+.

Integrated melt inclusion and crystal zoning study to track the timescales and pre-eruption dynamics of violent Strombolian eruptions at Llaima volcano, Chile

NASA Astrophysics Data System (ADS)

Ruth, D. C.; Costa Rodriguez, F.; Bouvet de Maisonneuve, C.; Calder, E. S.

2013-12-01

Melt inclusion compositions in crystals from many volcanic systems are notoriously variable and some times difficult to interpret. Their compositions can be a combination of rapid crystal growth, entrapment of local melt, and diffusive re-equilibration, among other processes. Additionally, chemical zoning in olivine records changing environmental conditions, most importantly temperature and magma composition. Many geochemical studies focus on either melt inclusion data or chemical zoning data to ascertain volcanic processes. Here we combine melt inclusion data with that of chemical zoning of the olivine host crystals from the 2008 violent Strombolian eruption of Llaima volcano, Chile, to obtain a more refined understanding of the processes related to crystal growth, melt inclusion formation, and magma dynamics. We investigated zoning characteristics in a suite of olivine crystals, created X-ray element maps (Al, Ca, Mg, P, Fe), and collected quantitative elemental abundances across chemical zones for detailed diffusion modeling. Melt inclusion compositions were collected via electron microprobe analysis and LA-ICPMS. We observe three types of zoning in the host olivine crystals: normal, reverse, and multiple zones with fluctuating Fo content. Reverse zoning was more common than the other types. Regardless of zoning character, multiple melt inclusions are present within a given olivine, often found near the crystal rim. For some of these melt inclusions, the olivine surrounding the melt inclusion was also zoned, often to a similar composition as the olivine rim. This implies that these inclusions remained connected with interstitial matrix melt until melt inclusion closure. These ';open' melt inclusions exhibited slightly different major (higher SiO2, Na2O+K2O, TiO2) and trace elements (positive Eu and Sr anomalies) compared to melt inclusions in the same olivine that were not surrounded by compositional zoning. Quantitative elemental profiles produce modeled

Phenytoin crystal growth rates in the presence of phosphate and chloride ions

NASA Astrophysics Data System (ADS)

Zipp, G. L.; Rodríguez-Hornedo, N.

1992-09-01

Phenytoin crystal growth kinetics have been measured as a function of supersaturation in pH 2.2 phosphoric acid and pH 2.2 hydrochloric acid solutions. Two different methods were used for the kinetic analysis. The first involved a zone-sensing device which provided an analysis of the distribution of crystals in a batch crystallizer. Crystal growth rates were calculated from the increase in the size of the distribution with time. In the second method, growth rates were evaluated from the change in size with time of individual crystals observed under an inverted microscope. The results from each method compare favorably. The use of both techniques provides an excellent opportunity to exploit the strengths of each: an average growth rate from a population of crystals from batch crystallization and insight into the effect of growth on the morphology of the crystals from the individual crystal measurements.

Crystals and Crystals: On the Mythology of Magmatic Processes

NASA Astrophysics Data System (ADS)

Marsh, B.

2008-12-01

The intimate records of the deep functioning of magmatic systems reside in the temporal and spatial records of magma flux, composition and crystal load. The records for a single system are piecemeal: Plutons show good spatial records, but poor temporal records. Volcanoes give through lava sequences good temporal records, but no spatial context. Because of this dichotomy, two, almost mutually exclusive, branches of magmatology have developed, whereas in Nature there is only a single process. The processes envisioned in these schools necessary to deliver the end rock record are distinct. It is our tools and historic perspectives that have steered the science, not the subject itself. Due to this approach an almost mythical conception of how magmas function has become commonplace. The circumvention of this dilemma rests in carefully evaluating the records on hand in the light of a broad understanding of the fundamental mechanics of how magma lives and dies. It is these basic principles that promise to unify plutonic and volcanic evidence to reveal the full nature of magmatism on all scales. The two most basic features of all magmatic processes are the universal presence of solidification fronts and the presence or absence of a crystal cargo. Almost without exception (e.g., shallow pressure quenching) all first generation crystals grow in marginal solidification fronts (SFs) bordering all magmas. The package of isotherms bounded by the liquidus and solidus define SFs, which propagate in response to the rate of cooling. All physical and chemical processes occurring within SFs compete with the advancement or retreat of solidification. SFs are governed by crystallinity regimes: Suspension Zone (<25 % xtals), Capture Front (~25 %), Mush Zone (25-55%), Rigidity Front (~55%; Critical Crystallinity), and Rigid Crust Zone (>55% xtals). Magmas are laced with nuclei that multiply and grow when overtaken. Crystal growth rates are bounded; tiny crystals reside at the front of SFs

Vector analysis of chemical variation in the lavas of Parícutin volcano, Mexico

USGS Publications Warehouse

Miesch, A.T.

1979-01-01

Compositional variations in the lavas of Parícutin volcano, Mexico, have been examined by an extended method of Q-mode factor analysis. Each sample composition is treated as a vector projected from an original eight-dimensional space into a vector system of three dimensions. The compositions represented by the vectors after projection are closely similar to the original compositions except for Na2Oand Fe2O3.The vectors in the three-dimensional system cluster about three different planes that represent three stages of compositional change in the Parícutin lavas. Because chemical data on the compositions of the minerals in the lavas are presently lacking, interpretations of the mineral phases that may have been involved in fractional crystallization are based on CIPW norm calculations. Changes during the first stage are attributed largely to the fractional crystallization of plagioclase and olivine. Changes during the second stage can be explained by the separation of plagioclase and pyroxene. Changes during the final stage may have resulted mostly from the assimilation of a granitic material, as previously proposed by R. E. Wilcox.

Topographically induced homeotropic alignment of liquid crystals on self-assembled opal crystals.

PubMed

Kumar, Pankaj; Oh, Su Yeon; Baliyan, Vijay K; Kundu, Sudarshan; Lee, Seung Hee; Kang, Shin-Woong

2018-04-02

The surface of multilayered opal crystals resulted in homeotropic alignment of liquid crystal (LC), originated from the surface topography of opal crystals rather than a chemical nature of the nanoparticles. The polar anchoring energy (5.51 × 10 -5 J/m 2 ) of the crystal surface for nematic LC molecules was in a similar range to the conventional polyimide alignment layer (2.11 × 10 -5 J/m 2 ) used for commercial applications. The critical length scale for anchoring transition was approximately Lw = ~1 μm. If a diameter of particle d < 1 μm for opal crystals, LC molecules preferred to anchor vertically to the surface to minimize elastic free energy of bulk LCs. The LC favored a planar anchoring if d > 1 μm. The results provide crucial insights to understand the homeotropic alignment of LCs on solid surfaces and therefore offer opportunities to develop novel materials for a vertical alignment of LCs.

Chemical analysis of acoustically levitated drops by Raman spectroscopy.

PubMed

Tuckermann, Rudolf; Puskar, Ljiljana; Zavabeti, Mahta; Sekine, Ryo; McNaughton, Don

2009-07-01

An experimental apparatus combining Raman spectroscopy with acoustic levitation, Raman acoustic levitation spectroscopy (RALS), is investigated in the field of physical and chemical analytics. Whereas acoustic levitation enables the contactless handling of microsized samples, Raman spectroscopy offers the advantage of a noninvasive method without complex sample preparation. After carrying out some systematic tests to probe the sensitivity of the technique to drop size, shape, and position, RALS has been successfully applied in monitoring sample dilution and preconcentration, evaporation, crystallization, an acid-base reaction, and analytes in a surface-enhanced Raman spectroscopy colloidal suspension.

Metastable Solution Thermodynamic Properties and Crystal Growth Kinetics

NASA Technical Reports Server (NTRS)

Kim, Soojin; Myerson, Allan S.

1996-01-01

The crystal growth rates of NH4H2PO4, KH2PO4, (NH4)2SO4, KAl(SO4)2 central dot 12H2O, NaCl, and glycine and the nucleation rates of KBr, KCl, NaBr central dot 2H2O, (NH4)2Cl, and (NH4)2SO4 were expressed in terms of the fundamental driving force of crystallization calculated from the activity of supersaturated solutions. The kinetic parameters were compared with those from the commonly used kinetic expression based on the concentration difference. From the viewpoint of thermodynamics, rate expressions based on the chemical potential difference provide accurate kinetic representation over a broad range of supersaturation. The rates estimated using the expression based on the concentration difference coincide with the true rates of crystallization only in the concentration range of low supersaturation and deviate from the true kinetics as the supersaturation increases.

The comparative toxicity to soil invertebrates of natural chemicals and their synthetic analogues.

PubMed

Whitaker, J; Chaplow, J S; Potter, E; Scott, W A; Hopkin, S; Harman, M; Sims, I; Sorokin, N

2009-07-01

The introduction of Registration, Evaluation and Authorisation of Chemicals (REACH), requires companies to register and risk assess all substances produced or imported in volumes of >1 tonne per year. Extrapolation methods which use existing data for estimating the effects of chemicals are attractive to industry, and comparative data are therefore increasingly in demand. Data on natural toxic chemicals could be used for extrapolation methods such as read-across. To test this hypothesis, the toxicity of natural chemicals and their synthetic analogues were compared using standardised toxicity tests. Two chemical pairs: the napthoquinones, juglone (natural) and 1,4-naphthoquinone (synthetic); and anthraquinones, emodin (natural) and quinizarin (synthetic) were chosen, and their comparative effects on the survival and reproduction of collembolans, earthworms, enchytraeids and predatory mites were assessed. Differences in sensitivity between the species were observed with the predatory mite (Hypoaspis aculeifer) showing the least sensitivity. Within the chemical pairs, toxicity to lethal and sub-lethal endpoints was very similar for the four invertebrate species. The exception was earthworm reproduction, which showed differential sensitivity to the chemicals in both naphthoquinone and anthraquinone pairs. Differences in toxicity identified in the present study may be related to degree of exposure and/or subtle differences in the mode of toxic action for the chemicals and species tested. It may be possible to predict differences by identifying functional groups which infer increased or decreased toxicity in one or other chemical. The development of such techniques would enable the use of read-across from natural to synthetic chemicals for a wider group of compounds.

Improved ferroelectric and pyroelectric parameters in iminodiacetic acid doped TGS crystal

NASA Astrophysics Data System (ADS)

Rai, Chitharanjan; Sreenivas, K.; Dharmaprakash, S. M.

2010-01-01

Single crystals of Iminodiacetic acid (HN(CH 2COOH) 2) doped Triglycine sulphate (IDATGS) has been grown from aqueous solution at constant temperature by slow evaporation technique. The concentration of the dopant in the TGS solution was 2 mol%. The X-ray diffraction analysis indicates that there is significant change in the lattice parameters compared to pure TGS crystal. The IDATGS crystal has larger transition temperature and observed higher and uniform figure of merit over most part of the ferroelectric phase. These crystals also exhibit higher internal bias field and micro-hardness number compared to pure TGS. Therefore IDATGS may be a potential material for IR detectors.

Temporal Chemical Variations during the Eruption Cycle at Crystal Geyser in Green River, Utah: Inverse Modeling of Fluid Sourcing and Implications to the Geyser Mechanism

NASA Astrophysics Data System (ADS)

Watson, Z. T.; Han, W. S.; Kampman, N.; Grundl, T.; Han, K.

2014-12-01

The most well-known example of a CO2-driven geyser is Crystal geyser in Green River, Utah. In situ monitoring of pressure and temperature and analysis of the elemental and isotopic composition of the emanating fluids has provided useful proxies for determining the geysering cycle, the source of water/CO2 and furthermore the physical constraints at depth which ultimately control the surficial expressions. Crystal geyser is the first geyser in the world which has been shown to go through repeated systematic chemical variations during its eruption cycle. The eruption cycle at Crystal geyser is comprised of 4 parts which follow the order of: minor eruption period (mEP), major eruption period (MEP), aftershock eruptions (Ae) and recharge period (R). Minor eruption periods are characterized by increasing specific conductivity (19.3 to 21.2 mS/cm), Na and Cl concentrations during the first half which plateau until the MEP. The beginning of the MEP denotes a sharp drop in temperature (17.4 to 16.8 ºC) Na, Cl, specific conductivity (21.2 to 18 mS/cm), and increasing concentrations of Fe, Sr, Ca, Mg and Mn. Downhole fluid sampling of the Entrada Sandstone and Navajo Sandstone provided 1 and 4 samples from the aquifers, respectively. The Entrada Sandstone in comparison to the deeper Navajo Sandstone has elevated concentrations of Sr and Fe and has lower concentrations of Na and Cl. Inverse modeling using the chemical characteristics of the Entrada Sandstone, Navajo Sandstone and brine was executed to determine the fractional inputs which comprise Crystal geyser's fluid. Variances in the fractional contribution are dependent on the depth of the sample chosen to be representative of the Navajo Sandstone because the concentration of Na and Cl, among other elements, changes over depth. During the mEP the Navajo Sandstone, Entrada Sandstone and brine supply 50-55%, 44-48% and 1-3% of the total fluid, respectively. During the MEP the Navajo Sandstone, Entrada Sandstone and brine

Shattuckite and plancheite: A crystal chemical study

USGS Publications Warehouse

Evans, Howard T.; Mrose, Mary E.

1966-01-01

The orthorhombic crystal structures of shattuckite, Cu5( SiO3)4(OH)2 and planchétite, Cu8(Si4011)2(OH)4 H2O, have been solved. Shattuckite contains silicate chains similar to pyroxene in a complex association with copper atoms, while the closely related planchéite contains silicate chains similar to amphibole.

Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells.

PubMed

Chutipongtanate, Somchai; Chaiyarit, Sakdithep; Thongboonkerd, Visith

2012-08-15

Dissolution therapy of calcium oxalate monohydrate (COM) kidney stone disease has not yet been implemented due to a lack of well characterized COM dissolution agents. The present study therefore aimed to identify potential COM crystal dissolution compounds. COM crystals were treated with deionized water (negative control), 5 mM EDTA (positive control), 5 mM sodium citrate, or 5mM sodium phosphate. COM crystal dissolution activities of these compounds were evaluated by phase-contrast and video-assisted microscopic examinations, semi-quantitative analysis of crystal size, number and total mass, and spectrophotometric oxalate-dissolution assay. In addition, effects of these compounds on detachment of COM crystals, which adhered tightly onto renal tubular cell surface, were also investigated. The results showed that citrate, not phosphate, had a significant dissolution effect on COM crystals as demonstrated by significant reduction of crystal size (approximately 37% decrease), crystal number (approximately 53% decrease) and total crystal mass (approximately 72% decrease) compared to blank and negative controls. Spectrophotometric oxalate-dissolution assay successfully confirmed the COM crystal dissolution property of citrate. Moreover, citrate could detach up to 85% of the adherent COM crystals from renal tubular cell surface. These data indicate that citrate is better than phosphate for dissolution and detachment of COM crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Manipulating crystallization with molecular additives.

PubMed

Shtukenberg, Alexander G; Lee, Stephanie S; Kahr, Bart; Ward, Michael D

2014-01-01

Given the importance of organic crystals in a wide range of industrial applications, the chemistry, biology, materials science, and chemical engineering communities have focused considerable attention on developing methods to control crystal structure, size, shape, and orientation. Tailored additives have been used to control crystallization to great effect, presumably by selectively binding to particular crystallographic surfaces and sites. However, substantial knowledge gaps still exist in the fundamental mechanisms that govern the formation and growth of organic crystals in both the absence and presence of additives. In this review, we highlight research discoveries that reveal the role of additives, either introduced by design or present adventitiously, on various stages of formation and growth of organic crystals, including nucleation, dislocation spiral growth mechanisms, growth inhibition, and nonclassical crystal morphologies. The insights from these investigations and others of their kind are likely to guide the development of innovative methods to manipulate crystallization for a wide range of materials and applications.

Single crystal X-ray diffraction study of the HgBa2CuO4+δ superconducting compound

NASA Astrophysics Data System (ADS)

Bordet, P.; Duc, F.; Lefloch, S.; Capponi, J. J.; Alexandre, E.; Rosa-Nunes, M.; Antipov, E. V.; Putilin, S.

1996-02-01

A high precision X-ray diffraction analysis up to sin θ/λ = 1.15 of a HgBa2CuO4+δ single crystal having a Tc of ~ 90 K is presented. The cell parameters are a = 3.8815(4), c = 9.485 (7) Å. The refinements indicate the existence of a split barium site due to the presence of excess oxygen in the mercury layer. The position of this excess oxygen might be slightly displaced from the (1/2 1/2 0) position. A 6% mercury deficiency is observed. Models, including mercury defects, substitution by copper cations, or carbonate groups, are compared. However, we obtain no definite evidence for either of the three models. A possible disorder of the Hg position, due to the formation of chemical bonds with neighbouring extra oxygen anions, could correlate to the refinements of mixed species at the Hg site. A low temperature single crystal x-ray diffraction study, and comparison of refinements for the same single crystal with different extra oxygen contents, are in progress to help clarify this problem.

Graphene chiral liquid crystals and macroscopic assembled fibres

PubMed Central

Xu, Zhen; Gao, Chao

2011-01-01

Chirality and liquid crystals are both widely expressed in nature and biology. Helical assembly of mesophasic molecules and colloids may produce intriguing chiral liquid crystals. To date, chiral liquid crystals of 2D colloids have not been explored. As a typical 2D colloid, graphene is now receiving unprecedented attention. However, making macroscopic graphene fibres is hindered by the poor dispersibility of graphene and by the lack of an assembly method. Here we report that soluble, chemically oxidized graphene or graphene oxide sheets can form chiral liquid crystals in a twist-grain-boundary phase-like model with simultaneous lamellar ordering and long-range helical frustrations. Aqueous graphene oxide liquid crystals were continuously spun into metres of macroscopic graphene oxide fibres; subsequent chemical reduction gave the first macroscopic neat graphene fibres with high conductivity and good mechanical performance. The flexible, strong graphene fibres were knitted into designed patterns and into directionally conductive textiles. PMID:22146390

Superconductivity and valence state in layered single-crystal HfAs1.67Te0.12

NASA Astrophysics Data System (ADS)

Peng, Jian; Yu, Jia; Zhang, Shuai; Chen, Genfu

2018-01-01

We report a detailed study on single crystals of HfAs1.67Te0.12 within a PbFCl-type layered structure. The single crystals of the title compound were successfully grown using a chemical transport reaction. The temperature dependence of electrical resistivity ρ (T), AC magnetic susceptibility {χ }{AC}(T) and specific heat C(T) show a bulk superconductivity with transition temperature T c = 1.67 K. The jump of C/T at T c is comparable to the traditional BCS weak-coupling model. A full H-T phase diagram is established using the results of ρ (T,H) and C(T) under fields, suggesting a rather weak anisotropy [({H}c2\\parallel {ab}(0)/{H}c2\\parallel c(0)] of 1.8 in orbital limit dominated three-dimension-like superconducting system. The mixed-valence states of Hf and As observed in the binding energy from x-ray photoelectron spectroscopy are consistent with the single-crystal x-ray diffraction analysis, indicating that the As-Te disorder prefers to occur in the [HfAs] layer and a large amount of vacancies are present in tetragonal As layer. As compared to HfAs1.7Se0.2 (T c = 0.52 K), a positive-like vacancy effect on T c has been confirmed in HfAs1.67Te0.12. The analysis of the Hall coefficient implies that the hole-type carriers dominate the transport properties, which is in good agreement with the hole pockets at Fermi surface obtained in a band structure calculation. The detailed study of single-crystal HfAs1.67Te0.12 provides a possible candidate to discuss the non-magnetic Kondo effect.

Fabrication and analysis of single-crystal KTiOPO₄ films with thicknesses in the micrometer range.

PubMed

Ma, Changdong; Lu, Fei; Xu, Bo; Fan, Ranran

2016-02-01

Single-crystal potassium titanyl phosphate (KTiOPO4, KTP) films with thicknesses less than 5 μm are obtained by using helium (He) implantation combined with ion-beam-enhanced etching. A heavily damaged layer created by a 4×10(16)  cm(-2) fluence of 2 MeV He implantation is removed by means of wet chemical etching in hydrofluoric acid (HF). Thus, free-standing films of KTP with thicknesses in the range of 3-5 μm are obtained. The etching rate can be adjusted over a wide range by choosing temperature and HF concentration, as well as annealing conditions. Sharp etching edges and the smooth surface of the film indicate that a high selective-etching rate is achieved in the damaged layer, and the remaining part of the crystal is undamaged. X-ray and Raman-scattering results prove that KTP films have good single-crystal properties.

[Relativity of commercial specification of Menthae Herba based on chemical analysis].

PubMed

Ye, Dan; Zhao, Ming; Shao, Yang; Ouyang, Zhen; Peng, Hua-sheng; Han Bang-xing; Zhang, Wei-wan-qi; Gu, Xue-mei

2015-01-01

In order to compare the differences of 35 Menthae Herba samples collected on the market and at producing areas, the contents of six total terpenoids, the essential oil and chromatographic fingerprints were analyzed, which provided evidences for drawing up the commodity specifications and grading criteria of Menthae Herba. GC-MS method was used to analyze the chemical constituents of 35 different samples. The chromatographic fingerprints obtained by using GC were then evaluated by similarity analysis, hierarchical clustering analysis and principal component analysis. The relativity between the content of six terpenoids and the essential oil were studied. In this study, the chemical profiles of 35 samples from different producing areas had significant disparity. All samples collected in the report could be categorized into four chemical types, L-menthol, pulegone, carvone and L-menthone, but the chemical profiles had no relationship with the areas. The chromatographic fingerprints of the samples from different types were dissimilar, while the different producing areas were difficult to be separated. It was indicated that the content of volatile oil was positively correlated with the content of L-menthol and the sum of six total terpenoids. The content of the essential oil, L-menthol and the sum of six total terpenoids of Menthae Herba were considered as one of the commercial specifications and grading criteria. These results in the research could be helpful to draw up the commercial specification and grading criteria of Menthae Herba from a view of chemical information.

Semiconducting icosahedral boron arsenide crystal growth for neutron detection

NASA Astrophysics Data System (ADS)

Whiteley, C. E.; Zhang, Y.; Gong, Y.; Bakalova, S.; Mayo, A.; Edgar, J. H.; Kuball, M.

2011-03-01

Semiconducting icosahedral boron arsenide, B12As2, is an excellent candidate for neutron detectors, thermoelectric converters, and radioisotope batteries, for which high quality single crystals are required. Thus, the present study was undertaken to grow B12As2 crystals by precipitation from metal solutions (nickel) saturated with elemental boron (or B12As2 powder) and arsenic in a sealed quartz ampoule. B12As2 crystals of 10-15 mm were produced when a homogeneous mixture of the three elements was held at 1150 °C for 48-72 h and slowly cooled (3.5 °C/h). The crystals varied in color and transparency from black and opaque to clear and transparent. X-ray topography (XRT), and elemental analysis by energy dispersive X-ray spectroscopy (EDS) confirmed that the crystals had the expected rhombohedral structure and chemical stoichiometry. The concentrations of residual impurities (nickel, carbon, etc.) were low, as measured by Raman spectroscopy and secondary ion mass spectrometry (SIMS). Additionally, low etch-pit densities (4.4×107 cm-2) were observed after etching in molten KOH at 500 °C. Thus, the flux growth method is viable for growing large, high-quality B12As2 crystals.

Studies on the growth, structural, spectral and third-order nonlinear optical properties of ammonium 3-carboxy-4-hydroxy benzenesulfonate monohydrate single crystal.

PubMed

Silambarasan, A; Krishna Kumar, M; Thirunavukkarasu, A; Mohan Kumar, R; Umarani, P R

2015-01-25

An organic nonlinear optical bulk single crystal, Ammonium 3-carboxy-4-hydroxy benzenesulfonate monohydrate (ACHBS) was successfully grown by solution growth technique. Single crystal X-ray diffraction study confirms that, the grown crystal belongs to P21/c space group. Powder X-ray diffraction and high resolution X-ray diffraction analyses revealed the crystallinity of the grown crystal. Infrared spectral analysis showed the vibrational behavior of chemical bonds and its functional groups. The thermal stability and decomposition stages of the grown crystal were studied by TG-DTA analysis. UV-Visible transmittance studies showed the transparency region and cut-off wavelength of the grown crystal. The third-order nonlinear optical susceptibility of the grown crystal was estimated by Z-scan technique using He-Ne laser source. The mechanical property of the grown crystal was studied by using Vicker's microhardness test. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural analysis of benzothienobenzothiophene-based soluble organic semiconducting crystals grown by liquid crystal solvent

NASA Astrophysics Data System (ADS)

Shibata, Yosei; Matsuzaki, Tomoya; Ishinabe, Takahiro; Fujikake, Hideo

2018-06-01

In this study, we analyzed organic semiconducting single crystals composed of benzothienobenzothiophene derivatives (2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene, C8-BTBT) grown by nematic-phase liquid crystal (LC) solvent. As a result, we clarified that the crystal b-axis direction of the C8-BTBT single crystals was consistent with the LC alignment direction. By optical evaluation and simulation based on density functional theory, we found that the C8-BTBT single crystals in LC solvent exhibited a novel molecular conformation having alkyl chains oriented toward the b-axis.

Structural, spectral and birefringence studies of semiorganic nonlinear optical single crystal: Calcium5-sulfosalicylate

NASA Astrophysics Data System (ADS)

Shalini, D.; Kalainathan, S.; Ambika, V. Revathi; Hema, N.; Jayalakshmi, D.

2017-11-01

Semi-organic nonlinear optical crystal Calcium5-Sulfosalicylate (CA5SS) was grown by slow evaporation solution growth technique. The cell parameters and molecular structure of the grown crystal were studied by single crystal x-ray diffraction analysis. The presence of various functional groups of the grown crystal was confirmed using Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman) analysis. UV-Visible spectrum shows that CA5SS crystals have high transmittance in the range of 330-900 nm. The refractive index, birefringence and transient photoluminescence properties of the grown crystal were analyzed. The frequency doubling of the grown crystal (CA5SS) were studied and compared with that of KDP.

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.

Identification and Control of Gravity Related Defect Formation During Melt Growth of Electro-Optic Single Crystals Bismuth Silicate(Bi12SiO20)

NASA Technical Reports Server (NTRS)

Becia, Piotr; Wiegel, Michaela E. K.

2004-01-01

A research carried out under Award Number NAG8-1487 was aimed at to the design, conduct and analysis of experiments directed at the identification and control of gravitational effects on crystal growth, segregation and defect formation in the Sillenite system: bismuth silicate (Bi(12)SiO(20)). Correlation analyses was conducted in order to establish the influence of gravity related defects introduced during crystal growth on critical, application specific properties. Achievement of the states objective was conducted during the period from Feb. 01, 1998 to Dec. 31, 2003 with the following anticipated milestones: 1. Establishment of capabilities for (a) reproducible Czochralski and Bridgman-type growth of BSO single crystals and (b) for comprehensive analysis of crystalline and chemical defects as well as for selective property characterization of grown crystals (year 1). 2. Design and execution of critical space growth experiment(s) based on analyses of prefatory space results (experiments aimed at establishing the viability of planned approaches and procedures) and on unresolved issues related to growth, segregation and defect formation associated with conventional growth in Bridgman geometries. Comparative analysis of growth under conventional and under mu-g conditions; identification of gravity related defect formation during conventional Bridgman growth and formulation of approaches for their control (years 2 and 3). Development of charge confinement system which permits growth interface demarcation (in a mu-g environment) as well as minimization of confinement related stress and contamination during growth; design of complementary mu-g growth experiments aimed at quantitative mu-g growth and segregation analyses (year 4). 3. Conduct of quantitative mu-g growth experiments directed at: (a) identification and control of gravity related crystalline and chemical defect formation during single crystal growth of Bi(12)SiO(20) and at (b) defect engineering -the

Aquatic concentrations of chemical analytes compared to ecotoxicity estimates

EPA Science Inventory

We describe screening level estimates of potential aquatic toxicity posed by 227 chemical analytes that were measured in 25 ambient water samples collected as part of a joint USGS/USEPA drinking water plant study. Measured concentrations were compared to biological effect concent...

Finite-Difference Time-Domain Analysis of Tapered Photonic Crystal Fiber

NASA Astrophysics Data System (ADS)

Ali, M. I. Md; Sanusidin, S. N.; Yusof, M. H. M.

2018-03-01

This paper brief about the simulation of tapered photonic crystal fiber (PCF) LMA-8 single-mode type based on correlation of scattering pattern at wavelength of 1.55 μm, analyzation of transmission spectrum at wavelength over the range of 1.0 until 2.5 μm and correlation of transmission spectrum with the refractive index change in photonic crystal holes with respect to taper size of 0.1 until 1.0 using Optiwave simulation software. The main objective is to simulate using Finite-Difference Time-Domain (FDTD) technique of tapered LMA-8 PCF and for sensing application by improving the capabilities of PCF without collapsing the crystal holes. The types of FDTD techniques used are scattering pattern and transverse transmission and principal component analysis (PCA) used as a mathematical tool to model the data obtained by MathCad software. The simulation results showed that there is no obvious correlation of scattering pattern at a wavelength of 1.55 μm, a correlation obtained between taper sizes with a transverse transmission and there is a parabolic relationship between the refractive index changes inside the crystal structure.

Structure analysis on synthetic emerald crystals

NASA Astrophysics Data System (ADS)

Lee, Pei-Lun; Lee, Jiann-Shing; Huang, Eugene; Liao, Ju-Hsiou

2013-05-01

Single crystals of emerald synthesized by means of the flux method were adopted for crystallographic analyses. Emerald crystals with a wide range of Cr3+-doping content up to 3.16 wt% Cr2O3 were examined by X-ray single crystal diffraction refinement method. The crystal structures of the emerald crystals were refined to R 1 (all data) of 0.019-0.024 and w R 2 (all data) of 0.061-0.073. When Cr3+ substitutes for Al3+, the main adjustment takes place in the Al-octahedron and Be-tetrahedron. The effect of substitution of Cr3+ for Al3+ in the beryl structure results in progressively lengthening of the Al-O distance, while the length of the other bonds remains nearly unchanged. The substitution of Cr3+ for Al3+ may have caused the expansion of a axis, while keeping the c axis unchanged in the emerald lattice. As a consequence, the Al-O-Si and Al-O-Be bonding angles are found to decrease, while the angle of Si-O-Be increases as the Al-O distance increases during the Cr replacement.

Crystal Growth and Characterization of CdTe Grown by Vertical Gradient Freeze

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Lehoczky, S. L.; Raghothamachar, B.; Dudley, M.

2007-01-01

In this study, crystals of CdTe were grown from melts by the unseeded vertical gradient freeze method. The quality of grown crystal were studied by various characterization techniques including Synchrotron White Beam X-ray Topography (SWBXT), chemical analysis by glow discharge mass spectroscopy (GDMS), low temperature photoluminescence (PL), and Hall measurements. The SWBXT images from various angles show nearly strain-free grains, grains with inhomogeneous strains, as well as twinning nucleated in the shoulder region of the boule. The GDMS chemical analysis shows the contamination of Ga at a level of 3900 ppb, atomic. The low temperature PL measurement exhibits the characteristic emissions of a Ga-doped sample. The Hall measurements show a resistivity of 1 x l0(exp 7) ohm-cm at room temperature to 3 x 10(exp 9) ohm-cm at 78K with the respective hole and electron concentration of 1.7 x 10(exp 9) cm(exp -3) and 3.9 x 10(exp 7) cm(exp -3) at room temperature.

Ytterbium- and neodymium-doped vanadate laser hose crystals having the apatite crystal structure

DOEpatents

Payne, Stephen A.; Kway, Wayne L.; DeLoach, Laura D.; Krupke, William F.; Chai, Bruce H. T.

1994-01-01

Yb.sup.3+ and Nd.sup.3+ doped Sr.sub.5 (VO.sub.4).sub.3 F crystals serve as useful infrared laser media that exhibit low thresholds of oscillation and high slope efficiencies, and can be grown with high optical quality. These laser media possess unusually high absorption and emission cross sections, which provide the crystals with the ability to generate greater gain for a given amount of pump power. Many related crystals such as Sr.sub.5 (VO.sub.4).sub.3 F crystals doped with other rare earths, transition metals, or actinides, as well as the many structural analogs of Sr.sub.5 (VO.sub.4).sub.3 F, where the Sr.sup.2+ and F.sup.- ions are replaced by related chemical species, have similar properties.

Band structure analysis of leaky Bloch waves in 2D phononic crystal plates.

PubMed

Mazzotti, Matteo; Miniaci, Marco; Bartoli, Ivan

2017-02-01

A hybrid Finite Element-Plane Wave Expansion method is presented for the band structure analysis of phononic crystal plates with two dimensional lattice that are in contact with acoustic half-spaces. The method enables the computation of both real (propagative) and imaginary (attenuation) components of the Bloch wavenumber at any given frequency. Three numerical applications are presented: a benchmark dispersion analysis for an oil-loaded Titanium isotropic plate, the band structure analysis of a water-loaded Tungsten slab with square cylindrical cavities and a phononic crystal plate composed of Aurum cylinders embedded in an epoxy matrix. Copyright © 2016 Elsevier B.V. All rights reserved.

Physical-Chemical Properties of the Chiral Fungicide Fenamidone and Strategies for Enantioselective Crystallization.

PubMed

Kort, Anne-Kathleen; Lorenz, Heike; Seidel-Morgenstern, Andreas

2016-06-01

Thermodynamic and kinetic parameters are of prime importance for designing crystallization processes. In this article, Preferential Crystallization, as a special approach to carry out enantioselective crystallization, is described to resolve the enantiomers of the chiral fungicide fenamidone. In preliminary investigations the melting behavior and solid-liquid equilibria in the presence of solvents were quantified. The analyses revealed a stable solid phase behavior of fenamidone in the applied solvents. Based on the results obtained, a two-step crystallization route was designed and realized capable of providing highly pure enantiomers. An initial Preferential Crystallization of the racemate was performed prior to crystallizing the target enantiomer preferentially out of the enriched mother liquor. Chirality 28:514-520, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

A statistical analysis of the elastic distortion and dislocation density fields in deformed crystals

DOE PAGES

Mohamed, Mamdouh S.; Larson, Bennett C.; Tischler, Jonathan Z.; ...

2015-05-18

The statistical properties of the elastic distortion fields of dislocations in deforming crystals are investigated using the method of discrete dislocation dynamics to simulate dislocation structures and dislocation density evolution under tensile loading. Probability distribution functions (PDF) and pair correlation functions (PCF) of the simulated internal elastic strains and lattice rotations are generated for tensile strain levels up to 0.85%. The PDFs of simulated lattice rotation are compared with sub-micrometer resolution three-dimensional X-ray microscopy measurements of rotation magnitudes and deformation length scales in 1.0% and 2.3% compression strained Cu single crystals to explore the linkage between experiment and the theoreticalmore » analysis. The statistical properties of the deformation simulations are analyzed through determinations of the Nye and Kr ner dislocation density tensors. The significance of the magnitudes and the length scales of the elastic strain and the rotation parts of dislocation density tensors are demonstrated, and their relevance to understanding the fundamental aspects of deformation is discussed.« less

Crystal Structure and Proteomics Analysis of Empty Virus-like Particles of Cowpea Mosaic Virus

PubMed Central

Huynh, Nhung T.; Hesketh, Emma L.; Saxena, Pooja; Meshcheriakova, Yulia; Ku, You-Chan; Hoang, Linh T.; Johnson, John E.; Ranson, Neil A.; Lomonossoff, George P.; Reddy, Vijay S.

2016-01-01

SUMMARY Empty virus-like particles (eVLPs) of Cowpea mosaic virus (CPMV) are currently being utilized as reagents in various biomedical and nanotechnology applications. Here, we report the crystal structure of CPMV eVLPs determined using X-ray crystallography at 2.3 Å resolution and compare it with previously reported cryo-electron microscopy (cryo-EM) of eVLPs and virion crystal structures. Although the X-ray and cryo-EM structures of eVLPs are mostly similar, there exist significant differences at the C terminus of the small (S) subunit. The intact C terminus of the S subunit plays a critical role in enabling the efficient assembly of CPMV virions and eVLPs, but undergoes proteolysis after particle formation. In addition, we report the results of mass spectrometry-based proteomics analysis of coat protein subunits from CPMV eVLPs and virions that identify the C termini of S subunits undergo proteolytic cleavages at multiple sites instead of a single cleavage site as previously observed. PMID:27021160

The Effect of Acidity Coefficient on Crystallization Behavior of Blast Furnace Slag Fibers

NASA Astrophysics Data System (ADS)

Tian, Tie-Lei; Zhang, Yu-Zhu; Xing, Hong-wei; Li, Jie; Zhang, Zun-Qian

2018-01-01

The chemical structure of mineral wool fiber was investigated by using Fourier Transform Infrared Spectroscopy (FTIR). Next, the glass transition temperature and the crystallization temperature of the fibers were studied. Finally, the crystallization kinetics of fiber was studied. The results show that the chemical bond structure of fibers gets more random with the increase of acidity coefficient. The crystallization phases of the fibers are mainly melilites, and also a few anorthites and diopsides. The growth mechanism of the crystals is three dimensional. The fibers with acidity coefficient of 1.2 exhibit the best thermal stability and is hard to crystallize as it has the maximum aviation energy of crystallization kinetics.

Chemical and Thermal Analysis

NASA Technical Reports Server (NTRS)

Bulluck, J. W.; Rushing, R. A.

1997-01-01

Work during the past three years has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution and the increased crosslinking of the Coflon material using Gel Permeation Chromatographic Analysis. Again these changes may result in variations in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, and Differential Scanning Calorimetry. We investigated a plethora of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed on powdered PVDF in a modified Fluid A, which we will call A-2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures.

Crystal Systems.

ERIC Educational Resources Information Center

Schomaker, Verner; Lingafelter, E. C.

1985-01-01

Discusses characteristics of crystal systems, comparing (in table format) crystal systems with lattice types, number of restrictions, nature of the restrictions, and other lattices that can accidently show the same metrical symmetry. (JN)

Self-assembled tunable photonic hyper-crystals.

PubMed

Smolyaninova, Vera N; Yost, Bradley; Lahneman, David; Narimanov, Evgenii E; Smolyaninov, Igor I

2014-07-16

We demonstrate a novel artificial optical material, the "photonic hyper-crystal", which combines the most interesting features of hyperbolic metamaterials and photonic crystals. Similar to hyperbolic metamaterials, photonic hyper-crystals exhibit broadband divergence in their photonic density of states due to the lack of usual diffraction limit on the photon wave vector. On the other hand, similar to photonic crystals, hyperbolic dispersion law of extraordinary photons is modulated by forbidden gaps near the boundaries of photonic Brillouin zones. Three dimensional self-assembly of photonic hyper-crystals has been achieved by application of external magnetic field to a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing.

Cadmium sulphide (CdS) thin films deposited by chemical bath deposition (CBD) and dip coating techniques—a comparative study

NASA Astrophysics Data System (ADS)

Khimani, Ankurkumar J.; Chaki, Sunil H.; Malek, Tasmira J.; Tailor, Jiten P.; Chauhan, Sanjaysinh M.; Deshpande, M. P.

2018-03-01

The CdS thin films were deposited on glass slide substrates by Chemical Bath Deposition and dip coating techniques. The films thickness variation with deposition time showed maximum films deposition at 35 min for both the films. The energy dispersive analysis of x-ray showed both the films to be stoichiometric. The x-ray diffraction analysis confirmed the films possess hexagonal crystal structure. The transmission electron, scanning electron and optical microscopy study showed the films deposition to be uniform. The selected area electron diffraction exhibited ring patterns stating the films to be polycrystalline in nature. The atomic force microscopy images showed surface formed of spherical grains, hills and valleys. The recorded optical absorbance spectra analysis revealed the films possess direct optical bandgap having values of 2.25 eV for CBD and 2.40 eV for dip coating. The refractive index (η), extinction coefficient (k), complex dielectric constant (ε) and optical conductivity (σ 0) variation with wavelength showed maximum photon absorption till the respective wavelengths corresponding to the optical bandgap energy values. The recorded photoluminescence spectra showed two emission peaks. All the obtained results have been discussed in details.

High Resolution Chemical Study of ALH84001

NASA Technical Reports Server (NTRS)

Conrad, Pamela G.; Douglas, Susanne; Kuhlman, Kimberly R.

2001-01-01

We have studied the chemistry of a sample of the SNC meteorite ALH84001 using an environmental scanning electron microscope (ESEM) with an energy dispersive chemical analytical detector and a focused ion beam secondary ion mass spectrometer (FIB-SIMS). Here we present the chemical data, both spectra and images, from two techniques that do not require sample preparation with a conductive coating, thus eliminating the possibility of preparation-induced textural artifacts. The FIB-SIMS instrument includes a column optimized for SEM with a quadrupole type mass spectrometer. Its spatial and spectral resolution are 20 nm and 0.4 AMU, respectively. The spatial resolution of the ESEM for chemical analysis is about 100 nm. Limits of detection for both instruments are mass dependent. Both the ESEM and the FIB-SIMS instrument revealed contrasting surficial features; crumbled, weathered appearance of the matrix in some regions as well as a rather ubiquitous presence of euhedral halite crystals, often associated with cracks or holes in the surface of the rock. Other halogen elements present in the vicinity of the NaCl crystals include K and Br. In this report, elemental inventories are shown as mass spectra and as X-ray maps.

Silicon chip integrated photonic sensors for biological and chemical sensing

NASA Astrophysics Data System (ADS)

Chakravarty, Swapnajit; Zou, Yi; Yan, Hai; Tang, Naimei; Chen, Ray T.

2016-03-01

We experimentally demonstrate applications of photonic crystal waveguide based devices for on-chip optical absorption spectroscopy for the detection of chemical warfare simulant, triethylphosphate as well as applications with photonic crystal microcavity devices in the detection of biomarkers for pancreatic cancer in patient serum and cadmium metal ions in heavy metal pollution sensing. At mid-infrared wavelengths, we experimentally demonstrate the higher sensitivity of photonic crystal based structures compared to other nanophotonic devices such as strip and slot waveguides with detection down to 10ppm triethylphosphate. We also detected 5ppb (parts per billion) of cadmium metal ions in water at near-infrared wavelengths using established techniques for the detection of specific probe-target biomarker conjugation chemistries.

Economic analysis of crystal growth in space

NASA Technical Reports Server (NTRS)

Ulrich, D. R.; Chung, A. M.; Yan, C. S.; Mccreight, L. R.

1972-01-01

Many advanced electronic technologies and devices for the 1980's are based on sophisticated compound single crystals, i.e. ceramic oxides and compound semiconductors. Space processing of these electronic crystals with maximum perfection, purity, and size is suggested. No ecomonic or technical justification was found for the growth of silicon single crystals for solid state electronic devices in space.

The Question of Impurities in Macromolecule Crystal Quality Improvement in Microgravity

NASA Technical Reports Server (NTRS)

Judge, Russell A.; Snell, Edward H.; Pusey, Marc L.; Sportiello, Michael G.; Todd, Paul; Bellamy, Henry; Borgstahl, Gloria E.; Pokros, Matthew; Cassanto, John M.

2000-01-01

While macromolecule impurities may affect crystal size and morphology the over-riding question is how do macromolecule impurities effect crystal X-ray quality and diffraction resolution. In the case of chicken egg white lysozyme previous researchers have reported that crystals grown in the presence of ovalbumin, ovotransferrin, and turkey egg white lysozyme show no difference in diffraction resolution compared to those grown in pure solutions. One impurity however, a naturally occurring lysozyme dimer, does negatively impact the X-ray crystal properties. For this impurity it has been reported that crystal quality improvement in microgravity may be due to improved impurity partitioning during crystallization. In this study we have examined the incorporation of the dimer into lysozyme crystals, both on the ground and in microgravity experiments, and have performed detailed X-ray analysis of the crystals using a new technique for finely probing the mosaicity of the crystal at the Stanford Synchrotron Radiation Laboratory. Dimer partitioning was not significantly different in microgravity compared to the ground based experiments, although it is significantly better than that previously reported in microgravity. Mosaicity analysis of pure crystals, 1422 indexed reflections (microgravity) and 752 indexed reflections (ground), gave average results of 0.0066 and 0.0092 degrees (FWHM) respectively. The microgravity crystals also provided an increased signal to noise. Dimer incorporation increased the average mosaicity in microgravity but not on the ground. However, dimer incorporation did greatly reduce the resolution limit in both ground and microgravity grown crystals. The data is being treated anisotropically to explore these effects. These results indicate that impurity effects in microgravity are complex and that the conditions or techniques employed may greatly affect the role of impurities.

Growth, Crystal Structure, Theoretical Analysis and Properties of Te4+-Doped KTiOPO4

NASA Astrophysics Data System (ADS)

Liu, Lintao; Yao, Qian; Zhang, Junying; Dong, Weimin; Li, Jing; Wang, Jiyang; Boughton, Robert I.

2018-04-01

A single crystal of Te4+-doped KTiOPO4(Te:KTP) has been grown by the flux method. The electronic structure and density of states of KTiOPO4 (KTP) and Te:KTP were calculated from first principles. As the results reveal, there is no change in the space group or lattice structure of Te:KTP, but that some increase in lattice parameters occurred. The chemical composition of Te:KTP was analyzed using x-ray photoelectron spectroscopy (XPS). The possible existence of Ti3+ has been evaluated by measuring the electron paramagnetic resonance spectrum, and the results reveal that the ion is absent from this crystal. It was observed that Te4+ doping reduces the conductivity of the crystal from measurements of its conductivity at different temperatures and frequencies, indicating that Te:KTP has excellent electro-optical properties. The effect of Te4+ doping on the second harmonic generation in KTP was also studied. The thermal expansion, thermal diffusivity, thermal conductivity and specific heat capacity of KTP and Te:KTP were determined.

Efficient green luminescence of terbium oxalate crystals: A case study with Judd-Ofelt theory and single crystal structure analysis and the effect of dehydration on luminescence

NASA Astrophysics Data System (ADS)

Alexander, Dinu; Joy, Monu; Thomas, Kukku; Sisira, S.; Biju, P. R.; Unnikrishnan, N. V.; Sudarsanakumar, C.; Ittyachen, M. A.; Joseph, Cyriac

2018-06-01

Design and synthesis of Lanthanide based metal organic framework is a frontier area of research owing to their structural diversity enabling specific applications. The luminescence properties of rare earths, tuned by the structural features of Ln-MOFs are investigated extensively. Rare earth oxalates which can be synthesized in a facile method, ensuring the structural features of MOFs with excellent photoluminescence characteristics deserves much attention. This work is the first time report on the single crystal structure and Judd-Ofelt (JO) theoretical analysis - their correlation with the intense and sharp green luminescence of Terbium oxalate crystals. The intense green luminescence observed for Terbium oxalate crystals for a wide range of excitation from DUV to visible region despite the luminescence limiting factors are discussed. The absence of concentration quenching and lifting up of forbidden nature of f-f transitions, allowing direct excitation of Terbium ions is analysed with the help of JO theory and single crystal structure analysis. The JO analysis predicted the asymmetry of Terbium sites, allowing the electric dipole transitions and from the JO intensity parameters, promising spectroscopic parameters - emission cross section, branching ratio, gain band width and gain coefficient of the material were calculated. The single crystal structure analysis revealed the asymmetry of Tb sites and structure of Terbium oxalate is formed by the hydrogen bonded stacking of overlapped six Terbium membered rings connected by the oxalate ligands. The molecularly thick layers thus formed on the crystal surface are imaged by the atomic force microscopy. The presence of water channels in the structure and the effect of lattice water molecules on the luminescence intensity are also investigated.

Discrimination of chemical vapor and temperature using an in-line modal interferometer based on an exterior hole-assisted polarization-maintaining photonic crystal fiber

NASA Astrophysics Data System (ADS)

Yoon, Min-Seok; Jun, Naram; Lee, Sang Bae; Han, Young-Geun

2014-05-01

A reflective in-line modal interferometer based on a polarization-maintaining photonic crystal fiber (PM-PCF) with two exterior air holes is proposed for simultaneous measurement of chemical vapor and temperature. After fusion-splicing the PM-PCF with a standard single-mode fiber, we collapse all of air holes in the PM-PCF resulting in two types of interference patterns between the core and the cladding modes in the PM-PCF depending on two polarization states. Since two large air holes at the facet of the proposed modal interferometer are left open, a chemical vapor can be infiltrated into the voids. Different sensitivities corresponding to input polarization states are utilized for discrimination between chemical vapor and temperature sensitivities.

Advanced Methods of Protein Crystallization.

PubMed

Moreno, Abel

2017-01-01

This chapter provides a review of different advanced methods that help to increase the success rate of a crystallization project, by producing larger and higher quality single crystals for determination of macromolecular structures by crystallographic methods. For this purpose, the chapter is divided into three parts. The first part deals with the fundamentals for understanding the crystallization process through different strategies based on physical and chemical approaches. The second part presents new approaches involved in more sophisticated methods not only for growing protein crystals but also for controlling the size and orientation of crystals through utilization of electromagnetic fields and other advanced techniques. The last section deals with three different aspects: the importance of microgravity, the use of ligands to stabilize proteins, and the use of microfluidics to obtain protein crystals. All these advanced methods will allow the readers to obtain suitable crystalline samples for high-resolution X-ray and neutron crystallography.

High quality self-separated GaN crystal grown on a novel nanoporous template by HVPE.

PubMed

Huo, Qin; Shao, Yongliang; Wu, Yongzhong; Zhang, Baoguo; Hu, Haixiao; Hao, Xiaopeng

2018-02-16

In this study, a novel nanoporous template was obtained by a two-step etching process from MOCVD-GaN/Al 2 O 3 (MGA) with electrochemical etching sequentially followed by chemical wet etching. The twice-etched MOCVD-GaN/Al 2 O 3 (TEMGA) templates were utilized to grow GaN crystals by hydride vapor phase epitaxy (HVPE) method. The GaN crystals were separated spontaneously from the TEMGA template with the assistance of voids formed by the etched nanopores. Several techniques were utilized to characterize the quality of the free-standing GaN crystals obtained from the TEMGA template. Results showed that the quality of the as-obtained GaN crystals was improved obviously compared with those grown on the MGA. This convenient technique can be applied to grow high-quality free-standing GaN crystals.

Growth and luminescent properties of Yb:YAG and Ca co-doped Yb:YAG ultrafast scintillation crystals

NASA Astrophysics Data System (ADS)

Zhu, Maodong; Qi, Hongji; Pan, Mingyan; Hou, Qing; Jiang, Benxue; Jin, Yaxue; Han, Hetong; Song, Zhaohui; Zhang, Hui

2018-05-01

In this work, Yb-doped Y3Al5O12 [yttrium aluminum garnet (YAG)] crystals and Ca co-doped Yb:YAG crystals were grown by the Czochralski (CZ) method. The chemical formulas of the two crystals are (Yb0.1Y0.9)3Al5O12 and (Ca0.001Yb0.1Y0.899)3Al5O12, respectively. The structural, optical and luminescent properties of the Yb:YAG and Ca, Yb:YAG crystals were investigated by X-ray rocking curve, X-ray diffraction, Raman spectra, UV-Visble-NIR absorption spectra and X-ray fluorescence. X-ray fluorescence spectrum with two emission peaks at 330 nm and 490 nm were observed in the two kinds of crystals, which would increase slightly after the annealing. Comparing to the Yb:YAG crystal, Ca co-doped Yb:YAG crystal behaved the better luminescent intensity without changing the crystal structure and vibrational modes. This indicates that by doping Ca2+ in Yb:YAG crystal may be an appropriate way to enhance the luminescent property of the scintillation crystal.

Ground Based Program for the Physical Analysis of Macromolecular Crystal Growth

NASA Technical Reports Server (NTRS)

Malkin, Alexander J.

1998-01-01

compared with catalase crystallization. Cessation of growth of xylanase and lysozyme crystals was also observed and appeared to be a consequence of the formation of dense impurity adsorption layers. Attachment: "An in situ AFM investigation of catalase crystallization", "Atomic force microscopy studies of living cells: visualization of motility, division, aggregation, transformation, and apoptosis", AFM studies on mechanisms of nucleation and growth of macromolecular crystals", and "In situ atomic force microscopy studies of surface morphology, growth kinetics, defect structure and dissolution in macromolecular crystallization".

Nature and Analysis of Chemical Species.

ERIC Educational Resources Information Center

Shuman, Mark S.; Fogleman, Wavell W.

1978-01-01

Presents a literature review of the nature and analysis of chemical species in water, covering publications of 1976-77. This review is concerned with inorganics, and it covers: (1) electrochemical analysis; (2) spectroscopy; (3) neutron activation, radiochemical analysis, and isotope dilution. A list of 262 references is also presented. (HM)

Analysis of thickness dependent on crystallization kinetics in thin isotactic-polysterene films

NASA Astrophysics Data System (ADS)

Khairuddin

2016-11-01

Crystalliaztion kinetics of thin film of Isotactic Polysterene (it-PS) films has been studied. Thin PET films having thickness of 338, 533, 712, 1096, 1473, and 2185 A° were prepared by using spin-cast technique. The it-PS crystals were grown on Linkam-hostage in the temperature range 130-240°C with an interval of 10°C. The crystal growths are measured by optical microscopy in lateral direction. It was found that a substantial thickness dependence on crystallisation rate. The analysis using fitting technique based on theory crystal growth of Lauritzen-Hoffman showed that the fitting technique could not resolve to predict the mechanism controlling the thickness dependence on the rate of crystallisation. The possible reasons were due to the crystallisation rate varies with the type of crystals (smooth, rough, overgrowth terrace), and the crystallisation rate changes with the time of crystallisation.

Self-assembled Tunable Photonic Hyper-crystals

DTIC Science & Technology

2014-07-16

a cobalt nanoparticle-based ferrofluid. Unique spectral properties of photonic hyper-crystals lead to extreme sensitivity of the material to...monolayer coatings of cobalt nanoparticles, which should find numerous applications in biological and chemical sensing. 2 Approved for public release...assembly of photonic hyper crystals has been achieved by application of external magnetic field to a cobalt nanoparticle based ferrofluid. Unique spectral

Stochastic flux analysis of chemical reaction networks

PubMed Central

2013-01-01

Background Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. Results We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. Conclusions We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network. PMID:24314153

Stochastic flux analysis of chemical reaction networks.

PubMed

Kahramanoğulları, Ozan; Lynch, James F

2013-12-07

Chemical reaction networks provide an abstraction scheme for a broad range of models in biology and ecology. The two common means for simulating these networks are the deterministic and the stochastic approaches. The traditional deterministic approach, based on differential equations, enjoys a rich set of analysis techniques, including a treatment of reaction fluxes. However, the discrete stochastic simulations, which provide advantages in some cases, lack a quantitative treatment of network fluxes. We describe a method for flux analysis of chemical reaction networks, where flux is given by the flow of species between reactions in stochastic simulations of the network. Extending discrete event simulation algorithms, our method constructs several data structures, and thereby reveals a variety of statistics about resource creation and consumption during the simulation. We use these structures to quantify the causal interdependence and relative importance of the reactions at arbitrary time intervals with respect to the network fluxes. This allows us to construct reduced networks that have the same flux-behavior, and compare these networks, also with respect to their time series. We demonstrate our approach on an extended example based on a published ODE model of the same network, that is, Rho GTP-binding proteins, and on other models from biology and ecology. We provide a fully stochastic treatment of flux analysis. As in deterministic analysis, our method delivers the network behavior in terms of species transformations. Moreover, our stochastic analysis can be applied, not only at steady state, but at arbitrary time intervals, and used to identify the flow of specific species between specific reactions. Our cases study of Rho GTP-binding proteins reveals the role played by the cyclic reverse fluxes in tuning the behavior of this network.

Structure and vibrational spectra of melaminium bis(trifluoroacetate) trihydrate: FT-IR, FT-Raman and quantum chemical calculations.

PubMed

Sangeetha, V; Govindarajan, M; Kanagathara, N; Marchewka, M K; Gunasekaran, S; Anbalagan, G

2014-05-05

Melaminium bis(trifluoroacetate) trihydrate (MTFA), an organic material has been synthesized and single crystals of MTFA have been grown by the slow solvent evaporation method at room temperature. X-ray powder diffraction analysis confirms that MTFA crystal belongs to the monoclinic system with space group P2/c. The molecular geometry, vibrational frequencies and intensity of the vibrational bands have been interpreted with the aid of structure optimization based on density functional theory (DFT) B3LYP method with 6-311G(d,p) and 6-311++G(d,p) basis sets. The X-ray diffraction data have been compared with the data of optimized molecular structure. The theoretical results show that the crystal structure can be reproduced by optimized geometry and the vibrational frequencies show good agreement with the experimental values. The nuclear magnetic resonance (NMR) chemical shift of the molecule has been calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results. HOMO-LUMO, and other related molecular and electronic properties are calculated. The Mulliken and NBO charges have also been calculated and interpreted. Copyright © 2014 Elsevier B.V. All rights reserved.

Biological and chemical removal of Cr(VI) from waste water: cost and benefit analysis.

PubMed

Demir, Aynur; Arisoy, Münevver

2007-08-17

The objective of the present study is cost and benefit analysis of biological and chemical removal of hexavalent chromium [Cr(VI)] ions. Cost and benefit analysis were done with refer to two separate studies on removal of Cr(VI), one of heavy metals with a crucial role concerning increase in environmental pollution and disturbance of ecological balance, through biological adsorption and chemical ion-exchange. Methods of biological and chemical removal were compared with regard to their cost and percentage in chrome removal. According to the result of the comparison, cost per unit in chemical removal was calculated 0.24 euros and the ratio of chrome removal was 99.68%, whereas those of biological removal were 0.14 and 59.3% euros. Therefore, it was seen that cost per unit in chemical removal and chrome removal ratio were higher than those of biological removal method. In the current study where chrome removal is seen as immeasurable benefit in terms of human health and the environment, percentages of chrome removal were taken as measurable benefit and cost per unit of the chemicals as measurable cost.

Finite Element Analysis of a Copper Single Crystal Shape Memory Alloy-Based Endodontic Instruments

NASA Astrophysics Data System (ADS)

Vincent, Marin; Thiebaud, Frédéric; Bel Haj Khalifa, Saifeddine; Engels-Deutsch, Marc; Ben Zineb, Tarak

2015-10-01

The aim of the present paper is the development of endodontic Cu-based single crystal Shape Memory Alloy (SMA) instruments in order to eliminate the antimicrobial and mechanical deficiencies observed with the conventional Nickel-Titane (NiTi) SMA files. A thermomechanical constitutive law, already developed and implemented in a finite element code by our research group, is adopted for the simulation of the single crystal SMA behavior. The corresponding material parameters were identified starting from experimental results for a tensile test at room temperature. A computer-aided design geometry has been achieved and considered for a finite element structural analysis of the endodontic Cu-based single crystal SMA files. They are meshed with tetrahedral continuum elements to improve the computation time and the accuracy of results. The geometric parameters tested in this study are the length of the active blade, the rod length, the pitch, the taper, the tip diameter, and the rod diameter. For each set of adopted parameters, a finite element model is built and tested in a combined bending-torsion loading in accordance with ISO 3630-1 norm. The numerical analysis based on finite element procedure allowed purposing an optimal geometry suitable for Cu-based single crystal SMA endodontic files. The same analysis was carried out for the classical NiTi SMA files and a comparison was made between the two kinds of files. It showed that Cu-based single crystal SMA files are less stiff than the NiTi files. The Cu-based endodontic files could be used to improve the root canal treatments. However, the finite element analysis brought out the need for further investigation based on experiments.

Crystal engineering: co-crystals of cinnamic acid derivatives with a pyridyl derivative co-crystallizer.

PubMed

Lorenzo, Daniel A; Forrest, Sebastian J K; Sparkes, Hazel A

2016-02-01

A number of hydrogen-bonded co-crystals, consisting of a cinnamic acid derivative and a pyridyl co-crystallizer, have been synthesized and their properties investigated by X-ray diffraction. Samples were prepared by recrystallization or solvent drop grinding of trans-cinnamic acid (1), 4-methylcinnamic acid (2), 4-methoxy cinnamic acid (3) or 3,4-methoxy cinnamic acid (4), with 4,4-dipyridyl (A), iso-nicotinamide (B) or nicotinamide (C). The X-ray single-crystal structures of seven novel co-crystals, obtained through recrystallization, are examined and the hydrogen-bonding interactions discussed. Consistent hydrogen-bonding motifs were observed for samples prepared when using 4,4-dipyridyl (A) or iso-nicotinamide (B) as the co-crystallizing agent. Powder X-ray diffraction analysis of the samples prepared by solvent drop grinding suggests the formation of ten co-crystals.

Crystal growth, structural, optical, dielectric and thermal studies of an amino acid based organic NLO material: L-phenylalanine L-phenylalaninium malonate.

PubMed

Prakash, M; Geetha, D; Caroline, M Lydia; Ramesh, P S

2011-12-01

Good transparent single crystals of L-phenylalanine L-phenylalaninium malonate (LPPMA) have been grown successfully by slow evaporation technique from aqueous solution. Single crystal X-ray diffractometer was utilized to measure unit cell parameter and to confirm the crystal structure. The chemical structure of compound was established by FT-NMR technique. The vibrational modes of the molecules of elucidated from FTIR spectra. Its optical behaviour has been examined by UV-vis spectral analysis, which shows the absence of absorbance in the visible region. Thermal properties of the LPPMA crystal were carried out by thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) techniques, which indicate that the material does not decompose before melting. The melting point of grown crystal was observed as 180°C by melting point apparatus. The NLO property was confirmed by the powder technique of Kurtz and Perry. The dielectric behaviour of the sample was also studied for the first time. Copyright © 2011 Elsevier B.V. All rights reserved.

Crystal growth, structural, optical, dielectric and thermal studies of an amino acid based organic NLO material: L-Phenylalanine L-phenylalaninium malonate

NASA Astrophysics Data System (ADS)

Prakash, M.; Geetha, D.; Lydia Caroline, M.; Ramesh, P. S.

2011-12-01

Good transparent single crystals of L-phenylalanine L-phenylalaninium malonate (LPPMA) have been grown successfully by slow evaporation technique from aqueous solution. Single crystal X-ray diffractometer was utilized to measure unit cell parameter and to confirm the crystal structure. The chemical structure of compound was established by FT-NMR technique. The vibrational modes of the molecules of elucidated from FTIR spectra. Its optical behaviour has been examined by UV-vis spectral analysis, which shows the absence of absorbance in the visible region. Thermal properties of the LPPMA crystal were carried out by thermo gravimetric analysis (TGA) and differential thermal analysis (DTA) techniques, which indicate that the material does not decompose before melting. The melting point of grown crystal was observed as 180 °C by melting point apparatus. The NLO property was confirmed by the powder technique of Kurtz and Perry. The dielectric behaviour of the sample was also studied for the first time.

On-line monitoring of the crystallization process: relationship between crystal size and electrical impedance spectra

NASA Astrophysics Data System (ADS)

Zhao, Yanlin; Yao, Jun; Wang, Mi

2016-07-01

On-line monitoring of crystal size in the crystallization process is crucial to many pharmaceutical and fine-chemical industrial applications. In this paper, a novel method is proposed for the on-line monitoring of the cooling crystallization process of L-glutamic acid (LGA) using electrical impedance spectroscopy (EIS). The EIS method can be used to monitor the growth of crystal particles relying on the presence of an electrical double layer on the charged particle surface and the polarization of double layer under the excitation of alternating electrical field. The electrical impedance spectra and crystal size were measured on-line simultaneously by an impedance analyzer and focused beam reflectance measurement (FBRM), respectively. The impedance spectra were analyzed using the equivalent circuit model and the equivalent circuit elements in the model can be obtained by fitting the experimental data. Two equivalent circuit elements, including capacitance (C 2) and resistance (R 2) from the dielectric polarization of the LGA solution and crystal particle/solution interface, are in relation with the crystal size. The mathematical relationship between the crystal size and the equivalent circuit elements can be obtained by a non-linear fitting method. The function can be used to predict the change of crystal size during the crystallization process.

Using Magnetic Fields to Control Convection during Protein Crystallization: Analysis and Validation Studies

NASA Technical Reports Server (NTRS)

Ramachandran, N.; Leslie, F. W.

2004-01-01

The effect of convection during the crystallization of proteins is not very well understood. In a gravitational field, convection is caused by crystal sedimentation and by solutal buoyancy induced flow and these can lead to crystal imperfections. While crystallization in microgravity can approach diffusion limited growth conditions (no convection), terrestrially strong magnetic fields can be used to control fluid flow and sedimentation effects. In this work, we develop the analysis for magnetic flow control and test the predictions using analog experiments. Specifically, experiments on solutal convection in a paramagnetic fluid were conducted in a strong magnetic field gradient using a dilute solution of Manganese Chloride. The observed flows indicate that the magnetic field can completely counter the settling effects of gravity locally and are consistent with the theoretical predictions presented. This phenomenon suggests that magnetic fields may be useful in mimicking the microgravity environment of space for some crystal growth ana biological applications where fluid convection is undesirable.

Ultra-Rapid Crystallization of L-alanine Using Monomode Microwaves, Indium Tin Oxide and Metal-Assisted and Microwave-Accelerated Evaporative Crystallization.

PubMed

Lansiquot, Carisse; Boone-Kukoyi, Zainab; Shortt, Raquel; Thompson, Nishone; Ajifa, Hillary; Kioko, Bridgit; Constance, Edward Ned; Clement, Travis; Ozturk, Birol; Aslan, Kadir

2017-01-01

The use of indium tin oxide (ITO) and focused monomode microwave heating for the ultra-rapid crystallization of L-alanine (a model amino acid) is reported. Commercially available ITO dots (< 5 mm) attached to blank poly(methyl)methacrylate (PMMA, 5 cm in diameter with 21-well silicon isolators: referred to as the iCrystal plates) were found to withstand prolonged microwave heating during crystallization experiments. Crystallization of L-alanine was performed at room temperature (a control experiment), with the use of two microwave sources: a 2.45 GHz conventional microwave (900 W, power level 1, a control experiment) and 8 GHz (20 W) solid state, monomode microwave source with an applicator tip that focuses the microwave field to a 5-mm cavity. Initial appearance of L-alanine crystals and on iCrystal plates with ITO dots took 47 ± 2.9 min, 12 ± 7.6 min and 1.5 ± 0.5 min at room temperature, using a conventional microwave and focused monomode microwave heating, respectively. Complete evaporation of the solvent using the focused microwaves was achieved in 3.2 ± 0.5 min, which is ~52-fold and ~172-fold faster than that observed at room temperature and using conventional microwave heating, respectively. The size and number of L-alanine crystals was dependent on the type of the 21-well iCrystal plates and the microwave heating method: 33 crystals of 585 ± 137 μm in size at room temperature > 37 crystals of 542 ± 100 μm in size with conventional microwave heating > 331 crystals of 311 ± 190 μm in size with focused monomode microwave. FTIR, optical microscopy and powder X-ray diffraction analysis showed that the chemical composition and crystallinity of the L-alanine crystals did not change when exposed to microwave heating and ITO surfaces. In addition, theoretical simulations for the binding of L-alanine molecules to ITO and other metals showed the predicted nature of hydrogen bonds formed between L-alanine and these surfaces.

Ultra-Rapid Crystallization of L-alanine Using Monomode Microwaves, Indium Tin Oxide and Metal-Assisted and Microwave-Accelerated Evaporative Crystallization

PubMed Central

Lansiquot, Carisse; Boone-Kukoyi, Zainab; Shortt, Raquel; Thompson, Nishone; Ajifa, Hillary; Kioko, Bridgit; Constance, Edward Ned; Clement, Travis; Ozturk, Birol; Aslan, Kadir

2018-01-01

The use of indium tin oxide (ITO) and focused monomode microwave heating for the ultra-rapid crystallization of L-alanine (a model amino acid) is reported. Commercially available ITO dots (< 5 mm) attached to blank poly(methyl)methacrylate (PMMA, 5 cm in diameter with 21-well silicon isolators: referred to as the iCrystal plates) were found to withstand prolonged microwave heating during crystallization experiments. Crystallization of L-alanine was performed at room temperature (a control experiment), with the use of two microwave sources: a 2.45 GHz conventional microwave (900 W, power level 1, a control experiment) and 8 GHz (20 W) solid state, monomode microwave source with an applicator tip that focuses the microwave field to a 5-mm cavity. Initial appearance of L-alanine crystals and on iCrystal plates with ITO dots took 47 ± 2.9 min, 12 ± 7.6 min and 1.5 ± 0.5 min at room temperature, using a conventional microwave and focused monomode microwave heating, respectively. Complete evaporation of the solvent using the focused microwaves was achieved in 3.2 ± 0.5 min, which is ~52-fold and ~172-fold faster than that observed at room temperature and using conventional microwave heating, respectively. The size and number of L-alanine crystals was dependent on the type of the 21-well iCrystal plates and the microwave heating method: 33 crystals of 585 ± 137 μm in size at room temperature > 37 crystals of 542 ± 100 μm in size with conventional microwave heating > 331 crystals of 311 ± 190 μm in size with focused monomode microwave. FTIR, optical microscopy and powder X-ray diffraction analysis showed that the chemical composition and crystallinity of the L-alanine crystals did not change when exposed to microwave heating and ITO surfaces. In addition, theoretical simulations for the binding of L-alanine molecules to ITO and other metals showed the predicted nature of hydrogen bonds formed between L-alanine and these surfaces. PMID:29657884

Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

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

Gaudet, J; Hallas, A. A.; Kolesnikov, Alexander I.

We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er 2B 2O 7 with B=Ge, Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4f 11Er 3+ and nonmagnetic B 4+. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er 2B 2O 7 pyrochlores. The different ionic sizes associated with different nonmagnetic B 4+ cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise tomore » different local environments at the Er 3+ site. Our results show that the g-tensor components are XY-like for all four members of the Er 2B 2O 7 series. However, the XY anisotropy is much stronger for Er 2Pt 2O 7 and Er 2Sn 2O 7(g⊥/gz>25) than for Er 2Ge 2O 7 and Er 2Ti 2O 7(g⊥/gz<4). The variation in the nature of the XY anisotropy in these systems correlates strongly with their ground states as Er 2Ge 2O 7 and Er 2Ti 2O 7 order into Γ 5 magnetic structures, whereas Er 2Pt 2O 7 and Er 2Sn 2O 7 order in the Γ 7 Palmer-Chalker structure.« less

Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

NASA Astrophysics Data System (ADS)

Gaudet, J.; Hallas, A. M.; Kolesnikov, A. I.; Gaulin, B. D.

2018-01-01

We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er2B2O7 with B =Ge , Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4 f11Er3 + and nonmagnetic B4 +. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er2B2O7 pyrochlores. The different ionic sizes associated with different nonmagnetic B4 + cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise to different local environments at the Er3 + site. Our results show that the g -tensor components are X Y -like for all four members of the Er2B2O7 series. However, the X Y anisotropy is much stronger for Er2Pt2O7 and Er2Sn2O7(g⊥/gz>25 ) than for Er2Ge2O7 and Er2Ti2O7(g⊥/gz<4 ) . The variation in the nature of the X Y anisotropy in these systems correlates strongly with their ground states as Er2Ge2O7 and Er2Ti2O7 order into Γ5 magnetic structures, whereas Er2Pt2O7 and Er2Sn2O7 order in the Γ7 Palmer-Chalker structure.

Effect of chemical pressure on the crystal electric field states of erbium pyrochlore magnets

DOE PAGES

Gaudet, J; Hallas, A. A.; Kolesnikov, Alexander I.; ...

2018-01-17

We have carried out a systematic study of the crystal electric field excitations in the family of cubic pyrochlores Er 2B 2O 7 with B=Ge, Ti, Pt, and Sn, using neutron spectroscopy. All members of this family are magnetic insulators based on 4f 11Er 3+ and nonmagnetic B 4+. At sufficiently low temperatures, long-range antiferromagnetic order is observed in each of these Er 2B 2O 7 pyrochlores. The different ionic sizes associated with different nonmagnetic B 4+ cations correspond to positive or negative chemical pressure, depending on the relative contraction or expansion of the crystal lattice, which gives rise tomore » different local environments at the Er 3+ site. Our results show that the g-tensor components are XY-like for all four members of the Er 2B 2O 7 series. However, the XY anisotropy is much stronger for Er 2Pt 2O 7 and Er 2Sn 2O 7(g⊥/gz>25) than for Er 2Ge 2O 7 and Er 2Ti 2O 7(g⊥/gz<4). The variation in the nature of the XY anisotropy in these systems correlates strongly with their ground states as Er 2Ge 2O 7 and Er 2Ti 2O 7 order into Γ 5 magnetic structures, whereas Er 2Pt 2O 7 and Er 2Sn 2O 7 order in the Γ 7 Palmer-Chalker structure.« less

Crystallization and preliminary X-ray diffraction analysis of red clover necrotic mosaic virus

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

Martin, Stanton L.; Guenther, Richard H.; Sit, Tim L.

2010-11-12

Red clover necrotic mosaic virus (RCNMV) is a species that belongs to the Tombusviridae family of plant viruses with a T = 3 icosahedral capsid. RCNMV virions were purified and were crystallized for X-ray analysis using the hanging-drop vapor-diffusion method. Self-rotation functions and systematic absences identified the space group as I23, with two virions in the unit cell. The crystals diffracted to better than 4 {angstrom} resolution but were very radiation-sensitive, causing rapid decay of the high-resolution reflections. The data were processed to 6 {angstrom} in the analysis presented here.

Physical and chemical properties of ice residuals during the 2013 and 2014 CLACE campaigns

NASA Astrophysics Data System (ADS)

Kupiszewski, Piotr; Weingartner, Ernest; Vochezer, Paul; Hammer, Emanuel; Gysel, Martin; Färber, Raphael; Fuchs, Claudia; Schnaiter, Martin; Baltensperger, Urs; Schmidt, Susan; Schneider, Johannes; Bigi, Alessandro; Toprak, Emre; Linke, Claudia; Klimach, Thomas

2014-05-01

The shortcomings in our understanding and, thus, representation of aerosol-cloud interactions are one of the major sources of uncertainty in climate model projections. Among the poorly understood processes is mixed-phase cloud formation via heterogeneous nucleation, and the subsequent spatial and temporal evolution of such clouds. Cloud glaciation augments precipitation formation, resulting in decreased cloud cover and lifetime, and affects cloud radiative properties. Meanwhile, the physical and chemical properties of atmospherically relevant ice nuclei (IN), the sub-population of aerosol particles which enable heterogeneous nucleation, are not well known. Extraction of ice residuals (IR) in mixed-phase clouds is a difficult task, requiring separation of the few small, freshly formed ice crystals (the IR within such crystals can be deemed representative of the original IN) not only from interstitial particles, but also from the numerous supercooled droplets which have aerodynamic diameters similar to those of the ice crystals. In order to address the difficulties with ice crystal sampling and IR extraction in mixed-phase clouds, the new Ice Selective Inlet (ISI) has been designed and deployed at the Jungfraujoch field site. Small ice crystals are selectively sampled via the inlet with simultaneous counting, sizing and imaging of hydrometeors contained in the cloud by a set of optical particle spectrometers, namely Welas optical particle counters (OPC) and a Particle Phase Discriminator (PPD). The heart of the ISI is a droplet evaporation unit with ice-covered inner walls, resulting in removal of droplets using the Wegener-Bergeron-Findeisen process, while transmitting a relatively high fraction of small ice crystals. The ISI was deployed in the winters of 2013 and 2014 at the high alpine Jungfraujoch site (3580 m.a.s.l) during the intensive CLACE field campaigns. The measurements focused on analysis of the physical and chemical characteristics of IR and the

Photonic crystal sensors: Physics and applications

NASA Astrophysics Data System (ADS)

Dinodiya, Sapna; Suthar, B.; Bhargava, A.

2018-05-01

Photonic sensors have evolved rapidly in last few decades because of the major requirement of sensing applications in optical communication and biomedical diagnostics. Photonic crystals are of tremendous use in designing photonic sensors. Any physical phenomenon, for instance temperature, pressure, strain, and presence of chemicals and bio molecules that can alter periodicity and refractive index of structure of the photonic crystal, can be sensed by measuring optical properties like spectral pattern of reflected and transmitted power. The physics and applications of various photonic crystal sensors are presented in this article.

Spectroscopic and quantum chemical perspectives on 2-amino 5-methylpyridinium 4-nitrobenzoate - An organic single crystals for optoelectronics device applications

NASA Astrophysics Data System (ADS)

Gandhimathi, A.; Karunakaran, R. T.; Kumaran, A. Elakkina; Prabahar, S.

2018-07-01

In this work, an optical quality single crystals of 2-amino 5-methylpyridinium 4-nitrobenzoate (2A5MPNB) were grown by slow evaporation solution growth technique using methanol as a solvent. The phases and functional groups of 2A5MPNB have been confirmed through powder X-ray diffraction and Fourier transform infrared (FTIR) studies, respectively. The optical transmittance window and the lower cut-off wavelength of the 2A5MPNB have been identified by UV-Vis-NIR studies. Dielectric and photoconductivity studies were also performed for the grown crystals. In order to analyze the mechanical strength Vickers hardness studies were taken for the grown crystal. The thermal behaviour was investigated by TG/DTA studies. NLO and laser damage properties were explored using Nd:YAG laser. Moreover, the quantum chemical calculations on 2A5MPNB have been performed by density functional theory (DFT) calculations using the B3LYP method with 6-311++G(d,p) basis set. The predicted first hyperpolarizability is found to be 14.45 times greater than that of urea and suggests that the title compound could be an attractive material for nonlinear optical applications.

Tribochemical wear of single crystal aluminum in NaCl solution studied by atomic force microscopy

NASA Astrophysics Data System (ADS)

Cai, M.; Langford, S. C.; Dickinson, J. T.

2011-09-01

We report a systematic study of chemically enhanced wear of single crystal aluminum surfaces in aqueous solutions using an environmentally equipped atomic force microscope (AFM). The experiments were conducted by using a standard Si3N4 AFM tip to apply a localized force on a polished, single crystal aluminum (110) surface. Most measurements were performed in 0.5 M NaCl solution. We show the effect of applied force, number of scans, chemical solution, and temperature on the chemical-mechanical wear of aluminum on the nanometer scale. Aggressive chemical environments significantly enhance the wear of aluminum relative to scanning in dry air. Quantitative measurements show that the wear volume increases in proportion to the square root of force and the number of scans (or time). Arrhenius plots of wear volume versus temperature are consistent with an activation energy of 31 kJ/mol for scanning in 0.5 M NaCl. The wear of the AFM tip and the aluminum substrate is explained in terms of the synergistic surface chemical reactions and mechanical action of the tip. We compare these results to previous studies of AFM wear of silicate glass.

Crystallization and preliminary X-ray diffraction analysis of Leishmania major dihydroorotate dehydrogenase

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

Cordeiro, Artur T.; Feliciano, Patricia R.; Nonato, M. Cristina, E-mail: cristy@fcfrp.usp.br

2006-10-01

Dihydroorotate dehydrogenase from L. major has been crystallized by the vapour-diffusion technique using lithium sulfate as the precipitant agent. A complete data set from a native crystal has been collected to 2.0 Å resolution using an in-house rotating-anode generator. Dihydroorotate dehydrogenases (DHODHs) are flavin-containing enzymes that catalyze the oxidation of l-dihydroorotate to orotate, the fourth step in the de novo pyrimidine nucleotide synthesis pathway. In this study, DHODH from Leishmania major has been crystallized by the vapour-diffusion technique using lithium sulfate as the precipitating agent. The crystals belong to space group P6{sub 1}, with unit-cell parameters a = 143.7, cmore » = 69.8 Å. X-ray diffraction data were collected to 2.0 Å resolution using an in-house rotating-anode generator. Analysis of the solvent content and the self-rotation function indicate the presence of two molecules in the asymmetric unit. The structure has been solved by the molecular-replacement technique.« less

Discrimination Enhancement with Transient Feature Analysis of a Graphene Chemical Sensor.

PubMed

Nallon, Eric C; Schnee, Vincent P; Bright, Collin J; Polcha, Michael P; Li, Qiliang

2016-01-19

A graphene chemical sensor is subjected to a set of structurally and chemically similar hydrocarbon compounds consisting of toluene, o-xylene, p-xylene, and mesitylene. The fractional change in resistance of the sensor upon exposure to these compounds exhibits a similar response magnitude among compounds, whereas large variation is observed within repetitions for each compound, causing a response overlap. Therefore, traditional features depending on maximum response change will cause confusion during further discrimination and classification analysis. More robust features that are less sensitive to concentration, sampling, and drift variability would provide higher quality information. In this work, we have explored the advantage of using transient-based exponential fitting coefficients to enhance the discrimination of similar compounds. The advantages of such feature analysis to discriminate each compound is evaluated using principle component analysis (PCA). In addition, machine learning-based classification algorithms were used to compare the prediction accuracies when using fitting coefficients as features. The additional features greatly enhanced the discrimination between compounds while performing PCA and also improved the prediction accuracy by 34% when using linear discrimination analysis.